[ { "id": "https://authors.library.caltech.edu/records/2kb3w-53552", "eprint_id": 113922, "eprint_status": "archive", "datestamp": "2023-08-20 07:17:04", "lastmod": "2023-10-23 23:16:33", "type": "monograph", "metadata_visibility": "show", "creators": { "items": [ { "id": "Brennon-Bradley-J", "name": { "family": "Brennon", "given": "Bradley" } }, { "id": "Ngo-Danh-X", "name": { "family": "Ngo", "given": "Danh X." }, "orcid": "0000-0001-6984-2538" }, { "id": "Kramer-Wesley-W", "name": { "family": "Kramer", "given": "Wesley W." }, "orcid": "0000-0002-1359-0519" } ] }, "title": "Pendent trifluoroethanol reveals solvation dependent mechanisms of electrocatalytic CO\u2082 reduction by rhenium(I) bipyridine fac-tricarbonyl", "ispublished": "unpub", "full_text_status": "public", "note": "The content is available under CC BY NC ND 4.0 License.\n\nWe acknowledged Harry Gray for his unwavering support and exceptional mentorship. We thank Larry Henling, Michael Takase, David VanderVelde, Mona Shahgholi, and Naseem Torian for experimental assistance and discussions. \n\nThis work was performed in the lab of Prof. Harry B. Gray and funded by NSF CCI Solar Fuels (CHE-130124). Additional support was provided by the Resnick Sustainability Institute at Caltech and a Dr. and Mrs. Daniel C. Harris SURF Fellowship. \n\nThe authors declare no competing financial interest.\n\nThe author(s) declare that they have sought and gained approval from the relevant ethics committee/IRB for this research and its publication.\n\n
Supplemental Material - supporting-information.pdf
", "abstract": "Local proton sources capable of interacting with catalytic intermediates have been shown to affect proton-dependent reactions. Herein we report the synthesis of a Re(diimine)(CO)\u2083Cl catalyst analog containing a trifluoroethanol-appended bipyridine ligand (bpy-CF\u2083OH), and the corresponding methyl-ether (bpy-CF\u2083OMe) to study the role of the pendent proton donor in electrocatalytic CO\u2082 reduction. Compared to the parent catalyst, Re(bpy)(CO)\u2083Cl, and Re(bpy-CF\u2083OMe)(CO)\u2083Cl, the alcohol analog revealed additional electrocatalytic features and a 200 mV anodic shift in catalytic onset potential. We also show evidence of proton-coupled electron transfer or hydrogen bond-assisted catalysis in all analogs, detailed by a progressive anodic shift in the main catalytic wave with increasing [H\u2082O] which displays slopes of ~120 mV log[H\u2082O]\u207b\u00b9. Multiple catalytic mechanisms appeared to occur simultaneously in all the analogs, and attempts were made to differentiate their dependence on [H\u2082O] and [CO\u2082]. The effect of a local proton source is significant under conditions where [H\u2082O] < 1 M but becomes negligible at high [H\u2082O]. These results suggest that the appended alcohol affects the solvation of the molecule, and may act directly as a proton source or as part of a proton shuttle.", "date": "2022-03-16", "date_type": "published", "id_number": "CaltechAUTHORS:20220315-626291000", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20220315-626291000", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-130124" }, { "agency": "Resnick Sustainability Institute" }, { "agency": "Caltech Summer Undergraduate Research Fellowship (SURF)" }, { "agency": "Dr. and Mrs. Daniel C. Harris" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" }, { "id": "Resnick-Sustainability-Institute" } ] }, "doi": "10.26434/chemrxiv-2022-480fn", "primary_object": { "basename": "pendent-trifluoroethanol-reveals-solvation-dependent-mechanisms-of-electrocatalytic-co2-reduction-by-rhenium-i-bipyridine-fac-tricarbonyl.pdf", "url": "https://authors.library.caltech.edu/records/2kb3w-53552/files/pendent-trifluoroethanol-reveals-solvation-dependent-mechanisms-of-electrocatalytic-co2-reduction-by-rhenium-i-bipyridine-fac-tricarbonyl.pdf" }, "related_objects": [ { "basename": "supporting-information.pdf", "url": "https://authors.library.caltech.edu/records/2kb3w-53552/files/supporting-information.pdf" } ], "pub_year": "2022", "author_list": "Brennon, Bradley; Ngo, Danh X.; et el." }, { "id": "https://authors.library.caltech.edu/records/ppn6p-w4f28", "eprint_id": 112157, "eprint_status": "archive", "datestamp": "2023-08-20 07:15:24", "lastmod": "2023-10-23 20:56:14", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Mazza-Michael-F", "name": { "family": "Mazza", "given": "Michael F." }, "orcid": "0000-0003-3995-3100" }, { "id": "Cab\u00e1n-Acevedo-Miguel", "name": { "family": "Cab\u00e1n-Acevedo", "given": "Miguel" }, "orcid": "0000-0003-0054-8044" }, { "id": "Fu-Harold-J", "name": { "family": "Fu", "given": "Harold J." }, "orcid": "0000-0001-9738-209X" }, { "id": "Meier-Madeline-C", "name": { "family": "Meier", "given": "Madeline C." }, "orcid": "0000-0003-1608-0810" }, { "id": "Thompson-Annelise-C", "name": { "family": "Thompson", "given": "Annelise C." }, "orcid": "0000-0003-2414-7050" }, { "id": "Ifkovits-Zachary-P", "name": { "family": "Ifkovits", "given": "Zachary P." }, "orcid": "0000-0003-2538-0794" }, { "id": "Carim-Azhar-I", "name": { "family": "Carim", "given": "Azhar I." }, "orcid": "0000-0003-3630-6872" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Selective-Area, Water-Free Atomic Layer Deposition of Metal Oxides on Graphene Defects", "ispublished": "pub", "full_text_status": "public", "keywords": "atomic layer deposition, graphene, defect driven reactivity, defect passivation, device integration", "note": "\u00a9 2021 The Authors. Published by American Chemical Society. Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0). \n\nReceived 20 September 2021. Accepted 11 November 2021. Revised 9 November 2021. Published online 19 November 2021. \n\nM.F.M. and N.S.L. acknowledge support from the U.S. Department of Energy under Award DE-FG02-04ER15483. M.C. acknowledges support from the Ford Foundation under the Postdoctoral Scholar Fellowship program. M.C. acknowledges support from the National Science Foundation CCI Solar Fuels Program under Grant No. CHE-1305124. A.C.T. and M.C.M. acknowledge support from National Science Foundation graduate research fellowships. M.C.M. also acknowledges the Resnick Sustainability Institute at Caltech for fellowship support. Research was in part carried out at the Molecular Materials Research Center in the Beckman Institute at the California Institute of Technology. \n\nThe authors declare no competing financial interest.\n\nPublished - acsmaterialsau.1c00049.pdf
Supplemental Material - mg1c00049_si_001.pdf
", "abstract": "Passivating defective regions on monolayer graphene with metal oxides remains an active area of research for graphene device integration. To effectively passivate these regions, a water-free atomic layer deposition (ALD) recipe was developed and yielded selective-area ALD (sa-ALD) of mixed-metal oxides onto line defects in monolayer graphene. The anisotropically deposited film targeted high-energy defect sites that were formed during synthesis or transfer of the graphene layer. The passivating layer exceeded 10 nm thickness with minimal deposition onto the basal plane of graphene. The mixed-metal oxide film was of comparable quality to films deposited using nonselective water-based ALD methods, as shown by X-ray photoelectron spectroscopy. The development of sa-ALD techniques to target defect regions on the graphene sheet, while keeping the basal plane intact, will provide a new mechanism to passivate graphene defects and modify the electronic and physical properties of graphene.", "date": "2022-03-09", "date_type": "published", "publication": "ACS Materials Au", "volume": "2", "number": "2", "publisher": "American Chemical Society", "pagerange": "74-78", "id_number": "CaltechAUTHORS:20211201-231211106", "issn": "2694-2461", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20211201-231211106", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG02-04ER15483" }, { "agency": "Ford Foundation" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "NSF Graduate Research Fellowship" }, { "agency": "Resnick Sustainability Institute" } ] }, "local_group": { "items": [ { "id": "Resnick-Sustainability-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acsmaterialsau.1c00049", "pmcid": "PMC9888651", "primary_object": { "basename": "acsmaterialsau.1c00049.pdf", "url": "https://authors.library.caltech.edu/records/ppn6p-w4f28/files/acsmaterialsau.1c00049.pdf" }, "related_objects": [ { "basename": "mg1c00049_si_001.pdf", "url": "https://authors.library.caltech.edu/records/ppn6p-w4f28/files/mg1c00049_si_001.pdf" } ], "pub_year": "2022", "author_list": "Mazza, Michael F.; Cab\u00e1n-Acevedo, Miguel; et el." }, { "id": "https://authors.library.caltech.edu/records/5htrq-kjp09", "eprint_id": 104162, "eprint_status": "archive", "datestamp": "2023-08-19 22:34:15", "lastmod": "2023-10-20 19:08:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Cab\u00e1n-Acevedo-M", "name": { "family": "Cab\u00e1n-Acevedo", "given": "Miguel" } }, { "id": "Papadantonakis-Kimberly-M", "name": { "family": "Papadantonakis", "given": "Kimberly M." }, "orcid": "0000-0002-9900-5500" }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Surface Passivation and Positive Band-Edge Shift of p-Si(111) Surfaces Functionalized with Mixed Methyl/Trifluoromethylphenylacetylene Overlayers", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2020 American Chemical Society. \n\nReceived: March 9, 2020; Revised: June 29, 2020; Published: June 30, 2020. \n\nM.C. acknowledges support from the Ford Foundation under the Postdoctoral Scholar Fellowship program. B.S.B. and M.C. acknowledge support from the National Science Foundation CCI Solar Fuels Program under grant no. CHE-1305124. N.S.L. and M.C. acknowledges support from the National Science Foundation under grant no. CHE-1808599. Instrumentation support was provided by the Molecular Materials Resource Center of the Beckman Institute at the California Institute of Technology. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - jp0c02017_si_001.pdf
", "abstract": "Chemical functionalization of semiconductor surfaces can provide high-efficiency photoelectrochemical devices through molecular-level control of the energetics, surface dipole, surface electronic defects, and chemical reactivity at semiconductor/electrolyte junctions. We describe the covalent functionalization by nucleophilic addition chemistry of p-Si(111) surfaces to produce mixed overlayers of trifluoromethylphenylacetylene (TFMPA) and methyl moieties. Functionalization of Cl-terminated Si(111) surfaces with TFMPA moieties introduced a positive surface molecular dipole that in contact with CH\u2083CN or Hg produced a positive band-edge shift of the semiconductor relative to junctions with CH\u2083-Si(111) surfaces. Methylation of the Cl/TFMPA surfaces using methylmagnesium chloride resulted in the degradation of the TFMPA moieties, whereas methylation using methylzinc chloride allowed controlled production of mixed TFMPA/methyl-terminated surfaces and permitted reversal of the order of the functionalization steps so that nucleophilic addition of TFMPA could be accomplished after methylation of Cl\u2013Si(111) surfaces. Mixed TFMPA/methyl functionalization resulted in a Si(111) surface with surface recombination velocities of 2 \u00d7 10\u00b2 cm s\u207b\u00b9 that exhibited an \u223c150 mV positive band-edge shift relative to CH\u2083\u2013Si(111) surfaces.", "date": "2020-07-30", "date_type": "published", "publication": "Journal of Physical Chemistry C", "volume": "124", "number": "30", "publisher": "American Chemical Society", "pagerange": "16338-16349", "id_number": "CaltechAUTHORS:20200630-105347382", "issn": "1932-7447", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200630-105347382", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Ford Foundation" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "NSF", "grant_number": "CHE-1808599" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.jpcc.0c02017", "primary_object": { "basename": "jp0c02017_si_001.pdf", "url": "https://authors.library.caltech.edu/records/5htrq-kjp09/files/jp0c02017_si_001.pdf" }, "pub_year": "2020", "author_list": "Cab\u00e1n-Acevedo, Miguel; Papadantonakis, Kimberly M.; et el." }, { "id": "https://authors.library.caltech.edu/records/3vefm-jhr06", "eprint_id": 102116, "eprint_status": "archive", "datestamp": "2023-08-19 20:55:11", "lastmod": "2023-10-19 23:51:41", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Mazza-M-F", "name": { "family": "Mazza", "given": "Michael F." } }, { "id": "Cab\u00e1n-Acevedo-M", "name": { "family": "Cab\u00e1n-Acevedo", "given": "Miguel" } }, { "id": "Wiensch-J-D", "name": { "family": "Wiensch", "given": "Joshua D." }, "orcid": "0000-0002-8235-6937" }, { "id": "Thompson-A-C", "name": { "family": "Thompson", "given": "Annelise C." }, "orcid": "0000-0003-2414-7050" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Defect-Seeded Atomic Layer Deposition of Metal Oxides on the Basal Plane of 2D Layered Materials", "ispublished": "pub", "full_text_status": "public", "keywords": "Defect driven growth, atomic layer deposition, dislocation networks, 2D\nlayered materials", "note": "\u00a9 2020 American Chemical Society. \n\nReceived: January 14, 2020; Revised: February 28, 2020; Published: March 25, 2020. \n\nM.C. acknowledges support from the Ford Foundation under the Postdoctoral Scholar Fellowship program. M.C. acknowledges support from the National Science Foundation CCI Solar Fuels Program under Grant No. CHE-1305124. M.F.M, J.D.W., and N.S.L. acknowledge support from the U.S. Department of Energy under award DE-FG02-03ER15483. A.C.T. acknowledges support from the Graduate Research Fellowship Program of the National Science Foundation. Research was in part carried out at the Molecular Materials Research Center in the Beckman Institute at the California Institute of Technology. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - nl0c00179_si_001.pdf
", "abstract": "Atomic layer deposition (ALD) on mechanically exfoliated 2D layered materials spontaneously produces network patterns of metal oxide nanoparticles in triangular and linear deposits on the basal surface. The network patterns formed under a range of ALD conditions and were independent of the orientation of the substrate in the ALD reactor. The patterns were produced on MoS2 or HOPG when either tetrakis(dimethylamido)titanium or bis(ethylcyclopentadienyl)manganese were used as precursors, suggesting that the phenomenon is general for 2D materials. Transmission electron microscopy revealed the presence, prior to deposition, of dislocation networks along the basal plane of mechanically exfoliated 2D flakes, indicating that periodical basal plane defects related to disruptions in the van der Waals stacking of layers, such as perfect line dislocations and triangular extended stacking faults networks, introduce a surface reactivity landscape that leads to the emergence of patterned deposition.", "date": "2020-04-08", "date_type": "published", "publication": "Nano Letters", "volume": "20", "number": "4", "publisher": "American Chemical Society", "pagerange": "2632-2638", "id_number": "CaltechAUTHORS:20200326-084207099", "issn": "1530-6984", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200326-084207099", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Ford Foundation" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG02-03ER15483" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.nanolett.0c00179", "primary_object": { "basename": "nl0c00179_si_001.pdf", "url": "https://authors.library.caltech.edu/records/3vefm-jhr06/files/nl0c00179_si_001.pdf" }, "pub_year": "2020", "author_list": "Mazza, Michael F.; Cab\u00e1n-Acevedo, Miguel; et el." }, { "id": "https://authors.library.caltech.edu/records/14nk5-0n489", "eprint_id": 100455, "eprint_status": "archive", "datestamp": "2023-08-19 19:41:01", "lastmod": "2023-10-18 20:33:31", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Sayler-R-I", "name": { "family": "Sayler", "given": "Richard I." } }, { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Fu-Wen", "name": { "family": "Fu", "given": "Wen" } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Britt-R-D", "name": { "family": "Britt", "given": "R. David" }, "orcid": "0000-0003-0889-8436" } ] }, "title": "EPR spectroscopy of iron- and nickel-doped [ZnAl]-layered double hydroxides: modeling active sites in heterogeneous water oxidation catalysts", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2019 American Chemical Society. \n\nReceived: September 23, 2019; Published: December 31, 2019. \n\nThis work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - ja9b10273_si_001.pdf
", "abstract": "Iron-doped nickel layered double hydroxides (LDHs) are among the most active heterogeneous water oxidation catalysts. Due to inter-spin interactions, however, the high density of magnetic centers results in line-broadening in magnetic resonance spectra. As a result, gaining atomic-level insight into the catalytic mechanism via electron paramagnetic resonance (EPR) is not generally possible. To circumvent spin-spin broadening, iron and nickel atoms were doped into non-magnetic [ZnAl]-LDH materials and the coordination environments of the isolated Fe(III) and Ni(II) sites were characterized. Multifrequency EPR spectroscopy identified two distinct Fe(III) sites (S = 5/2) in [Fe:ZnAl]-LDH. Changes in zero field splitting (ZFS) were induced by dehydration of the material, revealing that one of the Fe(III) sites is solvent-exposed (i.e. at an edge, corner, or defect site). These solvent-exposed sites feature an axial ZFS of 0.21 cm\u207b\u00b9 when hydrated. The ZFS increases dramatically upon dehydration (to -1.5 cm\u207b\u00b9), owing to lower symmetry and a decrease in the coordination number of iron. The ZFS of the other (\"inert\") Fe(III) site maintains an axial ZFS of 0.19-0.20 cm\u207b\u00b9 under both hydrated and dehydrated conditions. We observed a similar effect in [Ni:ZnAl]-LDH materials; notably, Ni(II) (S = 1) atoms displayed a single, small ZFS (\u00b10.30 cm\u207b\u00b9) in hydrated material, whereas two distinct Ni(II) ZFS values (\u00b10.30 and \u00b11.1 cm\u207b\u00b9) were observed in the dehydrated samples. Although the magnetically-dilute materials were not active catalysts, the identification of model sites in which the coordination environments of iron and nickel were particularly labile (e.g. by simple vacuum drying) is an important step towards identifying sites in which the coordination number may drop spontaneously in water, a probable mechanism of water oxidation in functional materials.", "date": "2020-01-29", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "142", "number": "4", "publisher": "American Chemical Society", "pagerange": "1838-1845", "id_number": "CaltechAUTHORS:20200102-104558690", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200102-104558690", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/jacs.9b10273", "primary_object": { "basename": "ja9b10273_si_001.pdf", "url": "https://authors.library.caltech.edu/records/14nk5-0n489/files/ja9b10273_si_001.pdf" }, "pub_year": "2020", "author_list": "Sayler, Richard I.; Hunter, Bryan M.; et el." }, { "id": "https://authors.library.caltech.edu/records/ham6d-jhk46", "eprint_id": 99536, "eprint_status": "archive", "datestamp": "2023-08-19 19:02:05", "lastmod": "2023-10-18 18:32:39", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Giesbrecht-P-K", "name": { "family": "Giesbrecht", "given": "Patrick K." }, "orcid": "0000-0003-2039-4791" }, { "id": "M\u00fcller-A-M", "name": { "family": "M\u00fcller", "given": "Astrid M." }, "orcid": "0000-0002-2785-6808" }, { "id": "Read-C-G", "name": { "family": "Read", "given": "Carlos G." } }, { "id": "Holdcroft-S", "name": { "family": "Holdcroft", "given": "Steven" } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Freund-M-S", "name": { "family": "Freund", "given": "Michael S." }, "orcid": "0000-0003-1104-2292" } ] }, "title": "Vapor-fed electrolysis of water using earth-abundant catalysts in Nafion or in bipolar Nafion/poly(benzimidazolium) membranes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2019 The Royal Society of Chemistry. \n\nThe article was received on 17 Aug 2019, accepted on 23 Oct 2019 and first published on 28 Oct 2019. \n\nSupport for this work was provided by the United States National Science Foundation (NSF) under the CCI Solar Fuels Program, Grant No. CHE-1305124, the Natural Sciences and Engineering Research Council of Canada (NSERC), as well as the Canada Foundation for Innovation (CFI). We are grateful to Kimberly Papadantonakis for helpful comments and technical editing of the manuscript. \n\nThere are no conflicts to declare.\n\nSupplemental Material - c9se00672a1_si.pdf
", "abstract": "Vapor-fed electrolysis of water has been performed using membrane-electrode assemblies (MEAs) incorporating earth-abundant catalysts and bipolar membranes (BPMs). Catalyst films containing CoP nanoparticles, carbon black, and Nafion were synthesized, characterized, and integrated into cathodes of MEAs. The CoP-containing MEAs exhibited stable (>16 h) vapor-fed electrolysis of water at room temperature at a current density of 10 mA cm\u207b\u00b2 with 350 mV of additional overvoltage relative to MEA's formed from Pt/C cathodic electrocatalysts due to slower hydrogen-evolution reaction kinetics under vapor-fed conditions and fewer available triple-phase boundaries in the catalyst film. Additionally, catalyst films containing a [NiFe]-layered double hydroxide ([NiFe]-LDH) as well as a hydroxide ion conductor, hexamethyl-p-terphenyl poly(benzimidazolium) (HMT-PMBI), were synthesized, characterized, and integrated into the anodes of the MEAs. The [NiFe]-LDH-containing MEAs exhibited overvoltages at 10 mA cm\u207b\u00b2 that were similar to those of IrO_x-containing MEAs for vapor-fed electrolysis of water at room temperature. A BPM was formed by pairing Nafion with HMT-PMBI, resulting in a locally alkaline environment of HMT-PMBI to stabilize the [NiFe]-LDH and a locally acidic environment to stabilize the CoP. BPM-based MEAs were stable (>16 h) for vapor-fed electrolysis of water at room temperature at a current density of 10 mA cm\u207b\u00b2, with a change in the pH gradient of 1 unit over 16 h of electrolysis for IrOx-containing MEAs. The stability of [NiFe]-LDH-based MEAs under vapor-fed conditions was dependent on the catalyst film morphology and resulting BPM interface, with stable operation at 10 mA cm\u207b\u00b2 achieved for 16 h. All MEAs exhibited a drift in the operating voltage over time associated with dehydration. These results demonstrate that earth-abundant catalysts and BPMs can be incorporated into stable, room-temperature, vapor-fed water-splitting cells operated at 10 mA cm\u207b\u00b2.", "date": "2019-12-01", "date_type": "published", "publication": "Sustainable Energy and Fuels", "volume": "3", "number": "12", "publisher": "Royal Society of Chemistry", "pagerange": "3611-3626", "id_number": "CaltechAUTHORS:20191029-113947239", "issn": "2398-4902", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20191029-113947239", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "Canada Foundation for Innovation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c9se00672a", "primary_object": { "basename": "c9se00672a1_si.pdf", "url": "https://authors.library.caltech.edu/records/ham6d-jhk46/files/c9se00672a1_si.pdf" }, "pub_year": "2019", "author_list": "Giesbrecht, Patrick K.; M\u00fcller, Astrid M.; et el." }, { "id": "https://authors.library.caltech.edu/records/wthpb-p9y50", "eprint_id": 89440, "eprint_status": "archive", "datestamp": "2023-08-19 12:04:59", "lastmod": "2023-10-18 22:45:17", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lau-Marcus", "name": { "family": "Lau", "given": "Marcus" } }, { "id": "Reichenberger-S", "name": { "family": "Reichenberger", "given": "Sven" } }, { "id": "Haxhiaj-I", "name": { "family": "Haxhiaj", "given": "Ina" } }, { "id": "Barcikowski-S", "name": { "family": "Barcikowski", "given": "Stephan" }, "orcid": "0000-0002-9739-7272" }, { "id": "M\u00fcller-A-M", "name": { "family": "M\u00fcller", "given": "Astrid M." }, "orcid": "0000-0002-2785-6808" } ] }, "title": "Mechanism of Laser-Induced Bulk and Surface Defect Generation in ZnO and TiO_2 Nanoparticles: Effect on Photoelectrochemical Performance", "ispublished": "pub", "full_text_status": "public", "keywords": "pulsed laser processing, defect density, photoelectrochemistry, zinc oxide, titanium dioxide", "note": "\u00a9 2018 American Chemical Society. \n\nReceived: June 15, 2018; Accepted: September 6, 2018; Published: September 6, 2018. \n\nWe thank Prof. Dr. Hartmut Wiggers (University of Duisburg-Essen) for access to the photoluminescence spectrometer. We also gratefully acknowledge financial support from the European Regional Development Fund (Interreg Europe) that funded M.L. within the SAILPRO (Safe and Amplified Industrial Laser Processing) project, part of the ROCKET-Project (RegiOnal Collaboration on Key Enabling Technologies). S.R. thanks the Mercator Research Center Ruhr (MERCUR), Grant Pr-2014-0044, and I.H. the German Federal Environmental Foundation (DBU). S.B. thanks the German Research Foundation for funding within CRC TRR 247. Research at the California Institute of Technology was carried out in the Molecular Materials Research Center of the Beckman Institute and was supported by the NSF CCI Solar Fuels Program (Grant CHE-1305124) and the Arnold and Mabel Beckman Foundation. \n\nAuthor Contributions: M.L. and S.R. contributed equally to this work, and both should be considered as the first author. All authors contributed to writing the manuscript and agreed on its final content. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - ae8b00977_si_001.pdf
", "abstract": "Laser processing of neat and gold-nanoparticle-functionalized ZnO and TiO_2 nanoparticles by nanosecond\u2013355 nm or picosecond\u2013532 nm light enabled control of photocurrent generation under simulated sunlight irradiation in neutral aqueous electrolytes. We obtained more than 2-fold enhanced photoelectrochemical performance of TiO2 nanoparticles upon irradiation by picosecond\u2013532 nm pulses that healed defects. Laser processing and gold nanoparticle functionalization of ZnO and TiO_2 nanomaterials resulted in color changes that did not originate from optical bandgaps or crystal structures. Two-dimensional photoluminescence data allowed us to differentiate and quantify surface and bulk defects that play a critical yet oft-underappreciated role for photoelectrochemical performance as sites for detrimental carrier recombination. We developed a detailed mechanistic model of how surface and bulk defects were generated as a function of laser processing parameters and obtained key insights on how these defects affected photocurrent production. The controlled healing of defects by pulsed-laser processing may be useful in the design of solar fuels materials.", "date": "2018-10-22", "date_type": "published", "publication": "ACS Applied Energy Materials", "volume": "1", "number": "10", "publisher": "American Chemical Society", "pagerange": "5366-5385", "id_number": "CaltechAUTHORS:20180907-072713927", "issn": "2574-0962", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180907-072713927", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "European Regional Development Fund" }, { "agency": "Mercator Research Center Ruhr", "grant_number": "Pr-2014-0044" }, { "agency": "Deutsche Bundesstiftung Umwelt (DBU)" }, { "agency": "Deutsche Forschungsgemeinschaft (DFG)", "grant_number": "CRC TRR 247" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acsaem.8b00977", "primary_object": { "basename": "ae8b00977_si_001.pdf", "url": "https://authors.library.caltech.edu/records/wthpb-p9y50/files/ae8b00977_si_001.pdf" }, "pub_year": "2018", "author_list": "Lau, Marcus; Reichenberger, Sven; et el." }, { "id": "https://authors.library.caltech.edu/records/etbm7-cz134", "eprint_id": 86213, "eprint_status": "archive", "datestamp": "2023-08-19 09:22:28", "lastmod": "2023-10-18 19:22:03", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Roberts-E-J", "name": { "family": "Roberts", "given": "Emily J." } }, { "id": "Read-C-G", "name": { "family": "Read", "given": "Carlos G." } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Brutchey-R-L", "name": { "family": "Brutchey", "given": "Richard L." }, "orcid": "0000-0002-7781-5596" } ] }, "title": "Phase Directing Ability of an Ionic Liquid Solvent for the Synthesis of HER-Active Ni_2P Nanocrystals", "ispublished": "pub", "full_text_status": "public", "keywords": "ionic liquid, nickel phosphide, nanocrystal, electrocatalyst, hydrogen evolution reaction", "note": "\u00a9 2018 American Chemical Society. \n\nReceived: February 13, 2018; Accepted: May 3, 2018; Published: May 3, 2018. \n\nR.L.B. acknowledges NSF for supporting the synthetic chemistry under CMMI-1728649. N.S.L. acknowledges NSF for supporting the electrochemical characterization work under the NSF CCI Solar Fuels Program CHE-1305124. C.G.R. acknowledges the Resnick Sustainability Institute for a postdoctral fellowship. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - ae8b00213_si_001.pdf
", "abstract": "An ionic liquid (IL) solvent was used to synthesize small, phase-pure nickel phosphide (Ni_2P) nanocrystals. In contrast, under analogous reaction conditions, substitution of the IL for the common high-boiling organic solvent 1-octadecene (ODE) results in phase-impure nanocrystals. The 5 nm Ni_2P nanocrystals prepared in IL were electrocatalytically active toward the hydrogen evolution reaction. The synthesis in IL was also extended to alloyed Ni_(2\u2013x)Co_xP nanocrystals, where 0.5 \u2264 x \u2264 1.5.", "date": "2018-05-29", "date_type": "published", "publication": "ACS Applied Energy Materials", "volume": "1", "number": "5", "publisher": "American Chemical Society", "pagerange": "1823-1827", "id_number": "CaltechAUTHORS:20180503-144511877", "issn": "2574-0962", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180503-144511877", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CMMI-1728649" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Resnick Sustainability Institute" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" }, { "id": "Resnick-Sustainability-Institute" } ] }, "doi": "10.1021/acsaem.8b00213", "primary_object": { "basename": "ae8b00213_si_001.pdf", "url": "https://authors.library.caltech.edu/records/etbm7-cz134/files/ae8b00213_si_001.pdf" }, "pub_year": "2018", "author_list": "Roberts, Emily J.; Read, Carlos G.; et el." }, { "id": "https://authors.library.caltech.edu/records/qrz5z-fcr89", "eprint_id": 84697, "eprint_status": "archive", "datestamp": "2023-08-21 23:12:00", "lastmod": "2023-10-18 16:37:30", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Thompson-N-B", "name": { "family": "Thompson", "given": "Niklas B." }, "orcid": "0000-0003-2745-4945" }, { "id": "M\u00fcller-A-M", "name": { "family": "M\u00fcller", "given": "Astrid M." }, "orcid": "0000-0002-2785-6808" }, { "id": "Rossman-G-R", "name": { "family": "Rossman", "given": "George R." }, "orcid": "0000-0002-4571-6884" }, { "id": "Hill-M-G", "name": { "family": "Hill", "given": "Michael G." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Trapping an Iron(VI) Water-Splitting Intermediate in Nonaqueous Media", "ispublished": "pub", "full_text_status": "public", "keywords": "electrocatalysis; water splitting; water oxidation; solar fuels; spectroscopy; layered double hydroxides; in situ electrochemistry; spectroelectrochemistry; catalysis", "note": "\u00a9 2018 Elsevier Inc. \n\nReceived: December 20, 2017. Revised: January 8, 2018. Accepted: January 11, 2018. Published: February 6, 2018. \n\nThis work was supported by the NSF CCI Solar Fuels Program ( CHE- 1305124 ) and the Arnold and Mabel Beckman Foundation, with additional support from NSF EAR-1322082 . B.M.H. is a Fellow of the Resnick Sustainability Institute at Caltech. The authors thank Jonas Peters for helpful discussions. Additional data and methods are available in the Supplemental Information. \n\nAuthor Contributions: B.M.H. designed and performed the experiments; N.B.T. collected and analyzed the M\u00f6ssbauer spectra; A.M.M. synthesized and characterized the materials; G.R.R. assisted with luminescence and Raman electrochemistry; M.G.H. assisted with electrochemistry and IR spectroelectrochemistry; J.R.W. and H.B.G., with the other authors, developed the proposed mechanism. All authors wrote the manuscript. \n\nThe authors declare no competing interests.\n\nSupplemental Material - mmc1.pdf
", "abstract": "We report in situ spectroscopic measurements in nonaqueous media designed to trap an exceptionally strong oxidant generated electrochemically from an iron-containing nickel layered double hydroxide ([NiFe]-LDH) material. Anodic polarization of this material in acetonitrile produces metal-oxo vibrational spectroscopic signatures along with an extremely narrow near-infrared luminescence peak that strongly indicate that the reactive intermediate is cis-dioxo-iron(VI). Chemical trapping experiments reveal that addition of H_2O to the polarized electrochemical cell produces hydrogen peroxide; and, most importantly, addition of HO\u2013 generates oxygen. Repolarization of the electrode restores the iron(VI) spectroscopic features, confirming that the high-valent oxo complex is active in the electrocatalytic water oxidation cycle.", "date": "2018-04-18", "date_type": "published", "publication": "Joule", "volume": "2", "number": "4", "publisher": "Elsevier", "pagerange": "747-763", "id_number": "CaltechAUTHORS:20180207-065509383", "issn": "2542-4351", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180207-065509383", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE- 1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "NSF", "grant_number": "EAR-1322082" }, { "agency": "Resnick Sustainability Institute" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" }, { "id": "Resnick-Sustainability-Institute" }, { "id": "Division-of-Geological-and-Planetary-Sciences" } ] }, "doi": "10.1016/j.joule.2018.01.008", "primary_object": { "basename": "mmc1.pdf", "url": "https://authors.library.caltech.edu/records/qrz5z-fcr89/files/mmc1.pdf" }, "pub_year": "2018", "author_list": "Hunter, Bryan M.; Thompson, Niklas B.; et el." }, { "id": "https://authors.library.caltech.edu/records/wxyrd-a4p23", "eprint_id": 85964, "eprint_status": "archive", "datestamp": "2023-08-21 23:04:51", "lastmod": "2023-10-18 19:08:20", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hunter-Bryan-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Winkler-Jay-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Iron Is the Active Site in Nickel/Iron Water Oxidation Electrocatalysts", "ispublished": "pub", "full_text_status": "public", "keywords": "oxygen evolution reaction; layered double hydroxide; electrocatalyst", "note": "\u00a9 2018 The Author(s). This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0). \n\nReceived: 28 February 2018 / Revised: 10 April 2018 / Accepted: 12 April 2018 / Published: 14 April 2018. \n\n(This article belongs to the Special Issue Artificial Photosynthesis: Recent Progress in Solar Energy Utilization).\n\nThis work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation. B.M.H. acknowledges a Fellowship from the Resnick Sustainability Institute at Caltech. \n\nThe authors declare no conflict of interest.\n\nPublished - molecules-23-00903.pdf
", "abstract": "Efficient catalysis of the oxygen-evolution half-reaction (OER) is a pivotal requirement for the development of practical solar-driven water splitting devices. Heterogeneous OER electrocatalysts containing first-row transition metal oxides and hydroxides have attracted considerable recent interest, owing in part to the high abundance and low cost of starting materials. Among the best performing OER electrocatalysts are mixed Fe/Ni layered double hydroxides (LDH). A review of the available experimental data leads to the conclusion that iron is the active site for [NiFe]-LDH-catalyzed alkaline water oxidation.", "date": "2018-04", "date_type": "published", "publication": "Molecules", "volume": "23", "number": "4", "publisher": "MDPI", "pagerange": "Art. No. 903", "id_number": "CaltechAUTHORS:20180418-165501153", "issn": "1420-3049", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180418-165501153", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Resnick Sustainability Institute" } ] }, "local_group": { "items": [ { "id": "Resnick-Sustainability-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.3390/molecules23040903", "pmcid": "PMC6017163", "primary_object": { "basename": "molecules-23-00903.pdf", "url": "https://authors.library.caltech.edu/records/wxyrd-a4p23/files/molecules-23-00903.pdf" }, "pub_year": "2018", "author_list": "Hunter, Bryan M.; Winkler, Jay R.; et el." }, { "id": "https://authors.library.caltech.edu/records/shqsf-m3z94", "eprint_id": 82837, "eprint_status": "archive", "datestamp": "2023-08-21 22:56:04", "lastmod": "2023-10-17 22:43:16", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Sinclair-T-S", "name": { "family": "Sinclair", "given": "Timothy S." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "M\u00fcller-A-M", "name": { "family": "M\u00fcller", "given": "Astrid M." }, "orcid": "0000-0002-2785-6808" } ] }, "title": "Photoelectrochemical Performance of BiVO_4 Photoanodes Integrated with [NiFe]-Layered Double Hydroxide Nanocatalysts", "ispublished": "pub", "full_text_status": "public", "keywords": "Artificial photosynthesis; Bismuth; Vanadium; Nanoparticles; Photocatalysis; Electrochemistry", "note": "\u00a9 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nIssue online: 1 March 2018; Version of record online: 6 December 2017; Accepted manuscript online: 31 October 2017; Manuscript Received: 18 October 2017. \n\nWe thank Chi Ma and June Wicks for help with SEM imaging and EDS mapping, and George Rossman for help with reflectance measurements. Research was carried out in the Laser Resource Center and the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology. T. S. S. acknowledges the Caltech SURF office, a Dr. Terry Cole SURF Fellowship, and a Jack and Edith Roberts SURF Fellowship. The National Science Foundation (NSF) CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation supported this work.\n\nSupplemental Material - ejic201701231-sup-0001-SI1.pdf
", "abstract": "We immobilized laser-made nickel iron layered double hydroxide ([NiFe]-LDH) nanocatalysts on BiVO_4 photoanodes. We compared photoelectrochemical performance of integrated [NiFe]-LDH\u2013BiVO_4 photoanodes in sulfite-free aqueous electrolyte with photocurrent generation of neat BiVO_4 photoanodes in aqueous electrolyte with sulfite added as sacrificial hole acceptor. We optimized catalyst mass loading, which is a tradeoff between most efficient depletion of photogenerated holes that drive catalytic turnover and parasitic light absorption by the catalyst particles. We also mitigated nanocatalyst aggregation on the BiVO_4 surface by a surfactant that selectively ligated the catalysts or by dispersing the catalyst suspension more rapidly on the photoanode surface. Our rational optimization strategies enhanced photoelectrochemical performance of integrated nanocatalyst photoanodes: Two thirds of all photogenerated holes escaped loss processes in our optimized integrated [NiFe]-LDH\u2013BiVO_4 photoanodes under 100 mW\u2009cm^(\u20132) of simulated air mass 1.5 G illumination in aqueous pH 9.2 buffered electrolyte. Our systematic optimization strategies for integration of highly efficient water oxidation nanocatalysts with a visible-light absorber provide a path towards functional artificial photosynthesis devices.", "date": "2018-03-07", "date_type": "published", "publication": "European Journal of Inorganic Chemistry", "volume": "2018", "number": "9", "publisher": "Wiley", "pagerange": "1060-1067", "id_number": "CaltechAUTHORS:20171101-124030260", "issn": "1434-1948", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20171101-124030260", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Caltech Summer Undergraduate Research Fellowship (SURF)" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1002/ejic.201701231", "primary_object": { "basename": "ejic201701231-sup-0001-SI1.pdf", "url": "https://authors.library.caltech.edu/records/shqsf-m3z94/files/ejic201701231-sup-0001-SI1.pdf" }, "pub_year": "2018", "author_list": "Sinclair, Timothy S.; Gray, Harry B.; et el." }, { "id": "https://authors.library.caltech.edu/records/wyp8v-cz592", "eprint_id": 87548, "eprint_status": "archive", "datestamp": "2023-08-19 08:08:44", "lastmod": "2023-10-18 21:15:43", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Schuttlefield-Christus-J-D", "name": { "family": "Schuttlefield Christus", "given": "Jennifer" } }, { "id": "DeBoever-M", "name": { "family": "DeBoever", "given": "Michelle" } } ] }, "title": "End of an era: Lessons learned from 10 years of outreach at a NSF-funded center", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2018 American Chemical Society.", "abstract": "Since 2005, the Center for Chem. Innovation (CCI) Solar Fuels has focused on one of the \"holy-grails\" of 21st Century chem. - the efficient and economical conversion of solar energy into stored chem. fuel, where researchers investigate the crit. science underpinning the solar-driven decompn. of water into hydrogen and oxygen. The CCI's outreach program has been deeply integrated into the research mission of the Center. Specifically, the outreach program developed three main themes. The first is real-time research experiences aimed at discovering inexpensive, stable oxide semiconductors that can efficiently photoelectrolyze water to a useable fuel, hydrogen. This manifested in three distinct projects developed at different stages by researchers at different universities: SHArK in 2008, SEAL in 2011, and HARPOON in 2013. The second project, Juice from Juice, is a classroom expt. aimed at middle and high school teachers where their\nstudents can build dye-sensitized solar cells from blackberry juice in a succinct, NGSS aligned lesson. Various\nextensions and addnl. resources have been developed over the years. The third theme was collaborations with informal\nscience education groups such as local science clubs, museums and science festivals, where renewable energy\nactivities were brought directly to the public. Lastly, in addn. to leadership and mentoring experiences gained by\nparticipation in outreach projects, the center also provided important professional development opportunities to\nundergraduates, graduate students, and post-doctoral students. As the end comes for the CCI Solar Fuels outreach\nprogram, we provide insight into the lessons learned from the various outreach activities which could be applied to the broader impacts and outreach communities.", "date": "2018-03", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20180705-095714420", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180705-095714420", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "pub_year": "2018", "author_list": "Schuttlefield Christus, Jennifer and DeBoever, Michelle" }, { "id": "https://authors.library.caltech.edu/records/cbcc7-b5f48", "eprint_id": 83257, "eprint_status": "archive", "datestamp": "2023-08-19 07:14:21", "lastmod": "2023-10-17 23:00:51", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Despagnet-Ayoub-E", "name": { "family": "Despagnet-Ayoub", "given": "E." }, "orcid": "0000-0002-9013-7574" }, { "id": "Kramer-W-W", "name": { "family": "Kramer", "given": "W. W." } }, { "id": "Sattler-W", "name": { "family": "Sattler", "given": "W." }, "orcid": "0000-0001-5316-260X" }, { "id": "Sattler-A", "name": { "family": "Sattler", "given": "A." } }, { "id": "LaBeaume-P-J", "name": { "family": "LaBeaume", "given": "P. J." } }, { "id": "Thackeray-J-W", "name": { "family": "Thackeray", "given": "J. W." } }, { "id": "Cameron-J-F", "name": { "family": "Cameron", "given": "J. F." } }, { "id": "Cardolaccia-T", "name": { "family": "Cardolaccia", "given": "T." } }, { "id": "Rachford-A-A", "name": { "family": "Rachford", "given": "A. A." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "J. R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "H. B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Triphenylsulfonium topophotochemistry", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 The Royal Society of Chemistry and Owner Societies. \n\nThe article was received on 25 Aug 2017, accepted on 03 Nov 2017 and first published on 03 Nov 2017. \n\nWe thank Dr VanderVelde for his help on the DOSY-NMR experiment. This work was supported by the National Science Foundation Center for Chemical Innovation in Solar Fuels (CHE-1305124) and in part by The Dow Chemical Company through a university partnership program (Agreement # 227027AK). \n\nThere are no conflicts to declare.\n\nSupplemental Material - c7pp00324b1_si.pdf
", "abstract": "The products from the 193 nm irradiation of triphenylsulfonium nonaflate (TPS) embedded in a poly(methyl methacrylate) (PMMA) film have been characterized. The analysis of the photoproduct formation was performed using chromatographic techniques including HPLC, GPC and GC-MS as well as UV-vis and NMR spectroscopic methods. Two previously unreported TPS photoproducts, triphenylene and dibenzothiophene, were detected; additionally, GPC and DOSY-NMR spectroscopic analyses after irradiation suggested that TPS fragments had been incorporated into the polymer film. The irradiation of acetonitrile solutions containing 10% w/v PMMA and 1% w/v TPS in a 1 cm-path-length cuvette showed only a trace amount of triphenylene or dibenzothiophene, indicating that topochemical factors were important for the formation of these molecules. The accumulated evidence indicates that both products were formed by in-cage, secondary photochemical reactions: 2-(phenylthio)biphenyl to triphenylene, and diphenylsulfide to dibenzothiophene.", "date": "2018-01-01", "date_type": "published", "publication": "Photochemical and Photobiological Sciences", "volume": "17", "number": "1", "publisher": "Royal Society of Chemistry", "pagerange": "27-34", "id_number": "CaltechAUTHORS:20171116-114003756", "issn": "1474-905X", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20171116-114003756", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Dow Chemical Company", "grant_number": "227027AK" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c7pp00324b", "primary_object": { "basename": "c7pp00324b1_si.pdf", "url": "https://authors.library.caltech.edu/records/cbcc7-b5f48/files/c7pp00324b1_si.pdf" }, "pub_year": "2018", "author_list": "Despagnet-Ayoub, E.; Kramer, W. W.; et el." }, { "id": "https://authors.library.caltech.edu/records/9xngc-6zf31", "eprint_id": 83220, "eprint_status": "archive", "datestamp": "2023-09-22 22:39:39", "lastmod": "2023-10-23 23:26:03", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Pi\u017el-M", "name": { "family": "Pi\u017el", "given": "Martin" } }, { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Greetham-G-M", "name": { "family": "Greetham", "given": "Gregory M." } }, { "id": "Towrie-M", "name": { "family": "Towrie", "given": "Michael" } }, { "id": "Z\u00e1li\u0161-S", "name": { "family": "Z\u00e1li\u0161", "given": "Stanislav" } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Vl\u010dek-A", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn" }, "orcid": "0000-0002-6413-8311" } ] }, "title": "Ultrafast Wiggling and Jiggling: Ir_2(1,8-diisocyanomenthane)_4^(2+)", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 American Chemical Society. \n\nReceived: October 15, 2017; Published: November 13, 2017. \n\nThis work was supported by the Czech Science Foundation Grant 17-011375, NSF CCI Solar Fuels Program (CHE-1305124) and STFC (UK). B.M.H. is a Fellow of the Resnick Sustainability Institute at Caltech. Additional support was provided by the Arnold and Mabel Beckman Foundation, the Ministry of Education of the Czech Republic (Grant LTC17052), and COST Action CM1405. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - jp7b10215_si_001.pdf
", "abstract": "Binuclear complexes of d^8 metals (Pt^(II), Ir^I, Rh^I,) exhibit diverse photonic behavior, including dual emission from relatively long-lived singlet and triplet excited states, as well as photochemical energy, electron, and atom transfer. Time-resolved optical spectroscopic and X-ray studies have revealed the behavior of the dimetallic core, confirming that M\u2013M bonding is strengthened upon d\u03c3* \u2192 p\u03c3 excitation. We report the bridging ligand dynamics of Ir2(1,8-diisocyanomenthane)_4^(2+)(Ir(dimen)), investigated by fs\u2013ns time-resolved IR spectroscopy (TRIR) in the region of C\u2261N stretching vibrations, \u03bd(C\u2261N), 2000\u20132300 cm^(\u20131). The \u03bd(C\u2261N) IR band of the singlet and triplet d\u03c3*p\u03c3 excited states is shifted by \u221222 and \u221216 cm^(\u20131) relative to the ground state due to delocalization of the p\u03c3 LUMO over the bridging ligands. Ultrafast relaxation dynamics of the ^1d\u03c3*p\u03c3 state depend on the initially excited Franck\u2013Condon molecular geometry, whereby the same relaxed singlet excited state is populated by two different pathways depending on the starting point at the excited-state potential energy surface. Exciting the long/eclipsed isomer triggers two-stage structural relaxation: 0.5 ps large-scale Ir\u2013Ir contraction and 5 ps Ir\u2013Ir contraction/intramolecular rotation. Exciting the short/twisted isomer induces a \u223c5 ps bond shortening combined with vibrational cooling. Intersystem crossing (70 ps) follows, populating a ^3d\u03c3*p\u03c3 state that lives for hundreds of nanoseconds. During the first 2 ps, the \u03bd(C\u2261N) IR bandwidth oscillates with the frequency of the \u03bd(Ir\u2013Ir) wave packet, ca. 80 cm^(\u20131), indicating that the dephasing time of the high-frequency (16 fs)^(\u22121) C\u2261N stretch responds to much slower (\u223c400 fs)^(\u22121)Ir\u2013Ir coherent oscillations. We conclude that the bonding and dynamics of bridging di-isocyanide ligands are coupled to the dynamics of the metal\u2013metal unit and that the coherent Ir\u2013Ir motion induced by ultrafast excitation drives vibrational dephasing processes over the entire binuclear cation.", "date": "2017-12-07", "date_type": "published", "publication": "Journal of Physical Chemistry A", "volume": "121", "number": "48", "publisher": "American Chemical Society", "pagerange": "9275-9283", "id_number": "CaltechAUTHORS:20171115-101044605", "issn": "1089-5639", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20171115-101044605", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Czech Science Foundation", "grant_number": "17-011375" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Science and Technology Facilities Council (STFC)" }, { "agency": "Resnick Sustainability Institute" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Ministry of Education (Czech Republic)", "grant_number": "LTC17052" }, { "agency": "European Cooperation in Science and Technology (COST)", "grant_number": "CM1405" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" }, { "id": "Resnick-Sustainability-Institute" } ] }, "doi": "10.1021/acs.jpca.7b10215", "primary_object": { "basename": "jp7b10215_si_001.pdf", "url": "https://authors.library.caltech.edu/records/9xngc-6zf31/files/jp7b10215_si_001.pdf" }, "pub_year": "2017", "author_list": "Pi\u017el, Martin; Hunter, Bryan M.; et el." }, { "id": "https://authors.library.caltech.edu/records/23a2d-y9j53", "eprint_id": 81675, "eprint_status": "archive", "datestamp": "2023-08-19 05:42:54", "lastmod": "2023-10-17 20:57:10", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Takematsu-Kana", "name": { "family": "Takematsu", "given": "Kana" }, "orcid": "0000-0002-2334-336X" }, { "id": "Wehlin-S-A-M", "name": { "family": "Wehlin", "given": "Sara A. M." } }, { "id": "Sattler-W", "name": { "family": "Sattler", "given": "Wesley" }, "orcid": "0000-0001-5316-260X" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Two-photon spectroscopy of tungsten(0) arylisocyanides using nanosecond-pulsed excitation", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 The Royal Society of Chemistry. \n\nThe article was received on 19 Jul 2017, accepted on 11 Sep 2017 and first published on 21 Sep 2017. \n\nResearch was supported by CCI Solar Fuels (NSF CHE-1305124) and the Arnold and Mabel Beckman Foundation. \n\nThere are no conflicts to declare.\n\nSupplemental Material - c7dt02632c1_si.pdf
", "abstract": "The two-photon absorption (TPA) cross sections (\u03b4) for tungsten(0) arylisocyanides (W(CNAr)6) were determined in the 800\u20131000 nm region using two-photon luminescence (TPL) spectroscopy. The complexes have high TPA cross sections, in the range 1000\u20132000 GM at 811.8 nm. In comparison, the cross section at 811.8 nm for tris-(2,2\u2032-bipyridine)ruthenium(II), [Ru(bpy)_3]^(2+), is 7 GM. All measurements were performed using a nanosecond-pulsed laser system.", "date": "2017-10-21", "date_type": "published", "publication": "Dalton Transactions", "volume": "46", "number": "39", "publisher": "Royal Society of Chemistry", "pagerange": "13188-13193", "id_number": "CaltechAUTHORS:20170921-104309376", "issn": "1477-9226", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170921-104309376", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c7dt02632c", "primary_object": { "basename": "c7dt02632c1_si.pdf", "url": "https://authors.library.caltech.edu/records/23a2d-y9j53/files/c7dt02632c1_si.pdf" }, "pub_year": "2017", "author_list": "Takematsu, Kana; Wehlin, Sara A. M.; et el." }, { "id": "https://authors.library.caltech.edu/records/y03fr-enj25", "eprint_id": 81403, "eprint_status": "archive", "datestamp": "2023-08-19 05:34:15", "lastmod": "2023-10-17 19:49:41", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lam-Yan-Choi", "name": { "family": "Lam", "given": "Yan Choi" }, "orcid": "0000-0001-7809-4471" }, { "id": "Nielsen-R-J", "name": { "family": "Nielsen", "given": "Robert J." }, "orcid": "0000-0002-7962-0186" }, { "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "orcid": "0000-0003-0097-5716" }, { "id": "Dash-A-K", "name": { "family": "Dash", "given": "Aswini K." } } ] }, "title": "The mechanism for catalytic hydrosilylation by bis(imino)pyridine iron olefin complexes supported by broken symmetry density functional theory", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 The Royal Society of Chemistry. \n\nThe article was received on 25 Jun 2017, accepted on 04 Sep 2017 and first published on 05 Sep 2017. \n\nDr Robert J. Nielsen and Prof. William A. Goddard III, gratefully acknowledge financial support from The Dow Chemical Company. Dr Yan Choi Lam was supported by the National Science Foundation (NSF) through the Centers for Chemical Innovation (CCI): Solar Fuels grant CHE-1305124. \n\nThere are no conflicts of interest to declare.\n\nSupplemental Material - c7dt02300f1_si.pdf
", "abstract": "Density functional theory (DFT, B3LYP-D3 with implicit solvation in toluene) was used to investigate the mechanisms of olefin hydrosilylation catalyzed by PDI(Fe) (bis(imino)pyridine iron) complexes, where PDI = 2,6-(ArN CMe)_2(C_5H_3N) with Ar = 2,6-R_2-C_6H_3. We find that the rate-determining step for hydrosilylation is hydride migration from Et3SiH onto the Fe-bound olefin to form (PDI)Fe(alkyl)(SiEt_3). This differs from the mechanism for the Pt Karstedt catalyst in that there is no prior Si\u2013H oxidative addition onto the Fe center. (PDI)Fe(alkyl)(SiEt_3) then undergoes C\u2013Si reductive elimination to form (PDI)Fe, which coordinates an olefin ligand to regenerate the resting state (PDI)Fe(olefin). In agreement with experimental observations, we found that anti-Markovnikov hydride migration has a 5.1 kcal mol\u22121 lower activation enthalpy than Markovnikov migration. This system has an unusual anti-ferromagnetic coupling between high spin electrons on the Fe center and the unpaired spin in the pi system of the non-innocent redox-active PDI ligand. To describe this with DFT, we used the \"broken-symmetry\" approach to establish the ground electronic and spin state of intermediates and transition states over the proposed catalytic cycles.", "date": "2017-10-07", "date_type": "published", "publication": "Dalton Transactions", "volume": "46", "number": "37", "publisher": "Royal Society of Chemistry", "pagerange": "12507-12515", "id_number": "CaltechAUTHORS:20170913-095452729", "issn": "1477-9226", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170913-095452729", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Dow Chemical Company" }, { "agency": "NSF", "grant_number": "CHE-1305124" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1039/c7dt02300f", "primary_object": { "basename": "c7dt02300f1_si.pdf", "url": "https://authors.library.caltech.edu/records/y03fr-enj25/files/c7dt02300f1_si.pdf" }, "pub_year": "2017", "author_list": "Lam, Yan Choi; Nielsen, Robert J.; et el." }, { "id": "https://authors.library.caltech.edu/records/6fk0t-1yb67", "eprint_id": 82541, "eprint_status": "archive", "datestamp": "2023-08-19 05:21:46", "lastmod": "2023-10-17 22:30:23", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "McNicholas-B-J", "name": { "family": "McNicholas", "given": "Brendon J." }, "orcid": "0000-0002-3654-681X" }, { "id": "Blumenfeld-C-M", "name": { "family": "Blumenfeld", "given": "Carl" } }, { "id": "Kramer-W-W", "name": { "family": "Kramer", "given": "Wesley W." } }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Electrochemistry in ionic liquids: Case study of a manganese corrole", "ispublished": "pub", "full_text_status": "restricted", "keywords": "ionic liquids, electrochemistry, corroles, axial coordination, homogeneous voltammetry", "note": "\u00a9 2017 Pleiades Publishing, Ltd. \n\nReceived January 6, 2017; in final form, February 3, 2017. First Online: 21 October 2017. \n\nThis paper is the authors' contribution to the special issue of Russian Journal of Electrochemistry dedicated to the 100th anniversary of the birth of the outstanding Soviet electrochemist Veniamin G. Levich. \n\nThe article is published in the original. \n\nThe authors thank Shabnam Hematian for helpful discussions. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) (H.B.G. and J. R. W.). Additional support was provided by King Fahd University of Petroleum and Minerals (R.H.G.). The authors declare no competing financial interest", "abstract": "Voltammetry of [5,10,15-tris(pentafluorophenylcorrole)]Mn(III) was investigated in four different ionic liquids (ILs): 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIm-TFSI); 1-ethyl-3-methylimidazolium ethylsulfate (EMIm-EtOSO_3); 1-ethyl-3-methylimidazolium triflate (EMIm-OTf); and 1-ethyl-3-methylimidazolium tetracyanoborate (EMIm-TCB). We found that Mn^(IV/III) E_(1/2) values depend on IL counter anion: OTf\u2013< EtOSO_3\u2212 < TFSI\u2212 < TCB\u2212. In EMIm-TCB and BMIm- TFSI, reversible, diffusion-controlled MnIV/III reactions occurred, as evidenced in each case by the ratio of anodic to cathodic diffusion coefficients over a range of scan rates. Axial coordination was evidenced by a cathodic to anodic diffusion coefficient ratio greater than one, an increasing cathodic to anodic peak current ratio with increasing scan rate, and a split Soret band in the UV-vis spectrum of the complex.", "date": "2017-10", "date_type": "published", "publication": "Russian Journal of Electrochemistry", "volume": "53", "number": "10", "publisher": "MAIK Nauka/Interperiodica", "pagerange": "1189-1193", "id_number": "CaltechAUTHORS:20171020-140056026", "issn": "1023-1935", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20171020-140056026", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "King Fahd University of Petroleum and Minerals (KFUPM)" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1134/S1023193517100068", "pub_year": "2017", "author_list": "McNicholas, Brendon J.; Blumenfeld, Carl; et el." }, { "id": "https://authors.library.caltech.edu/records/c2wt5-ern93", "eprint_id": 77775, "eprint_status": "archive", "datestamp": "2023-08-19 04:59:45", "lastmod": "2023-10-25 23:26:34", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Monni-R", "name": { "family": "Monni", "given": "Roberto" } }, { "id": "Aub\u00f6ck-G", "name": { "family": "Aub\u00f6ck", "given": "Gerald" } }, { "id": "Kinschel-D", "name": { "family": "Kinschel", "given": "Dominik" } }, { "id": "Aziz-Lange-K-M", "name": { "family": "Aziz-Lange", "given": "Kathrin M." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Vl\u010dek-A", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn" } }, { "id": "Chergui-M", "name": { "family": "Chergui", "given": "Majed" } } ] }, "title": "Conservation of vibrational coherence in ultrafast electronic relaxation: The case of diplatinum complexes in solution", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 Elsevier B.V. \n\nReceived 25 January 2017, Accepted 21 February 2017, Available online 24 February 2017. \n\nThis work was supported by the Swiss NSF via the NCCR:MUST, contract n\u00b0 200021_137717 and IZK0Z2_150425. We thank Yan Choi Lam and Tania Darnton for supplying samples (work at Caltech was supported by NSF CCI Solar Fuels CHE-1305124). Petr Posp\u00ed\u0161il (J. Heyrovsk\u00fd Inst.) and Igor Sazanovich (Rutherford Appleton Lab, UK) are thanked for their help with measurements of stationary emission-excitation and nanosecond time-resolved spectra, respectively. We also thank the European collaboration program COST Action CM1202, the Czech Ministry of Education grant LD14129, and the Czech Science Foundation grant 17-011375 for support.\n\nSupplemental Material - mmc1.docx
", "abstract": "We report the results of ultrafast transient absorption studies of tetrakis(\u03bc-pyrophosphito)diplatinate(II), [Pt_2(\u03bc-P_2O_5H_2)_4]^(4\u2212) (Pt(pop)) and its perfluoroborated derivative [Pt_2(\u03bc-P_2O_5(BF_2)_4]^(4\u2212) (Pt(pop-BF_2)) in water and acetonitrile upon excitation of high lying (<300 nm) UV absorption bands. We observe an ultrafast relaxation channel from high lying states to the lowest triplet state that partly (Pt(pop) in H_2O, Pt(pop-BF_2)) or fully (Pt(pop) in MeCN) bypasses the lowest singlet excited state. As a consequence, vibrational wave packets are detected in the lowest triplet state and/or the lowest excited singlet of both complexes, even though the electronic relaxation cascade spans ca. 2 and 1.3 eV, respectively. In the case of Pt(pop-BF_2), coherent wave packets generated by optical excitation of the lowest singlet ^1A_(2u) state also are reported. Overall, the reported dephasing times of the Pt-Pt oscillator in the ground, singlet and triplet states do not depend much on the solvent or the molecular structure.", "date": "2017-09-01", "date_type": "published", "publication": "Chemical Physics Letters", "volume": "683", "publisher": "Elsevier", "pagerange": "112-120", "id_number": "CaltechAUTHORS:20170525-154729378", "issn": "0009-2614", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170525-154729378", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Swiss National Science Foundation (SNSF)", "grant_number": "200021_137717" }, { "agency": "Swiss National Science Foundation (SNSF)", "grant_number": "IZK0Z2_150425" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "COST", "grant_number": "ActionCM1202" }, { "agency": "Ministry of Education (Czech Republic)", "grant_number": "LD14129" }, { "agency": "Czech Science Foundation", "grant_number": "17-011375" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1016/j.cplett.2017.02.071", "primary_object": { "basename": "mmc1.docx", "url": "https://authors.library.caltech.edu/records/c2wt5-ern93/files/mmc1.docx" }, "pub_year": "2017", "author_list": "Monni, Roberto; Aub\u00f6ck, Gerald; et el." }, { "id": "https://authors.library.caltech.edu/records/p4sps-rjn24", "eprint_id": 74420, "eprint_status": "archive", "datestamp": "2023-08-19 04:39:43", "lastmod": "2023-10-24 22:37:17", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Z\u00e1li\u0161-S", "name": { "family": "Z\u00e1li\u0161", "given": "Stanislav" } }, { "id": "Vl\u010dek-A", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn" } } ] }, "title": "Electronic structures and photophysics of d^8-d^8 complexes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2017 Elsevier B.V. \n\nReceived 29 October 2016, Revised 17 January 2017, Accepted 18 January 2017, Available online 21 January 2017. \n\nWe thank our colleagues for interesting discussions of d^8-d^8 chemistry as well as sharing some (yet) unpublished data, most especially Majed Chergui, Ivano Tavernelli, Roberto Moni, and Gloria Capano (EFPFL, Switzerland); and Jay Winkler, Bryan Hunter, and Yan-Choi Lam (Caltech). This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124), the Arnold and Mabel Beckman Foundation, the Ministry of Education of the Czech Republic - grant LH13015, and the COST Action CM1405. \n\nDedicated to Barry Lever, consummate scholar and treasured friend, in recognition of his deep and lasting contributions to coordination chemistry.", "abstract": "Research on d^8-d^8 complexes is being actively pursued, owing, in part, to newly developed time-resolved optical, IR, and X-ray methods that directly interrogate bonding changes upon excitation. Our review covers work on the ground- and electronic excited states, as well as the oxidized and reduced forms, of these complexes. Recent experimental and theoretical results add a new chapter to the rich history of d^8-d^8 spectroscopic and chemical behavior.", "date": "2017-08-15", "date_type": "published", "publication": "Coordination Chemistry Reviews", "volume": "345", "publisher": "Elsevier", "pagerange": "297-317", "id_number": "CaltechAUTHORS:20170221-084923487", "issn": "0010-8545", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170221-084923487", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Ministry of Education (Czech Republic)", "grant_number": "LH13015" }, { "agency": "COST Action", "grant_number": "CM1405" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1016/j.ccr.2017.01.008", "pub_year": "2017", "author_list": "Gray, Harry B.; Z\u00e1li\u0161, Stanislav; et el." }, { "id": "https://authors.library.caltech.edu/records/whw2r-1nb11", "eprint_id": 86183, "eprint_status": "archive", "datestamp": "2023-08-19 04:31:29", "lastmod": "2023-10-18 19:20:27", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Schuttlefield-Christus-J-D", "name": { "family": "Schuttlefield Christus", "given": "Jennifer" } }, { "id": "DeBoever-M", "name": { "family": "DeBoever", "given": "Michelle" } } ] }, "title": "Solar Army: Incorporating real-time research into outreach efforts", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2017 American Chemical Society.", "abstract": "The Solar Army is the international outreach effort for the NSF- funded Center for Chem. Innovation Solar Fuels based at the\nCalifornia Institute of Technol. The CCI Solar Fuel research focuses on one of the \"holy- grails\" of 21st Century chem. - the\nefficient and economical conversion of solar energy into stored chem. fuel. CCI Solar investigators are targeting the crit.\nscience underpinning the solar- driven decompn. of water into hydrogen and oxygen. The Solar Army utilizes three\noutreach kits to educate participants on solar energy conversion and provide students with an opportunity to participate in\nreal- time research searching for solar water- splitting catalysts. In these research experiences, students create unique\nmixed- metal oxide combination, analyze their materials to det. the potential of the material for being a good catalyst, and\nreport their findings to an online collaborative database. Student involvement has resulted in the discovery of a new material\nand many others worth investigating. To date, we have recruited hundreds of students at the high school and undergraduate\nlevels to join our \"Solar Army\" and search for the \"holy- grail\" catalyst.", "date": "2017-08", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20180502-084338872", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180502-084338872", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "pub_year": "2017", "author_list": "Schuttlefield Christus, Jennifer and DeBoever, Michelle" }, { "id": "https://authors.library.caltech.edu/records/ck0am-62580", "eprint_id": 78686, "eprint_status": "archive", "datestamp": "2023-08-19 03:33:42", "lastmod": "2023-10-26 00:17:59", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Chabi-Sakineh", "name": { "family": "Chabi", "given": "Sakineh" }, "orcid": "0000-0002-5578-3984" }, { "id": "Papadantonakis-Kimberly-M", "name": { "family": "Papadantonakis", "given": "Kimberly M." }, "orcid": "0000-0002-9900-5500" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Freund-M-S", "name": { "family": "Freund", "given": "Michael S." }, "orcid": "0000-0003-1104-2292" } ] }, "title": "Membranes for artificial photosynthesis", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2017 The Royal Society of Chemistry. \n\nReceived 30th January 2017, Accepted 5th May 2017, First published on 17 May 2017. \n\nThis work was supported by NSF under the NSF CCI Solar Fuels Program under Grant No. CHE-1305124. KMP and NSL acknowledge support for this work from the Gordon and Betty Moore Foundation, under grant GBMF1225.", "abstract": "Membrane-based architectures enable optimization of charge transport and electrochemical potential gradients in artificial photosynthesis. Spatial integration of the membrane-bound components reduces the impact of charge recombination and can reduce electrical resistances associated with ionic and electronic transport processes. In addition to eliminating the need for external electrical circuits, a membrane-based architecture also ensures separation of energetic products, thereby preventing the formation of potentially dangerous fuel/oxidant mixtures. Membrane-based structures may also be coupled with other devices, such as perovskite-based solar cells, to further benefit solar fuel production. This review discusses the key roles that various different types of membranes play in artificial photosynthetic systems.", "date": "2017-06-01", "date_type": "published", "publication": "Energy and Environmental Science", "volume": "10", "number": "6", "publisher": "Royal Society of Chemistry", "pagerange": "1320-1338", "id_number": "CaltechAUTHORS:20170629-083151598", "issn": "1754-5692", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170629-083151598", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Gordon and Betty Moore Foundation", "grant_number": "GBMF1225" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c7ee00294g", "pub_year": "2017", "author_list": "Chabi, Sakineh; Papadantonakis, Kimberly M.; et el." }, { "id": "https://authors.library.caltech.edu/records/jr5rp-nqw04", "eprint_id": 73614, "eprint_status": "archive", "datestamp": "2023-08-21 21:01:27", "lastmod": "2023-10-24 15:31:51", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Blumenfeld-C-M", "name": { "family": "Blumenfeld", "given": "Carl M." } }, { "id": "Lau-Marcus", "name": { "family": "Lau", "given": "Marcus" } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "M\u00fcller-A-M", "name": { "family": "M\u00fcller", "given": "Astrid M." }, "orcid": "0000-0002-2785-6808" } ] }, "title": "Mixed-Metal Tungsten Oxide Photoanode Materials Made by Pulsed-Laser in Liquids Synthesis", "ispublished": "pub", "full_text_status": "public", "keywords": "pulsed-laser synthesis; tungsten oxide; mixed-metal oxides; photoanodes; solar water splitting", "note": "\u00a9 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nManuscript received: November 22, 2016;\nAccepted Article published: January 17, 2017;\nFinal Article published: February 2, 2017.\n\nWe thank George Rossman for help with optical spectroscopy, Chi Ma for help with SEM (both Division of Geological and Planetary Sciences Caltech), and Nathan Dalleska (Environmental Analysis Center at Caltech) for help with ICP-MS. We performed research in the Laser Resource Center and the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology. The NSF CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation supported this work.\n\nConflict of interest:\nThe authors declare no conflict of interest.\n\nAccepted Version - Blumenfeld_et_al-2017-ChemPhysChem.pdf
Supplemental Material - cphc201601285-sup-0001-SI1.pdf
", "abstract": "Globally scalable sunlight-driven devices that convert solar energy into storable fuels will require efficient light absorbers that are made of non-precious elements. Suitable photoanode materials are yet to be discovered. Here we utilised the timesaving nature of pulsed-laser in liquids synthesis and prepared a series of neat and mixed-metal tungsten oxide photoanode materials to investigate the effect of ad-metals on optical and photocurrent generation properties. We obtained sub-\u03bcm-sized materials with different colours from W, Al, Ta, or first-row transition metal targets in water or aqueous ammonium metatungstate solutions. We observed metastable polymorphs of WO3 and tungsten oxides with varying degrees of oxygen deficiency. Pulsed-laser in liquids synthesis of Ni in ammonium metatungstate solutions produced hollow spheres (with \u2264 6% Ni with respect to W). Photocurrent generation in strong aqueous acid was highest in mixed-metal tungsten oxide photoanode materials with around 5% of iron or nickel.", "date": "2017-05-05", "date_type": "published", "publication": "ChemPhysChem", "volume": "18", "number": "9", "publisher": "Wiley", "pagerange": "1091-1100", "id_number": "CaltechAUTHORS:20170123-100309949", "issn": "1439-4235", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170123-100309949", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1002/cphc.201601285", "primary_object": { "basename": "Blumenfeld_et_al-2017-ChemPhysChem.pdf", "url": "https://authors.library.caltech.edu/records/jr5rp-nqw04/files/Blumenfeld_et_al-2017-ChemPhysChem.pdf" }, "related_objects": [ { "basename": "cphc201601285-sup-0001-SI1.pdf", "url": "https://authors.library.caltech.edu/records/jr5rp-nqw04/files/cphc201601285-sup-0001-SI1.pdf" } ], "pub_year": "2017", "author_list": "Blumenfeld, Carl M.; Lau, Marcus; et el." }, { "id": "https://authors.library.caltech.edu/records/9fktk-1qq53", "eprint_id": 77228, "eprint_status": "archive", "datestamp": "2023-08-19 02:24:49", "lastmod": "2023-10-25 21:59:44", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "DeBoever-M", "name": { "family": "DeBoever", "given": "Michelle" } }, { "id": "Schuttlefield-Christus-J-D", "name": { "family": "Schuttlefield Christus", "given": "Jennifer D." } } ] }, "title": "Juice from juice: Bringing solar energy education to the classroom", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2017 American Chemical Society.", "abstract": "The Center for Chem. Innovation in Solar Fuels (CCI Solar) has developed several diverse outreach programs over the 10 years of its existence that satisfy the National Science Foundation's Broader Impacts requirements, including citizen science, informal science education, and teacher professional development. Started in 2008, Juice from Juice is a teacher professional development program where researchers from the Center put on workshops for local teachers to introduce them to solar energy expts. and curriculum that they can implement in their classrooms. The program was originally local to the Pasadena area centered on the CCI's headquarters at Caltech. Teachers from the Pasadena Unified School District and researchers at Caltech developed the expts. and curriculum together, along with assembling kits for teachers to take back to their classroom. After professional evaluation of the program and feedback from the National Science Foundation program officer, multiple changes were implemented that not only improved the quality of the local Juice from Juice workshops, but also allowed the program to expand across the country. Now as the sunset of the Center is on the horizon, CCI Solar is reflecting on the success and challenges of the Juice from Juice program and looking\nto permanently secure the future of this robust, popular program. Director of Education, Outreach and Diversity at CCI Solar, Michelle DeBoever, will walk through the development of the Juice from Juice program, its evaluation, revisions to the program, and its potential future with a third party partner as Center funding\ncomes to a close. Hopefully the story of Juice from Juice can serve as a model for other outreach programs\nand offer insight to what works (and what doesn't) when developing a teacher professional development\nworkshop and offering classroom expt. kits and curriculum.", "date": "2017-04", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20170505-125605543", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170505-125605543", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "pub_year": "2017", "author_list": "DeBoever, Michelle and Schuttlefield Christus, Jennifer D." }, { "id": "https://authors.library.caltech.edu/records/pp8hk-e9g17", "eprint_id": 77152, "eprint_status": "archive", "datestamp": "2023-08-19 02:21:33", "lastmod": "2023-10-25 21:55:35", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Solar fuels science", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2017 American Chemical Society.", "abstract": "We and many others are designing solar-driven mol. machines that could be used on a global scale to store solar energy by splitting water into its elemental components. We are investigating the structures and mechanisms of hydrogen evolving catalysts made from Earth abundant elements such as cobalt, iron, and nickel. We also are employing pulsed laser ablation in water for synthesis of robust oxygen evolving catalysts. To aid our research, we have recruited hundreds of students to join a Solar Army whose mission is the discovery of new materials for the prodn. of solar fuels.", "date": "2017-04", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20170503-104240786", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170503-104240786", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "pub_year": "2017", "author_list": "Gray, Harry B." }, { "id": "https://authors.library.caltech.edu/records/qa8tf-zwe71", "eprint_id": 74435, "eprint_status": "archive", "datestamp": "2023-08-19 01:57:51", "lastmod": "2023-10-24 22:38:25", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Z\u00e1li\u0161-S", "name": { "family": "Z\u00e1li\u0161", "given": "Stanislav" } }, { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Vl\u010dek-A", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn" } } ] }, "title": "Electronic Structures of Reduced and Superreduced Ir_2(1,8-diisocyanomenthane)_4^(n+) Complexes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 American Chemical Society. \n\nReceived: December 8, 2016; Published: February 20, 2017. \n\nThis work was supported by the NSF CCI Solar Fuels Program (CHE-1305124). Additional support was provided by the Arnold and Mabel Beckman Foundation, the Ministry of Education of the Czech Republic (grant LD14129), and COST Actions CM1202 and CM1405.\n\nSupplemental Material - ic6b03001_si_001.pdf
", "abstract": "Molecular and electronic structures of Ir_2(1,8-diisocyanomenthane)_4^(n+) (Ir(dimen)^(n+)) complexes have been investigated by DFT for n = 2, 1, 0 (abbreviated 2+, 1+, 0). Calculations reproduced the experimental structure of 2+, \u03bd(C\u2261N) IR, and visible absorption spectra of all three oxidation states, as well as the EPR spectrum of 1+. We have shown that the two reduction steps correspond to successive filling of the Ir\u2013Ir p\u03c3 orbital. Complexes 2+ and 1+ have very similar structures with 1+ having a shorter Ir\u2013Ir distance. The unpaired electron density in 1+ is delocalized along the Ir\u2013Ir axis and over N atoms of the eight C\u2261N\u2013 ligands. The second reduction step 1+ \u2192 0 changes the Ir(CN\u2212)_4 coordination geometry at each Ir site from approximately planar to seesaw whereby one \u2212N\u2261C\u2013Ir\u2013C\u2261N\u2013 moiety is linear and the other bent at the Ir (137\u00b0) as well as N (146\u00b0) atoms. Although complex 0 is another example of a rare (p\u03c3)2 dimetallic species (after [Pt_2(\u03bc-P_2O_5(BF_2)_2)_4]^(6\u2013), J. Am. Chem. Soc. 2016, 138, 5699), the redistribution of lower lying occupied molecular orbitals increases electron density predominantly at the bent C\u2261N\u2013 ligands whose N atoms are predicted to be nucleophilic reaction centers.", "date": "2017-03-06", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "56", "number": "5", "publisher": "American Chemical Society", "pagerange": "2874-2883", "id_number": "CaltechAUTHORS:20170221-141613246", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170221-141613246", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Ministry of Education (Czech Republic)", "grant_number": "LD14129" }, { "agency": "COST Action", "grant_number": "CM1202" }, { "agency": "COST Action", "grant_number": "CM1405" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1021/acs.inorgchem.6b03001", "primary_object": { "basename": "ic6b03001_si_001.pdf", "url": "https://authors.library.caltech.edu/records/qa8tf-zwe71/files/ic6b03001_si_001.pdf" }, "pub_year": "2017", "author_list": "Z\u00e1li\u0161, Stanislav; Hunter, Bryan M.; et el." }, { "id": "https://authors.library.caltech.edu/records/rwdte-hvx35", "eprint_id": 73721, "eprint_status": "archive", "datestamp": "2023-08-19 01:56:48", "lastmod": "2023-10-24 16:23:00", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Plymale-N-T", "name": { "family": "Plymale", "given": "Noah T." }, "orcid": "0000-0003-2564-8009" }, { "id": "Dasog-M", "name": { "family": "Dasog", "given": "Mita" }, "orcid": "0000-0002-7846-3414" }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "A Mechanistic Study of the Oxidative Reaction of Hydrogen-Terminated Si(111) Surfaces with Liquid Methanol", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 American Chemical Society. \n\nReceived: November 16, 2016; Revised: January 14, 2017; Published: January 18, 2017. \n\nWe acknowledge the National Science Foundation grant No. CHE-1214152 for providing support for the materials used in this work. Instrumentation support was provided by the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology. N.T.P. acknowledges support from a National Science Foundation Graduate Research Fellowship. M.D. acknowledges support from a postdoctoral fellowship from the National Sciences and Engineering Research Council of Canada. N.T.P. and B.S.B acknowledge support from the National Science Foundation CCI Solar Fuels Program under Grant No. CHE-1305124. We thank Dr. Adam C. Nielander for insightful discussions during the preparation of this work.\n\nAccepted Version - acs_2Ejpcc_2E6b11555.pdf
Supplemental Material - jp6b11555_si_001.pdf
", "abstract": "H\u2013Si(111) surfaces have been reacted with liquid methanol (CH_3OH) in the absence or presence of a series of oxidants and/or illumination. Oxidant-activated methoxylation of H\u2013Si(111) surfaces was observed in the dark after exposure to CH_3OH solutions that contained the one-electron oxidants acetylferrocenium, ferrocenium, or 1,1'-dimethylferrocenium. The oxidant-activated reactivity toward CH_3OH of intrinsic and n-type H\u2013Si(111) surfaces increased upon exposure to ambient light. The results suggest that oxidant-activated methoxylation requires that two conditions be met: (1) the position of the quasi-Fermi levels must energetically favor oxidation of the H\u2013Si(111) surface and (2) the position of the quasi-Fermi levels must energetically favor reduction of an oxidant in solution. Consistently, illuminated n-type H\u2013Si(111) surfaces underwent methoxylation under applied external bias more rapidly and at more negative potentials than p-type H\u2013Si(111) surfaces. The results under potentiostatic control indicate that only conditions that favor oxidation of the H\u2013Si(111) surface need be met, with charge balance at the surface maintained by current flow at the back of the electrode. The results are described by a mechanistic framework that analyzes the positions of the quasi-Fermi levels relative to the energy levels relevant for each system.", "date": "2017-03-02", "date_type": "published", "publication": "Journal of Physical Chemistry C", "volume": "121", "number": "8", "publisher": "American Chemical Society", "pagerange": "4270-4282", "id_number": "CaltechAUTHORS:20170125-124627127", "issn": "1932-7447", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170125-124627127", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1214152" }, { "agency": "NSF Graduate Research Fellowship" }, { "agency": "National Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "NSF", "grant_number": "CHE-1305124" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1021/acs.jpcc.6b11555", "primary_object": { "basename": "acs_2Ejpcc_2E6b11555.pdf", "url": "https://authors.library.caltech.edu/records/rwdte-hvx35/files/acs_2Ejpcc_2E6b11555.pdf" }, "related_objects": [ { "basename": "jp6b11555_si_001.pdf", "url": "https://authors.library.caltech.edu/records/rwdte-hvx35/files/jp6b11555_si_001.pdf" } ], "pub_year": "2017", "author_list": "Plymale, Noah T.; Dasog, Mita; et el." }, { "id": "https://authors.library.caltech.edu/records/s5dxq-rk946", "eprint_id": 71730, "eprint_status": "archive", "datestamp": "2023-08-19 00:09:39", "lastmod": "2023-10-20 23:25:24", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "M\u00fcller-A-M", "name": { "family": "M\u00fcller", "given": "Astrid M." }, "orcid": "0000-0002-2785-6808" } ] }, "title": "Earth-Abundant Heterogeneous Water Oxidation Catalysts", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: June 23, 2016. Publication Date (Web): October 31, 2016. \n\nWe thank Dave Britt and Troy Stich for helpful discussions. Research was performed in the Laser Resource Center and the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology. The NSF CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation supported this work. B.M.H. is a fellow of the Resnick Sustainability Institute at Caltech.", "abstract": "Water oxidation is a key chemical transformation for the conversion of solar energy into chemical fuels. Our review focuses on recent work on robust earth-abundant heterogeneous catalysts for the oxygen-evolving reaction (OER). We point out that improvements in the performance of OER catalysts will depend critically on the success of work aimed at understanding reaction barriers based on atomic-level mechanisms. We highlight the challenge of obtaining acid-stable OER catalysts, with proposals for elements that could be employed to reach this goal. We suggest that future advances in solar fuels science will be accelerated by the development of new methods for materials synthesis and characterization, along with in-depth investigations of redox mechanisms at catalytic surfaces.", "date": "2016-11-23", "date_type": "published", "publication": "Chemical Reviews", "volume": "116", "number": "22", "publisher": "American Chemical Society", "pagerange": "14120-14136", "id_number": "CaltechAUTHORS:20161104-074948999", "issn": "0009-2665", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20161104-074948999", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Resnick Sustainability Institute" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" }, { "id": "Resnick-Sustainability-Institute", "value": "Resnick Sustainability Institute" } ] }, "doi": "10.1021/acs.chemrev.6b00398", "pub_year": "2016", "author_list": "Hunter, Bryan M.; Gray, Harry B.; et el." }, { "id": "https://authors.library.caltech.edu/records/rhphy-t6d94", "eprint_id": 70775, "eprint_status": "archive", "datestamp": "2023-08-20 14:09:39", "lastmod": "2023-10-20 23:30:16", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lam-Yan-Choi", "name": { "family": "Lam", "given": "Yan Choi" }, "orcid": "0000-0001-7809-4471" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" } ] }, "title": "Intersystem Crossing in Diplatinum Complexes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: August 4, 2016. Revised: September 13, 2016. \n\nPublication Date (Web): September 26, 2016.\n\nWe have enjoyed several stimulating discussions with Tony Vl\u010dek and Hartmut Yersin about the nature of excited-state decay pathways in diplatinum complexes. We thank them for their contributions to the field. Our work was supported by NSF CCI Solar Fuels (Grant CHE-1305124). \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - jp6b07891_si_001.pdf
", "abstract": "Intersystem crossing (ISC) in solid [(C_4H_9)_4N]4[Pt_2(\u03bc-P_2O_5(BF_2)_2)_4], abbreviated Pt(pop-BF2), is remarkably slow for a third-row transition metal complex, ranging from \u03c4_(ISC) \u2248 0.9 ns at 310 K to \u03c4_(ISC) \u2248 29 ns below 100 K. A classical model based on Boltzmann population of one temperature-independent and two thermally activated pathways was previously employed to account for the ISC rate behavior. An alternative we prefer is to treat Pt(pop-BF_2) ISC quantum mechanically, using expressions for multiphonon radiationless transitions. Here we show that a two-channel model with physically plausible parameters can account for the observed ISC temperature dependence. In channel 1, ^1A_(2u) intersystem crosses directly into ^3A_(2u) using a high energy B\u2013F or P\u2013O vibration as accepting mode, resulting in a temperature-independent ISC rate. In channel 2, ISC occurs via a deactivating state of triplet character (which then rapidly decays to ^3A_(2u)), using Pt\u2013Pt stretching (160 cm^(\u20131)) as a distorting mode to provide the energy needed. Fitting indicates that the deactivating state, ^3X, is moderately displaced (S = 0.5\u20133) and blue-shifted (\u0394E = 1420\u20132550 cm^(\u20131)) from ^1A_(2u). Our model accounts for the experimental observation that ISC in both temperature independent and thermally activated channels is faster for Pt(pop) than for Pt(pop-BF_2): in the temperature independent channel because O\u2013H modes in the former more effectively accept than B\u2013F modes in the latter, and in the thermally activated pathway because the energy gap to ^3X is larger in the latter complex.", "date": "2016-10-06", "date_type": "published", "publication": "Journal of Physical Chemistry A", "volume": "120", "number": "39", "publisher": "American Chemical Society", "pagerange": "7671-7676", "id_number": "CaltechAUTHORS:20161003-160458042", "issn": "1089-5639", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20161003-160458042", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.jpca.6b07891", "primary_object": { "basename": "jp6b07891_si_001.pdf", "url": "https://authors.library.caltech.edu/records/rhphy-t6d94/files/jp6b07891_si_001.pdf" }, "pub_year": "2016", "author_list": "Lam, Yan Choi; Gray, Harry B.; et el." }, { "id": "https://authors.library.caltech.edu/records/w57fw-crt07", "eprint_id": 71107, "eprint_status": "archive", "datestamp": "2023-08-20 13:48:34", "lastmod": "2023-10-23 15:20:25", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Callejas-J-F", "name": { "family": "Callejas", "given": "Juan F." } }, { "id": "Read-C-G", "name": { "family": "Read", "given": "Carlos G." } }, { "id": "Roske-C-W", "name": { "family": "Roske", "given": "Christopher W." } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Schaak-R-E", "name": { "family": "Schaak", "given": "Raymond E." } } ] }, "title": "Synthesis, Characterization, and Properties of Metal Phosphide Catalysts for the Hydrogen-Evolution Reaction", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: May 27, 2016. Revised: July 28, 2016. Published: August 7, 2016. \n\nThis work was supported by the National Science Foundation (NSF) Center for Chemical Innovation in Solar Fuels (CHE-1305124). C.W.R. thanks the Link Energy Foundation for a graduate research fellowship. \n\nAuthor Contributions: (J.F.C. and C.G.R.) These authors contributed equally. \n\nThe authors declare no competing financial interest.", "abstract": "Hydrogen gas obtained by the electrolysis of water has long been proposed as a clean and sustainable alternative to fossil fuels. Noble metals such as Pt are capable of splitting water at low overpotentials, but the implementation of inexpensive solar-driven water-splitting systems and electrolyzers could benefit from the development of robust, efficient, and abundant alternatives to noble metal catalysts. Transition metal phosphides (M_xP_y) have recently been identified as a promising family of Earth abundant electrocatalysts for the hydrogen-evolution reaction (HER) and are capable of operating with low overpotentials at operationally relevant current densities while exhibiting stability under strongly acidic conditions. In this review, we highlight the progress that has been made in this field and provide insights into the synthesis, characterization, and electrochemical behavior of transition metal phosphides as HER electrocatalysts. We also discuss strategies for the incorporation of metal phosphides into integrated solar-driven water-splitting systems and highlight key considerations involved in the testing and benchmarking of such devices.", "date": "2016-09-13", "date_type": "published", "publication": "Chemistry of Materials", "volume": "28", "number": "17", "publisher": "American Chemical Society", "pagerange": "6017-6044", "id_number": "CaltechAUTHORS:20161014-131500162", "issn": "0897-4756", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20161014-131500162", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Link Energy Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.chemmater.6b02148", "pub_year": "2016", "author_list": "Callejas, Juan F.; Read, Carlos G.; et el." }, { "id": "https://authors.library.caltech.edu/records/w77kh-txf17", "eprint_id": 70191, "eprint_status": "archive", "datestamp": "2023-08-20 13:45:36", "lastmod": "2023-10-20 21:55:57", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "McNicholas-B-J", "name": { "family": "McNicholas", "given": "Brendon J." }, "orcid": "0000-0002-3654-681X" }, { "id": "Blakemore-J-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Chang-Alice-B", "name": { "family": "Chang", "given": "Alice B." }, "orcid": "0000-0001-5036-2681" }, { "id": "Bates-C-M", "name": { "family": "Bates", "given": "Christopher M." }, "orcid": "0000-0002-1598-794X" }, { "id": "Kramer-W-W", "name": { "family": "Kramer", "given": "Wesley W." } }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Electrocatalysis of CO_2 Reduction in Brush Polymer Ion Gels", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: August 23, 2016; Published: August 25, 2016. \n\nThis work was supported by the NSF CCI Solar Fuels Program (CHE-1305124). Additional support was provided by King Fahd University of Petroleum and Minerals. C.M.B. thanks the Dreyfus Foundation for Environmental Postdoc Fellowship EP-13-142. A.B.C. thanks the U.S. Department of Defense for support through the NDSEG Fellowship. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - ja6b08795_si_001.pdf
", "abstract": "The electrochemical characterization of brush polymer ion gels containing embedded small-molecule redox-active species is reported. Gels comprising PS\u2013PEO\u2013PS triblock brush polymer, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIm-TFSI), and some combination of ferrocene (Fc), cobaltocenium (CoCp_2^+), and Re(bpy)(CO)_3Cl (1) exhibit diffusion-controlled redox processes with diffusion coefficients approximately one-fifth of those observed in neat BMIm-TFSI. Notably, 1 dissolves homogeneously in the interpenetrating matrix domain of the ion gel and displays electrocatalytic CO_2 reduction to CO in the gel. The catalytic wave exhibits a positive shift versus Fc^(+/0) compared with analogous nonaqueous solvents with a reduction potential 450 mV positive of onset and 90% Faradaic efficiency for CO production. These materials provide a promising and alternative approach to immobilized electrocatalysis, creating numerous opportunities for application in solid-state devices.", "date": "2016-09-07", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "138", "number": "35", "publisher": "American Chemical Society", "pagerange": "11160-11163", "id_number": "CaltechAUTHORS:20160907-092755707", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160907-092755707", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "King Fahd University of Petroleum and Minerals (KFUPM)" }, { "agency": "Camille and Henry Dreyfus Foundation", "grant_number": "EP-13-142" }, { "agency": "National Defense Science and Engineering Graduate (NDSEG) Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/jacs.6b08795", "primary_object": { "basename": "ja6b08795_si_001.pdf", "url": "https://authors.library.caltech.edu/records/w77kh-txf17/files/ja6b08795_si_001.pdf" }, "pub_year": "2016", "author_list": "McNicholas, Brendon J.; Blakemore, James D.; et el." }, { "id": "https://authors.library.caltech.edu/records/zxpy3-8t129", "eprint_id": 69808, "eprint_status": "archive", "datestamp": "2023-08-20 13:34:45", "lastmod": "2023-10-20 20:38:45", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Huo-Pengfei", "name": { "family": "Huo", "given": "Pengfei" }, "orcid": "0000-0002-8639-9299" }, { "id": "Uyeda-Christopher", "name": { "family": "Uyeda", "given": "Christopher" }, "orcid": "0000-0001-9396-915X" }, { "id": "Goodpaster-J-D", "name": { "family": "Goodpaster", "given": "Jason D." }, "orcid": "0000-0001-6461-4501" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Miller-T-F-III", "name": { "family": "Miller", "given": "Thomas F., III" }, "orcid": "0000-0002-1882-5380" } ] }, "title": "Breaking the Correlation between Energy Costs and Kinetic Barriers in Hydrogen Evolution via a Cobalt Pyridine-Diimine-Dioxime Catalyst", "ispublished": "pub", "full_text_status": "public", "keywords": "hydrogen evolution, cobalt diimine-dioxime catalysts, proton shuttle, electrochemistry, coupled-cluster theory, density functional theory, embedding", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: May 17, 2016; Revised: July 18, 2016; Publication Date (Web): July 26, 2016. \n\nThis work was supported by the Air Force Office of Scientific Research (USAFOSR) under Grant No. FA9550-11-1-0288, the (U.S.) Department of Energy (DOE) under Grant No. DESC0006598, and by the NSF Center for Chemical Innovation Solar Fuels Grant CHE-1305124. P.H. thanks Kara Bren and Richard Eisenberg for helpful discussions. Computing resources were provided by the National Energy Research Scientific Computing Center (NERSC) (DE-AC02-05CH11231) and XSEDE (TG-CHE130108). \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - cs6b01387_si_001.pdf
", "abstract": "A central challenge in the development of inorganic hydrogen evolution catalysts is to avoid deleterious coupling between the energetics of metal site reduction and the kinetics of metal hydride formation. In this work, we combine theoretical and experimental methods to investigate cobalt diimine-dioxime catalysts that show promise for achieving this aim by introducing an intramolecular proton shuttle via a pyridyl pendant group. Using over 200 coupled-cluster-level electronic structure calculations of the Co-based catalyst with a variety of pyridyl substituents, the energetic and kinetic barriers to hydrogen formation are investigated, revealing nearly complete decoupling of the energetics of Co reduction and the kinetics of intramolecular Co hydride formation. These calculations employ recently developed quantum embedding methods that allow for local regions of a molecule to be described using high-accuracy wavefunction methods (such as CCSD(T)), thus overcoming significant errors in the DFT-level description of transition-metal complexes. Experimental synthesis and cyclic voltammetry of the methyl-substituted form of the catalyst indicate that protonation of the pendant group leaves the Co reduction potential unchanged, which is consistent with the theoretical prediction that these catalysts can successfully decouple the electronic structures of the transition-metal and ligand-protonation sites. Additional computational analysis indicates that introduction of the pyridyl pendant group enhances the favorability of intramolecular proton shuttling in these catalysts by significantly reducing the energetic barrier for metal hydride formation relative to previously studied cobalt diimine-dioxime catalysts. These results demonstrate a promising proof of principle for achieving uncoupled and locally tunable intramolecular charge-transfer events in the context of homogeneous transition-metal catalysts.", "date": "2016-09", "date_type": "published", "publication": "ACS Catalysis", "volume": "6", "number": "9", "publisher": "American Chemical Society", "pagerange": "6114-6123", "id_number": "CaltechAUTHORS:20160822-125634395", "issn": "2155-5435", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160822-125634395", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Air Force Office of Scientific Research (AFOSR)", "grant_number": "FA9550-11-1-0288" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC0006598" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-AC02-05CH11231" }, { "agency": "NSF", "grant_number": "TG-CHE130108" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acscatal.6b01387", "primary_object": { "basename": "cs6b01387_si_001.pdf", "url": "https://authors.library.caltech.edu/records/zxpy3-8t129/files/cs6b01387_si_001.pdf" }, "pub_year": "2016", "author_list": "Huo, Pengfei; Uyeda, Christopher; et el." }, { "id": "https://authors.library.caltech.edu/records/j2adn-hqg33", "eprint_id": 67805, "eprint_status": "archive", "datestamp": "2023-08-20 12:47:49", "lastmod": "2023-10-18 21:46:02", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Plymale-N-T", "name": { "family": "Plymale", "given": "Noah T." }, "orcid": "0000-0003-2564-8009" }, { "id": "Ramachandran-A-A", "name": { "family": "Ramachandran", "given": "Anshul A." } }, { "id": "Lim-Alison-N", "name": { "family": "Lim", "given": "Allison" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Control of the Band-Edge Positions of Crystalline Si(111) by Surface Functionalization with 3,4,5-Trifluorophenylacetylenyl Moieties", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: April 14, 2016; Revised: June 1, 2016; Published: June 3, 2016. \n\nWe acknowledge the National Science Foundation Grant No. CHE-1214152 for support of supplies and equipment for this work. Instrumentation support was provided by the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology. N.T.P. acknowledges support from a National Science Foundation Graduate Research Fellowship. B.S.B. and N.T.P. acknowledge support from the National Science Foundation CCI Solar Fuels Program under Grant No. CHE-1305124. N.S.L. acknowledges support from a National Science Foundation Grant No. CHE-1214152. We thank Dr. Adam C. Nielander, Mr. Christopher W. Roske, and Dr. Kimberly M. Papadantonakis for helpful discussions.\n\nSupplemental Material - jp6b03824_si_001.pdf
", "abstract": "Functionalization of semiconductor surfaces with organic moieties can change the charge distribution, surface dipole, and electric field at the interface. The modified electric field will shift the semiconductor band-edge positions relative to those of a contacting phase. Achieving chemical control over the energetics at semiconductor surfaces promises to provide a means of tuning the band-edge energetics to form optimized junctions with a desired material. Si(111) surfaces functionalized with 3,4,5-trifluorophenylacetylenyl (TFPA) groups were characterized by transmission infrared spectroscopy (TIRS), X-ray photoelectron spectroscopy (XPS), and surface recombination velocity (S) measurements. Mixed methyl/TFPA-terminated (MMTFPA) n- and p-type Si(111) surfaces were synthesized and characterized by electrochemical methods. Current density versus voltage and Mott-Schottky measurements of Si(111)\u2013MMTFPA electrodes in contact with Hg indicated that the barrier height, \u03a6b, was a function of the fractional monolayer coverage of TFPA (\u03b8TFPA) in the alkyl monolayer. Relative to Si(111)\u2013CH3 surfaces, Si(111)\u2013MMTFPA samples with high \u03b8TFPA produced shifts in \u03a6b of \u22650.6 V for n-Si/Hg contacts and \u22650.5 V for p-Si/Hg contacts. Consistently, the open-circuit potential (Eoc) of Si(111)\u2013MMTFPA samples in contact with CH3CN solutions that contained the 1-electron redox couples decamethylferrocenium/decamethylferrocene (Cp*2Fe+/0) or methyl viologen (MV2+/+\u25cf) shifted relative to Si(111)\u2013CH3 samples by +0.27 V for n-Si and by up to +0.10 V for p-Si. Residual surface recombination limited the Eoc of p-Si samples at high \u03b8TFPA despite the favorable shift in the band-edge positions induced by the surface modification process.", "date": "2016-07-07", "date_type": "published", "publication": "Journal of Physical Chemistry C", "volume": "120", "number": "26", "publisher": "American Chemical Society", "pagerange": "14157-14169", "id_number": "CaltechAUTHORS:20160609-154706514", "issn": "1932-7447", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160609-154706514", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1214152" }, { "agency": "NSF Graduate Research Fellowship" }, { "agency": "NSF", "grant_number": "CHE-1305124" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.jpcc.6b03824", "primary_object": { "basename": "jp6b03824_si_001.pdf", "url": "https://authors.library.caltech.edu/records/j2adn-hqg33/files/jp6b03824_si_001.pdf" }, "pub_year": "2016", "author_list": "Plymale, Noah T.; Ramachandran, Anshul A.; et el." }, { "id": "https://authors.library.caltech.edu/records/151ed-5fd34", "eprint_id": 67333, "eprint_status": "archive", "datestamp": "2023-09-22 22:53:36", "lastmod": "2023-10-23 23:31:15", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Aguirre-Quintana-Luis-M", "name": { "family": "Aguirre Quintana", "given": "Luis M." }, "orcid": "0000-0003-0736-415X" }, { "id": "Johnson-Samantha-I.", "name": { "family": "Johnson", "given": "Samantha I." }, "orcid": "0000-0001-6495-9892" }, { "id": "Corona-Sydney-L", "name": { "family": "Corona", "given": "Sydney L." }, "orcid": "0000-0002-4962-619X" }, { "id": "Villatoro-Walther", "name": { "family": "Villatoro", "given": "Walther" } }, { "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "orcid": "0000-0003-0097-5716" }, { "id": "Takase-Michael-K", "name": { "family": "Takase", "given": "Michael K." }, "orcid": "0000-0001-8365-3645" }, { "id": "VanderVelde-D-G", "name": { "family": "VanderVelde", "given": "David G." }, "orcid": "0000-0002-2907-0366" }, { "id": "Winkler-Jay-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Blakemore-James-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" } ] }, "title": "Proton\u2013hydride tautomerism in hydrogen evolution catalysis", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 National Academy of Sciences. \n\nContributed by Harry B. Gray, April 17, 2016 (sent for review February 4, 2016; reviewed by Alexander Miller and David Milstein). Published online before print May 24, 2016. \n\nS.I.J. thanks Dr. Robert Nielsen for helpful discussions. This research, which was carried out in part at the Molecular Materials Research Center and the Laser Resource Center of the Beckman Institute (California Institute of Technology), was supported by NSF CCI Solar Fuels Program CHE-1305124. S.I.J. and J.D.B. acknowledge fellowships from the Resnick Sustainability Institute at Caltech. \n\nAuthor contributions: S.I.J., D.G.V., J.R.W., H.B.G., and J.D.B. designed research; L.M.A.Q., S.I.J., S.L.C., W.V., M.K.T., and J.D.B. performed research; W.A.G. contributed new reagents/analytic tools; L.M.A.Q., S.I.J., S.L.C., W.V., M.K.T., D.G.V., J.R.W., H.B.G., and J.D.B. analyzed data; and S.I.J., J.R.W., H.B.G., and J.D.B. wrote the paper. \n\nReviewers: A.M., University of North Carolina; and D.M., The Weizmann Institute of Science. \n\nThe authors declare no conflict of interest. \n\nData deposition: The atomic coordinates and structure factors have been deposited in the Cambridge Crystallographic Data Centre (accession no. 1424707). \n\nThis article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1606018113/-/DCSupplemental.\n\nPublished - 6409.full.pdf
Supplemental Material - pnas.1606018113.sapp.pdf
", "abstract": "Efficient generation of hydrogen from renewable resources requires development of catalysts that avoid deep wells and high barriers. Information about the energy landscape for H_2 production can be obtained by chemical characterization of catalytic intermediates, but few have been observed to date. We have isolated and characterized a key intermediate in 2e^\u2013 + 2H^+ \u2192 H_2 catalysis. This intermediate, obtained by treatment of Cp*Rh(bpy) (Cp*, \u03b7^5-pentamethylcyclopentadienyl; bpy, \u03ba^2-2,2\u2032-bipyridyl) with acid, is not a hydride species but rather, bears [\u03b7^4-Cp*H] as a ligand. Delivery of a second proton to this species leads to evolution of H_2 and reformation of \u03b7^5-Cp* bound to rhodium(III). With suitable choices of acids and bases, the Cp*Rh(bpy) complex catalyzes facile and reversible interconversion of H^+ and H_2.", "date": "2016-06-07", "date_type": "published", "publication": "Proceedings of the National Academy of Sciences of the United States of America", "volume": "113", "number": "23", "publisher": "National Academy of Sciences", "pagerange": "6409-6414", "id_number": "CaltechAUTHORS:20160525-080847791", "issn": "0027-8424", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160525-080847791", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Resnick Sustainability Institute" } ] }, "local_group": { "items": [ { "id": "Resnick-Sustainability-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1073/pnas.1606018113", "pmcid": "PMC4988566", "primary_object": { "basename": "6409.full.pdf", "url": "https://authors.library.caltech.edu/records/151ed-5fd34/files/6409.full.pdf" }, "related_objects": [ { "basename": "pnas.1606018113.sapp.pdf", "url": "https://authors.library.caltech.edu/records/151ed-5fd34/files/pnas.1606018113.sapp.pdf" } ], "pub_year": "2016", "author_list": "Aguirre Quintana, Luis M.; Johnson, Samantha I.; et el." }, { "id": "https://authors.library.caltech.edu/records/6hgjq-xax90", "eprint_id": 66485, "eprint_status": "archive", "datestamp": "2023-08-20 11:37:06", "lastmod": "2023-10-18 18:08:27", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Darnton-T-V", "name": { "family": "Darnton", "given": "Tania V." } }, { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Hill-M-G", "name": { "family": "Hill", "given": "Michael G." } }, { "id": "Z\u00e1li\u0161-S", "name": { "family": "Z\u00e1li\u0161", "given": "Stanislav" } }, { "id": "Vl\u010dek-A-Jr", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn, Jr." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Reduced and Superreduced Diplatinum Complexes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: March 9, 2016. Publication Date (Web): April 11, 2016. \n\nWe thank James Blakemore, Angelo Di Bilio, Yan-Choi Lam, and Jay R. Winkler for assistance with experiments and helpful discussions. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124). Additional support was provided by the Arnold and Mabel Beckman Foundation, the Ministry of Education of the Czech Republic (grants LH13015 and LD14129), and COST Actions CM1202 and CM1405. B.M.H. is a Fellow of the Resnick Sustainability Institute at Caltech; T.V.D. is an NSF Graduate Research Fellow. \n\nAuthor Contributions: T.V.D. and B.M.H. contributed equally. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - ja6b02559_si_001.pdf
", "abstract": "A d^8\u2013d^8 complex [Pt_2(\u03bc-P_2O_5(BF_2)_4]^(4\u2013) (abbreviated Pt(pop-BF_2)^(4\u2013)) undergoes two 1e\u2013 reductions at E_(1/2) = \u22121.68 and E_p = \u22122.46 V (vs Fc+/Fc) producing reduced Pt(pop-BF_2)^(5\u2013) and superreduced Pt(pop-BF_2)^(6\u2013) species, respectively. The EPR spectrum of Pt(pop-BF_2)^(5\u2013) and UV\u2013vis spectra of both the reduced and the superreduced complexes, together with TD-DFT calculations, reveal successive filling of the 6p\u03c3 orbital accompanied by gradual strengthening of Pt\u2013Pt bonding interactions and, because of 6p\u03c3 delocalization, of Pt\u2013P bonds in the course of the two reductions. Mayer\u2013Millikan Pt\u2013Pt bond orders of 0.173, 0.268, and 0.340 were calculated for the parent, reduced, and superreduced complexes, respectively. The second (5\u2013/6\u2212) reduction is accompanied by a structural distortion that is experimentally manifested by electrochemical irreversibility. Both reduction steps proceed without changing either d^8 Pt electronic configuration, making the superreduced Pt(pop-BF_2)^(6\u2013) a very rare 6p^2 \u03c3-bonded binuclear complex. However, the Pt\u2013Pt \u03c3 bonding interaction is limited by the relatively long bridging-ligand-imposed Pt\u2013Pt distance accompanied by repulsive electronic congestion. Pt(pop-BF_2)^(4\u2013) is predicted to be a very strong photooxidant (potentials of +1.57 and +0.86 V are estimated for the singlet and triplet d\u03c3*p\u03c3 excited states, respectively).", "date": "2016-05-04", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "138", "number": "17", "publisher": "American Chemical Society", "pagerange": "5699-5705", "id_number": "CaltechAUTHORS:20160426-131418190", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160426-131418190", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Ministry of Education of the Czech Republic", "grant_number": "LH13015" }, { "agency": "Ministry of Education of the Czech Republic", "grant_number": "LD14129" }, { "agency": "European Research Council (ERC)", "grant_number": "CM1202" }, { "agency": "European Research Council (ERC)", "grant_number": "CM1405" }, { "agency": "Resnick Sustainability Institute" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" }, { "id": "Resnick-Sustainability-Institute" } ] }, "doi": "10.1021/jacs.6b02559", "primary_object": { "basename": "ja6b02559_si_001.pdf", "url": "https://authors.library.caltech.edu/records/6hgjq-xax90/files/ja6b02559_si_001.pdf" }, "pub_year": "2016", "author_list": "Darnton, Tania V.; Hunter, Bryan M.; et el." }, { "id": "https://authors.library.caltech.edu/records/fc1t4-vyp84", "eprint_id": 65876, "eprint_status": "archive", "datestamp": "2023-08-20 11:25:18", "lastmod": "2023-10-18 16:53:14", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "B. M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Hieringer-W", "name": { "family": "Hieringer", "given": "W." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "J. R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "H. B." }, "orcid": "0000-0002-7937-7876" }, { "id": "M\u00fcller-A-M", "name": { "family": "M\u00fcller", "given": "A. M." }, "orcid": "0000-0002-2785-6808" } ] }, "title": "Effect of interlayer anions on [NiFe]-LDH nanosheet water oxidation activity", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 Royal Society of Chemistry. \n\nReceived 5th February 2016, Accepted 17th March 2016. First published online 17 Mar 2016. \n\nWe thank George Rossman for help with solid-state IR spectroscopy. Research was carried out in the Laser Resource Center and the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation. B. M. H. is a Fellow of the Resnick Sustainability Institute at Caltech. W. H. thanks the Deutsche Forschungsgemeinschaft and the Cluster of Excellence \"Engineering of Advanced Materials\" at the University of Erlangen-N\u00fcrnberg for support.\n\nPublished - c6ee00377j.pdf
Supplemental Material - c6ee00377j1.pdf
", "abstract": "We synthesized nickel\u2013iron layered double hydroxide ([NiFe]-LDH) nanosheets with different interlayer anions to probe their role in water oxidation catalysis. In alkaline electrolyte in ambient air, carbonate rapidly replaced other interlayer anions and catalytic activity was highest. Electrocatalytic water oxidation in virtually carbonate-free alkaline electrolyte revealed that activity was a function of anion basicity. Our [NiFe]-LDH nanosheets, prepared by pulsed laser ablation in liquids, were regenerated in carbonate-containing aqueous KOH. Anion binding motifs were assessed by X-ray photoelectron spectroscopy in combination with density functional theory calculations, suggesting that nitrite species bound to edge-site Fe in the precatalyst correlated with higher water oxidation activity.", "date": "2016-05", "date_type": "published", "publication": "Energy and Environmental Science", "volume": "2016", "number": "5", "publisher": "Royal Society of Chemistry", "pagerange": "1734-1743", "id_number": "CaltechAUTHORS:20160404-081907582", "issn": "1754-5692", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160404-081907582", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Resnick Sustainability Institute" }, { "agency": "Deutsche Forschungsgemeinschaft (DFG)" }, { "agency": "University of Erlangen-N\u00fcrnberg" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" }, { "id": "Resnick-Sustainability-Institute" } ] }, "doi": "10.1039/C6EE00377J", "primary_object": { "basename": "c6ee00377j1.pdf", "url": "https://authors.library.caltech.edu/records/fc1t4-vyp84/files/c6ee00377j1.pdf" }, "related_objects": [ { "basename": "c6ee00377j.pdf", "url": "https://authors.library.caltech.edu/records/fc1t4-vyp84/files/c6ee00377j.pdf" } ], "pub_year": "2016", "author_list": "Hunter, B. M.; Hieringer, W.; et el." }, { "id": "https://authors.library.caltech.edu/records/78p2t-m9d95", "eprint_id": 64634, "eprint_status": "archive", "datestamp": "2023-08-20 11:10:22", "lastmod": "2023-10-17 21:33:58", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kramer-W-W", "name": { "family": "Kramer", "given": "W. W." } }, { "id": "McCrory-Charles-C-L", "name": { "family": "McCrory", "given": "C. C. L." }, "orcid": "0000-0001-9039-7192" } ] }, "title": "Polymer coordination promotes selective CO\u2082 reduction by cobalt phthalocyanine", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 The Royal Society of Chemistry. This Open Access Article is licensed under a Creative Commons Attribution 3.0 Unported Licence. \n\nReceived 22nd October 2015. Accepted 1st February 2016. First published online 02 Feb 2016. Chem. Sci., 2016, Advance Article. \n\nWe are very grateful to Professor Harry Gray and Dr Xenia Amashukeli for helpful discussions and enthusiastic input during the preparation of this manuscript. We acknowledge additional useful discussions with Dr Ivonne M. Ferrer regarding the initial acquisition and analysis of controlled-potential electrolysis data. This work was supported by the California Energy Commission Agreement 500-11-023 \"Accelerating the Development of Liquid Fuels Directly from Sunlight\".\n\nPublished - c5sc04015a.pdf
Supplemental Material - c5sc04015a1.pdf
", "abstract": "Cobalt phthalocyanine (CoPc) is a known electrocatalyst for the carbon dioxide reduction reaction (CO_2RR) that, when adsorbed onto edge-plane graphite (EPG) electrodes, shows modest activity and selectivity for CO production along with co-generation of H_2. In contrast, electrodes modified with CoPc immobilized in a poly-4-vinylpridine (P4VP) film show dramatically enhanced activity and selectivity compared to those modified with CoPc alone. CoPc-P4VP films display a faradaic efficiency of \u223c90% for CO, with a turnover frequency of 4.8 s^(\u22121) at just \u22120.75 V vs. RHE. Two properties of P4VP contribute to enhancing the activity of CoPc: (1) the ability of individual pyridine residues to coordinate to CoPc and (2) the high concentration of uncoordinated pyridine residues throughout the film which may enhance the catalytic activity of CoPc through secondary and other outer coordination sphere effects. Electrodes modified with polymer-free, five-coordinate CoPc(py) films (py = pyridine) and with CoPc catalysts immobilized in non-coordinating poly-2-vinylpyridine films were prepared to independently investigate the role that each property plays in enhancing CO_2RR performance of CoPc-P4VP. These studies show that a synergistic relationship between the primary and outer coordination sphere effects is responsible for the enhanced catalytic activity of CoPc when embedded in the P4VP membrane.", "date": "2016-04-01", "date_type": "published", "publication": "Chemical Science", "volume": "7", "number": "4", "publisher": "Royal Society of Chemistry", "pagerange": "2506-2515", "id_number": "CaltechAUTHORS:20160222-115824828", "issn": "2041-6520", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160222-115824828", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "California Energy Commission", "grant_number": "500-11-023" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/C5SC04015A", "pmcid": "PMC5477023", "primary_object": { "basename": "c5sc04015a.pdf", "url": "https://authors.library.caltech.edu/records/78p2t-m9d95/files/c5sc04015a.pdf" }, "related_objects": [ { "basename": "c5sc04015a1.pdf", "url": "https://authors.library.caltech.edu/records/78p2t-m9d95/files/c5sc04015a1.pdf" } ], "pub_year": "2016", "author_list": "Kramer, W. W. and McCrory, C. C. L." }, { "id": "https://authors.library.caltech.edu/records/7j6zg-egz36", "eprint_id": 65383, "eprint_status": "archive", "datestamp": "2023-08-20 10:57:56", "lastmod": "2023-10-18 15:57:48", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Harshan-A-K", "name": { "family": "Harshan", "given": "Aparna Karippara" } }, { "id": "Solis-B-H", "name": { "family": "Solis", "given": "Brian H." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Hammes-Schiffer-S", "name": { "family": "Hammes-Schiffer", "given": "Sharon" } } ] }, "title": "Computational Study of Fluorinated Diglyoxime-Iron Complexes: Tuning the Electrocatalytic Pathways for Hydrogen Evolution", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: December 9, 2015; Publication Date (Web): March 4, 2016. \n\nThis work was supported by the Center for Chemical Innovation of the National Science Foundation (Solar Fuels, Grant No. CHE-1305124). B.H.S. thanks the Alexander von Humboldt-Stiftung/Foundation for postdoctoral support during the writing of this paper. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - ic5b02857_si_001.pdf
", "abstract": "The ability to tune the properties of hydrogen-evolving molecular electrocatalysts is important for developing alternative energy sources. Fluorinated diglyoxime-iron complexes have been shown to evolve hydrogen at moderate overpotentials. Herein two such complexes, [(dAr^FgBF_2)_2Fe(py)_2], denoted A, and [(dAr^Fg_2H-BF_2)Fe(py)_2], denoted B [dAr^Fg = bis(pentafluorophenyl-glyoximato); py = pyridine], are investigated with density functional theory calculations. B differs from A in that one BF_2 bridge is replaced by a proton bridge of the form O\u2013H\u2013O. According to the calculations, the catalytic pathway for A involves two consecutive reduction steps, followed by protonation of an Fe^0 species to generate the active Fe^(II)-hydride species. B is found to proceed via two parallel pathways, where one pathway is similar to that for A, and the additional pathway arises from protonation of the O\u2013H\u2013O bridge, followed by spontaneous reduction to an Fe^0 intermediate and intramolecular proton transfer from the ligand to the metal center or protonation by external acid to form the same active Fe^(II)-hydride species. Simulated cyclic voltammograms (CVs) based on these mechanisms are in qualitative agreement with experimental CVs. The two parallel pathways identified for B arise from an equilibrium between the protonated and unprotonated ligand and result in two catalytic peaks in the CVs. The calculations predict that the relative probabilities for the two pathways, and therefore the relative magnitudes of the catalytic peaks, could be tuned by altering the pK_a of the acid or the substituents on the ligands of the electrocatalyst. The ability to control the catalytic pathways through acid strength or ligand substituents is critical for designing more effective catalysts for energy conversion processes.", "date": "2016-03-21", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "55", "number": "6", "publisher": "American Chemical Society", "pagerange": "2934-2940", "id_number": "CaltechAUTHORS:20160316-073650099", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160316-073650099", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Alexander von Humboldt Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.inorgchem.5b02857", "primary_object": { "basename": "ic5b02857_si_001.pdf", "url": "https://authors.library.caltech.edu/records/7j6zg-egz36/files/ic5b02857_si_001.pdf" }, "pub_year": "2016", "author_list": "Harshan, Aparna Karippara; Solis, Brian H.; et el." }, { "id": "https://authors.library.caltech.edu/records/7p3s4-f0n98", "eprint_id": 64908, "eprint_status": "archive", "datestamp": "2023-08-20 10:53:30", "lastmod": "2023-10-17 21:58:25", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Connor-B-A", "name": { "family": "Connor", "given": "Bridget A." } }, { "id": "Rittle-J", "name": { "family": "Rittle", "given": "Jonathan" } }, { "id": "VanderVelde-D-G", "name": { "family": "VanderVelde", "given": "David" }, "orcid": "0000-0002-2907-0366" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "A Ni^0(\u03b7^2-(Si\u2013H))(\u03b7^2-H_2) Complex That Mediates Facile H Atom Exchange between Two \u03c3-Ligands", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: December 2, 2015;\nPublished: February 22, 2016.\n\nThis work was supported by the NSF Center for Chemical Innovation Solar Fuels Grant CHE-1305124. We also acknowledge the Gordon and Betty Moore Foundation for financial support. B.A.C. acknowledges an Arthur R. Adams SURF fellowship. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - om5b00985_si_001.pdf
Supplemental Material - om5b00985_si_002.cif
", "abstract": "\u03c3-adduct complexes of low-valent, late first-row metal complexes are highly unusual, and this is particularly true of d^(10) systems. We have discovered a nickel/phosphine/silyl system that undergoes reaction with H_2 in solution to generate a species best described as Ni^0(\u03b7^2-(Si\u2013H))(\u03b7^2-H_2) on the basis of multinuclear NMR studies. Theoretical calculations suggest that the Ni center facilitates H atom exchange between the \u03b7^2-(Si\u2013H) and \u03b7^2-H_2 ligands via interconversion with a higher valent Ni^(II) isomer. This exchange is exploited in the selective, catalytic deuteration of exogenous silanes.", "date": "2016-03-14", "date_type": "published", "publication": "Organometallics", "volume": "35", "number": "5", "publisher": "American Chemical Society", "pagerange": "686-690", "id_number": "CaltechAUTHORS:20160301-114837187", "issn": "0276-7333", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160301-114837187", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Caltech Summer Undergraduate Research Fellowship (SURF)" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.organomet.5b00985", "primary_object": { "basename": "om5b00985_si_001.pdf", "url": "https://authors.library.caltech.edu/records/7p3s4-f0n98/files/om5b00985_si_001.pdf" }, "related_objects": [ { "basename": "om5b00985_si_002.cif", "url": "https://authors.library.caltech.edu/records/7p3s4-f0n98/files/om5b00985_si_002.cif" } ], "pub_year": "2016", "author_list": "Connor, Bridget A.; Rittle, Jonathan; et el." }, { "id": "https://authors.library.caltech.edu/records/fpbsq-zhg40", "eprint_id": 64912, "eprint_status": "archive", "datestamp": "2023-08-20 10:49:41", "lastmod": "2023-10-17 21:58:34", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hofbeck-T", "name": { "family": "Hofbeck", "given": "Thomas" } }, { "id": "Lam-Yan-Choi", "name": { "family": "Lam", "given": "Yan Choi" }, "orcid": "0000-0001-7809-4471" }, { "id": "Kalb\u00e1\u010d-M", "name": { "family": "Kalb\u00e1\u010d", "given": "Martin" } }, { "id": "Z\u00e1li\u0161-S", "name": { "family": "Z\u00e1li\u0161", "given": "Stanislav" } }, { "id": "Vl\u010dek-A-Jr", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn, Jr." } }, { "id": "Yersin-H", "name": { "family": "Yersin", "given": "Hartmut" } } ] }, "title": "Thermally Tunable Dual Emission of the d^8\u2013d^8 Dimer [Pt_2(\u03bc-P_2O_5(BF_2)_2)_4]^(4\u2013)", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: December 7, 2015. Publication Date (Web): February 24, 2016. \n\nT.H. and H.Y. acknowledge the financial support of the German Ministry of Education and Research (BMBF) and the Bavaria California Technology Center (BaCaTeC) for a travel grant. Further financial support was provided by the Ministry of Education of the Czech Republic grants LH13015 and LD14129, the NSF CCI Solar Fuels Program (CHE-1305124), the Arnold and Mabel Beckman Foundation, and the COST Action CM1202. M.K. acknowledges the financial support of the MSMT ERC CZ project (LL1301). We thank Capano Gloria, Ivano Tavernelli, and Majed Chergui (EPFL, Switzerland) as well as Jay. R. Winkler and Harry B. Gray (Caltech) for interesting discussions on intersystem crossing mechanisms, spectroscopy, and photophysics. \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - ic5b02839_si_001.pdf
", "abstract": "High-resolution fluorescence, phosphorescence, as well as related excitation spectra, and, in particular, the emission decay behavior of solid [Bu_4N]_4[Pt_2(\u03bc-P_2O_5(BF_2)_2)_4], abbreviated Pt(pop-BF_2), have been investigated over a wide temperature range, 1.3\u2013310 K. We focus on the lowest excited states that result from d\u03c3^*p\u03c3 (5d_z2\u20136p_z) excitations, i.e., the singlet state S_1 (of ^1A_2u symmetry in D_(4h)) and the lowest triplet T_1, which splits into spin\u2013orbit substates A_(1u)(^3A_(2u)) and E_u(^3A_(2u)). After optical excitation, an unusually slow intersystem crossing (ISC) is observed. As a consequence, the compound shows efficient dual emission, consisting of blue fluorescence and green phosphorescence with an overall emission quantum yield of \u223c100% over the investigated temperature range. Our investigation sheds light on this extraordinary dual emission behavior, which is unique for a heavy-atom transition metal compound. Direct ISC processes in Pt(pop-BF_2) are largely forbidden due to spin-, symmetry-, and Franck\u2013Condon overlap-restrictions and, therefore, the ISC time is as long as 29 ns for T < 100 K. With temperature increase, two different thermally activated pathways, albeit still relatively slow, are promoted by spin-vibronic and vibronic mechanisms, respectively. Thus, distinct temperature dependence of the ISC processes results and, as a consequence, also of the fluorescence/phosphorescence intensity ratio. The phosphorescence lifetime also is temperature-dependent, reflecting the relative population of the triplet T_1 substates E_u and A_(1u). The highly resolved phosphorescence shows a \u223c220 cm^(\u20131) red shift below 10 K, attributable to zero-field splitting of 40 cm^(\u20131) plus a promoting vibration of 180 cm^(\u20131).", "date": "2016-03-07", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "55", "number": "5", "publisher": "American Chemical Society", "pagerange": "2441-2449", "id_number": "CaltechAUTHORS:20160301-121141487", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160301-121141487", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Bundesministerium f\u00fcr Bildung und Forschung (BMBF)" }, { "agency": "Bavaria California Technology Center (BaCaTeC)" }, { "agency": "Ministry of Education (Czech Republic)", "grant_number": "LH13015" }, { "agency": "Ministry of Education (Czech Republic)", "grant_number": "LD14129" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "EU Framework Programme Horizon 2020", "grant_number": "CM1202" }, { "agency": "Ministry of Education, Youth and Sports (MEYS)", "grant_number": "LL1301" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.inorgchem.5b02839", "primary_object": { "basename": "ic5b02839_si_001.pdf", "url": "https://authors.library.caltech.edu/records/fpbsq-zhg40/files/ic5b02839_si_001.pdf" }, "pub_year": "2016", "author_list": "Hofbeck, Thomas; Lam, Yan Choi; et el." }, { "id": "https://authors.library.caltech.edu/records/68pbh-6nz88", "eprint_id": 65845, "eprint_status": "archive", "datestamp": "2023-08-20 10:34:18", "lastmod": "2023-10-18 16:51:27", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "DeBoever-M", "name": { "family": "DeBoever", "given": "Michelle" } }, { "id": "Parsons-C", "name": { "family": "Parsons", "given": "Christopher" } }, { "id": "Henderson-J", "name": { "family": "Henderson", "given": "Jennifer" } }, { "id": "Ruffin-M", "name": { "family": "Ruffin", "given": "Monya" } }, { "id": "Hames-B", "name": { "family": "Hames", "given": "Becky" } }, { "id": "Krause-M", "name": { "family": "Krause", "given": "Miriam" } }, { "id": "Pererra-E", "name": { "family": "Pererra", "given": "Eve" } }, { "id": "Watt-D", "name": { "family": "Watt", "given": "Danielle" } }, { "id": "Weizman-H", "name": { "family": "Weizman", "given": "Haim" } } ] }, "title": "Dialogue with the Centers for Chemical Innovation: Pioneering chemistry outreach and education", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2016 American Chemical Society.", "abstract": "The nine NSF funded Centers for Chem. Innovation (CCI) have been tasked not only with collaboratively\nadvancing the frontiers of chem. research, but also with exploring new ways to share their science with the\npublic. Each center tackles a different grand challenge in chem. and each of the centers has found unique\nways to be actively engaged in chem. outreach and educational programming. Like CCI research, CCI\noutreach is high-risk, high reward; the approach to CCI chem. outreach is meant to be innovative and exptl.\nfor every program and audience. Examples include museum exhibits, broadcast programs, blogging, and citizen\nscience projects for the general public, informal science education for K-12 students, and professional\ndevelopment for their teachers. The CCIs recognize that through a broad range of outreach opportunities, not\nonly are chemists and chem. educators being trained in effective chem. communication, but also diverse\naudiences, of all ages and backgrounds, are learning important chem. concepts, being exposed to various chem.\nscience related fields and careers, and becoming more informed citizens. Chem. education outreach is\nimportant for everyone and its impacts extend well beyond the scientific community. A panel of Directors of\nEducation, Outreach, and Diversity (EOD) from multiple CCIs will discuss how they develop programs,\nnavigate hurdles, and evaluate progress. With the combined expertise of the EODs and their collaborators, the\npanel will present guiding philosophies, best practices, and success stories from effective outreach initiatives\nfor K-12 and general audiences, as well as developing the science communication skills of researchers.", "date": "2016-03", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20160401-105345401", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160401-105345401", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "pub_year": "2016", "author_list": "DeBoever, Michelle; Parsons, Christopher; et el." }, { "id": "https://authors.library.caltech.edu/records/8g4y2-0mr64", "eprint_id": 66113, "eprint_status": "archive", "datestamp": "2023-08-20 10:37:39", "lastmod": "2023-10-23 15:27:46", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "M\u00fcller-A-M", "name": { "family": "Mueller", "given": "Astrid M." }, "orcid": "0000-0002-2785-6808" } ] }, "title": "Effect of interlayer anions on [NiFe]-LDH nanosheet water oxidation activity", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2016 American Chemical Society.", "abstract": "Powering the planet with sustainable, carbon-neutral fuels affects every aspect of human life. Sunlight-driven water splitting is\nan attractive soln. to provide environmentally benign hydrogen fuel. Global scalability demands that all photoelectrode and\ncatalyst materials consist of earth- abundant elements. The water oxidn. half reaction requires four coupled electron and\nproton transfer steps, for which robust and efficient electrocatalysts are needed. We have shown previously that [NiFe] - layered double hydroxide (LDH) nanosheets are highly active water oxidn. catalysts [Hunter, Blakemore, Deimund, Gray,\nWinkler, Mueller, J. Am. Chem. Soc. 2014, 136, 13118]. They were synthesized by pulsed laser ablation in liqs. (PLAL), a\nmedium-throughput method that yields small, monodisperse, surfactant- free, size and compn. controlled nanomaterials\n[Blakemore, Gray, Winkler, Mueller, A. M. ACS Catal. 2013, 3, 2497]. Our [NiFe]-LDH nanosheets are among the best earthabundant\nwater oxidn. catalysts, reaching 10 mA cm^(-2) at only 280 mV overpotential on a flat electrode in 1 M aq. KOH. We\nhave now investigated the effect of interlayer anions on water oxidn. activity. Our [NiFe]-LDH materials consisted of\nsheets of edge- shared nickel oxide octahedra, with 22 % of ferric iron substituting at nickel sites. The excess pos. charges of\nFe^(3+) substituting for Ni^(2+) were balanced by interlayer anions; water was also present in the interlayer galleries. The small\nsize (<20 nm) of our nanosheets made by PLAL allowed for complete exchange of interlayer anions simply by soaking in aq.\nsolns. We synthesized twelve materials with different interlayer anions, either by anion exchange or directly by PLAL, and\nassessed their water oxidn. activity in strong aq. base. Const.- current electrolysis data showed that the basicity of\ninterlayer anions matters for water oxidn. catalysis. The catalysts were most active and self- healing in self-buffered\ncarbonate-contg. alk. electrolyte.", "date": "2016-03", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20160413-105235075", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160413-105235075", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "pub_year": "2016", "author_list": "Hunter, Bryan M.; Winkler, Jay R.; et el." }, { "id": "https://authors.library.caltech.edu/records/zp8k4-7nr08", "eprint_id": 65849, "eprint_status": "archive", "datestamp": "2023-08-20 10:34:30", "lastmod": "2023-10-18 16:51:40", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan" }, "orcid": "0000-0001-8559-9304" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay" }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry" }, "orcid": "0000-0002-7937-7876" }, { "id": "M\u00fcller-A-M", "name": { "family": "Mueller", "given": "Astrid" }, "orcid": "0000-0002-2785-6808" } ] }, "title": "In-situ spectroscopies of mixed-metal nanosheet water oxidation catalysts made by pulsed laser ablation in liquids", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2016 American Chemical Society.", "abstract": "Our ability to utilize sustainable resources will be crit. in meeting the ever-increasing global energy demand in\nan eco-friendly manner. The most reliable and available source of sustainable energy is the sun. The biggest\nchallenges to its practical utilization are its intermittency on earth and unequal local energy needs. As a\nconsequence, we must find a way to convert solar energy into storable, transportable fuels. We envision a solar\nwater splitting device that produces hydrogen fuel. Subsequent functionalization with carbon dioxide will\nproduce liq. fuels that are carbon neutral upon combustion. Water oxidn., the more demanding half-reaction in\nthe water splitting process, is a key component to such a working device. Earth-abundant, efficient, and robust\nwater oxidn. catalysts need to be rationally designed based on their catalytic mechanisms. We have employed\nnovel in-situ spectroelectrochem. techniques to identify short-lived catalytic intermediates under turnover\nconditions. We recently reported [NiFe]-LDH (layered double hydroxide) nanocatalyst materials that are highly\nactive for water oxidn. [Hunter, Blakemore, Deimund, Gray, Winkler, M.ovrddot.uller, J. Soc.2014, 136, 13118]\n. Our in-situ IR, Raman, and UV-visible spectroscopic data in non-aq. solvents suggest that the LDH framework\nmay support high-valent metal species. Strategic injection of substrate indicates that this transient species is\nquenched by water. Our isotope labeling expts. have shed light on the structure of catalytic intermediates.", "date": "2016-03", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20160401-110652850", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160401-110652850", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "pub_year": "2016", "author_list": "Hunter, Bryan; Winkler, Jay; et el." }, { "id": "https://authors.library.caltech.edu/records/swbcd-h2k65", "eprint_id": 66650, "eprint_status": "archive", "datestamp": "2023-08-20 10:42:21", "lastmod": "2023-10-18 18:40:00", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Del-Ciello-S-A", "name": { "family": "Del Ciello", "given": "Sarah A." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Mechanistic investigation of proton reduction by cobaloximes: Insight from H2 oxidation kinetics", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2016 American Chemical Society.", "abstract": "Cobaloximes are a class of earth- abundant proton redn. catalysts that have been known since the 1980's. Previous studies\nhave come to conflicting conclusions about the mechanism of proton redn. by these catalysts, with evidence existing for both a\nhomolytic and heterolytic mechanism. In this work, kinetic anal. of the reverse reaction is used to gain further insight.", "date": "2016-03", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20160504-105818808", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160504-105818808", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "pub_year": "2016", "author_list": "Del Ciello, Sarah A.; Winkler, Jay R.; et el." }, { "id": "https://authors.library.caltech.edu/records/vraa4-fn762", "eprint_id": 64635, "eprint_status": "archive", "datestamp": "2023-08-20 10:18:02", "lastmod": "2023-10-17 21:34:03", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Gupta-Ayush", "name": { "family": "Gupta", "given": "Ayush" } }, { "id": "Blakemore-James-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Brunschwig-Bruce-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Immobilization and electrochemical properties of ruthenium and iridium complexes on carbon electrodes", "ispublished": "pub", "full_text_status": "restricted", "keywords": "surface chemistry, x-ray photoelectron spectroscopy, cyclic voltammetry, solar fuels", "note": "\u00a9 2016 IOP Publishing Ltd. \n\nReceived 10 June 2015, revised 30 July 2015. Accepted for publication 11 August 2015. Published 12 February 2016. \n\nThis research was carried out in part at the Molecular materials Research Center of the Beckman Institute at Caltech. The research was supported by the Resnick Sustainability Institute at Caltech (Postdoctoral Fellowship to J D B) and the NSF CCI Solar Fuels Program (CHE-1305124 and a CCI Postdoctoral Fellowship to J D B). The x-ray photoelectron spectroscopy was supported by a contract with the California Energy Commission (500-11-023).", "abstract": "We report the synthesis and surface immobilization of two new pyrene-appended molecular metal complexes: a ruthenium tris(bipyridyl) complex (1) and a bipyridyl complex of [Cp^*Ir] (2) (Cp^*\u2009\u2009=\u2009\u2009pentamethylcyclopentadienyl). X-ray photoelectron spectroscopy confirmed successful immobilization on high surface area carbon electrodes, with the expected elemental ratios for the desired compounds. Electrochemical data collected in acetonitrile solution revealed a reversible reduction of 1 near\u2009\u2009\u22121.4\u2009V, and reduction of 2 near\u2009\u2009\u22120.75\u2009V. The noncovalent immobilization, driven by association of the appended pyrene groups with the surface, was sufficiently stable to enable studies of the molecular electrochemistry. Electroactive surface coverage of 1 was diminished by only 27% over three hours soaking in electrolyte solution as measured by cyclic voltammetry. The electrochemical response of 2 resembled its soluble analogues, and suggested that ligand exchange occurred on the surface. Together, the results demonstrate that noncovalent immobilization routes are suitable for obtaining fundamental understanding of immobilized metal complexes and their reductive electrochemical properties.", "date": "2016-02-12", "date_type": "published", "publication": "Journal of Physics: Condensed Matter", "volume": "28", "number": "9", "publisher": "IOP", "pagerange": "Art. No. 094002", "id_number": "CaltechAUTHORS:20160222-122103336", "issn": "0953-8984", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160222-122103336", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Caltech Beckman Institute" }, { "agency": "Resnick Sustainability Institute" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "California Energy Commission", "grant_number": "500-11-023" } ] }, "local_group": { "items": [ { "id": "Resnick-Sustainability-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1088/0953-8984/28/9/094002", "pub_year": "2016", "author_list": "Gupta, Ayush; Blakemore, James D.; et el." }, { "id": "https://authors.library.caltech.edu/records/sn6k2-ywg71", "eprint_id": 59302, "eprint_status": "archive", "datestamp": "2023-08-22 16:20:48", "lastmod": "2023-10-23 20:17:56", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Xing-Xiangyou", "name": { "family": "Xing", "given": "Xiangyou" }, "orcid": "0000-0002-2456-0825" }, { "id": "O'Connor-N-R", "name": { "family": "O'Connor", "given": "Nicholas R." } }, { "id": "Stoltz-B-M", "name": { "family": "Stoltz", "given": "Brian M." }, "orcid": "0000-0001-9837-1528" } ] }, "title": "Palladium(II)-Catalyzed Allylic C-H Oxidation of Hindered Substrates Featuring Tunable Selectivity Over Extent of Oxidation", "ispublished": "pub", "full_text_status": "public", "keywords": "allylic compounds; C-H functionalization; heterocycles; oxidation; palladium", "note": "\u00a9 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nReceived: May 5, 2015; Revised: June 23, 2015; Article first published online: 31 Jul 2015. \n\nThis work was supported by the NSF under the CCI Center for Selective C-H Functionalization, CHE-1205646. Additional support was provided by Caltech and Amgen. Dr. Scott C. Virgil is thanked for helpful discussions. Dr. David VanderVelde (NMR), Dr. Michael K. Takase (X-ray crystallography), and Dr. Mona Shahgholi (HRMS) are acknowledged for assistance with structural determination and characterization. Guillermo A. Guerrero-V\u00e1squez, Lukas J.\nHilpert, and Dr. Wen-Bo Liu are acknowledged for experimental assistance.\n\nSupplemental Material - anie_201504007_sm_miscellaneous_information.pdf
", "abstract": "The use of Oxone and a palladium(II) catalyst enables the efficient allylic C-H oxidation of sterically hindered \u03b1-quaternary lactams which are unreactive under known conditions for similar transformations. This simple, safe, and effective system for C-H activation allows for unusual tunable selectivity between a two-electron oxidation to the allylic acetates and a four-electron oxidation to the corresponding enals, with the dominant product depending on the presence or absence of water. The versatile synthetic utility of both the allylic acetate and enal products accessible through this methodology is also demonstrated.", "date": "2015-09-14", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "54", "number": "38", "publisher": "Wiley", "pagerange": "11186-11190", "id_number": "CaltechAUTHORS:20150807-090520766", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150807-090520766", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1205646" }, { "agency": "Caltech" }, { "agency": "Amgen" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1002/anie.201504007", "primary_object": { "basename": "anie_201504007_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/sn6k2-ywg71/files/anie_201504007_sm_miscellaneous_information.pdf" }, "pub_year": "2015", "author_list": "Xing, Xiangyou; O'Connor, Nicholas R.; et el." }, { "id": "https://authors.library.caltech.edu/records/q5krs-j2p63", "eprint_id": 59776, "eprint_status": "archive", "datestamp": "2023-08-20 08:09:06", "lastmod": "2023-10-23 22:42:09", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kvapilov\u00e1-H", "name": { "family": "Kvapilov\u00e1", "given": "Hana" } }, { "id": "Sattler-W", "name": { "family": "Sattler", "given": "Wesley" }, "orcid": "0000-0001-5316-260X" }, { "id": "Sattler-A", "name": { "family": "Sattler", "given": "Aaron" } }, { "id": "Sazanovich-I-V", "name": { "family": "Sazanovich", "given": "Igor V." } }, { "id": "Clark-I-P", "name": { "family": "Clark", "given": "Ian P." } }, { "id": "Towrie-M", "name": { "family": "Towrie", "given": "Michael" } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Z\u00e1li\u0161-S", "name": { "family": "Z\u00e1li\u0161", "given": "Stanislav" } }, { "id": "Vl\u010dek-A", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn" } } ] }, "title": "Electronic Excited States of Tungsten(0) Arylisocyanides", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. \n\nReceived: May 27, 2015. Publication Date (Web): August 12, 2015.\n\nThis work was supported by the STFC Rutherford Appleton Laboratory, Ministry of Education of the Czech Republic Grant LH13015 (program KONTAKT II), COST Action CM1202. Research at Caltech was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation.\n\nPublished - acs_2Einorgchem_2E5b01203.pdf
Supplemental Material - ic5b01203_si_001.pdf
", "abstract": "W(CNAryl)_6 complexes containing 2,6-diisopropylphenyl isocyanide (CNdipp) are powerful photoreductants with strongly emissive long-lived excited states. These properties are enhanced upon appending another aryl ring, e.g., W(CNdippPh^(OMe)_2)_6; CNdippPh^(OMe)_2 = 4-(3,5-dimethoxyphenyl)-2,6-diisopropylphenylisocyanide (Sattler et al. J. Am. Chem. Soc. 2015, 137, 1198\u22121205). Electronic transitions and low-lying excited states of these complexes were investigated by time-dependent density functional theory (TDDFT); the lowest triplet state was characterized by time-resolved infrared spectroscopy (TRIR) supported by density functional theory (DFT). The intense absorption band of W(CNdipp)_6 at 460 nm and that of W(CNdippPh^(OMe)_2)_6 at 500 nm originate from transitions of mixed \u03c0\u03c0*(C\u2261N\u2013C)/MLCT(W \u2192 Aryl) character, whereby W is depopulated by ca. 0.4 e\u2013 and the electron-density changes are predominantly localized along two equatorial molecular axes. The red shift and intensity rise on going from W(CNdipp)_6 to W(CNdippPh^(OMe)_2)_6 are attributable to more extensive delocalization of the MLCT component. The complexes also exhibit absorptions in the 300\u2013320 nm region, owing to W \u2192 C\u2261N MLCT transitions. Electronic absorptions in the spectrum of W(CNXy)_6 (Xy = 2,6-dimethylphenyl), a complex with orthogonal aryl orientation, have similar characteristics, although shifted to higher energies. The relaxed lowest W(CNAryl)_6 triplet state combines \u03c0\u03c0* excitation of a trans pair of C\u2261N\u2013C moieties with MLCT (0.21 e\u2013) and ligand-to-ligand charge transfer (LLCT, 0.24\u20130.27 e\u2013) from the other four CNAryl ligands to the axial aryl and, less, to C\u2261N groups; the spin density is localized along a single Aryl\u2013N\u2261C\u2013W\u2013C\u2261N\u2013Aryl axis. Delocalization of excited electron density on outer aryl rings in W(CNdippPh^(OMe)_2)_6 likely promotes photoinduced electron-transfer reactions to acceptor molecules. TRIR spectra show an intense broad bleach due to \u03bd(C\u2261N), a prominent transient upshifted by 60\u201365 cm^(\u20131), and a weak down-shifted feature due to antisymmetric C\u2261N stretch along the axis of high spin density. The TRIR spectral pattern remains unchanged on the femtosecond-nanosecond time scale, indicating that intersystem crossing and electron-density localization are ultrafast (<100 fs).", "date": "2015-09-08", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "54", "number": "17", "publisher": "American Chemical Society", "pagerange": "8518-8528", "id_number": "CaltechAUTHORS:20150819-154731553", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150819-154731553", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Science and Technology Facilities Council (STFC)" }, { "agency": "Czech Republic Ministry of Education Program Kontakt II", "grant_number": "LH13015" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.inorgchem.5b01203", "primary_object": { "basename": "acs_2Einorgchem_2E5b01203.pdf", "url": "https://authors.library.caltech.edu/records/q5krs-j2p63/files/acs_2Einorgchem_2E5b01203.pdf" }, "related_objects": [ { "basename": "ic5b01203_si_001.pdf", "url": "https://authors.library.caltech.edu/records/q5krs-j2p63/files/ic5b01203_si_001.pdf" } ], "pub_year": "2015", "author_list": "Kvapilov\u00e1, Hana; Sattler, Wesley; et el." }, { "id": "https://authors.library.caltech.edu/records/v2jf9-y3526", "eprint_id": 61574, "eprint_status": "archive", "datestamp": "2023-08-22 16:10:43", "lastmod": "2024-01-13 16:26:36", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Chan-Candace-K", "name": { "family": "Chan", "given": "Candace K." } }, { "id": "T\u00fcys\u00fcz-H", "name": { "family": "T\u00fcys\u00fcz", "given": "Harun" } }, { "id": "Braun-A", "name": { "family": "Braun", "given": "Artur" } }, { "id": "Ranjan-C", "name": { "family": "Ranjan", "given": "Chinmoy" } }, { "id": "La-Mantia-F", "name": { "family": "La Mantia", "given": "Fabio" } }, { "id": "Miller-B-K", "name": { "family": "Miller", "given": "Benjamin K." } }, { "id": "Zhang-Liuxian", "name": { "family": "Zhang", "given": "Liuxian" } }, { "id": "Crozier-P-A", "name": { "family": "Crozier", "given": "Peter A." } }, { "id": "Haber-J-A", "name": { "family": "Haber", "given": "Joel A." }, "orcid": "0000-0001-7847-5506" }, { "id": "Gregoire-J-M", "name": { "family": "Gregoire", "given": "John M." }, "orcid": "0000-0002-2863-5265" }, { "id": "Park-Hyun-S", "name": { "family": "Park", "given": "Hyun S." }, "orcid": "0000-0002-7960-9729" }, { "id": "Batchellor-A-S", "name": { "family": "Batchellor", "given": "Adam S." } }, { "id": "Trotochaud-L", "name": { "family": "Trotochaud", "given": "Lena" } }, { "id": "Boettcher-S-W", "name": { "family": "Boettcher", "given": "Shannon W." }, "orcid": "0000-0001-8971-9123" } ] }, "title": "Advanced and In Situ Analytical Methods for Solar Fuel Materials", "ispublished": "unpub", "full_text_status": "restricted", "keywords": "Electrocatalysis; In operando; In situ; Photocatalysis; Solar fuels", "note": "\u00a9 2016 Springer. \n\nA.S.B. thanks the United State Air Force Academy Faculty Pipeline program for support. L.T. and the synthesis/optical characterization of thin-film electrocatalysts were supported by the National Science Foundation under the Centers for Chemical Innovation Program, grant CHE-1102637. The development of the optocatalytic model was supported by the DOE Basic Energy Sciences grant DE-FG02-12ER16323. S.W.B. thanks the Research Corporation for Science Advancement for a Cottrell Scholar Award.", "abstract": "In situ and operando techniques can play important roles in the development of better performing photoelectrodes, photocatalysts, and electrocatalysts by helping to elucidate crucial intermediates and mechanistic steps. The development of high throughput screening methods has also accelerated the evaluation of relevant photoelectrochemical and electrochemical properties for new solar fuel materials. In this chapter, several in situ and high throughput characterization tools are discussed in detail along with their impact on our understanding of solar fuel materials.", "date": "2015-08-13", "date_type": "published", "publisher": "Springer", "place_of_pub": "New York, NY", "pagerange": "253-324", "id_number": "CaltechAUTHORS:20151027-135221593", "isbn": "978-3-319-23098-6", "book_title": "Solar Energy for Fuels", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20151027-135221593", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "United State Air Force Academy" }, { "agency": "NSF", "grant_number": "CHE-1102637" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG02-12ER16323" }, { "agency": "Cottrell Scholar of Research Corporation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "contributors": { "items": [ { "id": "T\u00fcys\u00fcz-H", "name": { "family": "T\u00fcys\u00fcz", "given": "Harun" } }, { "id": "Chan-Candace-K", "name": { "family": "Chan", "given": "Candace K." } } ] }, "doi": "10.1007/128_2015_650", "pub_year": "2015", "author_list": "Chan, Candace K.; T\u00fcys\u00fcz, Harun; et el." }, { "id": "https://authors.library.caltech.edu/records/7723a-zqd43", "eprint_id": 57042, "eprint_status": "archive", "datestamp": "2023-09-28 00:55:36", "lastmod": "2023-10-24 14:56:11", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Roske-C-W", "name": { "family": "Roske", "given": "Christopher W." } }, { "id": "Popczun-E-J", "name": { "family": "Popczun", "given": "Eric J." } }, { "id": "Seger-B", "name": { "family": "Seger", "given": "Brian" } }, { "id": "Read-C-G", "name": { "family": "Read", "given": "Carlos G." } }, { "id": "Pedersen-T", "name": { "family": "Pedersen", "given": "Thomas" } }, { "id": "Hansen-O", "name": { "family": "Hansen", "given": "Ole" } }, { "id": "Vesborg-P-C-K", "name": { "family": "Vesborg", "given": "Peter C. K." } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Schaak-R-E", "name": { "family": "Schaak", "given": "Raymond E." } }, { "id": "Chorkendorff-Ib", "name": { "family": "Chorkendorff", "given": "Ib" } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Comparison of the Performance of CoP-Coated and Pt-Coated Radial Junction n\u207ap-Silicon Microwire-Array Photocathodes for the Sunlight-Driven Reduction of Water to H\u2082(g)", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 American Chemical Society.\n\nReceived: March 9, 2015; Accepted: April 7, 2015; Publication Date (Web): April 20, 2015.\n\nThis work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and the Center for Individual Nanoparticle Functionality (CINF) (DNRF54). C.W.R. thanks the National Science Foundation and Link Energy Foundation for graduate research fellowships. Research was in part carried out at the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology. N.S.L. acknowledges support from the Energy from Sunlight Project funded by the Gordon and Betty Moore Foundation (GBMF1225).\n\nSupplemental Material - jz5b00495_si_001.pdf
", "abstract": "The electrocatalytic performance for hydrogen evolution has been evaluated for radial-junction n^+p-Si microwire (MW) arrays with Pt or cobalt phosphide, CoP, nanoparticulate catalysts in contact with 0.50 M H_2SO_4(aq). The CoP-coated (2.0 mg cm^(\u20132)) n^+p-Si MW photocathodes were stable for over 12 h of continuous operation and produced an open-circuit photovoltage (V_(oc)) of 0.48 V, a light-limited photocurrent density (J_(ph)) of 17 mA cm^(\u20132), a fill factor (ff) of 0.24, and an ideal regenerative cell efficiency (\u03b7_(IRC)) of 1.9% under simulated 1 Sun illumination. Pt-coated (0.5 mg cm^(\u20132)) n^+p-Si MW-array photocathodes produced V_(oc) = 0.44 V, J_(ph) = 14 mA cm^(\u20132), ff = 0.46, and \u03b7 = 2.9% under identical conditions. Thus, the MW geometry allows the fabrication of photocathodes entirely comprised of earth-abundant materials that exhibit performance comparable to that of devices that contain Pt.", "date": "2015-05-07", "date_type": "published", "publication": "Journal of Physical Chemistry Letters", "volume": "6", "number": "9", "publisher": "American Chemical Society", "pagerange": "1679-1683", "id_number": "CaltechAUTHORS:20150428-095042468", "issn": "1948-7185", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150428-095042468", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Danish National Research Foundation", "grant_number": "DNRF54" }, { "agency": "Link Energy Foundation" }, { "agency": "Gordon and Betty Moore Foundation", "grant_number": "GBMF1225" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.jpclett.5b00495", "primary_object": { "basename": "jz5b00495_si_001.pdf", "url": "https://authors.library.caltech.edu/records/7723a-zqd43/files/jz5b00495_si_001.pdf" }, "pub_year": "2015", "author_list": "Roske, Christopher W.; Popczun, Eric J.; et el." }, { "id": "https://authors.library.caltech.edu/records/bz1mc-d1625", "eprint_id": 55965, "eprint_status": "archive", "datestamp": "2023-08-22 15:32:34", "lastmod": "2023-10-20 23:29:17", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Varghese-J-O", "name": { "family": "Varghese", "given": "Joseph O." } }, { "id": "Agbo-P", "name": { "family": "Agbo", "given": "Peter" } }, { "id": "Sutherland-A-M", "name": { "family": "Sutherland", "given": "Alexander M." } }, { "id": "Brar-V-W", "name": { "family": "Brar", "given": "Victor W." } }, { "id": "Rossman-G-R", "name": { "family": "Rossman", "given": "George R." }, "orcid": "0000-0002-4571-6884" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Heath-J-R", "name": { "family": "Heath", "given": "James R." }, "orcid": "0000-0001-5356-4385" } ] }, "title": "The Influence of Water on the Optical Properties of Single-Layer Molybdenum Disulfide", "ispublished": "pub", "full_text_status": "public", "keywords": "2D materials; molybdenum disulfide; optics; photonics", "note": "\u00a9 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.\n\nReceived: February 3, 2015; Revised: February 26, 2015. Article first published online: 18 Mar 2015.\n\nThe authors thank Dr. Jamil Tahir-Kheli for helpful discussions. The authors acknowledge grants from the Department of Energy (Grant No. DE-FG03-01ER46175: J.R.H.) and the National Science Foundation (Grant No. EAR-1322082: G.R.R.). Collection of PL spectra was supported in part by NSF CCI Solar Fuels grant (Grant No. CHE-1305124: H.B.G).\n\nSupplemental Material - adma201500555-sup-0001-S1.pdf
", "abstract": "Adsorbed molecules can significantly affect the properties of atomically thin materials. Physisorbed water plays a significant role in altering the optoelectronic properties of single-layer MoS_2, one such 2D film. Here we demonstrate the distinct quenching effect of adsorbed water on the photoluminescence of single-layer MoS_2 through scanning-probe and optical microscopies.", "date": "2015-05-06", "date_type": "published", "publication": "Advanced Materials", "volume": "27", "number": "17", "publisher": "Wiley", "pagerange": "2734-2740", "id_number": "CaltechAUTHORS:20150323-101933830", "issn": "0935-9648", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150323-101933830", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG03-01ER46175" }, { "agency": "NSF", "grant_number": "EAR-1322082" }, { "agency": "NSF", "grant_number": "CHE-1305124" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" }, { "id": "Division-of-Geological-and-Planetary-Sciences" } ] }, "doi": "10.1002/adma.201500555", "primary_object": { "basename": "adma201500555-sup-0001-S1.pdf", "url": "https://authors.library.caltech.edu/records/bz1mc-d1625/files/adma201500555-sup-0001-S1.pdf" }, "pub_year": "2015", "author_list": "Varghese, Joseph O.; Agbo, Peter; et el." }, { "id": "https://authors.library.caltech.edu/records/1238k-km006", "eprint_id": 53059, "eprint_status": "archive", "datestamp": "2023-08-20 05:56:33", "lastmod": "2023-10-18 21:54:58", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Sinclair-T-S", "name": { "family": "Sinclair", "given": "Timothy S." } }, { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "M\u00fcller-A-M", "name": { "family": "M\u00fcller", "given": "Astrid M." }, "orcid": "0000-0002-2785-6808" } ] }, "title": "Factors affecting bismuth vanadate photoelectrochemical performance", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 The Royal Society of Chemistry.\n\nReceived 22 Aug 2014, Accepted 02 Dec 2014, First published online 02 Dec 2014.\n\nWe thank June Wicks for help with SEM imaging, Matthew Shaner for providing electrodeposited BiVO_4 samples on FTO-glass prepared according to Choi, Richard P. Gerhart for fabrication of the photoelectrochemical cell, and Robert H. Coridan for valuable discussions. Research was performed at the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology. T.S.S. acknowledges a SURF Fellowship in honour of Dr Terry Cole, and B.M.H. is an NSF Graduate Fellow. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation.\n\nPublished - c4mh00156g.pdf
Supplemental Material - c4mh00156g1.pdf
", "abstract": "Bismuth vanadate is a promising photoanode material, but recent reports on undoped BiVO_4 without sublayers and co-catalysts showed large variations in photocurrent generation. We addressed this issue by correlating photoelectrochemical performance with physical properties. We devised a novel anodic electrodeposition procedure with iodide added to the aqueous plating bath, which allowed us to prepare BiVO_4 photoanodes with virtually identical thicknesses but different morphologies, and we could control surface Bi content. Morphologies were quantified from SEM images as distributions of crystallite areas and aspect-ratio-normalised diameters, and their statistical moments were derived. We could obtain clear photocurrent generation trends only from bivariate data analysis. Our experimental evidence suggests that a combination of low Bi/V ratio, small aspect-ratio-normalised diameters, and crystallites sizes that were small enough to provide efficient charge separation yet sufficiently large to prevent mass transport limitations led to highest photoelectrochemical performance.", "date": "2015-05", "date_type": "published", "publication": "Materials Horizons", "volume": "2", "number": "3", "publisher": "Royal Society of Chemistry", "pagerange": "330-337", "id_number": "CaltechAUTHORS:20141222-075342492", "issn": "2051-6347", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20141222-075342492", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Caltech Summer Undergraduate Research Fellowship (SURF)" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c4mh00156g", "primary_object": { "basename": "c4mh00156g.pdf", "url": "https://authors.library.caltech.edu/records/1238k-km006/files/c4mh00156g.pdf" }, "related_objects": [ { "basename": "c4mh00156g1.pdf", "url": "https://authors.library.caltech.edu/records/1238k-km006/files/c4mh00156g1.pdf" } ], "pub_year": "2015", "author_list": "Sinclair, Timothy S.; Hunter, Bryan M.; et el." }, { "id": "https://authors.library.caltech.edu/records/2jtd0-9dr85", "eprint_id": 57364, "eprint_status": "archive", "datestamp": "2023-08-20 05:46:00", "lastmod": "2023-10-23 17:19:10", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Z\u00e1li\u0161-S", "name": { "family": "Z\u00e1li\u0161", "given": "Stanislav" } }, { "id": "Lam-Yan-Choi", "name": { "family": "Lam", "given": "Yan-Choi" }, "orcid": "0000-0001-7809-4471" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Vl\u010dek-A", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn" } } ] }, "title": "Spin\u2212Orbit TDDFT Electronic Structure of Diplatinum(II,II) Complexes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. \n\nReceived: January 9, 2015. Publication Date (Web): March 16, 2015. \n\nWe thank Mr. L. Henling (Beckman Institute) for his help with determining and presenting the X-ray structure. This work was supported by the Ministry of Education of the Czech Republic Grant No. LH13015 (Program KONTAKT II), the NSF CCI Solar Fuels Program (CHE-1305124), and the Arnold and Mabel Beckman Foundation.\n\nPublished - acs_2Einorgchem_2E5b00063.pdf
Supplemental Material - ic5b00063_si_001.pdf
Supplemental Material - ic5b00063_si_002.pdf
Supplemental Material - ic5b00063_si_003.cif
", "abstract": "[Pt_2(\u03bc-P_2O_5H_2)_4]^(4\u2013) (Pt(pop)) and its perfluoroborated derivative [Pt_2(\u03bc-P_2O_5(BF_2)_2)_4]^(4\u2013) (Pt(pop-BF_2)) are d^8\u2013d^8 complexes whose electronic excited states can drive reductions and oxidations of relatively inert substrates. We performed spin\u2013orbit (SO) TDDFT calculations on these complexes that account for their absorption spectra across the entire UV\u2013vis spectral region. The complexes exhibit both fluorescence and phosphorescence attributable, respectively, to singlet and triplet excited states of d\u03c3*p\u03c3 origin. These features are energetically isolated from each other (\u223c7000 cm^(\u20131) for (Pt(pop-BF_2)) as well as from higher-lying states (5800 cm^(\u20131)). The lowest ^3d\u03c3*p\u03c3 state is split into three SO states by interactions with higher-lying singlet states with d\u03c0p\u03c3 and, to a lesser extent, p\u03c0p\u03c3 contributions. The spectroscopically allowed d\u03c3*p\u03c3 SO state has \u223c96% singlet character with small admixtures of higher triplets of partial d\u03c0p\u03c3 and p\u03c0p\u03c3 characters that also mix with 3d\u03c3*p\u03c3, resulting in a second-order ^1d\u03c3*p\u03c3\u2013^3d\u03c3*p\u03c3 SO interaction that facilitates intersystem crossing (ISC). All SO interactions involving the d\u03c3*p\u03c3 states are weak because of large energy gaps to higher interacting states. The spectroscopically allowed d\u03c3*p\u03c3 SO state is followed by a dense manifold of ligand-to-metal\u2013metal charge transfer states, some with p\u03c0p\u03c3 (at lower energies) or d\u03c0p\u03c3 contributions (at higher energies). Spectroscopically active higher states are strongly spin-mixed. The electronic structure, state ordering, and relative energies are minimally perturbed when the calculation is performed at the optimized geometries of the ^1d\u03c3*p\u03c3 and ^3d\u03c3*p\u03c3 excited states (rather than the ground state). Results obtained for Pt(pop) are very similar, showing slightly smaller energy gaps and, possibly, an additional ^1d\u03c3*p\u03c3 \u2013 ^3d\u03c3*p\u03c3 second order SO interaction involving higher ^1d\u03c0p\u03c3* states that could account in part for the much faster ISC. It also appears that ^1d\u03c3*p\u03c3 \u2192 ^3d\u03c3*p\u03c3 ISC requires a structural distortion that has a lower barrier for Pt(pop) than for the more rigid Pt(pop-BF_2).", "date": "2015-04-06", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "54", "number": "7", "publisher": "American Chemical Society", "pagerange": "3491-3500", "id_number": "CaltechAUTHORS:20150508-082616550", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150508-082616550", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Ministry of Education (Czech Republic)", "grant_number": "LH13015" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/acs.inorgchem.5b00063", "primary_object": { "basename": "acs_2Einorgchem_2E5b00063.pdf", "url": "https://authors.library.caltech.edu/records/2jtd0-9dr85/files/acs_2Einorgchem_2E5b00063.pdf" }, "related_objects": [ { "basename": "ic5b00063_si_001.pdf", "url": "https://authors.library.caltech.edu/records/2jtd0-9dr85/files/ic5b00063_si_001.pdf" }, { "basename": "ic5b00063_si_002.pdf", "url": "https://authors.library.caltech.edu/records/2jtd0-9dr85/files/ic5b00063_si_002.pdf" }, { "basename": "ic5b00063_si_003.cif", "url": "https://authors.library.caltech.edu/records/2jtd0-9dr85/files/ic5b00063_si_003.cif" } ], "pub_year": "2015", "author_list": "Z\u00e1li\u0161, Stanislav; Lam, Yan-Choi; et el." }, { "id": "https://authors.library.caltech.edu/records/f2s8d-8np53", "eprint_id": 56590, "eprint_status": "archive", "datestamp": "2023-08-20 05:25:29", "lastmod": "2023-10-23 15:35:46", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Popczun-E-J", "name": { "family": "Popczun", "given": "Eric J." } }, { "id": "Roske-C-W", "name": { "family": "Roske", "given": "Christopher W." } }, { "id": "Read-C-G", "name": { "family": "Read", "given": "Carlos G." } }, { "id": "Crompton-J-C", "name": { "family": "Crompton", "given": "J. Chance" } }, { "id": "McEnaney-J-M", "name": { "family": "McEnaney", "given": "Joshua M." } }, { "id": "Callejas-J-F", "name": { "family": "Callejas", "given": "Juan F." } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Schaak-R-E", "name": { "family": "Schaak", "given": "Raymond E." } } ] }, "title": "Highly branched cobalt phosphide nanostructures for hydrogen-evolution electrocatalysis", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 The Royal Society of Chemistry.\n\nReceived 3rd December 2014; Accepted 15th January 2015; First published online 16 Jan 2015.\n\nThe work at PSU was supported by the National Science Foundation (NSF) Center for Chemical Innovation on Solar Fuels (CHE-1305124) and at Caltech by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993, as well as the Gordon and Betty Moore Foundation. TEM was performed in the Penn State Microscopy and Cytometry Facility (University Park, PA) and HRTEM, EDS, SEM, and BET data were acquired at the Materials Characterization Laboratory of the Penn State Materials Research Institute. C.W.R. thanks the NSF for a graduate research fellowship.\n\nPublished - c4ta06642a.pdf
Supplemental Material - c4ta06642a1_si.pdf
", "abstract": "CoP nanostructures that exposed predominantly (111) crystal facets were synthesized and evaluated for performance as electrocatalysts for the hydrogen-evolution reaction (HER). The branched CoP nanostructures were synthesized by reacting cobalt(II) acetylacetonate with trioctylphosphine in the presence of trioctylphosphine oxide. Electrodes comprised of the branched CoP nanostructures deposited at a loading density of ~1 mg cm^(\u22122) on Ti electrodes required an overpotential of \u2212117 mV to produce a current density of \u221220 mA cm^(\u22122) in 0.50 M H_2SO_4. Hence the branched CoP nanostructures belong to the growing family of highly active non-noble-metal HER electrocatalysts. Comparisons with related CoP systems have provided insights into the impact that shape-controlled nanoparticles and nanoparticle\u2013electrode interactions have on the activity and stability of nanostructured HER electrocatalysts.", "date": "2015-03-14", "date_type": "published", "publication": "Journal of Materials Chemistry A", "volume": "3", "number": "10", "publisher": "Royal Society of Chemistry", "pagerange": "5420-5425", "id_number": "CaltechAUTHORS:20150413-094253407", "issn": "2050-7488", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150413-094253407", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC0004993" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c4ta06642a", "primary_object": { "basename": "c4ta06642a.pdf", "url": "https://authors.library.caltech.edu/records/f2s8d-8np53/files/c4ta06642a.pdf" }, "related_objects": [ { "basename": "c4ta06642a1_si.pdf", "url": "https://authors.library.caltech.edu/records/f2s8d-8np53/files/c4ta06642a1_si.pdf" } ], "pub_year": "2015", "author_list": "Popczun, Eric J.; Roske, Christopher W.; et el." }, { "id": "https://authors.library.caltech.edu/records/r5z01-vwf27", "eprint_id": 56636, "eprint_status": "archive", "datestamp": "2023-08-20 05:08:38", "lastmod": "2023-10-23 15:39:06", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Blakemore-J-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Gupta-A", "name": { "family": "Gupta", "given": "Ayush" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Integrated catalyst-electrodes for the production of solar fuels", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2015 American Chemical Society.", "abstract": "Immobilization of selective catalysts for fuel- forming reactions on (photo) electrode surfaces is an appealing route to structures\nfor the generation of renewable fuel. Our recent work has focused on immobilization of mol. catalysts on graphitic carbon\nelectrode surfaces via noncovalent interactions. The general approach relies on a pyrene- appended bipyridyl ligand (P) that\nserves as the linker between the catalysts and the surface. With this method, proton redn. to dihydrogen was catalyzed with an\nimmobilized rhodium complex, [Cp*Rh(P) Cl] Cl, and CO_2 redn. to CO was catalyzed with a rhenium complex, Re(P) (CO)_3Cl.\nSpectroscopic studies of the [Cp*Rh] - and [Re(CO)_3] - functionalized electrodes are providing new insights into the activity of\nthese assemblies. Catalysis continues over the timescale of hours, and in the case of hydrogen evolution, with estd. turnover\nfrequency near 1 per s. We are also now extending work to earth- abundant systems, and have prepd. Mn(P) (CO)_3Br as a\ncandidate CO_2 - redn. catalyst. Immobilization results in electroactive material, and electrocatalytic CO prodn. has been\nmeasured. Recent results will be presented, including spectroscopic characterization, electrochem. stability, and electrocatalytic\nCO_2 redn. with these catalysts.", "date": "2015-03", "date_type": "published", "publication": "Abstracts of Papers of the American Chemical Society", "volume": "249", "publisher": "American Chemical Society", "pagerange": "INOR-821", "id_number": "CaltechAUTHORS:20150414-130714462", "issn": "0065-7727", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150414-130714462", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "pub_year": "2015", "author_list": "Blakemore, James D.; Gupta, Ayush; et el." }, { "id": "https://authors.library.caltech.edu/records/qw966-10p67", "eprint_id": 55975, "eprint_status": "archive", "datestamp": "2023-08-22 14:58:21", "lastmod": "2023-10-20 23:30:27", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lam-Yan-Choi", "name": { "family": "Lam", "given": "Yan Choi" }, "orcid": "0000-0001-7809-4471" }, { "id": "Nielsen-R-J", "name": { "family": "Nielsen", "given": "Robert J." }, "orcid": "0000-0002-7962-0186" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "orcid": "0000-0003-0097-5716" } ] }, "title": "A Mn Bipyrimidine Catalyst Predicted To Reduce CO_2 at Lower Overpotential", "ispublished": "pub", "full_text_status": "public", "keywords": "density functional theory; electrochemical CO2 reduction; reaction mechanism; chemoselectivity; overpotential", "note": "\u00a9 2015 American Chemical Society.\n\nReceived: September 18, 2014; Revised: February 12, 2015. Publication Date (Web): February 16, 2015.\n\nY.C.L., who performed the calculations and data analysis, was supported by the National Science Foundation (NSF) through the Centers for Chemical Innovation (CCI), Solar Fuels grant CHE-1305124, as was H.B.G. R.J.N. and W.A.G., who developed the computational strategy, interpretation, and analysis studies, are supported by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. We gratefully acknowledge Professor Clifford P. Kubiak for helpful discussions.\n\nSupplemental Material - cs501963v_si_001.pdf
", "abstract": "Experimentally, [(L)Mn(CO)_3]\u2212 (where L = bis-alkyl-substituted bipyridine) has been observed to catalyze the electrochemical reduction of CO_2 to CO in the presence of trifluoroethanol (TFEH). Here we report the atomistic level mechanism of complete catalytic cycles for this reaction, on the basis of DFT calculations (B3LYP-D3 with continuum solvation) of the free energies of reaction and activation, as well as reduction potentials for all catalytically relevant elementary steps. The highly exergonic homoconjugation and carbonation of TFE\u2013 play critical roles in reaction thermodynamics and kinetics, the overall half-reaction being 3CO_2 + 2TFEH + 2e\u2013 \u2192 CO + H_2O + 2[F_3CCH_2OCO_2]\u2212 (calculated standard reduction potential: \u22121.49 V vs SCE). In the catalytic cycle for CO formation, CO_2 coordinates to [(L)Mn(CO)_3]\u2212 (1a, L = bpy), and the adduct is then protonated to form [(L)Mn(CO)_3(CO_2H)] (3a). 3a subsequently reacts to form [(L)Mn(CO)_4]0 (5a) via one of two pathways: (a) TFEH-mediated dehydroxylation to [(L)Mn(CO)_4]+ (4a), followed by one-electron reduction to 5a, or (b) under more reducing potentials, one-electron reduction to [(L)Mn(CO)_3(CO_2H)]\u2212 (3\u2032a), followed by dehydroxylation to 5a. Pathway b has a lower activation energy by 2.2 kcal mol^(\u20131). Consequently, the maximum catalytic turnover frequency (TOF_(max)) is achieved at \u223c\u22121.75 V vs SCE (\u223c0.25 V overpotential). For the analogous bipyrimidine compound (not yet studied experimentally), reduction of 3b to 3\u2032b occurs at a potential 0.5 V more positive than that of 3a, and the overpotential required to achieve TOF_(max) is predicted to be lower by \u223c0.25 V. This improvement is, however, achieved at the price of a lower TOF_(max), and we predict that 1b has superior TOF at potentials above \u223c\u22121.6 V vs SCE. In addition, the various factors contributing to product selectivity (CO over H_2) are discussed.", "date": "2015-02-16", "date_type": "published", "publication": "ACS Catalysis", "volume": "5", "number": "4", "publisher": "American Chemical Society", "pagerange": "2521-2528", "id_number": "CaltechAUTHORS:20150323-132108582", "issn": "2155-5435", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150323-132108582", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC0004993" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/cs501963v", "primary_object": { "basename": "cs501963v_si_001.pdf", "url": "https://authors.library.caltech.edu/records/qw966-10p67/files/cs501963v_si_001.pdf" }, "pub_year": "2015", "author_list": "Lam, Yan Choi; Nielsen, Robert J.; et el." }, { "id": "https://authors.library.caltech.edu/records/181pz-w3261", "eprint_id": 54064, "eprint_status": "archive", "datestamp": "2023-08-20 04:41:21", "lastmod": "2023-10-19 23:36:25", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Sattler-W", "name": { "family": "Sattler", "given": "Wesley" }, "orcid": "0000-0001-5316-260X" }, { "id": "Henling-L-M", "name": { "family": "Henling", "given": "Lawrence M." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Bespoke Photoreductants: Tungsten Arylisocyanides", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 American Chemical Society. \n\nReceived October 24, 2014. Publication Date (Web): January 16, 2015. \n\nWe thank Michael Takase and David VanderVelde for assistance with X-ray and NMR experiments. Discussions with Aaron Rachford, Paul LaBeaume, Jim Thackeray, and Jim Cameron in the early stages of this work were very helpful. The Bruker KAPPA APEX II X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094). Our work is supported by the National Science Foundation Center for Chemical Innovation in Solar Fuels (CHE-1305124) and a CCI postdoctoral fellowship to W.S.\n\nSupplemental Material - ja510973h_si_001.cif
Supplemental Material - ja510973h_si_002.cif
Supplemental Material - ja510973h_si_003.cif
Supplemental Material - ja510973h_si_004.cif
Supplemental Material - ja510973h_si_005.pdf
", "abstract": "Modular syntheses of oligoarylisocyanide ligands that are derivatives of 2,6-diisopropylphenyl isocyanide (CNdipp) have been developed; tungsten complexes incorporating these oligoarylisocyanide ligands exhibit intense metal-to-ligand charge-transfer visible absorptions that are red-shifted and more intense than those of the parent W(CNdipp)_6 complex. Additionally, these W(CNAr)_6 complexes have enhanced excited-state properties, including longer lifetimes and very high quantum yields. The decay kinetics of electronically excited W(CNAr)_6 complexes (*W(CNAr)_6) show solvent dependences; faster decay is observed in higher dielectric solvents. *W(CNAr)_6 lifetimes are temperature dependent, suggestive of a strong coupling nonradiative decay mechanism that promotes repopulation of the ground state. Notably, *W(CNAr)_6 complexes are exceptionally strong reductants: [W(CNAr)_6]+/*W(CNAr)_6 potentials are more negative than \u22122.7 V vs [Cp_2Fe]^+/Cp_2Fe.", "date": "2015-01-28", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "137", "number": "3", "publisher": "American Chemical Society", "pagerange": "1198-1205", "id_number": "CaltechAUTHORS:20150126-093535146", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150126-093535146", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0639094" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "NSF Postdoctoral Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja510973h", "primary_object": { "basename": "ja510973h_si_001.cif", "url": "https://authors.library.caltech.edu/records/181pz-w3261/files/ja510973h_si_001.cif" }, "related_objects": [ { "basename": "ja510973h_si_002.cif", "url": "https://authors.library.caltech.edu/records/181pz-w3261/files/ja510973h_si_002.cif" }, { "basename": "ja510973h_si_003.cif", "url": "https://authors.library.caltech.edu/records/181pz-w3261/files/ja510973h_si_003.cif" }, { "basename": "ja510973h_si_004.cif", "url": "https://authors.library.caltech.edu/records/181pz-w3261/files/ja510973h_si_004.cif" }, { "basename": "ja510973h_si_005.pdf", "url": "https://authors.library.caltech.edu/records/181pz-w3261/files/ja510973h_si_005.pdf" } ], "pub_year": "2015", "author_list": "Sattler, Wesley; Henling, Lawrence M.; et el." }, { "id": "https://authors.library.caltech.edu/records/a3sqk-6yh94", "eprint_id": 52221, "eprint_status": "archive", "datestamp": "2023-08-20 04:01:53", "lastmod": "2023-10-18 19:40:38", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Laga-S-M", "name": { "family": "Laga", "given": "Stephanie M." } }, { "id": "Blakemore-J-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Henling-L-M", "name": { "family": "Henling", "given": "Lawrence M." } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Catalysis of Proton Reduction by a [BO_4]-Bridged Dicobalt Glyoxime", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society.\n\nReceived: July 28, 2014; published: November 19, 2014.\n\nThe authors thank Ivonne Ferrer for helpful discussions and\nAaron Sattler for assistance in preparation of Figure 2. This research was carried out in part at the Molecular Materials Research Center of the Beckman Institute at Caltech. The research was supported by the Resnick Sustainability Institute at Caltech (Postdoctoral Fellowship to J.D.B.) and the NSF CCI Solar Fuels Program (CHE-1305124 and a CCI Postdoctoral Fellowship to J.D.B.). The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094). Gas chromatographs were collected at the Joint Center for Artificial Photosynthesis at Caltech.\n\nSupplemental Material - ic501804h_si_001.pdf
Supplemental Material - ic501804h_si_002.cif
", "abstract": "We report the preparation of a dicobalt compound with two singly proton-bridged cobaloxime units linked by a central [BO_4] bridge. Reaction of a doubly proton-bridged cobaloxime complex with trimethyl borate afforded the compound in good yield. Single-crystal X-ray diffraction studies confirmed the bridging nature of the [BO_4] moiety. Using electrochemical methods, the dicobalt complex was found to be an electrocatalyst for proton reduction in acetonitrile solution. Notably, the overpotential for proton reduction (954 mV) was found to be higher than in the cases of two analogous single-site cobalt glyoximes under virtually identical conditions.", "date": "2014-12-15", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "53", "number": "24", "publisher": "American Chemical Society", "pagerange": "12668-12670", "id_number": "CaltechAUTHORS:20141201-105741726", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20141201-105741726", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Resnick Sustainability Institute" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "NSF Postdoctoral Fellowship" }, { "agency": "NSF", "grant_number": "CHE-0639094" } ] }, "local_group": { "items": [ { "id": "Resnick-Sustainability-Institute" }, { "id": "CCI-Solar-Fuels" }, { "id": "JCAP" } ] }, "doi": "10.1021/ic501804h", "primary_object": { "basename": "ic501804h_si_001.pdf", "url": "https://authors.library.caltech.edu/records/a3sqk-6yh94/files/ic501804h_si_001.pdf" }, "related_objects": [ { "basename": "ic501804h_si_002.cif", "url": "https://authors.library.caltech.edu/records/a3sqk-6yh94/files/ic501804h_si_002.cif" } ], "pub_year": "2014", "author_list": "Laga, Stephanie M.; Blakemore, James D.; et el." }, { "id": "https://authors.library.caltech.edu/records/x40p7-x3h66", "eprint_id": 53768, "eprint_status": "archive", "datestamp": "2023-08-22 14:29:06", "lastmod": "2023-10-19 22:11:55", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Blakemore-J-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Hernandez-E-S", "name": { "family": "Hernandez", "given": "Emilia S." } }, { "id": "Sattler-W", "name": { "family": "Sattler", "given": "Wesley" }, "orcid": "0000-0001-5316-260X" }, { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Henling-L-M", "name": { "family": "Henling", "given": "Lawrence M." } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Pentamethylcyclopentadienyl rhodium complexes", "ispublished": "pub", "full_text_status": "public", "keywords": "Vinyl bipyridine; Thallium formate reduction; Crystallographic characterization; Electronic absorption spectra; Metal-to-ligand charge transfer", "note": "\u00a9 2014 Elsevier Ltd. \n\nReceived 3 April 2014; Accepted 8 May 2014; Available online 20 May 2014. \n\nThe authors thank Aaron Sattler and Nathan Schley for helpful discussions. This research was carried out in part at the Molecular Materials Research Center of the Beckman Institute at Caltech. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and CCI Postdoctoral Fellowships to JDB and WS. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094).\n\nSupplemental Material - 995532.cif
Supplemental Material - 995548.cif
Supplemental Material - 995550.cif
Supplemental Material - 995557.cif
", "abstract": "We report syntheses and structures of pentamethylcyclopentadienyl (Cp\u2217) rhodium(III) and rhodium(I) complexes. Dicationic rhodium(III) complexes, [Cp\u2217Rh(bpy)(MeCN)](PF_6)_2 and [Cp\u2217Rh(vbpy)(MeCN)](PF_6)_2 (bpy = 2,2\u2032-bipyridyl and vbpy = 4-vinyl-2,2\u2032-bipyridyl), were prepared by treatment of [Cp\u2217Rh(MeCN)_3](PF_6)_2 with bpy and vbpy, respectively. The monocationic rhodium(III) complex, [Cp\u2217Rh(Me_4phen)Cl]Cl (Me_4phen = 3,4,7,8-tetramethyl-1,10-phenanthroline), was prepared by treatment of the chloride-bridged rhodium dimer, [Cp\u2217RhCl_2]_2, with Me_4phen. Two rhodium(I) complexes were synthesized via reduction of their rhodium(III) counterparts using two different methods: Cp\u2217Rh(bpy) was produced via a new route involving treatment of [Cp\u2217Rh(bpy)Cl]Cl with thallium formate in dry acetonitrile, whereas [Cp\u2217Rh(Me_4phen)Cl]Cl was reduced with Na(Hg) to give Cp\u2217Rh(Me_4phen). The colors of the Rh(I) complexes are attributable to relatively intense visible-region MLCT absorptions.", "date": "2014-12-14", "date_type": "published", "publication": "Polyhedron", "volume": "84", "publisher": "Elsevier", "pagerange": "14-18", "id_number": "CaltechAUTHORS:20150115-100257213", "issn": "0277-5387", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150115-100257213", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "NSF Postdoctoral Fellowship" }, { "agency": "NSF", "grant_number": "CHE-0639094" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1016/j.poly.2014.05.022", "primary_object": { "basename": "995532.cif", "url": "https://authors.library.caltech.edu/records/x40p7-x3h66/files/995532.cif" }, "related_objects": [ { "basename": "995548.cif", "url": "https://authors.library.caltech.edu/records/x40p7-x3h66/files/995548.cif" }, { "basename": "995550.cif", "url": "https://authors.library.caltech.edu/records/x40p7-x3h66/files/995550.cif" }, { "basename": "995557.cif", "url": "https://authors.library.caltech.edu/records/x40p7-x3h66/files/995557.cif" } ], "pub_year": "2014", "author_list": "Blakemore, James D.; Hernandez, Emilia S.; et el." }, { "id": "https://authors.library.caltech.edu/records/03rh5-j1z05", "eprint_id": 53452, "eprint_status": "archive", "datestamp": "2023-08-20 03:58:01", "lastmod": "2023-10-19 21:45:56", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Bruce-J-P", "name": { "family": "Bruce", "given": "Jared P." } }, { "id": "Asgari-S", "name": { "family": "Asgari", "given": "Sommayeh" } }, { "id": "Ardo-S", "name": { "family": "Ardo", "given": "Shane" }, "orcid": "0000-0001-7162-6826" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Oliver-D-R", "name": { "family": "Oliver", "given": "Derek R." } }, { "id": "Freund-M-S", "name": { "family": "Freund", "given": "Michael S." }, "orcid": "0000-0003-1104-2292" } ] }, "title": "Measurement of the Electrical Resistance of n-Type Si Microwire/p-Type Conducting Polymer Junctions for Use in Artificial Photosynthesis", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. \n\nReceived: September 11, 2014. Revised: October 29, 2014. Published: October 29, 2014. \n\nFinancial support from the Natural Sciences and Engineering\nResearch Council (NSERC) of Canada, the Canada Foundation\nfor Innovation (CFI), the Manitoba Research and Innovation Fund, and the University of Manitoba is gratefully acknowledged. The work reported made use of surface\ncharacterization infrastructure in the Manitoba Institute for Materials. This work was supported by a National Science\nFoundation (NSF) Center for Chemical Innovation (CCI)\nPowering the Planet (Grants CHE-0802907, CHE-0947829, and NSF-ACCF) and made use of the Molecular Materials Research Center of the Beckman Institute at Caltech and the Kavli Nanoscience Institute at Caltech. This research was undertaken, in part, thanks to funding from the Canada Research Chairs Program. S.A. acknowledges partial support from a U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE) Postdoctoral Research Award, under the EERE Fuel Cell Technologies Program. This material is based in part (support for NSL) upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award DE-SC0004993.\n\nSupplemental Material - jp509211k_si_001.pdf
", "abstract": "The junction between n-type silicon microwires and p-type conducting polymer PEDOT:PSS (poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)) was investigated using a soft contact method. Dopant levels within the microwires were varied during growth to give a highly-doped region for improved contact and a low-doped region for light absorption. The low-doped region of the microwires had a dopant density of 5 X 10(17) cm(-3) while the highly-doped region had an increased dopant density of 5 X 10(18) cm(-3) over similar to 20 mu m. Uniform, highly-doped microwires, with a dopant density of 4 X 10(19) cm(3), were used as a comparison. Regions of highly-doped n-type Si microwires (N-D = 5 X 10(18) cm(-3) and 4 X 10(19) cm(-3)) contacted by PEDOT:PSS showed a significantly lower junction resistance compared to the low-doped (3 X 10(17) cm(-3)) regions of the microwire. Junctions incorporating the metal catalyst used during growth were also investigated. Microwires with copper at the interface had similar currentvoltage characteristics to those observed for the highly-doped microwire/conducting polymer junction; however, junctions that incorporated gold exhibited significantly lower resistances, decreasing the iR contribution of the junction by an order of magnitude with respect to the total voltage drop in the entire structure.", "date": "2014-12-04", "date_type": "published", "publication": "Journal of Physical Chemistry C", "volume": "118", "number": "48", "publisher": "American Chemical Society", "pagerange": "27742-27748", "id_number": "CaltechAUTHORS:20150109-083207621", "issn": "1932-7447", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150109-083207621", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "Canada Foundation for Innovation" }, { "agency": "Manitoba Research and Innovation Fund" }, { "agency": "University of Manitoba" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Canada Research Chairs Program" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC0004993" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" }, { "id": "Kavli-Nanoscience-Institute" }, { "id": "JCAP" } ] }, "doi": "10.1021/jp509211k", "primary_object": { "basename": "jp509211k_si_001.pdf", "url": "https://authors.library.caltech.edu/records/03rh5-j1z05/files/jp509211k_si_001.pdf" }, "pub_year": "2014", "author_list": "Bruce, Jared P.; Asgari, Sommayeh; et el." }, { "id": "https://authors.library.caltech.edu/records/c64x9-wxs59", "eprint_id": 53260, "eprint_status": "archive", "datestamp": "2023-08-22 14:16:47", "lastmod": "2023-10-19 14:41:58", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Callejas-J-F", "name": { "family": "Callejas", "given": "Juan F." } }, { "id": "McEnaney-J-M", "name": { "family": "McEnaney", "given": "Joshua M." } }, { "id": "Read-C-G", "name": { "family": "Read", "given": "Carlos G." } }, { "id": "Crompton-J-C", "name": { "family": "Crompton", "given": "J. Chance" } }, { "id": "Biacchi-A_J", "name": { "family": "Biacchi", "given": "Adam J." } }, { "id": "Popczun-E-J", "name": { "family": "Popczun", "given": "Eric J." } }, { "id": "Gordon-T-R", "name": { "family": "Gordon", "given": "Thomas R." } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Schaak-R-E", "name": { "family": "Schaak", "given": "Raymond E." } } ] }, "title": "Electrocatalytic and Photocatalytic Hydrogen Production from Acidic and Neutral-pH Aqueous Solutions Using Iron Phosphide Nanoparticles", "ispublished": "pub", "full_text_status": "restricted", "keywords": "hydrogen evolution reaction; metal phosphides; nanoparticles; electrocatalysis; photocatalysis", "note": "\u00a9 2014 American Chemical Society.\n\nReceived for review August 28, 2014 and accepted September 24, 2014; published online September 24, 2014.\n\nThe work at PSU was supported by the National Science Foundation (NSF) Center for Chemical Innovation on Solar Fuels (CHE-1305124) and at Caltech by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. TEM was performed in the Penn State Microscopy and Cytometry Facility (University Park, PA), and HRTEM, EDS, XPS, and DRIFTS datawere acquired at theMaterials Characterization Laboratory of the Penn State Materials Research Institute. The authors thank Greg Barber, Jennifer Gray, Lymaris Ortiz Rivera, and Nella Vargas-Barbosa for technical support and helpful discussions.", "abstract": "Nanostructured transition-metal phosphides have recently emerged as Earth-abundant alternatives to platinum for catalyzing the hydrogen-evolution reaction (HER), which is central to several clean energy technologies because it produces molecular hydrogen through the electrochemical reduction of water. Iron-based catalysts are very attractive targets because iron is the most abundant and least expensive transition metal. We report herein that iron phosphide (FeP), synthesized as nanoparticles having a uniform, hollow morphology, exhibits among the highest HER activities reported to date in both acidic and neutral-pH aqueous solutions. As an electrocatalyst operating at a current density of \u221210 mA cm^\u20132, FeP nanoparticles deposited at a mass loading of \u223c1 mg cm^\u20132 on Ti substrates exhibited overpotentials of \u221250 mV in 0.50 M H_2SO_4 and \u2212102 mV in 1.0 M phosphate buffered saline. The FeP nanoparticles supported sustained hydrogen production with essentially quantitative faradaic yields for extended time periods under galvanostatic control. Under UV illumination in both acidic and neutral-pH solutions, FeP nanoparticles deposited on TiO_2 produced H_2 at rates and amounts that begin to approach those of Pt/TiO_2. FeP therefore is a highly Earth-abundant material for efficiently facilitating the HER both electrocatalytically and photocatalytically.", "date": "2014-11-25", "date_type": "published", "publication": "ACS Nano", "volume": "8", "number": "11", "publisher": "American Chemical Society", "pagerange": "11101-11107", "id_number": "CaltechAUTHORS:20150107-093231817", "issn": "1936-0851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150107-093231817", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC0004993" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/nn5048553", "pub_year": "2014", "author_list": "Callejas, Juan F.; McEnaney, Joshua M.; et el." }, { "id": "https://authors.library.caltech.edu/records/sjsxv-6v640", "eprint_id": 47359, "eprint_status": "archive", "datestamp": "2023-08-20 03:26:02", "lastmod": "2023-10-26 20:31:35", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lattimer-J-R-C", "name": { "family": "Lattimer", "given": "Judith R. C." } }, { "id": "Blakemore-J-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Sattler-W", "name": { "family": "Sattler", "given": "Wesley" }, "orcid": "0000-0001-5316-260X" }, { "id": "Gul-S", "name": { "family": "Gul", "given": "Sheraz" }, "orcid": "0000-0001-8920-8737" }, { "id": "Chatterjee-Ruchira", "name": { "family": "Chatterjee", "given": "Ruchira" }, "orcid": "0000-0002-0865-061X" }, { "id": "Yachandra-V-K", "name": { "family": "Yachandra", "given": "Vittal K." } }, { "id": "Yano-Junko", "name": { "family": "Yano", "given": "Junko" }, "orcid": "0000-0001-6308-9071" }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Assembly, characterization, and electrochemical properties of immobilized metal bipyridyl complexes on silicon(111) surface", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 Royal Society of Chemistry. \n\nAdvance Article. Received 18th April 2014; Accepted 9th July 2014. First published online 17 Jul 2014. \n\nThe authors thank Aaron Sattler for helpful discussions. Research was carried out in part at the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and CCI Postdoctoral Fellowships to JDB and WS. The synchrotron facility was provided by the Stanford Synchrotron Radiation Laboratory (SSRL) at beam line 7-3. The SSRL Biomedical Technology program is supported by the National Institute of Health (NIH), the National Center for Research Resources, and the DOE Office of Biological and Environmental Research. XAS work was funded by the Director, Office of Science, Office of Basic Energy Sciences (OBES), Division of Chemical Sciences, Geosciences, and Biosciences of the Department of Energy (DOE) under Contract DE-AC02-05CH11231.\n\nPublished - c4dt01149j.pdf
Supplemental Material - c4dt01149j1.pdf
", "abstract": "Silicon(111) surfaces have been functionalized with mixed monolayers consisting of submonolayer coverages of immobilized 4-vinyl-2,2\u2032-bipyridyl (1, vbpy) moieties, with the remaining atop sites of the silicon surface passivated by methyl groups. As the immobilized bipyridyl ligands bind transition metal ions, metal complexes can be assembled on the silicon surface. X-ray photoelectron spectroscopy (XPS) demonstrates that bipyridyl complexes of [Cp*Rh], [Cp*Ir], and [Ru(acac)2] were formed on the surface (Cp* is pentamethylcyclopentadienyl, acac is acetylacetonate). For the surface prepared with Ir, X-ray absorption spectroscopy at the Ir LIII edge showed an edge energy as well as post-edge features that were essentially identical with those observed on a powder sample of [Cp*Ir(bpy)Cl]Cl (bpy is 2,2\u2032-bipyridyl). Charge-carrier lifetime measurements confirmed that the silicon surfaces retain their highly favorable photoelectronic properties upon assembly of the metal complexes. Electrochemical data for surfaces prepared on highly doped, n-type Si(111) electrodes showed that the assembled molecular complexes were redox active. However the stability of the molecular complexes on the surfaces was limited to several cycles of voltammetry.", "date": "2014-10-28", "date_type": "published", "publication": "Dalton Transactions", "volume": "43", "number": "40", "publisher": "Royal Society of Chemistry", "pagerange": "15004-15012", "id_number": "CaltechAUTHORS:20140721-090909176", "issn": "1477-9226", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140721-090909176", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "NSF Postdoctoral Fellowship" }, { "agency": "NIH" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-AC02-05CH11231" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c4dt01149j", "primary_object": { "basename": "c4dt01149j.pdf", "url": "https://authors.library.caltech.edu/records/sjsxv-6v640/files/c4dt01149j.pdf" }, "related_objects": [ { "basename": "c4dt01149j1.pdf", "url": "https://authors.library.caltech.edu/records/sjsxv-6v640/files/c4dt01149j1.pdf" } ], "pub_year": "2014", "author_list": "Lattimer, Judith R. C.; Blakemore, James D.; et el." }, { "id": "https://authors.library.caltech.edu/records/d8a97-7fh05", "eprint_id": 120630, "eprint_status": "archive", "datestamp": "2023-08-22 14:00:13", "lastmod": "2023-10-23 19:09:56", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lattimer-Judith-R-C", "name": { "family": "Lattimer", "given": "Judith R. C." } }, { "id": "Blakemore-James-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Sattler-Wesley", "name": { "family": "Sattler", "given": "Wesley" }, "orcid": "0000-0001-5316-260X" }, { "id": "Gul-Sheraz", "name": { "family": "Gul", "given": "Sheraz" }, "orcid": "0000-0001-8920-8737" }, { "id": "Chatterjee-Ruchira", "name": { "family": "Chatterjee", "given": "Ruchira" }, "orcid": "0000-0002-0865-061X" }, { "id": "Yachandra-Vittal-K", "name": { "family": "Yachandra", "given": "Vittal K." }, "orcid": "0000-0002-3983-7858" }, { "id": "Yano-Junko", "name": { "family": "Yano", "given": "Junko" }, "orcid": "0000-0001-6308-9071" }, { "id": "Brunschwig-Bruce-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Assembly, characterization, and electrochemical properties of immobilized metal bipyridyl complexes on silicon(111) surfaces", "ispublished": "pub", "full_text_status": "public", "keywords": "Inorganic Chemistry", "note": "This article is part of the themed collection: Inorganic Chemistry for Renewable Energy Conversion and Storage. \n\nThe authors thank Aaron Sattler for helpful discussions. Research was carried out in part at the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and CCI Postdoctoral Fellowships to JDB and WS. The synchrotron facility was provided by the Stanford Synchrotron Radiation Laboratory (SSRL) at beam line 7-3. The SSRL Biomedical Technology program is supported by the National Institute of Health (NIH), the National Center for Research Resources, and the DOE Office of Biological and Environmental Research. XAS work was funded by the Director, Office of Science, Office of Basic Energy Sciences (OBES), Division of Chemical Sciences, Geosciences, and Biosciences of the Department of Energy (DOE) under Contract DE-AC02-05CH11231.", "abstract": "Silicon(111) surfaces have been functionalized with mixed monolayers consisting of submonolayer coverages of immobilized 4-vinyl-2,2\u2032-bipyridyl (1, vbpy) moieties, with the remaining atop sites of the silicon surface passivated by methyl groups. As the immobilized bipyridyl ligands bind transition metal ions, metal complexes can be assembled on the silicon surface. X-ray photoelectron spectroscopy (XPS) demonstrates that bipyridyl complexes of [Cp*Rh], [Cp*Ir], and [Ru(acac)2] were formed on the surface (Cp* is pentamethylcyclopentadienyl, acac is acetylacetonate). For the surface prepared with Ir, X-ray absorption spectroscopy at the Ir LIII edge showed an edge energy as well as post-edge features that were essentially identical with those observed on a powder sample of [Cp*Ir(bpy)Cl]Cl (bpy is 2,2\u2032-bipyridyl). Charge-carrier lifetime measurements confirmed that the silicon surfaces retain their highly favorable photoelectronic properties upon assembly of the metal complexes. Electrochemical data for surfaces prepared on highly doped, n-type Si(111) electrodes showed that the assembled molecular complexes were redox active. However the stability of the molecular complexes on the surfaces was limited to several cycles of voltammetry.", "date": "2014-10-28", "date_type": "published", "publication": "Dalton Transactions", "volume": "43", "number": "40", "publisher": "Royal Society of Chemistry", "pagerange": "15004-15012", "id_number": "CaltechAUTHORS:20230330-668861000.1", "issn": "1477-9226", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20230330-668861000.1", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Caltech Beckman Institute" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-AC02-05CH11231" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c4dt01149j", "pub_year": "2014", "author_list": "Lattimer, Judith R. C.; Blakemore, James D.; et el." }, { "id": "https://authors.library.caltech.edu/records/mt6gd-qtz79", "eprint_id": 50053, "eprint_status": "archive", "datestamp": "2023-08-20 03:14:20", "lastmod": "2023-10-20 23:17:22", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Agbo-P", "name": { "family": "Agbo", "given": "Peter" } }, { "id": "Heath-J-R", "name": { "family": "Heath", "given": "James R." }, "orcid": "0000-0001-5356-4385" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Modeling Dioxygen Reduction at Multicopper Oxidase Cathodes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. \n\nReceived: July 29, 2014. \n\nPublication Date (Web): September 4, 2014. \n\nWe thank Fan Liu, Joseph Varghese, and Jay Winkler for helpful discussions and the Beckman Institute Molecular Materials Research Center for access to equipment. This research was funded by the NSF CCI Solar Fuels Program (CHE-1305124) and a Perkins Grant (JRH.PERKINS3-1-GRANT.PERKINS3). \n\nThe authors declare no competing financial interest.\n\nSupplemental Material - ja5077519_si_002.pdf
Supplemental Material - ja5077519_si_003.pdf
Erratum - jacs.5b11603.pdf
", "abstract": "We report a general kinetics model for catalytic dioxygen reduction on multicopper oxidase (MCO) cathodes. Our rate equation combines Butler\u2013Volmer (BV) electrode kinetics and the Michaelis\u2013Menten (MM) formalism for enzymatic catalysis, with the BV model accounting for interfacial electron transfer (ET) between the electrode surface and the MCO type 1 copper site. Extending the principles of MM kinetics to this system produced an analytical expression incorporating the effects of subsequent intramolecular ET and dioxygen binding to the trinuclear copper cluster into the cumulative model. We employed experimental electrochemical data on Thermus thermophilus laccase as benchmarks to validate our model, which we suggest will aid in the design of more efficient MCO cathodes. In addition, we demonstrate the model's utility in determining estimates for both the electronic coupling and average distance between the laccase type-1 active site and the cathode substrate.", "date": "2014-10-01", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "136", "number": "39", "publisher": "American Chemical Society", "pagerange": "13882-13887", "id_number": "CaltechAUTHORS:20140926-091054210", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140926-091054210", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Perkins Foundation", "grant_number": "JRH.PERKINS3-1- GRANT.PERKINS3" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja5077519", "primary_object": { "basename": "ja5077519_si_002.pdf", "url": "https://authors.library.caltech.edu/records/mt6gd-qtz79/files/ja5077519_si_002.pdf" }, "related_objects": [ { "basename": "ja5077519_si_003.pdf", "url": "https://authors.library.caltech.edu/records/mt6gd-qtz79/files/ja5077519_si_003.pdf" }, { "basename": "jacs.5b11603.pdf", "url": "https://authors.library.caltech.edu/records/mt6gd-qtz79/files/jacs.5b11603.pdf" } ], "pub_year": "2014", "author_list": "Agbo, Peter; Heath, James R.; et el." }, { "id": "https://authors.library.caltech.edu/records/dhez1-yrq18", "eprint_id": 50808, "eprint_status": "archive", "datestamp": "2023-08-20 03:00:54", "lastmod": "2023-10-18 14:32:19", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Blakemore-J-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Deimund-M", "name": { "family": "Deimund", "given": "Mark" } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "M\u00fcller-A-M", "name": { "family": "M\u00fcller", "given": "Astrid M." }, "orcid": "0000-0002-2785-6808" } ] }, "title": "Highly Active Mixed-Metal Nanosheet Water Oxidation Catalysts Made by Pulsed-Laser Ablation in Liquids", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. Received: June 17, 2014.\nPublished: September 8, 2014. Publication Date (Web): September 8, 2014. \n\nWe thank Richard Gerhart for fabrication of an electrochemical\ncell, Alasdair McDowall for help with TEM, and George Rossman for help with solid-state Raman and IR spectroscopies.\nResearch was carried out in the Laser Resource Center and the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation.\n\nSupplemental Material - ja506087h_si_001.pdf
", "abstract": "Surfactant-free mixed-metal hydroxide water oxidation nanocatalysts were synthesized by pulsed-laser ablation in liquids. In a series of [Ni-Fe]-layered double hydroxides with intercalated nitrate and water, [Ni_(1\u2013x)Fe_x(OH)_2](NO_3)_y(OH)_(x\u2212y)\u00b7nH_2O, higher activity was observed as the amount of Fe decreased to 22%. Addition of Ti^(4+) and La^(3+) ions further enhanced electrocatalysis, with a lowest overpotential of 260 mV at 10 mA cm^(\u20132). Electrocatalytic water oxidation activity increased with the relative proportion of a 405.1 eV N 1s (XPS binding energy) species in the nanosheets.", "date": "2014-09-24", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "136", "number": "8", "publisher": "American Chemical Society", "pagerange": "13118-13121", "id_number": "CaltechAUTHORS:20141024-143748867", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20141024-143748867", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja506087h", "primary_object": { "basename": "ja506087h_si_001.pdf", "url": "https://authors.library.caltech.edu/records/dhez1-yrq18/files/ja506087h_si_001.pdf" }, "pub_year": "2014", "author_list": "Hunter, Bryan M.; Blakemore, James D.; et el." }, { "id": "https://authors.library.caltech.edu/records/s6p8s-xhd51", "eprint_id": 52282, "eprint_status": "archive", "datestamp": "2023-08-20 03:00:25", "lastmod": "2023-10-18 19:44:05", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Gunderson-W-A", "name": { "family": "Gunderson", "given": "William A." } }, { "id": "Suess-D-L-M", "name": { "family": "Suess", "given": "Daniel L. M." } }, { "id": "Fong-Henry-K-W", "name": { "family": "Fong", "given": "Henry" } }, { "id": "Wang-Xiaoping", "name": { "family": "Wang", "given": "Xiaoping" }, "orcid": "0000-0001-7143-8112" }, { "id": "Hoffmann-C-M", "name": { "family": "Hoffmann", "given": "Christina M." } }, { "id": "Cutsail-G-E-III", "name": { "family": "Cutsail", "given": "George E., III" } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Hoffman-B-M", "name": { "family": "Hoffman", "given": "Brian M." }, "orcid": "0000-0002-3100-0746" } ] }, "title": "Free H_2 Rotation vs Jahn\u2212Teller Constraints in the Nonclassical Trigonal (TPB)Co\u2212H_2 Complex", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. \n\nReceived: August 7, 2014. Published: September 22, 2014. Publication Date (Web): September 22, 2014. \n\nThis work is dedicated to Prof. Harden M. McConnell, whose\nrecognition of the role of quantum-statistical considerations in paramagnetic resonance spectroscopies occupies but a small place among his numerous scientific contributions, on the occasion of his 87th birthday. We thank Mrs. Junhong (Helen) He, Oak Ridge National Laboratory, for assistance with mounting crystal for neutron diffraction. This work was supported by the National Science Foundation (MCB 1118613, BMH; the NSF Center CHE-1305124, JCP; DGE-0824162, GEC). Research conducted at ORNL's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy, under Contract No. DE-AC05-00OR22725 with UT Battelle, LLC.\n\nSupplemental Material - ja508117h_si_001.pdf
Supplemental Material - ja508117h_si_002.cif
", "abstract": "Proton exchange within the M\u2013H_2 moiety of (TPB)Co(H_2) (Co\u2013H_2; TPB = B(o-C_6H_4PiPr_2)_3) by 2-fold rotation about the M\u2013H_2 axis is probed through EPR/ENDOR studies and a neutron diffraction crystal structure. This complex is compared with previously studied (SiP^(iPr)_3)Fe(H_2) (Fe\u2013H_2) (SiP^(iPr)_3 = [Si(o-C_6H_4PiPr_2)_3]). The g-values for Co\u2013H_2 and Fe\u2013H_2 show that both have the Jahn\u2013Teller (JT)-active ^2E ground state (idealized C_3 symmetry) with doubly degenerate frontier orbitals, (e)^3 = [|m_L \u00b1 2>]^3 = [x^2 \u2013 y^2, xy]^3, but with stronger linear vibronic coupling for Co\u2013H_2. The observation of ^1H ENDOR signals from the Co\u2013HD complex, ^2H signals from the Co\u2013D_2/HD complexes, but no ^1H signals from the Co\u2013H_2 complex establishes that H_2 undergoes proton exchange at 2 K through rotation around the Co\u2013H_2 axis, which introduces a quantum-statistical (Pauli-principle) requirement that the overall nuclear wave function be antisymmetric to exchange of identical protons (I = 1/2; Fermions), symmetric for identical deuterons (I = 1; Bosons). Analysis of the 1-D rotor problem indicates that Co\u2013H_2 exhibits rotor-like behavior in solution because the underlying C_3 molecular symmetry combined with H_2 exchange creates a dominant 6-fold barrier to H_2 rotation. Fe\u2013H_2 instead shows H_2 localization at 2 K because a dominant 2-fold barrier is introduced by strong Fe(3d)\u2192 H_2(\u03c3^*) \u03c0-backbonding that becomes dependent on the H_2 orientation through quadratic JT distortion. ENDOR sensitively probes bonding along the L_2\u2013M\u2013E axis (E = Si for Fe\u2013H_2; E = B for Co\u2013H_2). Notably, the isotropic ^1H/^2H hyperfine coupling to the diatomic of Co\u2013H_2 is nearly 4-fold smaller than for Fe\u2013H_2.", "date": "2014-09-22", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "136", "number": "42", "publisher": "American Chemical Society", "pagerange": "14998-15009", "id_number": "CaltechAUTHORS:20141202-135435499", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20141202-135435499", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "MCB-1118613" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "NSF", "grant_number": "DGE-0824162" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-AC05-00OR22725" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja508117h", "primary_object": { "basename": "ja508117h_si_001.pdf", "url": "https://authors.library.caltech.edu/records/s6p8s-xhd51/files/ja508117h_si_001.pdf" }, "related_objects": [ { "basename": "ja508117h_si_002.cif", "url": "https://authors.library.caltech.edu/records/s6p8s-xhd51/files/ja508117h_si_002.cif" } ], "pub_year": "2014", "author_list": "Gunderson, William A.; Suess, Daniel L. M.; et el." }, { "id": "https://authors.library.caltech.edu/records/vddy0-6wp73", "eprint_id": 50117, "eprint_status": "archive", "datestamp": "2023-08-20 02:37:31", "lastmod": "2023-10-17 22:31:44", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "McEnaney-J-M", "name": { "family": "McEnaney", "given": "Joshua M." } }, { "id": "Crompton-J-C", "name": { "family": "Crompton", "given": "J. Chance" } }, { "id": "Callejas-J-F", "name": { "family": "Callejas", "given": "Juan F." } }, { "id": "Popczun-E-J", "name": { "family": "Popczun", "given": "Eric J." } }, { "id": "Biacchi-A-J", "name": { "family": "Biacchi", "given": "Adam J." } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Schaak-R-E", "name": { "family": "Schaak", "given": "Raymond E." } } ] }, "title": "Amorphous Molybdenum Phosphide Nanoparticles for Electrocatalytic Hydrogen Evolution", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society.\n\nReceived: June 4, 2014; revised: July 15, 2014; published: July 17, 2014.\n\nThis work was supported at PSU by the National Science\nFoundation (NSF) Center for Chemical Innovation on Solar\nFuels (CHE-1305124) and at Caltech by the Joint Center for\nArtificial Photosynthesis, a DOE Energy Innovation Hub,\nsupported through the Office of Science of the U.S.\nDepartment of Energy under Award DE-SC0004993. TEM\nimaging was performed in the Penn State Microscopy and\nCytometry Facility (University Park, PA) and HRTEM\nimaging, EDS spectra, XPS spectra, and DRIFTS spectra\nwere acquired at the Materials Characterization Laboratory of the Penn State Materials Research Institute. J.M.M. thanks Jennifer Gray for assistance with analyzing the XPS spectra and Dr. Thomas Gordon for assistance with quantitative yield experiments.\n\nSupplemental Material - cm502035s_si_001.pdf
", "abstract": "Amorphous molybdenum phosphide (MoP) nanoparticles have been synthesized and characterized as electrocatalysts for the hydrogen-evolution reaction (HER) in 0.50 M H_2SO_4 (pH 0.3). Amorphous MoP nanoparticles (having diameters of 4.2 \u00b1 0.5 nm) formed upon heating Mo(CO)6 and trioctylphosphine in squalane at 320 \u00b0C, and the nanoparticles remained amorphous after heating at 450 \u00b0C in H_2(5%)/Ar(95%) to remove the surface ligands. At mass loadings of 1 mg cm^\u20132, MoP/Ti electrodes exhibited overpotentials of \u221290 and \u2212105 mV (\u2212110 and \u2212140 mV without iR correction) at current densities of \u221210 and \u221220 mA cm^\u20132, respectively. These HER overpotentials remained nearly constant over 500 cyclic voltammetric sweeps and 18 h of galvanostatic testing, indicating stability in acidic media under operating conditions. Amorphous MoP nanoparticles are therefore among the most active known molybdenum-based HER systems and are part of a growing family of active, acid-stable, non-noble-metal HER catalysts.", "date": "2014-08-26", "date_type": "published", "publication": "Chemistry of Materials", "volume": "26", "number": "16", "publisher": "American Chemical Society", "pagerange": "4826-4831", "id_number": "CaltechAUTHORS:20140930-095609063", "issn": "0897-4756", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140930-095609063", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC0004993" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/cm502035s", "primary_object": { "basename": "cm502035s_si_001.pdf", "url": "https://authors.library.caltech.edu/records/vddy0-6wp73/files/cm502035s_si_001.pdf" }, "pub_year": "2014", "author_list": "McEnaney, Joshua M.; Crompton, J. Chance; et el." }, { "id": "https://authors.library.caltech.edu/records/71ry9-s6y66", "eprint_id": 46395, "eprint_status": "archive", "datestamp": "2023-08-22 12:43:06", "lastmod": "2023-10-26 19:42:59", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Popczun-E-J", "name": { "family": "Popczun", "given": "Eric J." } }, { "id": "Read-C-G", "name": { "family": "Read", "given": "Carlos G." } }, { "id": "Roske-C-W", "name": { "family": "Roske", "given": "Christopher W." } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Schaak-R-E", "name": { "family": "Schaak", "given": "Raymond E." } } ] }, "title": "Highly Active Electrocatalysis of the Hydrogen Evolution Reaction by Cobalt Phosphide Nanoparticles", "ispublished": "pub", "full_text_status": "restricted", "keywords": "electrocatalysis; hydrogen evolution; metal phosphide; nanomaterials; water splitting", "note": "\u00a9 2014 Wiley-VCH Verlag GmbH & Co. \n\nReceived: February 20, 2014;\nPublished online: April 11, 2014. \n\nThis work was supported by the National Science Foundation (NSF) Center for Chemical Innovation on Solar Fuels (CHE-1305124). C.W.R. thanks the NSF for a graduate research fellowship. Research was in part performed at the Beckman Institute Molecular Materials\nResearch Center. TEM and BET data were acquired using facilities in the Materials Characterization Lab of the Penn State Materials Research Institute. E.J.P. and C.G.R. thank Trevor Clark, Ke Wang, and Lymaris Ortiz Rivera for assistance.", "abstract": "Nanoparticles of cobalt phosphide, CoP, have been prepared and evaluated as electrocatalysts for the hydrogen evolution reaction (HER) under strongly acidic conditions (0.50\u2009M H_2SO_4, pH\u20050.3). Uniform, multi-faceted CoP nanoparticles were synthesized by reacting Co nanoparticles with trioctylphosphine. Electrodes comprised of CoP nanoparticles on a Ti support (2\u2005mg\u2009cm^(\u22122) mass loading) produced a cathodic current density of 20\u2005mA\u2009cm^(\u22122) at an overpotential of \u221285\u2005mV. The CoP/Ti electrodes were stable over 24\u2005h of sustained hydrogen production in 0.50\u2009M H_2SO_4. The activity was essentially unchanged after 400 cyclic voltammetric sweeps, suggesting long-term viability under operating conditions. CoP is therefore amongst the most active, acid-stable, earth-abundant HER electrocatalysts reported to date.", "date": "2014-05-19", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "53", "number": "21", "publisher": "Wiley", "pagerange": "5427-5430", "id_number": "CaltechAUTHORS:20140620-100535755", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140620-100535755", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Center for Chemical Innovation on Solar Fuels", "grant_number": "CHE-1305124" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1002/anie.201402646", "pub_year": "2014", "author_list": "Popczun, Eric J.; Read, Carlos G.; et el." }, { "id": "https://authors.library.caltech.edu/records/kwtn6-3ab68", "eprint_id": 45866, "eprint_status": "archive", "datestamp": "2023-08-19 23:56:06", "lastmod": "2024-01-13 16:05:20", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Bracher-P-J", "name": { "family": "Bracher", "given": "Paul J." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Chemists: Public Outreach Is an Essential Investment of Time, Not a Waste of It", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2014 American Chemical Society. Publication Date (Web): March 10, 2014. Our research on solar fuels and the outreach efforts that accompany it are supported by the NSF CCI Program (CCI Solar, CHE-1305124). We thank the many scientists in ccr Solar who power our outreach efforts with their dedicated service as mentors in local schools and clubs. CCI Solar's outreach efforts are coordinated and managed by Carolyn Panerson and Siddharth Dasgupta. The\nSHArK and SEAL programs owe their success to the instrument platforms developed by Bruce Parkinson, Jay Winkler, and their coworkers. The SEAL program has been coordinated at Caltech by Jillian Dempsey, James McKone, Hill Harman, and James Blakemore, and on an international scale by Jennifer\nSchuttlefield. The Juice-from-Juice kit was developed by Qixi Mi and Michael Walter (Caltech), along with Debbie Hawks (Blair High School) and Gurupreet Khalsa (Pasadena Unified School District). The project has subsequently been\ncoordinated at Caltech by Shane Ardo, Tania Damton, and Amanda Shing. CCI Solar's ISE efforts have been spearheaded by Benjamin Dickow (WSSC), Ariel Levi Simons (Wildwood School), Anna Beck (Caltech), and P.J.B. (Caltech). P.J.B. gratefully acknowledges an NSF American Competitiveness in Chemistry postdoctoral fellowship grant (CHE-0936996). We also thank ACS President Marinda Li Wu, H. N. Cheng, and Sadiq Shah for organizing the Vision 2025 symposium and for the opportunity to discuss these important issues that face the chemical enterprise.", "abstract": "In this chapter, we discuss the state of the public image of chemistry and some of the potential consequences of its deterioration. We explain why it is important that chemists engage the public to educate citizens about science and communicate the value of scientific research. Next, as an example of how chemists can interact with the public in a meaningful manner related to their research, we discuss the development and implementation of a multifaceted outreach program by our group at Caltech. We close with suggestions for how chemists can create their own outreach activities and how our field can encourage this work by recognizing and rewarding it.", "date": "2014-03-10", "date_type": "published", "publisher": "American Chemical Society", "place_of_pub": "Washington, DC", "pagerange": "37-50", "id_number": "CaltechAUTHORS:20140521-093549336", "isbn": "9780841229389", "book_title": "Vision 2025: How To Succeed in the Global Chemistry Enterprise", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140521-093549336", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "NSF American Competitiveness in Chemistry Postdoctoral Fellowship", "grant_number": "CHE-0936996" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "contributors": { "items": [ { "id": "Cheng-H-N", "name": { "family": "Cheng", "given": "H. N." } }, { "id": "Shah-S", "name": { "family": "Shah", "given": "Sadiq" } }, { "id": "Wu-M-L", "name": { "family": "Wu", "given": "Marinda Li" } } ] }, "doi": "10.1021/bk-2014-1157.ch005", "pub_year": "2014", "author_list": "Bracher, Paul J. and Gray, Harry B." }, { "id": "https://authors.library.caltech.edu/records/7rmqk-cpg13", "eprint_id": 44644, "eprint_status": "archive", "datestamp": "2023-08-19 23:36:35", "lastmod": "2023-10-26 14:50:39", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "McKone-J-R", "name": { "family": "McKone", "given": "James R." }, "orcid": "0000-0001-6445-7884" }, { "id": "Marinescu-S-C", "name": { "family": "Marinescu", "given": "Smaranda C." }, "orcid": "0000-0003-2106-8971" }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Earth-abundant hydrogen evolution electrocatalysts", "ispublished": "pub", "full_text_status": "public", "note": "This journal is \u00a9 The Royal Society of Chemistry 2014. \n\nReceived 19th June 2013; Accepted 4th November 2013. First published online 05 Nov 2013. \n\nThis work was supported by the National Science Foundation \"Powering the Planet\" Center for Chemical Innovation (CHE-1305124). S.C.M. acknowledges the National Science Foundation for a CCI postdoctoral fellowship. J.R.M. additionally acknowledges the U.S. Department of Energy, Office of Science, for a graduate research fellowship.\n\nPublished - c3sc51711j.pdf
", "abstract": "Splitting water to hydrogen and oxygen is a promising approach for storing energy from intermittent renewables, such as solar power. Efficient, scalable solar-driven electrolysis devices require active electrocatalysts made from earth-abundant elements. In this mini-review, we discuss recent investigations of homogeneous and heterogeneous hydrogen evolution electrocatalysts, with emphasis on our own work on cobalt and iron complexes and nickel-molybdenum alloys.", "date": "2014-03", "date_type": "published", "publication": "Chemical Science", "volume": "5", "number": "3", "publisher": "Royal Society of Chemistry", "pagerange": "865-878", "id_number": "CaltechAUTHORS:20140403-143550660", "issn": "2041-6520", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140403-143550660", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Department of Energy (DOE)" }, { "agency": "NSF Postdoctoral Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/C3SC51711J", "primary_object": { "basename": "c3sc51711j.pdf", "url": "https://authors.library.caltech.edu/records/7rmqk-cpg13/files/c3sc51711j.pdf" }, "pub_year": "2014", "author_list": "McKone, James R.; Marinescu, Smaranda C.; et el." }, { "id": "https://authors.library.caltech.edu/records/a5zwr-6wm04", "eprint_id": 44645, "eprint_status": "archive", "datestamp": "2023-08-19 23:34:05", "lastmod": "2023-10-26 14:50:41", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Long-Range Electron Tunneling", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. \n\nPublished In Issue: February 26, 2014. Article ASAP: February 18, 2014. Just Accepted Manuscript: February 05, 2014. Received: January 08, 2014. \n\nOur electron transfer research is supported by the National\nInstitutes of Health (DK-019038), the National Science\nFoundation (CHE-1305124), the Gordon and Betty Moore\nFoundation, and the Arnold and Mabel Beckman Foundation. \n\nSupporting Information: Estimation of the gas-phase Fc+/Fc electron exchange\ntunneling energy and additional comparisons of amino acid\noccurrence frequencies. This material is available free of charge\nvia the Internet at http://pubs.acs.org.\n\nPublished - ja500215j.pdf
Supplemental Material - ja500215j_si_001.pdf
", "abstract": "Electrons have so little mass that in less than a second they can tunnel through potential energy barriers that are several electron-volts high and several nanometers wide. Electron tunneling is a critical functional element in a broad spectrum of applications, ranging from semiconductor diodes to the photosynthetic and respiratory charge transport chains. Prior to the 1970s, chemists generally believed that reactants had to collide in order to effect a transformation. Experimental demonstrations that electrons can transfer between reactants separated by several nanometers led to a revision of the chemical reaction paradigm. Experimental investigations of electron exchange between redox partners separated by molecular bridges have elucidated many fundamental properties of these reactions, particularly the variation of rate constants with distance. Theoretical work has provided critical insights into the superexchange mechanism of electronic coupling between distant redox centers. Kinetics measurements have shown that electrons can tunnel about 2.5 nm through proteins on biologically relevant time scales. Longer-distance biological charge flow requires multiple electron tunneling steps through chains of redox cofactors. The range of phenomena that depends on long-range electron tunneling continues to expand, providing new challenges for both theory and experiment.", "date": "2014-02-26", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "136", "number": "8", "publisher": "American Chemical Society", "pagerange": "2930-2939", "id_number": "CaltechAUTHORS:20140403-144433692", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140403-144433692", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "DK-019038" }, { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja500215j", "pmcid": "PMC3986022", "primary_object": { "basename": "ja500215j.pdf", "url": "https://authors.library.caltech.edu/records/a5zwr-6wm04/files/ja500215j.pdf" }, "related_objects": [ { "basename": "ja500215j_si_001.pdf", "url": "https://authors.library.caltech.edu/records/a5zwr-6wm04/files/ja500215j_si_001.pdf" } ], "pub_year": "2014", "author_list": "Winkler, Jay R. and Gray, Harry B." }, { "id": "https://authors.library.caltech.edu/records/q808g-h1651", "eprint_id": 43824, "eprint_status": "archive", "datestamp": "2023-08-22 11:31:24", "lastmod": "2023-10-25 23:55:04", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Harman-W-H", "name": { "family": "Harman", "given": "W. Hill" } }, { "id": "Lin-Tzu-Pin", "name": { "family": "Lin", "given": "Tzu-Pin" }, "orcid": "0000-0001-7041-7213" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "A d^10 Ni\u2013(H_2) Adduct as an Intermediate in H-H Oxidative Addition across a Ni-B Bond", "ispublished": "pub", "full_text_status": "public", "keywords": "borane ligands; H_2 activation; H_2 complexes; nickel; reaction mechanisms", "note": "\u00a9 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.\n\nPublished online: December 9, 2013; Received: September 17, 2013.\n\nSupporting information for this article is available on the WWW under http://dx.doi.org/10.1002/anie.201308175.\n\nThis research was supported by the NSF Center for Chemical Innovation: Solar Fuels (grant CHE-0802907) and by the Gordon and Betty Moore Foundation. We thank Prof. Christopher C. Cummins and Dr. Smith Nielsen for insightful discussions.\n\nSupplemental Material - anie_201308175_sm_miscellaneous_information.pdf
", "abstract": "Bifunctional E-H activation offers a promising approach for the design of two-electron-reduction catalysts with late first-row metals, such as Ni. To this end, we have been pursuing H_2 activation reactions at late-metal boratranes and herein describe a diphosphine\u2013borane-supported Ni\u2014(H_2) complex, [(^(Ph)DPB^(iPr))Ni(H_2)], which has been characterized in solution. ^1H NMR spectroscopy confirms the presence of an intact H_2 ligand. A range of data, including electronic-structure calculations, suggests a d^(10) configuration for [(^(Ph)DPB^(iPr))Ni(H_2)] as most appropriate. Such a configuration is highly unusual among transition-metal H_2 adducts. The nonclassical H_2 adduct is an intermediate in the complete activation of H_2 across the Ni-B interaction. Reaction-coordinate analysis suggests synergistic activation of the H_2 ligand by both the Ni and B centers of the nickel boratrane subunit, thus highlighting an important role of the borane ligand both in stabilizing the d^(10) Ni\u2014(H_2) interaction and in the H\u2014H cleavage step.", "date": "2014-01-20", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "53", "number": "4", "publisher": "Wiley", "pagerange": "1081-1086", "id_number": "CaltechAUTHORS:20140213-154635896", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140213-154635896", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1002/anie.201308175", "primary_object": { "basename": "anie_201308175_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/q808g-h1651/files/anie_201308175_sm_miscellaneous_information.pdf" }, "pub_year": "2014", "author_list": "Harman, W. Hill; Lin, Tzu-Pin; et el." }, { "id": "https://authors.library.caltech.edu/records/bdpep-gw588", "eprint_id": 44051, "eprint_status": "archive", "datestamp": "2023-08-22 11:27:17", "lastmod": "2023-10-26 00:08:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "McKone-J-R", "name": { "family": "McKone", "given": "James R." }, "orcid": "0000-0001-6445-7884" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Will Solar-Driven Water-Splitting Devices See the Light of Day?", "ispublished": "pub", "full_text_status": "restricted", "keywords": "solar fuels; hydrogen evolution; HER; oxygen evolution; OER; photoelectrochemistry; electrocatalysis; semiconductor; ion-exchange membrane", "note": "\u00a9 2013 American Chemical Society.\n\nPublished In Issue January 14, 2014; Article ASAP October 14, 2013; Just Accepted Manuscript August 27, 2013; Received: July 01, 2013; Revised: August 22, 2013.\n\nThis article is part of the Celebrating Twenty-Five Years of Chemistry of Materials special issue.\n\nN.S.L. acknowledges support from the Joint Center for\nArtificial Photosynthesis, a DOE Energy Innovation Hub,\nsupported through the Office of Science of the U.S.\nDepartment of Energy under Award Number DE-SC0004993.\nJ.R.M. and H.B.G. acknowledge the National Science\nFoundation for support through the Powering the Planet\nCenter for Chemical Innovation, Grant CHE-1305124. J.R.M.\nacknowledges the DOE Office of Science for a graduate\nresearch fellowship. The authors thank Dr. Shane Ardo and\nAdam Nielander for helpful comments during the preparation\nof this manuscript.", "abstract": "Through decades of sustained effort, researchers have made substantial progress on developing technologies for solar-driven water splitting. Nevertheless, more basic research is needed before prototype devices with a chance for commercial success can be demonstrated. In this Perspective, we summarize the major design constraints that motivate continued research in the field of solar-driven water splitting. Additionally, we discuss key device components that are now available for use in demonstration systems and prototypes. Finally, we highlight research areas where breakthroughs will be critical for continued progress toward commercial viability for solar-driven water-splitting devices.", "date": "2014-01-14", "date_type": "published", "publication": "Chemistry of Materials", "volume": "26", "number": "1", "publisher": "American Chemical Society", "pagerange": "407-414", "id_number": "CaltechAUTHORS:20140228-085825144", "issn": "0897-4756", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140228-085825144", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC0004993" }, { "agency": "NSF", "grant_number": "CHE-1305124" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" }, { "id": "JCAP" } ] }, "doi": "10.1021/cm4021518", "pub_year": "2014", "author_list": "McKone, James R.; Lewis, Nathan S.; et el." }, { "id": "https://authors.library.caltech.edu/records/tnk2z-pz394", "eprint_id": 43700, "eprint_status": "archive", "datestamp": "2023-08-19 22:40:20", "lastmod": "2023-10-25 23:47:28", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lattimer-J-R-C", "name": { "family": "Lattimer", "given": "Judith R. C." } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Redox Properties of Mixed Methyl/Vinylferrocenyl Monolayers on Si(111) Surfaces", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society. \n\nReceived: October 7, 2013; revised: November 27, 2013; published: December 2, 2013. \n\nWe thank Dr. James Blakemore for helpful discussions, Dr.\nLeslie O'Leary for training in silicon surface modification and discussions, and Joseph Beardslee and Dr. Ron Grimm for\nassistance with the instrumentation. This work was supported\nby the NSF Powering the Planet Center for Chemical\nInnovation (CHE-1305124), the National Science Foundation\n(CHE-1214152), and the Molecular Materials Research Center\nof the Beckman Institute at the California Institute of\nTechnology.\n\nSupplemental Material - jp409958c_si_001.pdf
", "abstract": "We report the redox properties of Si(111) surfaces functionalized with a mixed monolayer of vinylferrocenyl and methyl moieties that have been characterized using spectroscopic, electrical, and electrochemical techniques. The silicon was functionalized using reaction conditions analogous to those of hydrosilylation, but instead of a H-terminated Si surface, a chlorine-terminated Si precursor surface was used to produce the linked vinyl-modified functional group. The functionalized surfaces were characterized by time-resolved photoconductivity decay, X-ray photoelectron spectroscopy, electrochemical measurements, and photoelectrochemical measurements. The functionalized Si surface was well passivated, exhibited high surface coverage and few remaining reactive Si atop sites, had a very low surface recombination velocity, and displayed little initial surface oxidation. The surface was stable toward atmospheric and electrochemical oxidation. The surface coverage of vinylferrocene (or fluorostyrene) was controllably varied from 0 up to 30% of a monolayer. Interfacial charge transfer to the attached ferrocene group was relatively rapid, and a photovoltage of 0.4 V was generated upon illumination of functionalized n-type silicon surfaces in CH_(3)CN.", "date": "2013-12-27", "date_type": "published", "publication": "Journal of Physical Chemistry C", "volume": "117", "number": "51", "publisher": "American Chemical Society", "pagerange": "27012-27022", "id_number": "CaltechAUTHORS:20140206-113901424", "issn": "1932-7447", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140206-113901424", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "NSF", "grant_number": "CHE-1214152" }, { "agency": "Caltech Beckman Institute" } ] }, "local_group": { "items": [ { "id": "Kavli-Nanoscience-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/jp409958c", "primary_object": { "basename": "jp409958c_si_001.pdf", "url": "https://authors.library.caltech.edu/records/tnk2z-pz394/files/jp409958c_si_001.pdf" }, "pub_year": "2013", "author_list": "Lattimer, Judith R. C.; Brunschwig, Bruce S.; et el." }, { "id": "https://authors.library.caltech.edu/records/a8kma-pba33", "eprint_id": 43592, "eprint_status": "archive", "datestamp": "2023-08-19 22:39:42", "lastmod": "2023-10-25 23:41:37", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Herbert-D-E", "name": { "family": "Herbert", "given": "David E." } }, { "id": "Lionetti-D", "name": { "family": "Lionetti", "given": "Davide" }, "orcid": "0000-0002-4937-886X" }, { "id": "Rittle-J", "name": { "family": "Rittle", "given": "Jonathan" } }, { "id": "Agapie-T", "name": { "family": "Agapie", "given": "Theodor" }, "orcid": "0000-0002-9692-7614" } ] }, "title": "Heterometallic Triiron-Oxo/Hydroxo Clusters: Effect of Redox-Inactive Metals", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society.\n\nPublished In Issue December 26, 2013; Article ASAP December 16, 2013; Just Accepted Manuscript December 04, 2013; Received: October 13, 2013.\n\nThe authors declare no competing financial interest.\n\nThis work was supported by the California Institute of\nTechnology, the Searle Scholars Program, the NSF CAREER\nCHE-1151918 (T.A.), a Camille & Henry Dreyfus Environmental\nChemistry Fellowship (D.E.H.), and a Resnick\nSustainability Institute graduate fellowship (D.L.). T.A. is a\nSloan and Cottrell Fellow. We thank Larry M. Henling and Dr.\nMichael Takase for assistance with crystallography and Prof.\nJonas C. Peters for use of a M\u00f6ssbauer spectrometer. Collection\nof M\u00f6ssbauer data was made possible by use of an instrument\npurchased with funds from the National Science Foundation\nCenter for Chemical Innovation on Solar Fuels (CCI Solar,\nGrant CHE-1305124). The Bruker KAPPA APEXII X-ray\ndiffractometer was purchased via an NSF Chemistry Research\nInstrumentation award to Caltech (CHE-0639094). We\nacknowledge the Gordon and Betty Moore Foundation, the\nBeckman Institute, and the Sanofi-Aventis BRP at Caltech for\ntheir generous support of the Molecular Observatory at Caltech.\nOperations at SSRL are supported by the U.S. DOE and NIH.\n\nAccepted Version - nihms550402.pdf
Supplemental Material - ja4104974_si_001.pdf
Supplemental Material - ja4104974_si_002.zip
", "abstract": "A series of tetranuclear oxo/hydroxo clusters comprised of three Fe centers and a redox-inactive metal (M) of various charge is reported. Crystallographic\nstudies show an unprecedented Fe_3M(\u03bc_4-O)(\u03bc_2-OH) core\nthat remains intact upon changing M or the oxidation state\nof iron. Electrochemical studies reveal that the reduction\npotentials (E_(1/2)) span a window of 500 mV and depend\nupon the Lewis acidity of M. Using the pK_a of the M-aqua\ncomplex as a measure of Lewis acidity, these compounds\ndisplay a linear dependence between E1/2 and acidity, with\na slope of \u223c70 mV per pK_a unit. The current study of\n[Fe_3MO(OH)] and previous ones of [Mn_3MO_n] (n = 2,4)\nmoieties support the generality of the above relationship\nbetween the reduction potentials of heterometallic oxido\nclusters and the Lewis acidity of incorporated cations, as\napplied to clusters of different redox-active metals.", "date": "2013-12-26", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "51", "publisher": "American Chemical Society", "pagerange": "19075-19078", "id_number": "CaltechAUTHORS:20140130-144616034", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140130-144616034", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Caltech" }, { "agency": "Searle Scholars Program" }, { "agency": "NSF", "grant_number": "CHE-1151918" }, { "agency": "Camille and Henry Dreyfus Foundation" }, { "agency": "Resnick Sustainability Institute" }, { "agency": "NSF", "grant_number": "CHE-0639094" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "local_group": { "items": [ { "id": "Resnick-Sustainability-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja4104974", "pmcid": "PMC3953215", "primary_object": { "basename": "ja4104974_si_001.pdf", "url": "https://authors.library.caltech.edu/records/a8kma-pba33/files/ja4104974_si_001.pdf" }, "related_objects": [ { "basename": "ja4104974_si_002.zip", "url": "https://authors.library.caltech.edu/records/a8kma-pba33/files/ja4104974_si_002.zip" }, { "basename": "nihms550402.pdf", "url": "https://authors.library.caltech.edu/records/a8kma-pba33/files/nihms550402.pdf" } ], "pub_year": "2013", "author_list": "Herbert, David E.; Lionetti, Davide; et el." }, { "id": "https://authors.library.caltech.edu/records/af9aq-m9x39", "eprint_id": 42806, "eprint_status": "archive", "datestamp": "2023-08-19 22:34:09", "lastmod": "2023-10-25 23:02:24", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Blakemore-J-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Gupta-Ayush", "name": { "family": "Gupta", "given": "Ayush" } }, { "id": "Warren-J-J", "name": { "family": "Warren", "given": "Jeffrey J." }, "orcid": "0000-0002-1747-3029" }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Noncovalent Immobilization of Electrocatalysts on Carbon Electrodes for Fuel Production", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society. \n\nReceived: September 26, 2013. Publication Date (Web): November 18, 2013. \n\nThe authors thank Peter Agbo for helpful discussions regarding surface preparation and David Lacy for assistance with the GC product analysis. Research was carried out in part at the Molecular Materials Research Center of the Beckman Institute at Caltech. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and a CCI Postdoctoral Fellowship to J.D.B.\n\nSupplemental Material - ja4099609_si_001.pdf
", "abstract": "We show that molecular catalysts for fuel-forming reactions can be immobilized on graphitic carbon electrode surfaces via noncovalent interactions. A pyrene-appended bipyridine ligand (P) serves as the linker between each complex and the surface. Immobilization of a rhodium proton-reduction catalyst, [Cp*Rh(P)Cl]Cl (1), and a rhenium CO_2-reduction catalyst, Re(P)(CO)_3Cl (2), afford electrocatalytically active assemblies. X-ray photoelectron spectroscopy and electrochemistry confirm catalyst immobilization. Reduction of 1 in the presence of p-toluenesulfonic acid results in catalytic H_2 production, while reduction of 2 in the presence of CO_2 results in catalytic CO production.", "date": "2013-12-11", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "49", "publisher": "American Chemical Society", "pagerange": "18288-18291", "id_number": "CaltechAUTHORS:20131203-150617731", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20131203-150617731", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "NSF Postdoctoral Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja4099609", "primary_object": { "basename": "ja4099609_si_001.pdf", "url": "https://authors.library.caltech.edu/records/af9aq-m9x39/files/ja4099609_si_001.pdf" }, "pub_year": "2013", "author_list": "Blakemore, James D.; Gupta, Ayush; et el." }, { "id": "https://authors.library.caltech.edu/records/ry4gj-8mq96", "eprint_id": 42848, "eprint_status": "archive", "datestamp": "2023-08-22 10:43:52", "lastmod": "2023-10-25 23:05:36", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Blakemore-J-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "M\u00fcller-A-M", "name": { "family": "M\u00fcller", "given": "Astrid M." } } ] }, "title": "Co_3O_4 Nanoparticle Water-Oxidation Catalysts Made by Pulsed-Laser Ablation in Liquids", "ispublished": "pub", "full_text_status": "public", "keywords": "water splitting catalysis; cobalt oxide; electrochemistry; nanoparticles; quantum confinement; oxygen evolution", "note": "\u00a9 2013 American Chemical Society.\n\nReceived: August 2, 2013; Revised: October 1, 2013; Published: October 3, 2013.\n\nWe thank Richard P. Gerhart for fabrication of the electrochemical\ncell used for the oxygen-detection experiment, and Bryce F. Sadtler and Alasdair W. McDowall for help with TEM. Research was carried out in the Laser Resource Center and the\nMolecular Materials Research Center of the Beckman Institute of the California Institute of Technology. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation.\n\nSupplemental Material - cs400639b_si_001.pdf
", "abstract": "Surfactant-free, size- and composition-controlled, unsupported, <5-nm, quantum-confined cobalt oxide nanoparticles with high electrocatalytic oxygen-evolution activity were synthesized by pulsed laser ablation in liquids. These crystalline Co_3O_4 nanoparticles have a turnover frequency per cobalt surface site among the highest ever reported for Co_3O_4 nanoparticle oxygen evolution catalysts in base and overpotentials competitive with the best electrodeposited cobalt oxides, with the advantage that they are suitable for mechanical deposition on photoanode materials and incorporation in integrated solar water-splitting devices.", "date": "2013-11", "date_type": "published", "publication": "ACS Catalysis", "volume": "3", "number": "11", "publisher": "American Chemical Society", "pagerange": "2497-2500", "id_number": "CaltechAUTHORS:20131205-085654384", "issn": "2155-5435", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20131205-085654384", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/cs400639b", "primary_object": { "basename": "cs400639b_si_001.pdf", "url": "https://authors.library.caltech.edu/records/ry4gj-8mq96/files/cs400639b_si_001.pdf" }, "pub_year": "2013", "author_list": "Blakemore, James D.; Gray, Harry B.; et el." }, { "id": "https://authors.library.caltech.edu/records/0e6bf-1r871", "eprint_id": 43544, "eprint_status": "archive", "datestamp": "2023-08-19 21:58:34", "lastmod": "2023-10-25 23:38:53", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "MacMillan-S-N", "name": { "family": "MacMillan", "given": "Samantha N." } }, { "id": "Harman-W-H", "name": { "family": "Harman", "given": "W. Hill" } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Facile Si\u2013H bond activation and hydrosilylation catalysis mediated by a nickel\u2013borane complex", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 Royal Society of Chemistry.\n\nReceived 18th September 2013; accepted 22nd October 2013.\n\nFirst published online 22 Oct 2013.\nThis work was supported by the National Science Foundation\nCenter for Chemical Innovation on Solar Fuels (CCI Solar, Grant CHE-1305124) and the Gordon and Betty Moore Foundation.\nWe thank David VanderVelde for assistance with NMR\nexperiments.\n\nSupplemental Material - c3sc52626g.pdf
Supplemental Material - c3sc52626g.txt
", "abstract": "Metal\u2013borane complexes are emerging as promising systems for study in the context of bifunctional catalysis. Herein we describe diphosphineborane nickel complexes that activate Si\u2013H bonds and catalyze the hydrosilylation of aldehydes. Treatment of [^(Mes)DPB^(Ph)]Ni (1) ([^(Mes)DPB^Ph] = ^(Mes)B(o-Ph_2PC_6H_4)_2) with organosilanes affords the complexes [^(Mes)DPB^(Ph)](\u03bc-H)NiE (E = SiH_2Ph (3), SiHPh_2 (4)). Complex 4 is in solution equilibrium with 1 and the thermodynamic and kinetic parameters of their exchange have been characterized by NMR spectroscopy. Complex 1 is a catalyst for the hydrosilylation of a range of para-substituted benzaldehydes. Mechanistic studies on this reaction via multinuclear NMR spectroscopy are consistent with the intermediacy of a borohydrido-Ni-siloxyalkyl species.", "date": "2013-10-22", "date_type": "published", "publication": "Chemical Science", "volume": "5", "number": "2", "publisher": "Royal Society of Chemistry", "pagerange": "590-597", "id_number": "CaltechAUTHORS:20140129-104856793", "issn": "2041-6520", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140129-104856793", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Center for Chemical Innovation on Solar Fuels", "grant_number": "CHE-1305124" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c3sc52626g", "primary_object": { "basename": "c3sc52626g.pdf", "url": "https://authors.library.caltech.edu/records/0e6bf-1r871/files/c3sc52626g.pdf" }, "related_objects": [ { "basename": "c3sc52626g.txt", "url": "https://authors.library.caltech.edu/records/0e6bf-1r871/files/c3sc52626g.txt" } ], "pub_year": "2013", "author_list": "MacMillan, Samantha N.; Harman, W. Hill; et el." }, { "id": "https://authors.library.caltech.edu/records/dcdfj-qzp44", "eprint_id": 42820, "eprint_status": "archive", "datestamp": "2023-08-22 10:29:45", "lastmod": "2023-10-25 23:03:54", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Anunson-P-N", "name": { "family": "Anunson", "given": "Paige N." } }, { "id": "Winkler-G-R", "name": { "family": "Winkler", "given": "Gates R." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Parkinson-Bruce-Alan", "name": { "family": "Parkinson", "given": "Bruce A." }, "orcid": "0000-0002-8950-1922" }, { "id": "Schuttlefield-Christus-J-D", "name": { "family": "Schuttlefield Christus", "given": "Jennifer D." } } ] }, "title": "Involving Students in a Collaborative Project To Help Discover Inexpensive, Stable Materials for Solar Photoelectrolysis", "ispublished": "pub", "full_text_status": "public", "keywords": "High School/Introductory Chemistry; Upper-Division Undergraduate; Public Understanding/Outreach; Interdisciplinary/Multidisciplinary; Inquiry-Based/Discovery Learning; Combinatorial Chemistry; Electrochemistry; Semiconductors; Solid State Chemistry; Undergraduate Research", "note": "\u00a9 2013 American Chemical Society and Division of Chemical Education, Inc. Published: September 9, 2013. This research was supported by the National Science Foundation Center for Chemical Innovation in Solar Fuels (grant CHE-1305124). The authors would also like to acknowledge all of the outreach sites and participants. Additionally, thanks to the University of Wisconsin\u2212Oshkosh CHEM221 Modern Analytical Chemistry class, especially Jason Maciolek and Matthew Trantow for their contributions to the data collected for the poster; Harry Gray, who created the term \"Solar Army\"; Robert Herrick II for his contributions to the SHArK software; Tom Fredrickson for his contributions to the SHArK system; Lee Sharpe and Casey Raymond for their discussions on spray deposition; and the students who participated in the Solar Army summer camp that created the instructional videos.\n\nSupplemental Material - ed300574x_si_001.pdf
Supplemental Material - ed300574x_si_002.pdf
Supplemental Material - ed300574x_si_003.docx
Supplemental Material - ed300574x_si_004.pdf
", "abstract": "In general, laboratory experiments focus on traditional chemical disciplines. While this approach allows students the ability to learn and explore fundamental concepts in a specific area, it does not always encourage students to explore interdisciplinary science. Often little transfer of knowledge from one area to another is observed, as students are given step-by-step instructions on how to complete their task with little involvement or problem solving. Herein, we provide an example of a real-time research laboratory experiment that is aimed at individual's exploration and development, with the scientific goal of discovering inexpensive, stable oxide semiconductors that can efficiently photoelectrolyze water to a useable fuel, hydrogen. Students create unique metal oxide semiconductors combinations, scan the samples for photoactivity using a purchased scan station, and report their findings to a collaborative database. A distinctive feature of the project is its ability to be implemented in a variety of educational levels with a breadth and depth of material covered accordingly. Currently, kits are being used in secondary education classrooms, at undergraduate institutions, or as outreach activities. The project provides students and scientists from different disciplines the opportunity to collaborate in research pertaining to clean energy and the global energy crisis.", "date": "2013-10", "date_type": "published", "publication": "Journal of Chemical Education", "volume": "90", "number": "10", "publisher": "American Chemical Society, Division of Chemical Education", "pagerange": "1333-1340", "id_number": "CaltechAUTHORS:20131204-095347280", "issn": "0021-9584", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20131204-095347280", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-1305124" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ed300574x", "primary_object": { "basename": "ed300574x_si_002.pdf", "url": "https://authors.library.caltech.edu/records/dcdfj-qzp44/files/ed300574x_si_002.pdf" }, "related_objects": [ { "basename": "ed300574x_si_003.docx", "url": "https://authors.library.caltech.edu/records/dcdfj-qzp44/files/ed300574x_si_003.docx" }, { "basename": "ed300574x_si_004.pdf", "url": "https://authors.library.caltech.edu/records/dcdfj-qzp44/files/ed300574x_si_004.pdf" }, { "basename": "ed300574x_si_001.pdf", "url": "https://authors.library.caltech.edu/records/dcdfj-qzp44/files/ed300574x_si_001.pdf" } ], "pub_year": "2013", "author_list": "Anunson, Paige N.; Winkler, Gates R.; et el." }, { "id": "https://authors.library.caltech.edu/records/4thqb-5tr89", "eprint_id": 41099, "eprint_status": "archive", "datestamp": "2023-08-19 21:13:00", "lastmod": "2023-10-24 23:27:31", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Mi-Qixi", "name": { "family": "Mi", "given": "Qixi" } }, { "id": "Coridan-R-H", "name": { "family": "Coridan", "given": "Robert H." }, "orcid": "0000-0003-1916-4446" }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Photoelectrochemical oxidation of anions by WO_3 in aqueous and nonaqueous electrolytes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 The Royal Society of Chemistry. \n\nReceived 1st March 2013; Accepted 18th June 2013. First published online 18 Jun 2013. \n\nWe acknowledge the National Science Foundation (NSF) Powering the Planet Center for Chemical Innovation (CCI-Solar),\nGrants CHE-0802907 and CHE-0947829, and the Molecular Materials Research Center of the Beckman Institute at the\nCalifornia Institute of Technology, for support. QM acknowledges Dr Elizabeth A. Santori for assistance with the spectral response experiments, and the NSF for support as a CCI-Solar Postdoctoral Fellow.\n\nPublished - c3ee40712h.pdf
Supplemental Material - c3ee40712h_si.pdf
", "abstract": "The behavior of WO_3 photoanodes has been investigated in contact with a combination of four anions (Cl\u2212, CH_3SO_3\u2212, HSO_4\u2212, and ClO_4\u2212) and three solvents (water, acetonitrile, and propylene carbonate), to elucidate the role of the semiconductor surface, the electrolyte, and redox kinetics on the current density vs. potential properties of n-type WO_3. In 1.0 M aqueous strong acids, although the flat-band potential (E_(fb)) of WO_3 was dominated by electrochemical intercalation of protons into WO_3, the nature of the electrolyte influenced the onset potential (E_(on)) of the anodic photocurrent. In aprotic solvents, the electrolyte anion shifted both E_(fb) and E_(on), but did not significantly alter the overall profile of the voltammetric data. For 0.50 M tetra(n-butyl)ammonium perchlorate in propylene carbonate, the internal quantum yield exceeded unity at excitation wavelengths of 300\u2013390 nm, indicative of current doubling. A regenerative photoelectrochemical cell based on the reversible redox couple B_(10)Br_(10)^(\u02d9\u2212/2\u2212) in acetonitrile, with a solution potential of 1.7 V vs. the normal hydrogen electrode, exhibited an open-circuit photovoltage of 1.32 V under 100 mW cm^(\u22122) of simulated Air Mass 1.5 global illumination.", "date": "2013-09", "date_type": "published", "publication": "Energy and Environmental Science", "volume": "6", "number": "9", "publisher": "Royal Society of Chemistry", "pagerange": "2646-2653", "id_number": "CaltechAUTHORS:20130905-093517424", "issn": "1754-5692", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130905-093517424", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Caltech Beckman Institute" }, { "agency": "NSF Postdoctoral Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c3ee40712h", "primary_object": { "basename": "c3ee40712h.pdf", "url": "https://authors.library.caltech.edu/records/4thqb-5tr89/files/c3ee40712h.pdf" }, "related_objects": [ { "basename": "c3ee40712h_si.pdf", "url": "https://authors.library.caltech.edu/records/4thqb-5tr89/files/c3ee40712h_si.pdf" } ], "pub_year": "2013", "author_list": "Mi, Qixi; Coridan, Robert H.; et el." }, { "id": "https://authors.library.caltech.edu/records/k3889-7c569", "eprint_id": 41360, "eprint_status": "archive", "datestamp": "2023-08-19 21:05:27", "lastmod": "2023-10-24 23:40:45", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Uyeda-Christopher", "name": { "family": "Uyeda", "given": "Christopher" }, "orcid": "0000-0001-9396-915X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Selective Nitrite Reduction at Heterobimetallic CoMg Complexes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society. \n\nReceived: May 29, 2013; Published: July 18, 2013. \n\nThis work was supported by the National Science Foundation Center for Chemical Innovation on Solar Fuels (CCI Solar, Grant CHE-0802907) and the Gordon and Betty Moore Foundation. We thank Larry M. Henling for assistance with crystallography, Angelo Di Bilio for assistance with EPR measurements, and David Lacy for assistance with IR spectroelectrochemical experiments.\n\nSupplemental Material - ja4053653_si_001.pdf
Supplemental Material - ja4053653_si_002.cif
", "abstract": "Heme-containing nitrite reductases bind and activate nitrite by a mechanism that is proposed to involve interactions with Br\u00f8nsted acidic residues in the secondary coordination sphere. To model this functionality using synthetic platforms that incorporate a Lewis acidic site, heterobimetallic CoMg complexes supported by diimine\u2013dioxime ligands are described. The neutral (\u03bc-NO_2)CoMg species 3 is synthesized from the [(\u03bc-OAc)(Br)CoMg]+ complex 1 by a sequence of one-electron reduction and ligand substitution reactions. Data are presented for a redox series of nitrite adducts, featuring a conserved \u03bc-(\u03b7^1-N:\u03b7^1-O)-NO_2 motif, derived from this synthon. Conditions are identified for the proton-induced N\u2013O bond heterolysis of bound NO_2\u2013 in the most reduced member of this series, affording the [(NO)(Cl)CoMg(H_2O)]+ complex 6. Reduction of this complex followed by protonation leads to the evolution of free N_2O. On the basis of these stoichiometric reactivity studies, the competence of complex 1 as a NO_2\u2013 reduction catalyst is evaluated using electrochemical methods. In bulk electrolysis experiments, conducted at \u22121.2 V vs SCE using Et_3NHCl as a proton source, N_2O is produced selectively without the competing formation of NH_3, NH_2OH, or H_2.", "date": "2013-08-14", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "32", "publisher": "American Chemical Society", "pagerange": "12023-12031", "id_number": "CaltechAUTHORS:20130917-100711754", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130917-100711754", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja4053653", "primary_object": { "basename": "ja4053653_si_001.pdf", "url": "https://authors.library.caltech.edu/records/k3889-7c569/files/ja4053653_si_001.pdf" }, "related_objects": [ { "basename": "ja4053653_si_002.cif", "url": "https://authors.library.caltech.edu/records/k3889-7c569/files/ja4053653_si_002.cif" } ], "pub_year": "2013", "author_list": "Uyeda, Christopher and Peters, Jonas C." }, { "id": "https://authors.library.caltech.edu/records/df6tt-q1b39", "eprint_id": 41649, "eprint_status": "archive", "datestamp": "2023-08-22 10:01:00", "lastmod": "2023-10-24 23:54:14", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lee-Chang-Hoon", "name": { "family": "Lee", "given": "Chang Hoon" } }, { "id": "Vill\u00e1gran-Dino", "name": { "family": "Vill\u00e1gran", "given": "Dino" } }, { "id": "Cook-Timothy-R", "name": { "family": "Cook", "given": "Timothy R." } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Nocera-Daniel-G", "name": { "family": "Nocera", "given": "Daniel G." }, "orcid": "0000-0001-5055-320X" } ] }, "title": "Pacman and Hangman Metal Tetraazamacrocycles", "ispublished": "pub", "full_text_status": "restricted", "keywords": "cobalt; electrochemistry; homogeneous catalysis; hydrogen; palladium", "note": "\u00a9 2013 Wiley-VCH Verlag GmbH& Co. KGaA, Weinheim.\n\nReceived: January 21, 2013;\nRevised: April 11, 2013;\nPublished online on July 26, 2013.\n\nThis research was supported by DOE grant DE-FG02-05ER15745\n(D.G.N.) and the NSF Center for Chemical Innovation: Powering\nthe Planet CHE-0802907 (J.C.P.). We thank Prof. M. Din\u010da for SEM\nand EDX analysis.", "abstract": "Metal complexes of derivatized 2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),2,11,13,15-pentane (bapa) ligands were prepared from 4-substituted diacetylpyridine derivatives by templated condensation with 3,3\u2032-diaminodipropylamine in the presence of a metal halide or nitrate. The diacetylpyridine derivatives with Pacman and Hangman scaffolds are delivered from borylation of the 4-postion of diacetylpyridine and subsequent Suzuki coupling with the appropriate Hangman or Pacman backbone. Electrochemical examination of the parent [Co(bapa)]^(2+) scaffold reveals it to be a catalyst for the hydrogen evolution reaction (HER) in acetonitrile. Similar studies of the Hangman complex appear to be obscured by trace amounts of residual palladium remaining from the Suzuki coupling reaction to provide a cautionary note for the use of such cross-coupling methodologies in the preparation of HER catalysts.", "date": "2013-08", "date_type": "published", "publication": "ChemSusChem", "volume": "6", "number": "8", "publisher": "Wiley", "pagerange": "1541-1544", "id_number": "CaltechAUTHORS:20131003-085853977", "issn": "1864-5631", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20131003-085853977", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG02-05ER15745" }, { "agency": "NSF", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1002/cssc.201300068", "pub_year": "2013", "author_list": "Lee, Chang Hoon; Vill\u00e1gran, Dino; et el." }, { "id": "https://authors.library.caltech.edu/records/2nxrc-f2606", "eprint_id": 42069, "eprint_status": "archive", "datestamp": "2023-08-19 20:53:11", "lastmod": "2023-10-25 15:04:52", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Warren-J-J", "name": { "family": "Warren", "given": "Jeffrey J." }, "orcid": "0000-0002-1747-3029" }, { "id": "Herrera-N", "name": { "family": "Herrera", "given": "Nadia" }, "orcid": "0000-0003-4157-9429" }, { "id": "Hill-M-G", "name": { "family": "Hill", "given": "Michael G." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Electron Flow through Nitrotyrosinate in Pseudomonas aeruginosa Azurin", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society.\n\nReceived: April 15, 2013; published: July 16, 2013.\n\nOur work was supported by NIH (DK019038 to H.B.G. and\nJ.R.W.; GM095037 to J.J.W.), an NSF Center for Chemical\nInnovation (Powering the Planet, CHE-0947829), and the\nArnold and Mabel Beckman Foundation. We also acknowledge\nthe Gordon and Betty Moore Foundation and the Sanofi-\nAventis Bioengineering Research Program for their support of\nthe Molecular Observatory facilities at the California Institute of Technology. X-ray crystallography data was collected at the Stanford Synchrotron Radiation Lightsource (SSRL), a Directorate of the SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the U.S. Department of Energy, Office of Molecular Biology Program and Environmental Research, and by the National Institutes of Health, National Center for Research Resources, Biomedical Technology Program (P41RR001209), and the National Institute of General Medical Sciences.\n\nAccepted Version - nihms-506875.pdf
Supplemental Material - ja403734n_si_001.pdf
", "abstract": "We have designed ruthenium-modified Pseudomonas aeruginosa azurins that incorporate 3-nitrotyrosine (NO_(2)YOH) between Ru(2,2\u2032-bipyridine)_2(imidazole)(histidine) and Cu redox centers in electron transfer (ET) pathways. We investigated the structures and reactivities of three different systems: RuH107NO_(2)YOH109, RuH124NO_(2)YOH122, and RuH126NO_(2)YOH122. RuH107NO_(2)YOH109, unlabeled H124NO_(2)YOH122, and unlabeled H126NO_(2)YOH122 were structurally characterized. The pKa's of NO_(2)YOH at positions 122 and 109 are 7.2 and 6.0, respectively. Reduction potentials of 3-nitrotyrosinate (NO_(2)YO^\u2013)-modified azurins were estimated from cyclic and differential pulse voltammetry data: oxidation of NO_(2)YO^(\u2013)122 occurs near 1.1 versus NHE; oxidation of NO_(2)YO^(\u2013)109 is near 1.2 V. Our analysis of transient optical spectroscopic experiments indicates that hopping via NO_(2)YO^\u2013 enhances Cu^I oxidation rates over single-step ET by factors of 32 (RuH107NO_(2)YO^(\u2013)109), 46 (RuH126NO_(2)YO^(\u2013)122), and 13 (RuH124NO_(2)YO^(\u2013)122).", "date": "2013-07-31", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "30", "publisher": "American Chemical Society", "pagerange": "11151-11158", "id_number": "CaltechAUTHORS:20131025-104510564", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20131025-104510564", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "DK019038" }, { "agency": "NIH", "grant_number": "GM095037" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Sanofi-Aventis Bioengineering Research Program" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja403734n", "pmcid": "PMC3839300", "primary_object": { "basename": "ja403734n_si_001.pdf", "url": "https://authors.library.caltech.edu/records/2nxrc-f2606/files/ja403734n_si_001.pdf" }, "related_objects": [ { "basename": "nihms-506875.pdf", "url": "https://authors.library.caltech.edu/records/2nxrc-f2606/files/nihms-506875.pdf" } ], "pub_year": "2013", "author_list": "Warren, Jeffrey J.; Herrera, Nadia; et el." }, { "id": "https://authors.library.caltech.edu/records/9k7g8-vxp12", "eprint_id": 41469, "eprint_status": "archive", "datestamp": "2023-08-19 20:51:43", "lastmod": "2023-10-24 23:46:07", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Reyes-Gil-K-R", "name": { "family": "Reyes-Gil", "given": "Karla R." } }, { "id": "Wiggenhorn-C", "name": { "family": "Wiggenhorn", "given": "Craig" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Comparison between the Quantum Yields of Compact and Porous WO_3 Photoanodes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society. \n\nReceived: March 13, 2013; Revised: June 15, 2013; Published: June 17, 2013. \n\nThis work was funded by the NSF Powering the Planet Center for Chemical Innovation, grant CHE-0947829, and by the Defense Advanced Research Projects Agency. Use of facilities at the Molecular Materials Research Center (MMRC) at Caltech is gratefully acknowledged. The authors also acknowledge the technical work of Miguel Ortiz from California State University, Los Angeles.\n\nSupplemental Material - jp4025624_si_001.pdf
", "abstract": "Ordered structures offer the potential for producing photoanodes with enhanced minority-carrier collection. To evaluate this approach to visible-light-driven oxidation in aqueous electrolytes, porous WO_3 structures were synthesized by the potentiostatic anodization of W foil. The photoelectrochemical behavior of the porous WO_3 photoanodes was compared to that of compact WO_3 films. Relative to planar electrodes, the porous WO_3 electrodes exhibited a 6-fold increase in photocurrent density, from 0.12 to 0.75 mA cm^(\u20132), under 100 mW cm^(\u20132) of simulated solar illumination. Spectral response measurements indicated that the porous electrodes exhibited internal quantum yields of 0.5 throughout most of the region of WO_3 absorption. The external quantum yield of the porous WO_3 films was a function of the angle of incidence of the light, increasing from 0.25 at normal incidence to 0.50 at 65\u00b0 off normal. The porous WO_3 films showed excellent stability against photodegradation. This work demonstrates that morphological control can improve the internal quantum yield of photoanodes in contact with aqueous electrolytes.", "date": "2013-07-25", "date_type": "published", "publication": "Journal of Physical Chemistry C", "volume": "117", "number": "29", "publisher": "American Chemical Society", "pagerange": "14947-14957", "id_number": "CaltechAUTHORS:20130923-093622415", "issn": "1932-7447", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130923-093622415", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Defense Advanced Research Projects Agency (DARPA)" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/jp4025624", "primary_object": { "basename": "jp4025624_si_001.pdf", "url": "https://authors.library.caltech.edu/records/9k7g8-vxp12/files/jp4025624_si_001.pdf" }, "pub_year": "2013", "author_list": "Reyes-Gil, Karla R.; Wiggenhorn, Craig; et el." }, { "id": "https://authors.library.caltech.edu/records/gn6kh-xs112", "eprint_id": 41736, "eprint_status": "archive", "datestamp": "2023-08-19 20:50:55", "lastmod": "2023-10-25 14:42:43", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Sattler-W", "name": { "family": "Sattler", "given": "Wesley" }, "orcid": "0000-0001-5316-260X" }, { "id": "Ener-M-E", "name": { "family": "Ener", "given": "Maraia E." } }, { "id": "Blakemore-J-D", "name": { "family": "Blakemore", "given": "James D." }, "orcid": "0000-0003-4172-7460" }, { "id": "Rachford-A-D", "name": { "family": "Rachford", "given": "Aaron D." } }, { "id": "LaBeaume-P-J", "name": { "family": "LaBeaume", "given": "Paul J." } }, { "id": "Thackeray-J-W", "name": { "family": "Thackeray", "given": "James W." } }, { "id": "Cameron-J-F", "name": { "family": "Cameron", "given": "James F." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Generation of Powerful Tungsten Reductants by Visible Light Excitation", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society.\n\nReceived: May 10, 2013; Published: July 15, 2013.\n\nDedicated to the memory of Nicholas J. Turro. The authors\nthank Jeffrey J. Warren, James R. McKone, and Oliver S.\nShafaat for helpful discussions. Our work is supported by the\nNational Science Foundation Center for Chemical Innovation\nin Solar Fuels (CHE-0802907); CCI postdoctoral fellowship to\nW.S.; and the Dow Chemical Company through the university\npartnership program (Agreement No. 227027AH).\n\nSupplemental Material - ja4047119_si_001.pdf
Supplemental Material - ja4047119_si_002.cif
", "abstract": "The homoleptic arylisocyanide tungsten complexes, W(CNXy)_6 and W(CNIph)_6 (Xy = 2,6-dimethylphenyl, Iph = 2,6-diisopropylphenyl), display intense metal to ligand charge transfer (MLCT) absorptions in the visible region (400\u2013550 nm). MLCT emission (\u03bb_max \u2248 580 nm) in tetrahydrofuran (THF) solution at rt is observed for W(CNXy)6 and W(CNIph)_6 with lifetimes of 17 and 73 ns, respectively. Diffusion-controlled energy transfer from electronically excited W(CNIph)_6 (*W) to the lowest energy triplet excited state of anthracene (anth) is the dominant quenching pathway in THF solution. Introduction of tetrabutylammonium hexafluorophosphate, [Bun4N][PF_6], to the THF solution promotes formation of electron transfer (ET) quenching products, [W(CNIph)6]+ and [anth]^\u2022\u2013. ET from *W to benzophenone and cobalticenium also is observed in [Bun4N][PF6]/THF solutions. The estimated reduction potential for the [W(CNIph)6]^(+)/*W couple is \u22122.8 V vs Cp_(2)Fe^(+/0), establishing W(CNIph)_6 as one of the most powerful photoreductants that has been generated with visible light.", "date": "2013-07-24", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "29", "publisher": "American Chemical Society", "pagerange": "10614-10617", "id_number": "CaltechAUTHORS:20131008-104014521", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20131008-104014521", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF Postdoctoral Fellowship" }, { "agency": "Dow Chemical Company", "grant_number": "227027AH" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja4047119", "primary_object": { "basename": "ja4047119_si_001.pdf", "url": "https://authors.library.caltech.edu/records/gn6kh-xs112/files/ja4047119_si_001.pdf" }, "related_objects": [ { "basename": "ja4047119_si_002.cif", "url": "https://authors.library.caltech.edu/records/gn6kh-xs112/files/ja4047119_si_002.cif" } ], "pub_year": "2013", "author_list": "Sattler, Wesley; Ener, Maraia E.; et el." }, { "id": "https://authors.library.caltech.edu/records/myy8f-aad89", "eprint_id": 54276, "eprint_status": "archive", "datestamp": "2023-08-22 09:56:19", "lastmod": "2023-10-20 15:45:51", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dempsey-J-L", "name": { "family": "Dempsey", "given": "J. L." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "J. R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "H. B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Solar Fuels: Approaches to Catalytic Hydrogen Evolution", "ispublished": "unpub", "full_text_status": "restricted", "keywords": "Catalysis; Cobaloxime; Hydrogen; Molecular catalysts; Solar energy; Solar fuel", "note": "\u00a9 2013 Elsevier Ltd.\n\nAvailable online 23 July 2013;\nReviewed 26 November 2014.\n\nThis work was supported by NSF Center for Chemical Innovation\n(Powering the Planet, CHE-0947829), the Arnold and\nMabel Beckman Foundation, and CCSER (Gordon and Betty\nMoore Foundation). J.L.D. was supported by an NSF Graduate\nResearch Fellowship.", "abstract": "In response to political and environmental motivations to develop alternative energy resources, researchers have taken a variety of approaches to develop solar energy conversion technologies. Solar fuel production is an area of enormous promise where, in analogy to natural photosynthesis, sunlight drives the conversion of energy-poor molecules (H_2O and CO_2) to energy-rich ones (O_2, H_2, and (CH_2O)_n). To realize a solar-driven water splitting device based on earth-abundant materials, new chemistry is needed, including materials for light harvesting and electrocatalysts for fuel production. In this chapter, we focus on molecular hydrogen production catalysts capable of evolving H_2 at low overpotentials. Recent synthetic advances in catalyst design, detailed electrochemical and photochemical studies, and developments in mechanistic understandings are covered.", "date": "2013-07-23", "date_type": "published", "publisher": "Elsevier", "place_of_pub": "Amsterdam", "pagerange": "553-565", "id_number": "CaltechAUTHORS:20150202-083557905", "isbn": "978-0-08-096529-1", "book_title": "Comprehensive Inorganic Chemistry II", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150202-083557905", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "CCSER" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "contributors": { "items": [ { "id": "Reedijk-J", "name": { "family": "Reedijk", "given": "Jan" } }, { "id": "Poeppelmeier-K", "name": { "family": "Poeppelmeier", "given": "Kenneth" } } ] }, "doi": "10.1016/B978-0-08-097774-4.00806-8", "pub_year": "2013", "author_list": "Dempsey, J. L.; Winkler, J. R.; et el." }, { "id": "https://authors.library.caltech.edu/records/1mge0-dre42", "eprint_id": 39891, "eprint_status": "archive", "datestamp": "2023-08-19 20:29:39", "lastmod": "2023-10-24 17:17:33", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Popczun-E-J", "name": { "family": "Popczun", "given": "Eric J." } }, { "id": "McKone-J-R", "name": { "family": "McKone", "given": "James R." }, "orcid": "0000-0001-6445-7884" }, { "id": "Read-C-G", "name": { "family": "Read", "given": "Carlos G." } }, { "id": "Biacchi-A-J", "name": { "family": "Biacchi", "given": "Adam J." } }, { "id": "Wiltrout-A-M", "name": { "family": "Wiltrout", "given": "Alex M." } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Schaak-R-E", "name": { "family": "Schaak", "given": "Raymond E." } } ] }, "title": "Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society.\n\nReceived: April 6, 2013;\nPublished: June 13, 2013.\n\nThis work was supported by the U.S. National Science\nFoundation \"Powering the Planet\" Center for Chemical\nInnovation (CHE-0802907). J.R.M. acknowledges the Department of Energy, Office of Science for a graduate research\nfellowship. TEM imaging was performed in the Electron\nMicroscopy Facility of the Huck Institutes of the Life Sciences,\nand HRTEM and SEM imaging was performed in the Materials\nCharacterization Lab of the Penn State Materials Research\nInstitute. The authors thank Melisa Yashinski, Julie Anderson,\nand Trevor Clark for assistance with SEM imaging, Josh\nStapleton for assistance with DRIFTS data collection and\ninterpretation, and Jason Binz and Robert Rioux for assistance\nwith the BET surface area measurements.\n\nSupplemental Material - ja403440e_si_001.pdf
", "abstract": "Nanoparticles of nickel phosphide (Ni_2P) have been investigated for electrocatalytic activity and stability for the hydrogen evolution reaction (HER) in acidic solutions, under which proton exchange membrane-based electrolysis is operational. The catalytically active Ni_2P nanoparticles were hollow and faceted to expose a high density of the Ni_2P(001) surface, which has previously been predicted based on theory to be an active HER catalyst. The Ni2P nanoparticles had among the highest HER activity of any non-noble metal electrocatalyst reported to date, producing H_2(g) with nearly quantitative faradaic yield, while also affording stability in aqueous acidic media.", "date": "2013-06-26", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "25", "publisher": "American Chemical Society", "pagerange": "9267-9270", "id_number": "CaltechAUTHORS:20130813-110523757", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130813-110523757", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Department of Energy (DOE)" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja403440e", "primary_object": { "basename": "ja403440e_si_001.pdf", "url": "https://authors.library.caltech.edu/records/1mge0-dre42/files/ja403440e_si_001.pdf" }, "pub_year": "2013", "author_list": "Popczun, Eric J.; McKone, James R.; et el." }, { "id": "https://authors.library.caltech.edu/records/tdz15-45m83", "eprint_id": 39779, "eprint_status": "archive", "datestamp": "2023-08-19 20:25:38", "lastmod": "2023-10-24 17:11:49", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Pinaud-B-A", "name": { "family": "Pinaud", "given": "Blaise A." } }, { "id": "Benck-J-D", "name": { "family": "Benck", "given": "Jesse D." } }, { "id": "Seitz-L-C", "name": { "family": "Seitz", "given": "Linsey C." } }, { "id": "Forman-A-J", "name": { "family": "Forman", "given": "Arnold J." } }, { "id": "Chen-Zhebo", "name": { "family": "Chen", "given": "Zhebo" } }, { "id": "Deutsch-T-G", "name": { "family": "Deutsch", "given": "Todd G." }, "orcid": "0000-0001-6577-1226" }, { "id": "James-B-D", "name": { "family": "James", "given": "Brian D." } }, { "id": "Baum-K-N", "name": { "family": "Baum", "given": "Kevin N." } }, { "id": "Baum-G-N", "name": { "family": "Baum", "given": "George N." } }, { "id": "Ardo-S", "name": { "family": "Ardo", "given": "Shane" }, "orcid": "0000-0001-7162-6826" }, { "id": "Wang-Heli", "name": { "family": "Wang", "given": "Heli" } }, { "id": "Miller-E", "name": { "family": "Miller", "given": "Eric" } }, { "id": "Jaramillo-T-F", "name": { "family": "Jaramillo", "given": "Thomas F." }, "orcid": "0000-0001-9900-0622" } ] }, "title": "Technical and economic feasibility of centralized facilities for solar hydrogen production via photocatalysis and photoelectrochemistry", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 Royal Society of Chemistry.\n\nReceived 10th March 2013; accepted 20th May 2013.\n\nFirst published online 12 Jun 2013.\nThe authors would like to thank the U.S. Department of Energy's PEC Working Group, organized by the Office of Energy Efficiency and Renewable Energy's Fuel Cell Technologies Office, for its instrumental role in initiating and sustaining the technoeconomic analysis of the photoelectrochemical hydrogen production pathway. We also thank Steven Y. Reece, Joep J. H. Pijpers, Niels H. Damrauer, and Thomas D. Jarvi for their constructive feedback on this paper. BAP received funding from NSF grant CHE-0802907 for CCI Solar Fuels, a United Technologies\nResearch Center fellowship in Sustainable Energy, and a Natural Sciences and Engineering Research Council of Canada\ngraduate award. JDB received support from the National\nScience Foundation Graduate Research Fellowship Program\nand a Stanford Graduate Fellowship. LCS also received funding from the National Science Foundation Graduate Research Fellowship Program. AJF and TFJ received support from the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy through Subcontract no. NFT-9-88567-01 and AGB-2-11473-01 under Prime Contract no. DE-AC36-08-GO28308. JDB, LCS, and ZC were supported by the Center on Nanostructuring for Efficient Energy Conversion (CNEEC) at Stanford University, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award no. DE-SC0001060. TGD was supported by the U.S. Department of Energy Fuel Cell Technologies Office under Contract no. DE-AC36-08-G028303 with the National Renewable Energy Laboratory. SA received support through a DOE-EERE Postdoctoral Research Award under the EERE Fuel Cell Technologies Program.\n\nPublished - c3ee40831k.pdf
", "abstract": "Photoelectrochemical water splitting is a promising route for the renewable production of hydrogen fuel. This work presents the results of a technical and economic feasibility analysis conducted for four hypothetical, centralized, large-scale hydrogen production plants based on this technology. The four reactor types considered were a single bed particle suspension system, a dual bed particle suspension system, a fixed panel array, and a tracking concentrator array. The current performance of semiconductor absorbers and electrocatalysts were considered to compute reasonable solar-to-hydrogen conversion efficiencies for each of the four systems. The U.S. Department of Energy H2A model was employed to calculate the levelized cost of hydrogen output at the plant gate at 300 psi for a 10 tonne per day production scale. All capital expenditures and operating costs for the reactors and auxiliaries (compressors, control systems, etc.) were considered. The final cost varied from $1.60\u2013$10.40 per kg H2 with the particle bed systems having lower costs than the panel-based systems. However, safety concerns due to the cogeneration of O_2 and H_2 in a single bed system and long molecular transport lengths in the dual bed system lead to greater uncertainty in their operation. A sensitivity analysis revealed that improvement in the solar-to-hydrogen efficiency of the panel-based systems could substantially drive down their costs. A key finding is that the production costs are consistent with the Department of Energy's targeted threshold cost of $2.00\u2013$4.00 per kg H_2 for dispensed hydrogen, demonstrating that photoelectrochemical water splitting could be a viable route for hydrogen production in the future if material performance targets can be met.", "date": "2013-06-12", "date_type": "published", "publication": "Energy and Environmental Science", "volume": "6", "number": "7", "publisher": "Royal Society of Chemistry", "pagerange": "1983-2002", "id_number": "CaltechAUTHORS:20130806-102709429", "issn": "1754-5692", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130806-102709429", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "United Technologies Research Center" }, { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "NSF Graduate Research Fellowship" }, { "agency": "Stanford University" }, { "agency": "Department of Energy (DOE)", "grant_number": "NFT-9-88567-01" }, { "agency": "Department of Energy (DOE)", "grant_number": "AGB-2-11473-01" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-AC36-08-GO28308" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC0001060" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-AC36-08-G028303" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c3ee40831k", "primary_object": { "basename": "c3ee40831k.pdf", "url": "https://authors.library.caltech.edu/records/tdz15-45m83/files/c3ee40831k.pdf" }, "pub_year": "2013", "author_list": "Pinaud, Blaise A.; Benck, Jesse D.; et el." }, { "id": "https://authors.library.caltech.edu/records/773fn-pfn10", "eprint_id": 44275, "eprint_status": "archive", "datestamp": "2023-08-19 20:14:19", "lastmod": "2023-10-26 00:21:13", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "An Integrated, Systems Approach to the Development of Solar Fuel Generators", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 Electrochemical Society. Summer 2013. Support for solar fuels R&D by the NSF Powering the Planet Center for Chemical Innovation, CHE-0947829 (development of electrocatalysts), by the DOE DEFG02-03ER15483 (earth-abundant light absorbers), and by the Office of Science of\nthe U.S. Department of Energy under Award No. DE-SC0004993 to the Joint Center for Artificial Photosynthesis, a DOE Energy\nInnovation Hub (translational research in solar fuels generators), has enabled the preparation of this article.\n\nPublished - sum13_p043_049.pdf
", "abstract": "Two major technological challenges in the development of a sustainable, clean energy system are providing massive grid-scale energy storage and an ample supply of carbon-neutral, high energy-density, transportation fuels. The\ndevelopment and deployment of massive, grid-scale energy storage is imperative for reliably and robustly compensating for the intermittency involved with the utilization of very large amounts of wind energy and\nsolar energy.", "date": "2013-06", "date_type": "published", "publication": "Interface", "volume": "22", "number": "2", "publisher": "Electrochemical Society", "pagerange": "43-49", "id_number": "CaltechAUTHORS:20140312-095955949", "issn": "1064-8208", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140312-095955949", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Powering the Planet Center for Chemical Innovation (CCI)", "grant_number": "CHE-0947829" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG02-03ER15483" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC0004993" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "primary_object": { "basename": "sum13_p043_049.pdf", "url": "https://authors.library.caltech.edu/records/773fn-pfn10/files/sum13_p043_049.pdf" }, "pub_year": "2013", "author_list": "Lewis, Nathan S." }, { "id": "https://authors.library.caltech.edu/records/p7t2q-9jx63", "eprint_id": 38837, "eprint_status": "archive", "datestamp": "2023-09-26 23:49:26", "lastmod": "2023-10-24 14:54:21", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Bingol-Bahar", "name": { "family": "Bingol", "given": "Bahar" } }, { "id": "Durrell-A-C", "name": { "family": "Durrell", "given": "Alec C." } }, { "id": "Keller-G-E", "name": { "family": "Keller", "given": "Gretchen E." } }, { "id": "Palmer-J-H", "name": { "family": "Palmer", "given": "Joshua H." } }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Electron Transfer Triggered by Optical Excitation of Phenothiazin-tris(meta-phenylene-ethynylene)-(tricarbonyl)(bpy)(py)rhenium(I)", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. \n\nReceived: January 31, 2012; Revised: April 9, 2012; Published: April 25, 2012. \n\nDedicated to the memory of Paul Barbara, a great scientist and dear friend. We thank Tony Vlcek for many helpful discussions and Angelo Di Bilio for assistance with EPR experiments. Supported by a NSF Center for Chemical Innovation grant (Powering the Planet CHE-0802907) and the Arnold and Mabel Beckman Foundation.\n\nSupplemental Material - jp3010053_si_001.pdf
", "abstract": "We have investigated excited-state electron transfer in a donor-bridge-acceptor complex containing phenothiazine (PTZ) linked via tris(meta-phenylene-ethynylene) to a tricarbonyl(bipyridine)(pyridine)Re(I) unit. Time-resolved luminescence experiments reveal two excited-state (*Re) decay regimes, a multiexponential component with a mean lifetime of 2.7 ns and a longer monoexponential component of 530 ns in dichloromethane solution. The faster decay is attributed to PTZ \u2192 *Re electron transfer in a C-shaped PTZ-bridge-Re conformer (PTZ\u2013Re \u2248 7.5 \u00c5). We assign the longer lifetime, which is virtually identical to that of free *Re, to an extended conformer (PTZ\u2013Re > 20 \u00c5). The observed biexponential *Re decay requires that interconversion of PTZ-bridge-Re conformers be slower than 10^6 s^(\u20131).", "date": "2013-04-25", "date_type": "published", "publication": "Journal of Physical Chemistry B", "volume": "117", "number": "16", "publisher": "American Chemical Society", "pagerange": "4177-4182", "id_number": "CaltechAUTHORS:20130606-115526109", "issn": "1520-6106", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130606-115526109", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/jp3010053", "primary_object": { "basename": "jp3010053_si_001.pdf", "url": "https://authors.library.caltech.edu/records/p7t2q-9jx63/files/jp3010053_si_001.pdf" }, "pub_year": "2013", "author_list": "Bingol, Bahar; Durrell, Alec C.; et el." }, { "id": "https://authors.library.caltech.edu/records/cj15p-fq416", "eprint_id": 37888, "eprint_status": "archive", "datestamp": "2023-08-19 19:03:19", "lastmod": "2023-10-23 19:05:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Li-Y", "name": { "family": "Li", "given": "Yan" } }, { "id": "O'Leary-L-E", "name": { "family": "O'Leary", "given": "Leslie E." } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Galli-G-A", "name": { "family": "Galli", "given": "Giulia A." } } ] }, "title": "Combined Theoretical and Experimental Study of Band-Edge Control of Si through Surface Functionalization", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society.\n\nReceived: December 18, 2012; Revised: February 5, 2013;\nPublished: February 13, 2013.\n\nY.L. was supported by Brookhaven Science Associates, LLC\nunder Contract No. DE-AC02-98CH10886, with the U.S.\nDepartment of Energy. L.E.O. was supported through a Link\nFoundation Energy fellowship. Part of the work was funded by\nNSF-CHE-0802907. The calculations were performed at the\nNERSC and TeraGrid facilities. We thank M. Hybertsen for\nuseful discussions.\n\nPublished - jp3124583.pdf
Supplemental Material - jp3124583_si_001.pdf
", "abstract": "The band-edge positions of H-, Cl-, Br-, methyl-, and ethyl-terminated Si(111) surfaces were investigated through a combination of density functional theory (DFT) and many-body perturbation theory, as well as by photoelectron spectroscopy and electrical device measurements. The calculated trends in surface potential shifts as a function of the adsorbate type and coverage are consistent with the calculated strength and direction of the dipole moment of the adsorbate radicals in conjunction with simple electronegativity-based expectations. The quasi-particle energies, such as the ionization potential (IP), that were calculated by use of many-body perturbation theory were in good agreement with experiment. The IP values that were calculated by DFT exhibited substantial errors, but nevertheless, the IP differences, i.e., IP_(R\u2013Si(111))\u2013IP_(H\u2013Si(111)), computed using DFT were in good agreement with spectroscopic and electrical measurements.", "date": "2013-03-14", "date_type": "published", "publication": "Journal of Physical Chemistry C", "volume": "117", "number": "10", "publisher": "American Chemical Society", "pagerange": "5188-5194", "id_number": "CaltechAUTHORS:20130411-103710875", "issn": "1932-7447", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130411-103710875", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-AC02-98CH10886" }, { "agency": "Link Foundation Energy fellowship" }, { "agency": "NSF", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/jp3124583", "primary_object": { "basename": "jp3124583_si_001.pdf", "url": "https://authors.library.caltech.edu/records/cj15p-fq416/files/jp3124583_si_001.pdf" }, "related_objects": [ { "basename": "jp3124583.pdf", "url": "https://authors.library.caltech.edu/records/cj15p-fq416/files/jp3124583.pdf" } ], "pub_year": "2013", "author_list": "Li, Yan; O'Leary, Leslie E.; et el." }, { "id": "https://authors.library.caltech.edu/records/4xdmh-sqd40", "eprint_id": 37867, "eprint_status": "archive", "datestamp": "2023-08-19 19:01:14", "lastmod": "2024-01-13 06:00:26", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marinescu-S-C", "name": { "family": "Marinescu", "given": "Smaranda C." }, "orcid": "0000-0003-2106-8971" }, { "id": "Bracher-P-J", "name": { "family": "Bracher", "given": "Paul J." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Solar fuels", "ispublished": "unpub", "full_text_status": "public", "keywords": "catalysts, hydrogen production, oxidation, solar power, sunlight", "note": "\u00a9 2013 American Institute of Physics.\n\nPublished - APC000064.pdf
", "abstract": "The generation of hydrogen from water and sunlight may provide the clean, renewable fuel that solves our planet's growing demand for energy. However, for any approach to be practical, we will need to develop robust catalysts containing earthabundant elements for the efficient reduction of protons to H_2 and oxidation of water to O_2.", "date": "2013-03-08", "date_type": "published", "publisher": "American Institute of Physics", "place_of_pub": "Melville, NY", "pagerange": "64-67", "id_number": "CaltechAUTHORS:20130410-140848013", "isbn": "978-0-7354-1142-5", "book_title": "Nanoscale Energy Converters", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130410-140848013", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "contributors": { "items": [ { "id": "Linker-H", "name": { "family": "Linke", "given": "Heiner" } }, { "id": "Borgstr\u00f6m-M", "name": { "family": "Borgstr\u00f6m", "given": "Magnus" } }, { "id": "Pullerits-T", "name": { "family": "Pullerits", "given": "T\u00f6nu" } }, { "id": "Samuelson-L", "name": { "family": "Samuelson", "given": "Lars" } }, { "id": "Sundstr\u00f6m-V", "name": { "family": "Sundstr\u00f6m", "given": "Villy" } }, { "id": "Ingan\u00e4s-O", "name": { "family": "Ingan\u00e4s", "given": "Olle" } } ] }, "doi": "10.1063/1.4794711", "primary_object": { "basename": "APC000064.pdf", "url": "https://authors.library.caltech.edu/records/4xdmh-sqd40/files/APC000064.pdf" }, "pub_year": "2013", "author_list": "Marinescu, Smaranda C.; Bracher, Paul J.; et el." }, { "id": "https://authors.library.caltech.edu/records/qysmr-6sf18", "eprint_id": 38320, "eprint_status": "archive", "datestamp": "2023-08-22 08:48:39", "lastmod": "2023-10-23 20:03:06", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Durrell-A-C", "name": { "family": "Durrell", "given": "Alec C." } }, { "id": "Jackson-M-N", "name": { "family": "Jackson", "given": "Megan N." } }, { "id": "Hazari-N", "name": { "family": "Hazari", "given": "Nilay" } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Making Carbon\u2013Chlorine Bonds by Dipalladium Electrocatalysis", "ispublished": "pub", "full_text_status": "restricted", "keywords": "Palladium; Electrochemistry; C\u2013H activation; C\u2013Cl bond formation", "note": "\u00a9 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.\n\nReceived: December 11, 2012; Published Online: January 18, 2013.\n\nThis work was supported by an National Science Foundation\n(NSF) Center for Innovation (CCI Solar, CHE-0802907), the\nAmgen Foundation (M. N. J.), and the Caltech Summer Undergraduate Research Fellowship Program (M. N. J.).", "abstract": "[(Benzo[h]quinolinyl)Pd^(II)(\u03bc-OAc)]_2 and [(2-phenylpyridinyl)PdII(\u03bc-OAc)]_2 undergo one-electron oxidation to afford mixed-valent (Pd^(II)\u2013Pd^(III)) species. Electrochemical oxidation of the Pd^(II)\u2013Pd^(II) complexes in the presence of chloride at the Pd^(III)\u2013Pd^(II)/Pd^(II)\u2013Pd^(II) potential results in a two-electron loss with addition of two chlorides to form [(benzo[h]quinolinyl)Pd^(III)Cl(\u03bc-OAc)]_2 and [(2-phenylpyridinyl)Pd^(III)Cl(\u03bc-OAc)]_2, respectively. When both excess benzo[h]quinoline and chloride are present, [(benzo[h]quinolinyl)Pd^(II)(\u03bc-OAc)]2 electrocatalyzes the chlorination of the substrate to afford 10-chlorobenzo[h]quinoline with high chemical and Faradaic yields.", "date": "2013-03", "date_type": "published", "publication": "European Journal of Inorganic Chemistry", "volume": "2013", "number": "7", "publisher": "Wiley-VCH Verlag", "pagerange": "1134-1137", "id_number": "CaltechAUTHORS:20130507-103535110", "issn": "1434-1948", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130507-103535110", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Center for Innovation", "grant_number": "CHE-0802907" }, { "agency": "Amgen Foundation" }, { "agency": "Caltech Summer Undergraduate Research Fellowship (SURF)" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1002/ejic.201201498", "pub_year": "2013", "author_list": "Durrell, Alec C.; Jackson, Megan N.; et el." }, { "id": "https://authors.library.caltech.edu/records/84a5g-vpa07", "eprint_id": 37699, "eprint_status": "archive", "datestamp": "2023-08-19 14:45:49", "lastmod": "2023-10-23 17:57:52", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dasgupta-S", "name": { "family": "Dasgupta", "given": "Siddharth" }, "orcid": "0000-0002-9161-7457" }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Solar fuels editorial", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 The Royal Society of Chemistry.\n\nFirst published on the web 21 Feb 2013.\n\nThis article is part of the collection: Solar fuels\n\nPublished - c3cs90016a.pdf
", "abstract": "Every major change in the living\nstandards for humans on our planet has\nhad an energy revolution at its heart \u2013 the\nadvent of the industrial age with the\nsteam engine and use of coal, the internal\ncombustion engine and large-scale\nelectricity generation. The energy demand,\nprimarily from emerging economies, will\ndouble by 2050. The countervailing\nurgency of the threat of climate change\nrequires a major shift in our energy\nsourcing, creating four new trends that\nwill shape the current century: electrification,\ndecarbonization, localization,\nand optimization.", "date": "2013-02-21", "date_type": "published", "publication": "Chemical Society Reviews", "volume": "42", "number": "6", "publisher": "Royal Society of Chemistry", "pagerange": "2213-2214", "id_number": "CaltechAUTHORS:20130401-100227836", "issn": "0306-0012", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130401-100227836", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c3cs90016a", "primary_object": { "basename": "c3cs90016a.pdf", "url": "https://authors.library.caltech.edu/records/84a5g-vpa07/files/c3cs90016a.pdf" }, "pub_year": "2013", "author_list": "Dasgupta, Siddharth; Brunschwig, Bruce S.; et el." }, { "id": "https://authors.library.caltech.edu/records/z7ryh-8sk10", "eprint_id": 37403, "eprint_status": "archive", "datestamp": "2023-08-19 14:31:21", "lastmod": "2023-10-23 17:25:59", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "McKone-J-R", "name": { "family": "McKone", "given": "James R." }, "orcid": "0000-0001-6445-7884" }, { "id": "Sadtler-B-F", "name": { "family": "Sadtler", "given": "Bryce F." } }, { "id": "Werlang-C-A", "name": { "family": "Werlang", "given": "Caroline A." } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Ni\u2013Mo Nanopowders for Efficient Electrochemical Hydrogen Evolution", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. \n\nReceived: October 26, 2012. Revised: November 30, 2012. Published: December 3, 2012. \n\nThis work was supported by the National Science Foundation\n\"Powering the Planet\" Center for Chemical Innovation (CHE-\n0802907). We thank Carol M. Garland for assistance with\ntransmission electron microscopy. J.R.M. acknowledges the\nDepartment of Energy, Office of Science for a graduate research\nfellowship. C.A.W. thanks the Caltech Summer Undergraduate\nResearch Fellowship (SURF) program for support during the\nsummer of 2012. B.F.S. acknowledges the Beckman Institute\nfor a postdoctoral fellowship.\n\nPublished - cs300691m.pdf
Supplemental Material - cs300691m_si_001.pdf
Supplemental Material - cs300691m_si_002.xlsx
", "abstract": "Earth-abundant metals are attractive alternatives to the noble metal composite catalysts that are used in water electrolyzers based on proton-exchange membrane technology. Ni\u2013Mo alloys have been previously developed for the hydrogen evolution reaction (HER), but synthesis methods to date have been limited to formation of catalyst coatings directly on a substrate. We report a method for generating unsupported nanopowders of Ni\u2013Mo, which can be suspended in common solvents and cast onto arbitrary substrates. The mass-specific catalytic activity under alkaline conditions approaches that of the most active reported non-noble HER catalysts, and the coatings display good stability under alkaline conditions. We have also estimated turnover frequencies per surface atom at various overpotentials and conclude that the activity enhancement for Ni\u2013Mo relative to pure Ni is due to a combination of increased surface area and increased fundamental catalytic activity.", "date": "2013-02", "date_type": "published", "publication": "ACS Catalysis", "volume": "3", "number": "2", "publisher": "American Chemical Society", "pagerange": "166-169", "id_number": "CaltechAUTHORS:20130308-080802822", "issn": "2155-5435", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130308-080802822", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Department of Energy (DOE)" }, { "agency": "Caltech Summer Undergraduate Research Fellowship (SURF)" }, { "agency": "Caltech Beckman Institute" } ] }, "local_group": { "items": [ { "id": "Kavli-Nanoscience-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/cs300691m", "primary_object": { "basename": "cs300691m.pdf", "url": "https://authors.library.caltech.edu/records/z7ryh-8sk10/files/cs300691m.pdf" }, "related_objects": [ { "basename": "cs300691m_si_001.pdf", "url": "https://authors.library.caltech.edu/records/z7ryh-8sk10/files/cs300691m_si_001.pdf" }, { "basename": "cs300691m_si_002.xlsx", "url": "https://authors.library.caltech.edu/records/z7ryh-8sk10/files/cs300691m_si_002.xlsx" } ], "pub_year": "2013", "author_list": "McKone, James R.; Sadtler, Bryce F.; et el." }, { "id": "https://authors.library.caltech.edu/records/88hyv-d3a09", "eprint_id": 36741, "eprint_status": "archive", "datestamp": "2023-08-22 08:09:28", "lastmod": "2023-10-23 15:26:40", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Warren-J-J", "name": { "family": "Warren", "given": "Jeffrey J." }, "orcid": "0000-0002-1747-3029" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Hopping maps for photosynthetic reaction centers", "ispublished": "pub", "full_text_status": "public", "keywords": "Electron transfer; Multistep tunneling; Hopping maps; Photosynthesis; Bacterial photosynthetic reaction centers", "note": "\u00a9 2012 Elsevier B.V. \n\nReceived 16 May 2012; \nReceived in revised form 3 July 2012; Accepted 4 July 2012; \nAvailable online 14 July 2012.\n\n\nOur work is supported by NIH (DK019038 to HBG and JRW;\nGM095037 to JJW), and an NSF Center for Chemical Innovation\n(Powering the Planet, CHE-0947829).\n\nAccepted Version - nihms394131.pdf
", "abstract": "Photosynthetic reaction centers (PRCs) employ multiple-step tunneling (hopping) to separate electrons and holes that ultimately drive the chemistry required for metabolism. We recently developed hopping maps that can be used to interpret the rates and energetics of electron/hole hopping in three-site (donor\u2013intermediate\u2013acceptor) tunneling reactions, including those in PRCs. Here we analyze several key ET reactions in PRCs, including forward ET in the L-branch, and hopping that could involve thermodynamically uphill intermediates in the M-branch, which is ET-inactive in vivo. We also explore charge recombination reactions, which could involve hopping. Our hopping maps support the view that electron flow in PRCs involves strong electronic coupling between cofactors and reorganization energies that are among the lowest in biology (\u22640.4 eV).", "date": "2013-01-01", "date_type": "published", "publication": "Coordination Chemistry Reviews", "volume": "257", "number": "1", "publisher": "Elsevier", "pagerange": "165-170", "id_number": "CaltechAUTHORS:20130201-110533889", "issn": "0010-8545", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130201-110533889", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "DK019038" }, { "agency": "NIH", "grant_number": "GM095037" }, { "agency": "NSF", "grant_number": "CHE-0947829" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1016/j.ccr.2012.07.002", "pmcid": "PMC3530024", "primary_object": { "basename": "nihms394131.pdf", "url": "https://authors.library.caltech.edu/records/88hyv-d3a09/files/nihms394131.pdf" }, "pub_year": "2013", "author_list": "Warren, Jeffrey J.; Winkler, Jay R.; et el." }, { "id": "https://authors.library.caltech.edu/records/p54mg-sp418", "eprint_id": 36198, "eprint_status": "archive", "datestamp": "2023-08-19 13:37:19", "lastmod": "2023-10-20 22:21:53", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Yahyaie-I", "name": { "family": "Yahyaie", "given": "Iman" } }, { "id": "Ardo-S", "name": { "family": "Ardo", "given": "Shane" }, "orcid": "0000-0001-7162-6826" }, { "id": "Oliver-D-R", "name": { "family": "Oliver", "given": "Derek R." } }, { "id": "Thomson-D-J", "name": { "family": "Thomson", "given": "Douglas J." } }, { "id": "Freund-M-S", "name": { "family": "Freund", "given": "Michael S." }, "orcid": "0000-0003-1104-2292" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Comparison between the electrical junction properties of H-terminated and methyl-terminated individual Si microwire/polymer assemblies for photoelectrochemical fuel production", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 The Royal Society of Chemistry.\n\nReceived 8th August 2012, Accepted 24th September 2012.\nFirst published on the web 25 Sep 2012.\n\nFinancial support from the Natural Sciences and Engineering\nResearch Council (NSERC) of Canada, the Canada Foundation\nfor Innovation (CFI), the Manitoba Research and Innovation\nFund, and the University of Manitoba is gratefully acknowledged. \n\nThe work reported made use of surface characterization\ninfrastructure in the Manitoba Institute for Materials. This work\nwas supported by a National Science Foundation (NSF) Center\nfor Chemical Innovation (CCI) Powering the Planet (grants\nCHE-0802907, CHE-0947829, and NSF-ACCF) and made use\nof the Molecular Materials Research Center of the Beckman\nInstitute at Caltech and the Kavli Nanoscience Institute at Caltech. \n\nThis research was undertaken, in part, thanks to funding\nfrom the Canada Research Chairs Program. S. A. acknowledges\npartial support from a U. S. Department of Energy, Office of\nEnergy Efficiency and Renewable Energy (EERE) Postdoctoral\nResearch Award under the EERE Fuel Cell Technologies\nProgram.\n\nPublished - c2ee23115h.pdf
Supplemental Material - c2ee23115h_si.pdf
", "abstract": "The photoelectrical properties and stability of individual p-silicon (Si) microwire/polyethylenedioxythiophene/polystyrene sulfonate:Nafion/n-Si microwire structures, designed for use as arrays for solar fuel production, were investigated for both H-terminated and CH_3-terminated Si microwires. Using a tungsten probe method, the resistances of individual wires, as well as between individual wires and the conducting polymer, were measured vs. time. For the H-terminated samples, the n-Si/polymer contacts were initially rectifying, whereas p-Si microwire/polymer contacts were initially ohmic, but the resistance of both the n-Si and p-Si microwire/polymer contacts increased over time. In contrast, relatively stable, ohmic behavior was observed at the junctions between CH_3-terminated p-Si microwires and conducting polymers. CH_3-terminated n-Si microwire/polymer junctions demonstrated strongly rectifying behavior, attributable to the work function mismatch between the Si and polymer. Hence, a balance must be found between the improved stability of the junction electrical properties achieved by passivation, and the detrimental impact on the effective resistance associated with the additional rectification at CH_3-terminated n-Si microwire/polymer junctions. Nevertheless, the current system under study would produce a resistance drop of ~20 mV during operation under 100 mW cm^(\u22122) of Air Mass 1.5 illumination with high quantum yields for photocurrent production in a water-splitting device.", "date": "2012-12", "date_type": "published", "publication": "Energy and Environmental Science", "volume": "5", "number": "12", "publisher": "Royal Society of Chemistry", "pagerange": "9789-9794", "id_number": "CaltechAUTHORS:20130107-103859564", "issn": "1754-5692", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130107-103859564", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "Canada Foundation for Innovation" }, { "agency": "Manitoba Research and Innovation Fund" }, { "agency": "University of Manitoba" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Department of Energy (DOE)" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" }, { "id": "Kavli-Nanoscience-Institute" } ] }, "doi": "10.1039/c2ee23115h", "primary_object": { "basename": "c2ee23115h.pdf", "url": "https://authors.library.caltech.edu/records/p54mg-sp418/files/c2ee23115h.pdf" }, "related_objects": [ { "basename": "c2ee23115h_si.pdf", "url": "https://authors.library.caltech.edu/records/p54mg-sp418/files/c2ee23115h_si.pdf" } ], "pub_year": "2012", "author_list": "Yahyaie, Iman; Ardo, Shane; et el." }, { "id": "https://authors.library.caltech.edu/records/bqm2e-ej654", "eprint_id": 36870, "eprint_status": "archive", "datestamp": "2023-08-19 13:26:45", "lastmod": "2023-10-23 15:53:02", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Mi-Qixi", "name": { "family": "Mi", "given": "Qixi" } }, { "id": "Ping-Yuan", "name": { "family": "Ping", "given": "Yuan" } }, { "id": "Li-Yan", "name": { "family": "Li", "given": "Yan" } }, { "id": "Cao-Bingfei", "name": { "family": "Cao", "given": "Bingfei" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Khalifah-P-G", "name": { "family": "Khalifah", "given": "Peter G." } }, { "id": "Galli-G-A", "name": { "family": "Galli", "given": "Giulia A." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Thermally Stable N_2-Intercalated WO_3 Photoanodes for Water Oxidation", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. \n\nReceived: July 14, 2012. Published: September 28, 2012. \n\nWe thank Prof. George R. Rossman for discussions and for assistance with the Raman microscope, and Prof. Francois Gygi for discussions of ab initio calculations. This work was supported by the National Science Foundation (NSF) Powering the Planet Center for Chemical Innovation (CCISolar), Grants CHE-0802907 and CHE-0947829. Q.M. was a CCI-Solar Postdoctoral Fellow. P.G.K. thanks the support of the U.S. Department of Energy under the Hydrogen Fuel Initiative. Research was in part carried out in the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology, and in part carried out at Brookhaven National Laboratory under No. DE-AC02-98CH10886 with the U.S. Department of Energy. Use of the Teragrid computational facilities is gratefully acknowledged.\n\nSupplemental Material - ja3067622_si_001.pdf
", "abstract": "We describe stable intercalation compounds of the composition xN_2\u2022WO_3 (x = 0.034\u20130.039), formed by trapping N_2 in WO_3. The incorporation of N_2 significantly reduced the absorption threshold of WO_3; notably, 0.039N_2\u2022WO_3 anodes exhibited photocurrent under illumination at wavelengths \u2264640 nm with a faradaic efficiency for O_2 evolution in 1.0 M HClO_4(aq) of nearly unity. Spectroscopic and computational results indicated that deformation of the WO3 host lattice, as well as weak electronic interactions between trapped N_2 and the WO_3 matrix, contributed to the observed red shift in optical absorption. Noble-gas-intercalated WO_3 materials similar to xN_2\u2022WO_3 are predicted to function as photoanodes that are responsive to visible light.", "date": "2012-11-07", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "44", "publisher": "American Chemical Society", "pagerange": "18318-18324", "id_number": "CaltechAUTHORS:20130212-095922217", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130212-095922217", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "NSF Postdoctoral Fellowship" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-AC02-98CH10886" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja3067622", "primary_object": { "basename": "ja3067622_si_001.pdf", "url": "https://authors.library.caltech.edu/records/bqm2e-ej654/files/ja3067622_si_001.pdf" }, "pub_year": "2012", "author_list": "Mi, Qixi; Ping, Yuan; et el." }, { "id": "https://authors.library.caltech.edu/records/e5jgc-kqt19", "eprint_id": 35511, "eprint_status": "archive", "datestamp": "2023-08-22 07:13:43", "lastmod": "2023-10-20 16:26:15", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Warren-J-J", "name": { "family": "Warren", "given": "Jeffrey J." }, "orcid": "0000-0002-1747-3029" }, { "id": "Ener-M-E", "name": { "family": "Ener", "given": "Maraia E." } }, { "id": "Vl\u010dek-A-Jr", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn, Jr." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Electron hopping through proteins", "ispublished": "pub", "full_text_status": "public", "keywords": "Electron transfer; Multistep tunneling; Hopping maps; Redox proteins azurin; Ribonucleotide reductase; DNA photolyase; MauG", "note": "\u00a9 2012 Elsevier B.V. \n\nReceived 17 December 2011; Accepted 30 March 2012; Available online 5 April 2012. \n\nOur work is supported by NIH (DK019038 to H.B.G. and J.R.W.;\nGM095037 to J.J.W.), an NSF Center for Chemical Innovation\n(Powering the Planet, CHE-0947829) and by a Czech Ministry of\nEducation Grant ME10124 to A.V. \n\nThis article belongs to a special issue \"Solar Fuels- by invitation only,\" edited By Tony Vlcek.\n\nAccepted Version - nihms378660.pdf
", "abstract": "Biological redox machines require efficient transfer of electrons and holes for function. Reactions involving multiple tunneling steps, termed \"hopping,\" often promote charge separation within and between proteins that is essential for energy storage and conversion. Here we show how semiclassical electron transfer theory can be extended to include hopping reactions: graphical representations (called hopping maps) of the dependence of calculated two-step reaction rate constants on driving force are employed to account for flow in a rhenium-labeled azurin mutant as well as in two structurally characterized redox enzymes, DNA photolyase and MauG. Analysis of the 35 \u00c5 radical propagation in ribonucleotide reductases using hopping maps shows that all tyrosines and tryptophans on the radical pathway likely are involved in function. We suggest that hopping maps can facilitate the design and construction of artificial photosynthetic systems for the production of fuels and other chemicals.", "date": "2012-11", "date_type": "published", "publication": "Coordination Chemistry Reviews", "volume": "256", "number": "21-22", "publisher": "Elsevier", "pagerange": "2478-2487", "id_number": "CaltechAUTHORS:20121116-101610363", "issn": "0010-8545", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20121116-101610363", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "DK019038" }, { "agency": "NIH", "grant_number": "GM095037" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Ministry of Education (Czech Republic)", "grant_number": "ME10124" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1016/j.ccr.2012.03.032", "pmcid": "PMC3570191", "primary_object": { "basename": "nihms378660.pdf", "url": "https://authors.library.caltech.edu/records/e5jgc-kqt19/files/nihms378660.pdf" }, "pub_year": "2012", "author_list": "Warren, Jeffrey J.; Ener, Maraia E.; et el." }, { "id": "https://authors.library.caltech.edu/records/kpwsg-dwn92", "eprint_id": 35514, "eprint_status": "archive", "datestamp": "2023-08-19 13:16:51", "lastmod": "2023-10-20 16:26:26", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Warren-E-L", "name": { "family": "Warren", "given": "Emily L." }, "orcid": "0000-0001-8568-7881" }, { "id": "McKone-J-R", "name": { "family": "McKone", "given": "James R." }, "orcid": "0000-0001-6445-7884" }, { "id": "Atwater-H-A", "name": { "family": "Atwater", "given": "Harry A." }, "orcid": "0000-0001-9435-0201" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Hydrogen-evolution characteristics of Ni\u2013Mo-coated, radial junction, n+p-silicon microwire array photocathodes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 Royal Society of Chemistry. \n\nReceived 16 August 2012; Accepted 13 September 2012; First published on the web 08 October 2012. \n\nELW and NSL acknowledge support from the Department of\nEnergy (DE-FG02-05ER15754) for Si MW growth and device\nfabrication. JRM and HBG acknowledge support from the\nNational Science Foundation (NSF) Powering the Planet Center\nfor Chemical Innovation (CHE-0802907) for catalyst preparation and characterization. The authors would like to thank Hal Emmer, Dan Turner-Evans, and Elizabeth Santori for help with device fabrication and spectral response data collection. We acknowledge critical support and infrastructure provided for this work by the Kavli Nanoscience Institute at Caltech. JRM would like to thank the Department of Energy, Office of Science, for a graduate research fellowship.\n\nSupplemental Material - c2ee23192a.pdf
", "abstract": "The photocathodic H_2-evolution performance of Ni\u2013Mo-coated radial n+p junction Si microwire (Si MW) arrays has been evaluated on the basis of thermodynamic energy-conversion efficiency as well as solar cell figures of merit. The Ni\u2013Mo-coated n^(+)p-Si MW electrodes yielded open-circuit photovoltages (V_oc) of 0.46 V, short-circuit photocurrent densities (J_sc) of 9.1 mA cm^(\u22122), and thermodynamically based energy-conversion efficiencies (\u03b7) of 1.9% under simulated 1 Sun illumination. Under nominally the same conditions, the efficiency of the Ni\u2013Mo-coated system was comparable to that of Pt-coated n+p-Si MW array photocathodes (V_oc = 0.44 V, J_sc = 13.2 mA cm^(\u22122_, \u03b7 = 2.7%). This demonstrates that, at 1 Sun light intensity on high surface area microwire arrays, earth-abundant electrocatalysts can provide performance comparable to noble-metal catalysts for photoelectrochemical hydrogen evolution. The formation of an emitter layer on the microwires yielded significant improvements in the open-circuit voltage of the microwire-array-based photocathodes relative to Si MW arrays that did not have a buried n^(+)p junction. Analysis of the spectral response and light-intensity dependence of these devices allowed for optimization of the catalyst loading and photocurrent density. The microwire arrays were also removed from the substrate to create flexible, hydrogen-evolving membranes that have potential for use in a solar water-splitting device.", "date": "2012-11", "date_type": "published", "publication": "Energy and Environmental Science", "volume": "5", "number": "11", "publisher": "Royal Society of Chemistry", "pagerange": "9653-9661", "id_number": "CaltechAUTHORS:20121116-105842933", "issn": "1754-5692", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20121116-105842933", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG02-05ER15754" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Kavli Nanoscience Institute" } ] }, "local_group": { "items": [ { "id": "Kavli-Nanoscience-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/C2EE23192A", "primary_object": { "basename": "c2ee23192a.pdf", "url": "https://authors.library.caltech.edu/records/kpwsg-dwn92/files/c2ee23192a.pdf" }, "pub_year": "2012", "author_list": "Warren, Emily L.; McKone, James R.; et el." }, { "id": "https://authors.library.caltech.edu/records/52151-mcg57", "eprint_id": 33819, "eprint_status": "archive", "datestamp": "2023-08-22 06:57:30", "lastmod": "2023-10-18 20:56:55", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Valdez-C-N", "name": { "family": "Valdez", "given": "Carolyn N." } }, { "id": "Dempsey-J-L", "name": { "family": "Dempsey", "given": "Jillian L." } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Catalytic hydrogen evolution from a covalently linked dicobaloxime", "ispublished": "pub", "full_text_status": "public", "keywords": "hydrogen evolving catalysts; solar fuel", "note": "\u00a9 2012 by the National Academy of Sciences. \n\nEdited by Thomas J. Meyer, University of North Carolina at Chapel Hill, Chapel Hill, NC, and approved June 14, 2012 (received for review February 7, 2012). Published online before print July 11, 2012. \n\nWe thank Ian Stewart, Alex Miller, Bryan Stubbert, Charles McCrory, Xile Hu, and Jonas Peters for insightful discussions. This work was supported by the NSF Center for Chemical Innovation (Powering the Planet, CHE-0802907), the Arnold and Mabel Beckman Foundation, CCSER (Gordon and Betty Moore Foundation), and the BP MC2 program. CNV is grateful for support from the Caltech Summer Undergraduate Research Program and an Amgen Scholars Fellowship. JLD was supported by an NSF Graduate Research Fellowship. \n\nAuthor contributions: C.N.V., J.L.D., J.R.W., and H.B.G. designed research; C.N.V. and J.L.D. performed research; C.N.V. and J.L.D. contributed new reagents/analytic tools; C.N.V., J.L.D., and B.S.B. analyzed data; and C.N.V., J.L.D., J.R.W., and H.B.G. wrote the paper. \n\nThe authors declare no conflict of interest. \n\nThis article is a PNAS Direct Submission.\n\nPublished - PNAS-2012-Valdez-15589-93.pdf
Supplemental Material - pnas.1118329109_SI.pdf
", "abstract": "A dicobaloxime in which monomeric Co(III) units are linked by an octamethylene bis(glyoxime) catalyzes the reduction of protons from p-toluenesulfonic acid as evidenced by electrocatalytic waves at -0.4 V vs. the saturated calomel electrode (SCE) in acetonitrile solutions. Rates of hydrogen evolution were determined from catalytic current peak heights (k_(app) = 1100 \u00b1 70 M^(-1) s^(-1)). Electrochemical experiments reveal no significant enhancement in the rate of H2 evolution from that of a monomeric analogue: The experimental rate law is first order in catalyst and acid consistent with previous findings for similar mononuclear cobaloximes. Our work suggests that H_2 evolution likely occurs by protonation of reductively generated Co^(II)H rather than homolysis of two Co^(III)H units.", "date": "2012-09-25", "date_type": "published", "publication": "Proceedings of the National Academy of Sciences of the United States of America", "volume": "109", "number": "39", "publisher": "National Academy of Sciences", "pagerange": "15589-15593", "id_number": "CaltechAUTHORS:20120904-101007499", "issn": "0027-8424", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120904-101007499", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "BP MC2 program" }, { "agency": "Caltech Summer Undergraduate Research Fellowship (SURF)" }, { "agency": "Amgen" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1073/pnas.1118329109", "pmcid": "PMC3465440", "primary_object": { "basename": "PNAS-2012-Valdez-15589-93.pdf", "url": "https://authors.library.caltech.edu/records/52151-mcg57/files/PNAS-2012-Valdez-15589-93.pdf" }, "related_objects": [ { "basename": "pnas.1118329109_SI.pdf", "url": "https://authors.library.caltech.edu/records/52151-mcg57/files/pnas.1118329109_SI.pdf" } ], "pub_year": "2012", "author_list": "Valdez, Carolyn N.; Dempsey, Jillian L.; et el." }, { "id": "https://authors.library.caltech.edu/records/9qgj9-q0858", "eprint_id": 35009, "eprint_status": "archive", "datestamp": "2023-08-22 06:54:43", "lastmod": "2023-10-19 23:38:13", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marinescu-S-C", "name": { "family": "Marinescu", "given": "Smaranda C." }, "orcid": "0000-0003-2106-8971" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Molecular mechanisms of cobalt-catalyzed hydrogen evolution", "ispublished": "pub", "full_text_status": "public", "keywords": "catalysis; renewable fuel", "note": "\u00a9 2012 National Academy of Sciences.\n\nContributed by Harry B. Gray, August 6, 2012; sent for review July 19, 2012; Published online before print September 4, 2012.\n\nWe thank Lawrence M. Henling and the late Dr. Michael\nW. Day for crystallographic assistance, and Dr. Jay A. Labinger for insightful comments. Our work is supported by the National Science Foundation Center for Chemical Innovation in Solar Fuels (CHE-0802907); Center for Chemical\nInnovation postdoctoral fellowship to S.C.M. We thank Chevron-Phillips for additional support. The Bruker KAPPA APEX II X-ray diffractometer was purchased via a National Science Foundation Chemistry Research Instrumentation\nand Facilities: Departmental Multi-User Instrumentation (CRIF:MU) award to the California Institute of Technology, CHE-0639094.\n\nAuthor contributions: S.C.M. designed research; S.C.M. performed research; S.C.M.\ncontributed new reagents/analytic tools; S.C.M., J.R.W., and H.B.G. analyzed data; and\nS.C.M., J.R.W., and H.B.G. wrote the paper.\nThe authors declare no conflict of interest.\nData deposition: The atomic coordinates have been deposited in the Cambridge Structural Database, Cambridge Crystallographic Data Centre, Cambridge CB2 1EZ, United\nKingdom http://www.ccdc.cam.ac.uk, [CSD reference numbers 838815 (1), 844589 (2), and 846384 (3)].\n\nPublished - PNAS-2012-Marinescu-15127-31.pdf
Supplemental Material - Appendix.pdf
", "abstract": "Several cobalt complexes catalyze the evolution of hydrogen from acidic solutions, both homogeneously and at electrodes. The detailed molecular mechanisms of these transformations remain unresolved, largely owing to the fact that key reactive intermediates have eluded detection. One method of stabilizing reactive intermediates\ninvolves minimizing the overall reaction free-energy\nchange. Here, we report a new cobalt(I) complex that reacts with tosylic acid to evolve hydrogen with a driving force of just 30 meV\u2215Co. Protonation of Co^I produces a transient Co^(IIII)-H complex that was characterized by nuclear magnetic resonance spectroscopy.\nThe Co^(IIII)-H intermediate decays by second-order kinetics\nwith an inverse dependence on acid concentration. Analysis of the kinetics suggests that Co^(IIII)-H produces hydrogen by two competing pathways: a slower homolytic route involving two Co^(IIII)-H species and a dominant heterolytic channel in which a highly reactive Co^(II)-H transient is generated by Co^I reduction of Co^(IIII)-H.", "date": "2012-09-18", "date_type": "published", "publication": "Proceedings of the National Academy of Sciences of the United States of America", "volume": "109", "number": "38", "publisher": "National Academy of Sciences", "pagerange": "15127-15131", "id_number": "CaltechAUTHORS:20121022-125521843", "issn": "0027-8424", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20121022-125521843", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Chevron-Phillips" }, { "agency": "NSF", "grant_number": "CHE-0639094" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1073/pnas.1213442109", "pmcid": "PMC3458341", "primary_object": { "basename": "Appendix.pdf", "url": "https://authors.library.caltech.edu/records/9qgj9-q0858/files/Appendix.pdf" }, "related_objects": [ { "basename": "PNAS-2012-Marinescu-15127-31.pdf", "url": "https://authors.library.caltech.edu/records/9qgj9-q0858/files/PNAS-2012-Marinescu-15127-31.pdf" } ], "pub_year": "2012", "author_list": "Marinescu, Smaranda C.; Winkler, Jay R.; et el." }, { "id": "https://authors.library.caltech.edu/records/s33he-9b617", "eprint_id": 36156, "eprint_status": "archive", "datestamp": "2023-08-19 12:42:09", "lastmod": "2023-10-20 22:18:30", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Uyeda-Christopher", "name": { "family": "Uyeda", "given": "Christopher" }, "orcid": "0000-0001-9396-915X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Access to formally Ni(I) states in a heterobimetallic NiZn system", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 The Royal Society of Chemistry.\nReceived 10th August 2012.\nAccepted 10th September 2012.\nFirst published on the web 12 Sep 2012.\n\nThis work was supported by the NSF Center for Chemical\nInnovation: Powering the Planet grant CHE-0802907, and by the\nGordon and Betty Moore Foundation. We thank Larry Henling\nand Charlene Tsay for assistance with crystallography, Dr\nAngelo Di Bilio for EPR measurements, and Dr Limei Zhang and\nDr Jens Kaiser for XAS measurements. We acknowledge the\nGordon and Betty Moore Foundation, the Beckman Institute,\nand the Sanofi-Aventis BRP at Caltech for their generous\nsupport of the Molecular Observatory at Caltech. SSRL is operated\nfor the DOE and supported by its Office of Biological and\nEnvironmental Research, and by the NIH, NIGMS (including\nP41GM103393) and the NCRR (P41RR001209).\n\nPublished - c2sc21231e.pdf
Supplemental Material - c2sc21231e.txt
Supplemental Material - c2sc21231e_SI.pdf
", "abstract": "Heterobimetallic NiZn complexes featuring metal centers in distinct coordination environments have been synthesized using diimine\u2013dioxime ligands as binucleating scaffolds. A tetramethylfuran-containing ligand derivative enables a stable one-electron-reduced S = 1/2 species to be accessed using Cp_2Co as a chemical reductant. The resulting pseudo-square planar complex exhibits spectroscopic and crystallographic characteristics of a ligand-centered radical bound to a Ni(II) center. Upon coordination of a \u03c0-acidic ligand such as PPh_3, however, a five-coordinate Ni(I) metalloradical is formed. The electronic structures of these reduced species provide insight into the subtle effects of ligand structure on the potential and reversibility of the Ni^(II/I) couple for complexes of redox-active tetraazamacrocycles.", "date": "2012-09-12", "date_type": "published", "publication": "Chemical Science", "volume": "4", "number": "1", "publisher": "Royal Society of Chemistry", "pagerange": "157-163", "id_number": "CaltechAUTHORS:20130103-150617672", "issn": "2041-6520", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130103-150617672", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Department of Energy (DOE)" }, { "agency": "NIH", "grant_number": "P41GM103393" }, { "agency": "NIH", "grant_number": "P41RR001209" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c2sc21231e", "pmcid": "PMC4300139", "primary_object": { "basename": "c2sc21231e.pdf", "url": "https://authors.library.caltech.edu/records/s33he-9b617/files/c2sc21231e.pdf" }, "related_objects": [ { "basename": "c2sc21231e.txt", "url": "https://authors.library.caltech.edu/records/s33he-9b617/files/c2sc21231e.txt" }, { "basename": "c2sc21231e_SI.pdf", "url": "https://authors.library.caltech.edu/records/s33he-9b617/files/c2sc21231e_SI.pdf" } ], "pub_year": "2012", "author_list": "Uyeda, Christopher and Peters, Jonas C." }, { "id": "https://authors.library.caltech.edu/records/kr91j-m9394", "eprint_id": 35226, "eprint_status": "archive", "datestamp": "2023-08-22 06:26:49", "lastmod": "2023-10-20 15:52:11", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Strandwitz-N-C", "name": { "family": "Strandwitz", "given": "Nicholas C." } }, { "id": "Turner-Evans-D-B", "name": { "family": "Turner-Evans", "given": "Daniel B." } }, { "id": "Tamboli-A-C", "name": { "family": "Tamboli", "given": "Adele C." } }, { "id": "Chen-Christopher-T", "name": { "family": "Chen", "given": "Christopher T." }, "orcid": "0000-0001-5848-961X" }, { "id": "Atwater-H-A", "name": { "family": "Atwater", "given": "Harry A." }, "orcid": "0000-0001-9435-0201" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Photoelectrochemical Behavior of Planar and Microwire-Array Si|GaP Electrodes", "ispublished": "pub", "full_text_status": "restricted", "keywords": "semiconductors; composites; electrodes; electro-optical materials", "note": "\u00a9 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Received: November 29, 2011.\nPublished online: June 15, 2012. We acknowledge the National Science Foundation (NSF) Center for Chemical Innovation (CHE-0802907) and DARPA for support. NCS\nacknowledges the NSF for an American Competitiveness in Chemistry\npostdoctoral fellowship (CHE-1042006). DBTE acknowledges the NSF\nfor a Graduate Research Fellowship. The authors acknowledge helpful\ndiscussions from Dr. Chengxiang Xiang and Prof. Shannon W. Boettcher.", "abstract": "Gallium phosphide exhibits a short diffusion length relative to its optical absorption length, and is thus a candidate for use in wire array geometries that allow light absorption to be decoupled from minority carrier collection. Herein is reported the photoanodic performance of heteroepitaxially grown gallium phosphide on planar and microwire-array Si substrates. The n-GaP|n-Si heterojunction results in a favorable conduction band alignment for electron collection in the silicon. A conformal electrochemical contact to the outer GaP layer is produced using the ferrocenium/ferrocene (Fc^+/Fc) redox couple in acetonitrile. Photovoltages of \u223c750 mV under 1 sun illumination are observed and are attributed to the barrier formed at the (Fc^+/Fc)|n-GaP junction. The short-circuit current densities of the composite microwire-arrays are similar to those observed using single-crystal n-GaP photoelectrodes. Spectral response measurements along with a finite-difference-time-domain optical model indicate that the minority carrier diffusion length in the GaP is \u223c80 nm. Solid-state current\u2013voltage measurements show that shunting occurs through thin GaP layers that are present near the base of the microwire-arrays. The results provide guidance for further studies of 3D multi-junction photoelectrochemical cells.", "date": "2012-09", "date_type": "published", "publication": "Advanced Energy Materials", "volume": "2", "number": "9", "publisher": "Wiley", "pagerange": "1109-1116", "id_number": "CaltechAUTHORS:20121101-091407028", "issn": "1614-6832", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20121101-091407028", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Defense Advanced Research Projects Agency (DARPA)" }, { "agency": "NSF American Competitiveness in Chemistry Postdoctoral Fellowship", "grant_number": "CHE-1042006" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1002/aenm.201100728", "pub_year": "2012", "author_list": "Strandwitz, Nicholas C.; Turner-Evans, Daniel B.; et el." }, { "id": "https://authors.library.caltech.edu/records/e550v-thq05", "eprint_id": 33959, "eprint_status": "archive", "datestamp": "2023-08-19 12:24:56", "lastmod": "2023-10-18 21:40:10", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Suess-D-L-M", "name": { "family": "Suess", "given": "Daniel L. M." } }, { "id": "Tsay-C", "name": { "family": "Tsay", "given": "Charlene" } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Dihydrogen Binding to Isostructural S = 1/2 and S = 0 Cobalt Complexes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. \n\nReceived: May 30, 2012. Publication Date (Web): August 14, 2012. \n\nWe thank the Gordon and Betty Moore Foundation and the NSF Center for Chemical Innovation on Solar Fuels (CCI Solar, CHE-0802907 and CHE-0947829) for funding. We thank Prof. George Rossman (solid-state Raman studies), Maraia Ener (solution-state Raman studies), and Lawrence Henling (X-ray crystallography) for experimental assistance.\n\nPublished - ja305248f.pdf
Supplemental Material - ja305248f_si_001.pdf
Supplemental Material - ja305248f_si_002.cif
", "abstract": "Two isostructural, nonclassical Co(H_2) complexes are prepared from their Co(N_2) precursors using tris(phosphino)silyl and tris(phosphino)borane ancillary ligands. Comproportionation of CoBr_2 and Co metal in the presence of TPB (tris-(o-diisopropylphophinophenyl)borane) gives (TPB)CoBr (4). One-electron reduction of 4 triggers N_2 binding to give (TPB)Co(N_2) (2-N_2) which is isostructural to previously reported [SiP_3]Co(N_2) (1-N_2) ([SiP_3] = tris-(o-diisopropylphosphinophenyl)silyl). Both 1-N_2 and 2-N_2 react with 1 atm H_2 to generate thermally stable H_2 complexes 1-H_2 and 2-H_2, respectively. Both complexes are characterized by a suite of spectroscopic techniques in solution and by X-ray crystallography. The H_2 and N_2 ligands in 2-H_2 and 2-N_2 are labile under ambient conditions and the binding equilibria are observable by temperature-dependent UV/vis. A van't Hoff analysis allows for the ligand binding energetics to be determined (H_2: \u0394H\u00ba = \u221212.5(3) kcal mol^(\u20131) and \u0394S\u00ba = \u221226(3) cal K^(\u20131) mol^(\u20131); N_2: \u0394H\u00ba = \u221213.9(7) kcal mol^(\u20131) and \u0394S\u00ba = \u221232(5) cal K^(\u20131) mol^(\u20131)).", "date": "2012-08-29", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "34", "publisher": "American Chemical Society", "pagerange": "14158-14164", "id_number": "CaltechAUTHORS:20120910-104427509", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120910-104427509", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja305248f", "primary_object": { "basename": "ja305248f_si_002.cif", "url": "https://authors.library.caltech.edu/records/e550v-thq05/files/ja305248f_si_002.cif" }, "related_objects": [ { "basename": "ja305248f.pdf", "url": "https://authors.library.caltech.edu/records/e550v-thq05/files/ja305248f.pdf" }, { "basename": "ja305248f_si_001.pdf", "url": "https://authors.library.caltech.edu/records/e550v-thq05/files/ja305248f_si_001.pdf" } ], "pub_year": "2012", "author_list": "Suess, Daniel L. M.; Tsay, Charlene; et el." }, { "id": "https://authors.library.caltech.edu/records/8cnvh-9a515", "eprint_id": 33960, "eprint_status": "archive", "datestamp": "2023-08-19 12:25:02", "lastmod": "2023-10-18 21:40:14", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Durrell-A-C", "name": { "family": "Durrell", "given": "Alec C." } }, { "id": "Keller-G-E", "name": { "family": "Keller", "given": "Gretchen E." } }, { "id": "Lam-Yan-Choi", "name": { "family": "Lam", "given": "Yan-Choi" }, "orcid": "0000-0001-7809-4471" }, { "id": "S\u00fdkora-J", "name": { "family": "S\u00fdkora", "given": "Jan" }, "orcid": "0000-0003-0936-9368" }, { "id": "Vl\u010dek-A-Jr", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn, Jr." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Structural Control of ^1A_(2u)-to-^3A_(2u) Intersystem Crossing in Diplatinum(II,II) Complexes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. Received: June 15, 2012. Publication Date (Web): August 6, 2012. We thank Renske van der Veen for interesting discussions. Research at Caltech was supported by the NSF Center for Chemical Innovation (Powering the Planet CHE-0802907 and CHE-0947829) and CSER (Gordon and Betty Moore Foundation). Work at the J. Heyrovsk\u00fd Institute was funded by the Czech Ministry of Education program KONTAKT\n(grant ME10124).\n\nPublished - ja305666b.pdf
Supplemental Material - ja305666b_si_001.pdf
", "abstract": "Analysis of variable-temperature fluorescence quantum yield and lifetime data for per(difluoroboro)tetrakis(pyrophosphito)diplatinate(II) ([Pt_2(\u03bc-P_2O_5(BF_2)_(2)4)]^(4\u2013), abbreviated Pt(pop-BF_2)), yields a radiative decay rate (k_r = 1.7 \u00d7 10^8 s^(\u20131)) an order of magnitude greater than that of the parent complex, Pt(pop). Its temperature-independent and activated intersystem crossing (ISC) pathways are at least 18 and 142 times slower than those of Pt(pop) [ISC activation energies: 2230 cm^(\u20131) for Pt(pop-BF_2); 1190 cm^(\u20131) for Pt(pop)]. The slowdown in the temperature-independent ISC channel is attributed to two factors: (1) reduced spin\u2013orbit coupling between the ^1A_(2u) state and the mediating triplet(s), owing to increases of LMCT energies relative to the excited singlet; and (2) diminished access to solvent, which for Pt(pop) facilitates dissipation of the excess energy into solvent vibrational modes. The dramatic increase in E_a is attributed to increased P-O-P framework rigidity, which impedes symmetry-lowering distortions, in particular asymmetric vibrations in the Pt_2(P-O-P)_4 core that would allow direct ^1A_(2u)\u2013^3A_(2u) spin\u2013orbit coupling.", "date": "2012-08-29", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "34", "publisher": "American Chemical Society", "pagerange": "14201-14207", "id_number": "CaltechAUTHORS:20120910-110255434", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120910-110255434", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Caltech Center for Sustainable Energy Research" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Ministry of Education (Czech Republic)", "grant_number": "ME10124" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja305666b", "primary_object": { "basename": "ja305666b.pdf", "url": "https://authors.library.caltech.edu/records/8cnvh-9a515/files/ja305666b.pdf" }, "related_objects": [ { "basename": "ja305666b_si_001.pdf", "url": "https://authors.library.caltech.edu/records/8cnvh-9a515/files/ja305666b_si_001.pdf" } ], "pub_year": "2012", "author_list": "Durrell, Alec C.; Keller, Gretchen E.; et el." }, { "id": "https://authors.library.caltech.edu/records/edg0a-g8p72", "eprint_id": 33552, "eprint_status": "archive", "datestamp": "2023-09-14 19:28:45", "lastmod": "2023-10-23 20:52:09", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Rose-M-J", "name": { "family": "Rose", "given": "Michael J." } }, { "id": "Bellone-D-E", "name": { "family": "Bellone", "given": "Donatela E." } }, { "id": "Di-Bilio-A-J", "name": { "family": "Di Bilio", "given": "Angel J." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Spectroscopic and magnetic properties of an iodo Co^I tripodal phosphine complex", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 Royal Society of Chemistry.\n\nReceived 7th June 2012, Accepted 31st July 2012.\nFirst published on the web 20 Aug 2012.\nWe thank Larry Henling and the late Michael Day for X-ray data collection and crystal structure refinement. We gratefully acknowledge Markus Ribbe (UC Irvine) for generous use of a dual mode EPR cavity. Our work was supported by the NSF CCI Solar Fuels program (CHE-0802907) and by CSER (Gordon and Betty Moore Foundation); MJR acknowledges an ACC-F postdoctoral fellowship from the NSF (CHE-1042009). DEB thanks the Rossum family for a SURF award. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094).\n\nPublished - c2dt31229h.pdf
Supplemental Material - c2dt31229h.txt
", "abstract": "Reaction of the tripodal phosphine ligand 1,1,1-tris((diphenylphosphino)phenyl)ethane (PhP3) with CoI_2 spontaneously generates a one-electron reduced complex, [(PhP3)Co^(I)(I)] (1). The crystal structure of 1 reveals a distorted tetrahedral environment, with an apical Co\u2013I bond distance of ~2.52 \u00c5. Co^(II/I) redox occurs at an unusually high potential (+0.38 V vs. SCE). The electronic absorption spectrum of 1 exhibits an MLCT peak at 320 nm (\u03b5 = 8790 M^(\u22121) cm^(\u22121)) and a d\u2013d feature at 850 nm (\u03b5 = 840 M^(\u22121) cm^(\u22121)). Two more d\u2013d bands are observed in the NIR region, 8650 (\u03b5 = 450) and 7950 cm\u22121 (\u03b5 = 430 M\u22121 cm^(\u22121)). Temperature dependent magnetic measurements (SQUID) on 1 (solid state, 20\u2013300 K) give \u03bc_eff = 2.99(6) \u03bcB, consistent with an S = 1 ground state. Magnetic susceptibilities below 20 K are consistent with a zero field splitting (zfs) |D| = 8 cm^(\u22121). DFT calculations also support a spin-triplet ground state for 1, as optimized (6-31G*/PW91) geometries (S = 1) closely match the X-ray structure. EPR measurements performed in parallel mode (X-band; 0\u201315 000 G, 15 K) on polycrystalline 1 or frozen solutions of 1 (THF/toluene) exhibit a feature at g \u2248 4 that arises from a (\u0394m = 2) transition within the MS = <+1,\u22121> manifold. Below 10 K, the EPR signal decreases significantly, consistent with a solution zfs parameter (|D| \u2248 8 cm^(\u22121)) similar to that obtained from SQUID measurements. Our work provides an EPR signature for high-spin Co^I in trigonal ligation.", "date": "2012-08-20", "date_type": "published", "publication": "Dalton Transactions", "volume": "41", "number": "38", "publisher": "Royal Society of Chemistry", "pagerange": "11788-11797", "id_number": "CaltechAUTHORS:20120827-095929289", "issn": "1477-9226", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120827-095929289", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF CCI Solar Fuels program", "grant_number": "CHE-0802907" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "NSF ACC-F postdoctoral fellowship", "grant_number": "CHE-1042009" }, { "agency": "Rossum family SURF award" }, { "agency": "NSF CRIF:MU award", "grant_number": "CHE-0639094" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c2dt31229h", "primary_object": { "basename": "c2dt31229h.pdf", "url": "https://authors.library.caltech.edu/records/edg0a-g8p72/files/c2dt31229h.pdf" }, "related_objects": [ { "basename": "c2dt31229h.txt", "url": "https://authors.library.caltech.edu/records/edg0a-g8p72/files/c2dt31229h.txt" } ], "pub_year": "2012", "author_list": "Rose, Michael J.; Bellone, Donatela E.; et el." }, { "id": "https://authors.library.caltech.edu/records/b6xkg-gby26", "eprint_id": 35105, "eprint_status": "archive", "datestamp": "2023-08-19 12:04:48", "lastmod": "2023-10-20 15:21:21", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Huang-Zhuangqun", "name": { "family": "Huang", "given": "Zhuangqun" } }, { "id": "Lin-Yongjing", "name": { "family": "Lin", "given": "Yongjing" } }, { "id": "Xiang-Xu", "name": { "family": "Xiang", "given": "Xu" } }, { "id": "Rodr\u00edguez-C\u00f3rdoba-W", "name": { "family": "Rodr\u00edguez-C\u00f3rdoba", "given": "William" } }, { "id": "McDonald-K-J", "name": { "family": "McDonald", "given": "Kenneth J." } }, { "id": "Hagen-K-S", "name": { "family": "Hagen", "given": "Karl S." } }, { "id": "Choi-Kyoung-Shin", "name": { "family": "Choi", "given": "Kyoung-Shin" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Musaev-D-G", "name": { "family": "Musaev", "given": "Djamaladdin G." }, "orcid": "0000-0003-1160-6131" }, { "id": "Hill-C-L", "name": { "family": "Hill", "given": "Craig L." } }, { "id": "Wang-Dunwei", "name": { "family": "Wang", "given": "Dunwei" } }, { "id": "Lian-Tianquan", "name": { "family": "Lian", "given": "Tianquan" } } ] }, "title": "In situ probe of photocarrier dynamics in water-splitting hematite (\u03b1-Fe_(2)O_3) electrodes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 Royal Society of Chemistry. \n\nReceived 27th June 2012, Accepted 9th August 2012. First published on the web 09 Aug 2012. \n\nDGM, CLH and TL acknowledge the support of the U.S. Department of Energy, Office of Basic Energy Sciences, Solar Photochemistry Program (DE-FG02-07ER-15906); financial support for BSB was provided by an NSF Center for Chemical Innovation (CHE-0802907) at Caltech. YJ and DW are supported by NSF through a CAREER Award (DMR-1055762). KJM and KSC acknowledge the support by the U.S. Department of Energy, Office of BasicEnergy Sciences, Solar Photochemistry Program (DE-FG02-05ER15752); steady-state Stark spectral data were collected at the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology. ZH is grateful to the productive discussion with the members of Lewis group.\n\nSupplemental Material - c2ee22681b.pdf
", "abstract": "The spectra and dynamics of photogenerated electrons and holes in excited hematite (\u03b1-Fe_(2)O_3) electrodes are investigated by transient absorption (from visible to infrared and from femto- to micro-seconds), bias-dependent differential absorption and Stark spectroscopy. Comparison of results from these techniques enables the assignment of the spectral signatures of photogenerated electrons and holes. Under the pulse illumination conditions of transient absorption (TA) measurement, the absorbed photon to electron conversion efficiency (APCE) of the films at 1.43 V (vs. reversible hydrogen electrode, RHE) is 0.69%, significantly lower than that at AM 1.5. TA kinetics shows that under these conditions, >98% of the photogenerated electrons and holes have recombined by 6 \u03bcs. Although APCE increases with more positive bias (from 0.90 to 1.43 V vs. RHE), the kinetics of holes up to 6 \u03bcs show negligible change, suggesting that the catalytic activity of the films is determined by holes with longer lifetimes.", "date": "2012-08-09", "date_type": "published", "publication": "Energy and Environmental Science", "volume": "5", "number": "10", "publisher": "Royal Society of Chemistry", "pagerange": "8923-8926", "id_number": "CaltechAUTHORS:20121025-155412662", "issn": "1754-5692", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20121025-155412662", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG02-07ER-15906" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "DMR-1055762" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG02-05ER15752" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c2ee22681b", "primary_object": { "basename": "c2ee22681b.pdf", "url": "https://authors.library.caltech.edu/records/b6xkg-gby26/files/c2ee22681b.pdf" }, "pub_year": "2012", "author_list": "Huang, Zhuangqun; Lin, Yongjing; et el." }, { "id": "https://authors.library.caltech.edu/records/7z7j6-m2m18", "eprint_id": 32334, "eprint_status": "archive", "datestamp": "2023-08-19 11:23:43", "lastmod": "2023-10-17 23:19:36", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hunter-B-M", "name": { "family": "Hunter", "given": "Bryan M." }, "orcid": "0000-0001-8559-9304" }, { "id": "Villahermosa-R-M", "name": { "family": "Villahermosa", "given": "Randy M." } }, { "id": "Exstrom-C-L", "name": { "family": "Exstrom", "given": "Christopher L." } }, { "id": "Hill-M-G", "name": { "family": "Hill", "given": "Michael G." } }, { "id": "Mann-K-R", "name": { "family": "Mann", "given": "Kent R." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "M\u2013M Bond-Stretching Energy Landscapes for M_2(dimen)_(4)^(2+) (M = Rh, Ir; dimen = 1,8-Diisocyanomenthane) Complexes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society.\n\nPublication Date (Web): May 23, 2012.\n\nWe thank Jay Winkler for helpful discussions. Our work was\nsupported by the NSF Center for Chemical Innovation (Grant\nCHE-0802907) and by the David & Lucille Packard\nFoundation Initiative for Interdisciplinary Research. B.M.H. is an NSF Graduate Fellow.\n\nSupplemental Material - ic300716q_si_001.pdf
", "abstract": "Isomers of Ir_2(dimen)_(4)^(2+) (dimen = 1,8-diisocyanomenthane) exhibit different Ir\u2013Ir bond distances in a 2:1 MTHF/EtCN solution (MTHF = 2-methyltetrahydrofuran). Variable-temperature absorption data suggest that the isomer with the shorter Ir\u2013Ir distance is favored at room temperature [K = ~8; \u0394H\u00b0 = \u22120.8 kcal/mol; \u0394S\u00b0 = 1.44 cal mol^(\u20131) K^(\u20131)]. We report calculations that shed light on M_2(dimen)_(4)^(2+) (M = Rh, Ir) structural differences: (1) metal\u2013metal interaction favors short distances; (2) ligand deformational-strain energy favors long distances; (3) out-of-plane (A_(2u)) distortion promotes twisting of the ligand backbone at short metal\u2013metal separations. Calculated potential-energy surfaces reveal a double minimum for Ir_2(dimen)_(4)^(2+) (4.1 \u00c5 Ir\u2013Ir with 0\u00b0 twist angle and ~3.6 \u00c5 Ir\u2013Ir with \u00b112\u00b0 twist angle) but not for the rhodium analogue (4.5 \u00c5 Rh\u2013Rh with no twisting). Because both the ligand strain and A_(2u) distortional energy are virtually identical for the two complexes, the strength of the metal\u2013metal interaction is the determining factor. On the basis of the magnitude of this interaction, we obtain the following results: (1) a single-minimum (along the Ir\u2013Ir coordinate), harmonic potential-energy surface for the triplet electronic excited state of Ir_2(dimen)_(4)^(2+) (R_(e,Ir\u2013Ir) = 2.87 \u00c5; F_(Ir\u2013Ir) = 0.99 mdyn \u00c5^(\u20131)); (2) a single-minimum, anharmonic surface for the ground state of Rh_2(dimen)_(4)^(2+) (R_(e,Rh\u2013Rh) = 3.23 \u00c5; F_(Rh\u2013Rh) = 0.09 mdyn \u00c5^(\u20131)); (3) a double-minimum (along the Ir\u2013Ir coordinate) surface for the ground state of Ir_2(dimen)_(4)^(2+) (R_(e,Ir\u2013Ir) = 3.23 \u00c5; F_(Ir\u2013Ir) = 0.16 mdyn \u00c5^(\u20131)).", "date": "2012-06-18", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "51", "number": "12", "publisher": "American Chemical Society", "pagerange": "6898-6905", "id_number": "CaltechAUTHORS:20120710-133619920", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120710-133619920", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "David and Lucile Packard Foundation" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ic300716q", "primary_object": { "basename": "ic300716q_si_001.pdf", "url": "https://authors.library.caltech.edu/records/7z7j6-m2m18/files/ic300716q_si_001.pdf" }, "pub_year": "2012", "author_list": "Hunter, Bryan M.; Villahermosa, Randy M.; et el." }, { "id": "https://authors.library.caltech.edu/records/h52ra-tt269", "eprint_id": 32012, "eprint_status": "archive", "datestamp": "2023-08-19 11:21:11", "lastmod": "2023-10-17 22:21:57", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Cho-Clara-J", "name": { "family": "Cho", "given": "Clara J." } }, { "id": "O'Leary-L-E", "name": { "family": "O'Leary", "given": "Leslie" } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Greer-J-R", "name": { "family": "Greer", "given": "Julia R." }, "orcid": "0000-0002-9675-1508" } ] }, "title": "In Situ Nanomechanical Measurements of Interfacial Strength in Membrane-Embedded Chemically Functionalized Si Microwires for Flexible Solar Cells", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society.\n\nReceived: April 14, 2012;\nRevised: May 9, 2012;\nPublished: May 21, 2012.\n\nC.J.C. gratefully acknowledges the financial support of the\nResnick Institute at Caltech through her graduate fellowship\nand E. Warren for help with wafer patterning. L.O'L. thanks the\nfinancial support of the Link Foundation Energy fellowship.\nN.S.L.'s portion of this work was supported by the National\nScience Foundation (NSF-CHE-0911682) and (NSF-CHE-0802907). J.R.G. is grateful to the Caltech's CI-2 Innovation\nGrant for supporting this work.\n\nSupplemental Material - nl3014007_si_001.pdf
Supplemental Material - nl3014007_si_002.mp4
Supplemental Material - nl3014007_si_003.mp4
", "abstract": "Arrays of vertically aligned Si microwires embedded in polydimethylsiloxane (PDMS) have emerged as a promising candidate for use in solar energy conversion devices. Such structures are lightweight and concurrently demonstrate competitive efficiency and mechanical flexibility. To ensure reliable functioning under bending and flexing, strong interfacial adhesion between the nanowire and the matrix is needed. In situ uniaxial tensile tests of individual, chemically functionalized, Si microwires embedded in a compliant PDMS matrix reveal that chemical functionality on Si microwire surfaces is directly correlated with interfacial adhesion strength. Chemical functionalization can therefore serve as an effective methodology for accessing a wide range of interfacial adhesion between the rigid constituents and the soft polymer matrix; the adhesion can be quantified by measuring the mechanical strength of such systems.", "date": "2012-06-13", "date_type": "published", "publication": "Nano Letters", "volume": "12", "number": "6", "publisher": "American Chemical Society", "pagerange": "3296-3301", "id_number": "CaltechAUTHORS:20120621-133116661", "issn": "1530-6984", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120621-133116661", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Resnick Institute" }, { "agency": "Link Foundation Energy fellowship" }, { "agency": "NSF", "grant_number": "CHE-0911682" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Caltech's CI-2 Innovation Grant" } ] }, "local_group": { "items": [ { "id": "Resnick-Sustainability-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/nl3014007", "primary_object": { "basename": "nl3014007_si_001.pdf", "url": "https://authors.library.caltech.edu/records/h52ra-tt269/files/nl3014007_si_001.pdf" }, "related_objects": [ { "basename": "nl3014007_si_002.mp4", "url": "https://authors.library.caltech.edu/records/h52ra-tt269/files/nl3014007_si_002.mp4" }, { "basename": "nl3014007_si_003.mp4", "url": "https://authors.library.caltech.edu/records/h52ra-tt269/files/nl3014007_si_003.mp4" } ], "pub_year": "2012", "author_list": "Cho, Clara J.; O'Leary, Leslie; et el." }, { "id": "https://authors.library.caltech.edu/records/7v061-xek39", "eprint_id": 31996, "eprint_status": "archive", "datestamp": "2023-08-19 11:01:34", "lastmod": "2023-10-17 21:45:53", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Rose-M-J", "name": { "family": "Rose", "given": "Michael J." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" } ] }, "title": "Hydrogen Generation Catalyzed by Fluorinated Diglyoxime\u2212Iron\n Complexes at Low Overpotentials", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. Received: January 17, 2012. Publication Date (Web): May 14, 2012. This work was supported by the NSF CCI Solar Fuels Program (CHE-0802907). M.J.R. was supported by an NSF ACC-F Fellowship (CHE-1042009). The Bruker APEXII diffractometer\nwas obtained via an NSF CRIF:MU Award (CHE-0639094). We thank Larry Henling and Michael Day for solving the crystal structures.\n\nSupplemental Material - ja300534r_si_001.pdf
Supplemental Material - ja300534r_si_002.cif
", "abstract": "Fe^(II) complexes containing the fluorinated ligand 1,2-bis(perfluorophenyl)ethane-1,2-dionedioxime (dAr^FgH_2; H = dissociable proton) exhibit relatively positive Fe^(II/I) reduction potentials. The air-stable difluoroborated species [(dAr^FgBF_2)_2Fe(py)_2] (2) electrocatalyzes H_2 generation at \u22120.9 V vs SCE with i_(cat)/i_p \u2248 4, corresponding to a turnover frequency (TOF) of ~ 20 s^(\u20131) [Faradaic yield (FY) = 82 \u00b1 13%]. The corresponding monofluoroborated, proton-bridged complex [(dArFg2H-BF2)Fe(py)2] (3) exhibits an improved TOF of ~ 200 s^(\u20131) (i_(cat)/i_p \u2248 8; FY = 68 \u00b1 14%) at \u22120.8 V with an overpotential of 300 mV. Simulations of the electrocatalytic cyclic voltammograms of 2 suggest rate-limiting protonation of an Fe\"0\" intermediate (k_(RLS) \u2248 200 M^(\u20131) s^(\u20131)) that undergoes hydride protonation to form H_2. Complex 3 likely reacts via protonation of an Fe^I intermediate that subsequently forms H_2 via a bimetallic mechanism (k_(RLS) \u2248 2000 M^(\u20131) s^(\u20131)). 3 catalyzes production at relatively positive potentials compared with other iron complexes.", "date": "2012-05-23", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "20", "publisher": "American Chemical Society", "pagerange": "8310-8313", "id_number": "CaltechAUTHORS:20120621-073446298", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120621-073446298", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF Postdoctoral Fellowship", "grant_number": "CHE-1042009" }, { "agency": "NSF", "grant_number": "CHE-0639094" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja300534r", "primary_object": { "basename": "ja300534r_si_001.pdf", "url": "https://authors.library.caltech.edu/records/7v061-xek39/files/ja300534r_si_001.pdf" }, "related_objects": [ { "basename": "ja300534r_si_002.cif", "url": "https://authors.library.caltech.edu/records/7v061-xek39/files/ja300534r_si_002.cif" } ], "pub_year": "2012", "author_list": "Rose, Michael J.; Gray, Harry B.; et el." }, { "id": "https://authors.library.caltech.edu/records/6xnxw-s3c84", "eprint_id": 31693, "eprint_status": "archive", "datestamp": "2023-08-19 10:54:53", "lastmod": "2023-10-17 18:46:57", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Tonks-I-A", "name": { "family": "Tonks", "given": "Ian A." } }, { "id": "Durrell-A-C", "name": { "family": "Durrell", "given": "Alec C." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." } } ] }, "title": "Groups 5 and 6 Terminal Hydrazido(2\u2212) Complexes: N_\u03b2 Substituent Effects on Ligand-to-Metal Charge-Transfer Energies and Oxidation States", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. Received: March 7, 2012. Publication Date (Web): April 16, 2012. We thank Lawrence Henling and Dr. Michael Day for assistance with the X-ray studies. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU Award (CHE-0639094) to the California Institute of Technology. This work was supported by the U.S. DOE Office of Basic Energy Sciences (DE-FG03-85ER13431 to J.E.B.). Photophysics investigations were supported by an NSF Center for Chemical Innovation Grant (CHE-0802907 to H.B.G.).\n\nSupplemental Material - ja302275j_si_001.pdf
Supplemental Material - ja302275j_si_002.cif
", "abstract": "Brightly colored terminal hydrazido(2\u2212) (dme)MCl_3(NNR_2) (dme = 1,2-dimethoxyethane; M = Nb, Ta; R = alkyl, aryl) or (MeCN)WCl_4(NNR_2) complexes have been synthesized and characterized. Perturbing the electronic environment of the \u03b2 (NR_2) nitrogen affects the energy of the lowest-energy charge-transfer (CT) transition in these complexes. For group 5 complexes, increasing the energy of the N_\u03b2 lone pair decreases the ligand-to-metal CT (LMCT) energy, except for electron-rich niobium dialkylhydrazides, which pyramidalize N_\u03b2 in order to reduce the overlap between the Nb\u2550N\u03b1 \u03c0 bond and the N\u03b2 lone pair. For W complexes, increasing the energy of N_\u03b2 eventually leads to reduction from formally [W^(VI)\u2261N\u2013NR_2] with a hydrazido(2\u2212) ligand to [W^(IV)\u2550N\u2550NR_2] with a neutral 1,1-diazene ligand. The photophysical properties of these complexes highlight the potential redox noninnocence of hydrazido ligands, which could lead to ligand- and/or metal-based redox chemistry in early transition metal derivatives.", "date": "2012-05-02", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "17", "publisher": "American Chemical Society", "pagerange": "7301-7304", "id_number": "CaltechAUTHORS:20120530-084227048", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120530-084227048", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF CRIF:MU Award", "grant_number": "CHE-0639094" }, { "agency": "Department of Energy (DOE) Office of Basic Energy Sciences", "grant_number": "DE-FG03-85ER13431" }, { "agency": "NSF Center for Chemical Innovation", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja302275j", "primary_object": { "basename": "ja302275j_si_001.pdf", "url": "https://authors.library.caltech.edu/records/6xnxw-s3c84/files/ja302275j_si_001.pdf" }, "related_objects": [ { "basename": "ja302275j_si_002.cif", "url": "https://authors.library.caltech.edu/records/6xnxw-s3c84/files/ja302275j_si_002.cif" } ], "pub_year": "2012", "author_list": "Tonks, Ian A.; Durrell, Alec C.; et el." }, { "id": "https://authors.library.caltech.edu/records/74hyr-d1q72", "eprint_id": 31601, "eprint_status": "archive", "datestamp": "2023-08-19 10:20:47", "lastmod": "2023-10-17 18:42:43", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Harman-W-H", "name": { "family": "Harman", "given": "W. Hill" } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Reversible H_2 Addition across a Nickel\u2212Borane Unit as a Promising Strategy for Catalysis", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. Received: December 6, 2011. Publication Date (Web): March 1, 2012. This work was supported by the NSF Center for Chemical Innovation: Powering the Planet grant CHE-0802907, and by the Gordon and Betty Moore Foundation. We thank Professor Greg Fu for a helpful suggestion.\n\nSupplemental Material - ja211419t_si_001.cif
Supplemental Material - ja211419t_si_002.pdf
", "abstract": "We report the synthesis and characterization of a series of nickel complexes of the chelating diphosphine-borane ligands ArB(o-Ph_2PC_6H_4)_2 ([^(Ar)DPB^(Ph)]; Ar = Ph, Mes). The [^(Ar)DPB^(Ph)] framework supports pseudo-tetrahedral nickel complexes featuring \u03b7^2-B,C coordination from the ligand backbone. For the B-phenyl derivative, the THF adduct [^(Ph)DPB^(Ph)]Ni(THF) has been characterized by X-ray diffraction and features a very short interaction between nickel and the \u03b7^2-B,C ligand. For the B-mesityl derivative, the reduced nickel complex [^(Mes)DPB^(Ph)]Ni is isolated as a pseudo-three-coordinate \"naked\" species that undergoes reversible, nearly thermoneutral oxidative addition of dihydrogen to give a borohydrido-hydride complex of nickel(II) which has been characterized in solution by multinuclear NMR. Furthermore, [^(Mes)DPB^(Ph)]Ni is an efficient catalyst for the hydrogenation of olefin substrates under mild conditions.", "date": "2012-03-21", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "11", "publisher": "American Chemical Society", "pagerange": "5080-5082", "id_number": "CaltechAUTHORS:20120523-074508665", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120523-074508665", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja211419t", "primary_object": { "basename": "ja211419t_si_001.cif", "url": "https://authors.library.caltech.edu/records/74hyr-d1q72/files/ja211419t_si_001.cif" }, "related_objects": [ { "basename": "ja211419t_si_002.pdf", "url": "https://authors.library.caltech.edu/records/74hyr-d1q72/files/ja211419t_si_002.pdf" } ], "pub_year": "2012", "author_list": "Harman, W. Hill and Peters, Jonas C." }, { "id": "https://authors.library.caltech.edu/records/n3r88-4dt19", "eprint_id": 30235, "eprint_status": "archive", "datestamp": "2023-08-19 10:00:23", "lastmod": "2023-10-17 15:34:40", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Rose-M-J", "name": { "family": "Rose", "given": "Michael J." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Fe_4 Cluster and a Buckled Macrocycle Complex from the Reduction of [(dmgBF_2)_(2)Fe(L)_2] (L = MeCN, ^(t)Bu^(i)NC)", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society.\n\nReceived: October 19, 2011; Published: February 9, 2012.\n\nThe authors thank Larry Henling and Michael Day for X-ray\nstructures and Angelo Di Bilio for assistance with EPR spectra.\nWe acknowledge Allen Oliver (University of Notre Dame) and\nJeannette Krause (University of Cincinati) for X-ray data\ncollection on 3 via the SCrALS program at Beamline 11.3.1,\nAdvanced Light Source (LBNL), supported by the U.S. DOE,\nEnergy Material Sciences Division. The Bruker KAPPA APEX\nII was purchased via an NSF CRIF:MU. The authors thank\nNicole Fry for obtaining magnetic susceptibility data on 4.\nFunding sources: NSF Grant CHE-0802907 (to M.J.R., J.R.W.,\nand H.B.G.); NSF Grant CHE-1042009 (to M.J.R.); Grant\nDOE-AC02-05CH11231 (synchrotron X-ray structure); NSF\nGrant CHE-0639094 (Mo K\u03b1 X-ray structures).\n\nSupplemental Material - ic202253v_si_001.pdf
Supplemental Material - ic202253v_si_002.cif
", "abstract": "We report the syntheses, X-ray structures, and reductive electrochemistry of the Fe^(II) complexes [(dmgBF_2)_(2)Fe(MeCN)_2] (1; dmg = dimethylglyoxime, MeCN = acetonitrile) and [(dmgBF_2)Fe(^(t)Bu^(i)NC)_2] (2; ^(t)Bu^(i)NC = tert-butylisocyanide). The reaction of 1 with Na/Hg amalgam led to isolation and the X-ray structure of [(dmgBF_2)_(2)Fe(glyIm)] (3; glyIm = glyimine), wherein the (dmgBF_2)_2 macrocyclic frame is bent to accommodate the binding of a bidentate apical ligand. We also report the X-ray structure of a rare mixed-valence Fe4 cluster with supporting dmg-type ligands. In the structure of [(dmg_(2)BF_2)_(3)Fe_3(1/2dmg)_(3)Fe(O)_6] (4), the (dmgBF_(2))_2 macrocycle has been cleaved, eliminating BF_2 groups. Density functional theory calculations and electron paramagnetic resonance data are in accordance with a central FeIII ion surrounded by three formally Fe^(II)dmg_(2)BF_2 units.", "date": "2012-02-20", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "51", "number": "4", "publisher": "American Chemical Society", "pagerange": "1980-1982", "id_number": "CaltechAUTHORS:20120420-132701817", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120420-132701817", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF Postdoctoral Fellowship", "grant_number": "CHE-1042009" }, { "agency": "Department of Energy (DOE)", "grant_number": "DOE-AC02-05CH11231" }, { "agency": "NSF", "grant_number": "CHE-0639094" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ic202253v", "primary_object": { "basename": "ic202253v_si_001.pdf", "url": "https://authors.library.caltech.edu/records/n3r88-4dt19/files/ic202253v_si_001.pdf" }, "related_objects": [ { "basename": "ic202253v_si_002.cif", "url": "https://authors.library.caltech.edu/records/n3r88-4dt19/files/ic202253v_si_002.cif" } ], "pub_year": "2012", "author_list": "Rose, Michael J.; Winkler, Jay R.; et el." }, { "id": "https://authors.library.caltech.edu/records/4h5wz-9rc23", "eprint_id": 30135, "eprint_status": "archive", "datestamp": "2023-08-19 09:57:26", "lastmod": "2023-10-17 15:24:15", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "McCrory-C-C-L", "name": { "family": "McCrory", "given": "Charles C. L." }, "orcid": "0000-0001-9039-7192" }, { "id": "Uyeda-Christopher", "name": { "family": "Uyeda", "given": "Christopher" }, "orcid": "0000-0001-9396-915X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Electrocatalytic Hydrogen Evolution in Acidic Water with Molecular Cobalt Tetraazamacrocycles", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society.\n\nPublished In Issue February 15, 2012; Article ASAP February 06, 2012; Just Accepted Manuscript January 12, 2012; Received: November 12, 2011.\n\nFinancial support for this work was provided by an NSF Center for Chemical Innovation (CHE-0802907).\n\nSupplemental Material - ja210661k_si_001.pdf
Supplemental Material - ja210661k_si_002.cif
", "abstract": "A series of water-soluble molecular cobalt complexes of tetraazamacrocyclic ligands are reported for the electrocatalytic production of H2 from pH 2.2 aqueous solutions. The comparative data reported for this family of complexes shed light on their relative efficiencies for hydrogen evolution in water. Rotating disk electrode voltammetry data are presented for each of the complexes discussed, as are data concerning their respective pH-dependent electrocatalytic activity. In particular, two diimine\u2013dioxime complexes were identified as exhibiting catalytic onset at comparatively low overpotentials relative to other reported homogeneous cobalt and nickel electrocatalysts in aqueous solution. These complexes are stable at pH 2.2 and produce hydrogen with high Faradaic efficiency in bulk electrolysis experiments over time intervals ranging from 2 to 24 h.", "date": "2012-02-15", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "4", "publisher": "American Chemical Society", "pagerange": "3164-3170", "id_number": "CaltechAUTHORS:20120417-113331818", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120417-113331818", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja210661k", "primary_object": { "basename": "ja210661k_si_001.pdf", "url": "https://authors.library.caltech.edu/records/4h5wz-9rc23/files/ja210661k_si_001.pdf" }, "related_objects": [ { "basename": "ja210661k_si_002.cif", "url": "https://authors.library.caltech.edu/records/4h5wz-9rc23/files/ja210661k_si_002.cif" } ], "pub_year": "2012", "author_list": "McCrory, Charles C. L.; Uyeda, Christopher; et el." }, { "id": "https://authors.library.caltech.edu/records/g8d20-k7103", "eprint_id": 29496, "eprint_status": "archive", "datestamp": "2023-08-19 09:45:18", "lastmod": "2023-10-24 22:15:11", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Mi-Qixi", "name": { "family": "Mi", "given": "Qixi" } }, { "id": "Zhanaidarova-A", "name": { "family": "Zhanaidarova", "given": "Almagul" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "A quantitative assessment of the competition between water and anion oxidation at WO_3 photoanodes in acidic aqueous electrolytes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 The Royal Society of Chemistry. \n\nReceived 19th October 2011, Accepted 7th December 2011. First published on the web 03 Jan 2012. \n\nWe acknowledge the National Science Foundation (NSF) Powering the Planet Center for Chemical Innovation (CCI-Solar), Grants CHE-0802907 and CHE-0947829, and the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology, for support. QM also acknowledges the NSF for support as a CCI-Solar Postdoctoral Fellow.\n\nPublished - Mi2012p17291Energ_Environ_Sci.pdf
", "abstract": "The faradaic efficiency for O_2(g) evolution at thin-film WO_3 photoanodes has been evaluated in a series of acidic aqueous electrolytes. In 1.0 M H_2SO_4, persulfate was the predominant photoelectrochemical oxidation product, and no O_2 was detected unless catalytic quantities of Ag^+(aq) were added to the electrolyte. In contact with 1.0 M HClO_4, dissolved O_2 was observed with nearly unity faradaic efficiency, but addition of a hole scavenger, 4-cyanopyridine N-oxide, completely suppressed O_2 formation. In 1.0 M HCl, Cl_2(g) was the primary oxidation product. These results indicate that at WO_3 photoanodes, water oxidation is dominated by oxidation of the acid anions in 1.0 M HCl, H_2SO_4, and HClO_4, respectively.", "date": "2012-02", "date_type": "published", "publication": "Energy and Environmental Science", "volume": "5", "number": "2", "publisher": "Royal Society of Chemistry", "pagerange": "5694-5700", "id_number": "CaltechAUTHORS:20120228-074506627", "issn": "1754-5692", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120228-074506627", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Caltech Beckman Institute" }, { "agency": "NSF Postdoctoral Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c2ee02929d", "primary_object": { "basename": "Mi2012p17291Energ_Environ_Sci.pdf", "url": "https://authors.library.caltech.edu/records/g8d20-k7103/files/Mi2012p17291Energ_Environ_Sci.pdf" }, "pub_year": "2012", "author_list": "Mi, Qixi; Zhanaidarova, Almagul; et el." }, { "id": "https://authors.library.caltech.edu/records/avpj4-yhc78", "eprint_id": 28696, "eprint_status": "archive", "datestamp": "2023-08-19 08:40:21", "lastmod": "2023-10-24 18:05:25", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Stubbert-B-D", "name": { "family": "Stubbert", "given": "Bryand D." } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Rapid Water Reduction to H_2 Catalyzed by a Cobalt Bis(iminopyridine) Complex", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 American Chemical Society. Received: August 17, 2011. Publication Date (Web): October 24, 2011. We thank Charles C. L. McCrory, Christopher Uyeda, and\nJames R. McKone for helpful discussions. Our work was supported by the NSF Center for Chemical Innovation on Solar\nFuels (CCI Solar, CHE-0802907 and CHE-0947829) and the\nStanford Global Climate and Energy Project (GCEP).\n\nSupplemental Material - ja2078015_si_001.pdf
", "abstract": "A cobalt bis(iminopyridine) complex is a highly active electrocatalyst for water reduction, with an estimated apparent second order rate constant k_(app) \u2264 10^7 M^(\u20131)s^(\u20131) over a range of buffer/salt concentrations. Scan rate dependence data are consistent with freely diffusing electroactive species over pH 4\u20139 at room temperature for each of two catalytic reduction events, one of which is believed to be ligand based. Faradaic H_2 yields up to 87 \u00b1 10% measured in constant potential electrolyses (\u22121.4 V vs SCE) confirm high reactivity and high fidelity in a catalyst supported by the noninnocent bis(iminopyridine) ligand. A mechanism involving initial reduction of Co^(2+) and subsequent protonation is proposed.", "date": "2011-11-16", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "133", "number": "45", "publisher": "American Chemical Society", "pagerange": "18070-18073", "id_number": "CaltechAUTHORS:20120106-104425949", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120106-104425949", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Stanford Global Climate and Energy Project (GCEP)" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja2078015", "primary_object": { "basename": "ja2078015_si_001.pdf", "url": "https://authors.library.caltech.edu/records/avpj4-yhc78/files/ja2078015_si_001.pdf" }, "pub_year": "2011", "author_list": "Stubbert, Bryand D.; Peters, Jonas C.; et el." }, { "id": "https://authors.library.caltech.edu/records/basby-n5s93", "eprint_id": 28446, "eprint_status": "archive", "datestamp": "2023-08-19 08:38:59", "lastmod": "2023-10-24 17:54:21", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Coe-B-J", "name": { "family": "Coe", "given": "Benjamin J." }, "orcid": "0000-0002-5998-3895" }, { "id": "Fielden-J", "name": { "family": "Fielden", "given": "John" }, "orcid": "0000-0001-5963-7792" }, { "id": "Foxon-S-P", "name": { "family": "Foxon", "given": "Simon P." } }, { "id": "Asselberghs-I", "name": { "family": "Asselberghs", "given": "Inge" } }, { "id": "Clays-K", "name": { "family": "Clays", "given": "Koen" } }, { "id": "Van-Cleuvenbergen-S", "name": { "family": "Van Cleuvenbergen", "given": "Stjn" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" } ] }, "title": "Ferrocenyl Diquat Derivatives: Nonlinear Optical Activity, Multiple Redox States, and Unusual Reactivity", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 American Chemical Society. \n\nReceived: July 8, 2011. Published: October 12, 2011. \n\nWe thank the EPSRC for support (grants EP/E000738 and EP/D070732) and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08), the University of Leuven (GOA/2006/3), and the NSF (grant CHE-0802907, \"Powering the Planet: an NSF Center for Chemical Innovation\"). I.A. is a postdoctoral fellow of the FWO-V. We thank Ayele Teshome of the University of Leuven for technical assistance with the HRS measurements, and Dr Simon Teat of the Advanced Light Source at the University of California Berkeley for collecting the X-ray data for [6][PF6][OTf].\n\nSupplemental Material - om200604f_si_001.pdf
Supplemental Material - om200604f_si_002.cif
", "abstract": "Four new dipolar cations have been synthesized, containing ferrocenyl electron donor groups and diquaternized 2,2\u2032-bipyridyl (diquat) acceptors. To our knowledge, these are the first organometallic diquat derivatives to be reported and have been characterized as their PF_6^\u2013 salts by using various techniques including ^1H NMR and electronic absorption spectroscopies and cyclic voltammetry. UV\u2013vis spectra show multiple intramolecular charge-transfer bands, and three reversible redox processes are observed for each compound. Molecular quadratic nonlinear optical (NLO) responses have been determined by using hyper-Rayleigh scattering at 1064 nm and Stark (electroabsorption) spectroscopic studies on the intense \u03c0\u2192 \u03c0^* intraligand and d \u2192 \u03c0^* metal-to-ligand charge-transfer bands. The most active compounds have estimated, Stark-derived \u03b20 values approaching that of the chromophore in the technologically important material (E)-4\u2032-(dimethylamino)-N-methyl-4-stilbazolium tosylate. Single-crystal X-ray structures have been obtained for three of the salts, with one adopting the orthorhombic space group Aba2 and having potential for bulk NLO behavior due to its polar structure. Attempted crystallizations of the remaining chromophore revealed that it undergoes an unusual intermolecular formal Michael cycloaddition between an activated methyl group and a double bond, forming a dimeric species. This diastereomeric cyclic complex has also been characterized via single-crystal X-ray diffraction.", "date": "2011-11-14", "date_type": "published", "publication": "Organometallics", "volume": "30", "number": "21", "publisher": "American Chemical Society", "pagerange": "5731-5743", "id_number": "CaltechAUTHORS:20111213-110615737", "issn": "0276-7333", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20111213-110615737", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/E000738" }, { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/D070732" }, { "agency": "Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)", "grant_number": "G.0312.08" }, { "agency": "University of Leuven", "grant_number": "GOA/2006/3" }, { "agency": "NSF", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/om200604f", "primary_object": { "basename": "om200604f_si_001.pdf", "url": "https://authors.library.caltech.edu/records/basby-n5s93/files/om200604f_si_001.pdf" }, "related_objects": [ { "basename": "om200604f_si_002.cif", "url": "https://authors.library.caltech.edu/records/basby-n5s93/files/om200604f_si_002.cif" } ], "pub_year": "2011", "author_list": "Coe, Benjamin J.; Fielden, John; et el." }, { "id": "https://authors.library.caltech.edu/records/12tr3-vdm54", "eprint_id": 28794, "eprint_status": "archive", "datestamp": "2023-08-19 08:31:49", "lastmod": "2023-10-24 18:09:39", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Winkler-G-R", "name": { "family": "Winkler", "given": "Gates R." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" } ] }, "title": "A light emitting diode based photoelectrochemical screener for distributed combinatorial materials discovery", "ispublished": "pub", "full_text_status": "public", "keywords": "light emitting diodes, radiation effects, solar cell arrays", "note": "\u00a9 2011 American Institute of Physics. Received 20 July 2011; accepted 6 October 2011; published online 2 November 2011. We thank Claire Drolen for preparation of the iron oxide test plate. This research was supported by the Caltech Center for Sustainable Energy Research (Gordon and Betty Moore Foundation) and the National Science Foundation Center for Chemical Innovation in Solar Fuels (CHE 0802907).\n\nPublished - Winkler2011p16753Rev_Sci_Instrum.pdf
", "abstract": "Combinatorial approaches for targeted discovery of new materials require rapid screening systems to evaluate large numbers of new material compositions. High-throughput combinatorial materials discovery is a capital-intensive undertaking requiring sophisticated robotic sample preparation and rapid screening assays. A distributed approach to combinatorial materials discovery can achieve similar goals by increasing the breadth of participation and reducing the size of the capital investment. The discovery of new photoactive materials for solar fuels production demands a screening device to probe materials for electrochemical current production upon irradiation with visible light. We have developed a system that uses an array of pulsed light-emitting diodes (LEDs) synchronized with a two-electrode potentiostat that can measure the photoelectrochemical responses of combinatorial sample arrays deposited on conducting glass plates. Compared to raster scanning methods, this LED system trades spatial resolution for a substantial reduction in scan time.", "date": "2011-11", "date_type": "published", "publication": "Review of Scientific Instruments", "volume": "82", "number": "11", "publisher": "American Institute of Physics", "pagerange": "Art. No. 114101", "id_number": "CaltechAUTHORS:20120113-131251359", "issn": "0034-6748", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120113-131251359", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Caltech Center for Sustainable Energy Research (CCSER)" }, { "agency": "NSF", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1063/1.3657155", "primary_object": { "basename": "Winkler2011p16753Rev_Sci_Instrum.pdf", "url": "https://authors.library.caltech.edu/records/12tr3-vdm54/files/Winkler2011p16753Rev_Sci_Instrum.pdf" }, "pub_year": "2011", "author_list": "Winkler, Gates R. and Winkler, Jay R." }, { "id": "https://authors.library.caltech.edu/records/10bjc-86783", "eprint_id": 25353, "eprint_status": "archive", "datestamp": "2023-08-19 08:28:02", "lastmod": "2023-10-24 15:48:54", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dempsey-J-L", "name": { "family": "Dempsey", "given": "Jillian L." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Redox reactivity of photogenerated osmium(II) complexes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 The Royal Society of Chemistry. Received 16th June 2011, Accepted 8th August 2011. \nFirst published on the web 02 September 2011. This research was supported by an NSF Center for Chemical Innovation (CHE-0802907), the Arnold and Mabel Beckman Foundation, and CCSER (Gordon and Betty Moore Foundation).\n\nPublished - c1dt11138h_1_.pdf
Supplemental Material - c1dt11138h_supp.pdf
", "abstract": "Powerful reductants [Os^(II)(NH_3)_5(L]^(2+) (L = OH_ 2, CH_3, CN can be generated upon ultraviolet excitation of relatively inert [Os^(II)(NH_3)_5(N_2)]^(2+) in aqueous and acetonitrile solutions. Reactions of photogenerated Os(II) complexes with methyl viologen to form methyl viologen radical cation and [Os^(III)(NH_3)_5L]^(3+) were monitored by transient absorption spectroscopy. Rate constants range from 4.9 \u00d7 10^4 M^(\u22121) s^(\u22121) in acetonitrile solution to 3.2 \u00d7 10^7 (pH 3) and 2.5 \u00d7 10^8 M^(\u22121) s^(\u22121) (pH 12) in aqueous media. Photogeneration of five-coordinate Os(II) complexes opens the way for mechanistic investigations of activation/reduction of CO_2 and other relatively inert molecules.", "date": "2011-10-28", "date_type": "published", "publication": "Dalton Transactions", "volume": "2011", "number": "40", "publisher": "Royal Society of Chemistry", "pagerange": "10633-10636", "id_number": "CaltechAUTHORS:20110916-103243483", "issn": "1477-9226", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110916-103243483", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Caltech Center for Sustainable Energy Research" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/C1DT11138H", "primary_object": { "basename": "c1dt11138h_1_.pdf", "url": "https://authors.library.caltech.edu/records/10bjc-86783/files/c1dt11138h_1_.pdf" }, "related_objects": [ { "basename": "c1dt11138h_supp.pdf", "url": "https://authors.library.caltech.edu/records/10bjc-86783/files/c1dt11138h_supp.pdf" } ], "pub_year": "2011", "author_list": "Dempsey, Jillian L.; Winkler, Jay R.; et el." }, { "id": "https://authors.library.caltech.edu/records/ph4t6-4yp83", "eprint_id": 27791, "eprint_status": "archive", "datestamp": "2023-08-19 08:23:32", "lastmod": "2023-10-24 17:25:36", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dong-Q", "name": { "family": "Dong", "given": "Qingchen" } }, { "id": "Rose-M-J", "name": { "family": "Rose", "given": "Michael J." } }, { "id": "Wong-W-Y", "name": { "family": "Wong", "given": "Wai-Yeung" } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Dual Coordination Modes of Ethylene-Linked NP2 Ligands in Cobalt(II) and Nickel(II) Iodides", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 American Chemical Society. Received: June 7, 2011. Publication Date (Web): September 13, 2011. This work was supported by the NSF CCI Solar Fuels Research Program (CHE-0802907). M.J.R. also received support from an NSF ACC-F postdoctoral fellowship (NSF CHE-1042009). W.Y.W. and Q.C.D. thank the Hong Kong Research Grants Council (HKBU202508), the University Grants Committee of HKSAR, China (Project No. [AoE/P-03/08]) and Hong Kong Baptist University for support. We thank Drs. Larry Henling and Michael Day for assistance in solving crystal structures, and Dr. Angelo Di Bilio for assistance in recording EPR spectra. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094).\n\nSupplemental Material - ic201213c_si_001.pdf
Supplemental Material - ic201213c_si_002.cif
", "abstract": "Here we report the syntheses and crystal structures of a series of cobalt(II) and nickel(II) complexes derived from _RNP2 ligands (where R = OMe_(Bz), H_(Bz), Br_(Bz), Ph) bearing ethylene linkers between a single N and two P donors. The Co^(II) complexes generally adopt a tetrahedral configuration of general formula [(NP2)Co(I)_2], wherein the two phosphorus donors are bound to the metal center but the central N-donor remains unbound. We have found one case of structural isomerism within a single crystal structure. The Co^(II) complex derived from _(Bz)NP2 displays dual coordination modes: one in the tetrahedral complex [(_(Bz)NP2)Co(I)_2]; and the other in a square pyramidal variant, [(_(Bz)NP2)Co(I)_2]. In contrast, the Ni^(II) complexes adopt a square planar geometry in which the P(Et)N(Et)P donors in the ligand backbone are coordinated to the metal center, resulting in cationic species of formula [(_RNP2)Ni(I)]^+ with iodide as counterion. All Ni^(II) complexes exhibit sharp ^1H and ^(31)P spectra in the diamagnetic region. The Co^(II) complexes are high-spin (S = 3/2) in the solid state as determined by SQUID measurements from 4 to 300 K. Solution electron paramagnetic resonance (EPR) experiments reveal a high-spin/low-spin Co^(II) equilibrium that is dependent on solvent and ligand substituent.", "date": "2011-10-17", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "50", "number": "20", "publisher": "American Chemical Society", "pagerange": "10213-10224", "id_number": "CaltechAUTHORS:20111115-152532868", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20111115-152532868", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF CCI Solar Fuels Research Program", "grant_number": "CHE-0802907" }, { "agency": "NSF ACC-F postdoctoral fellowship", "grant_number": "CHE-1042009" }, { "agency": "Hong Kong Research", "grant_number": "HKBU202508" }, { "agency": "University Grants Committee of HKSAR, China", "grant_number": "AoE/P-03/08" }, { "agency": "Hong Kong Baptist University" }, { "agency": "NSF CRIF", "grant_number": "CHE-0639094" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ic201213c", "primary_object": { "basename": "ic201213c_si_001.pdf", "url": "https://authors.library.caltech.edu/records/ph4t6-4yp83/files/ic201213c_si_001.pdf" }, "related_objects": [ { "basename": "ic201213c_si_002.cif", "url": "https://authors.library.caltech.edu/records/ph4t6-4yp83/files/ic201213c_si_002.cif" } ], "pub_year": "2011", "author_list": "Dong, Qingchen; Rose, Michael J.; et el." }, { "id": "https://authors.library.caltech.edu/records/qx9jj-2x527", "eprint_id": 27792, "eprint_status": "archive", "datestamp": "2023-08-19 08:23:40", "lastmod": "2023-10-24 17:25:42", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Eisenberg-R", "name": { "family": "Eisenberg", "given": "Richard" } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Noninnocence in Metal Complexes: A Dithiolene Dawn", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2011 American Chemical Society. Received: May 31, 2011. Publication Date (Web): September 13, 2011. We dedicate this Forum contribution to the memory of our dear friend, Ed Stiefel, who made deep and lasting contributions to our story of dithiolene noninnocence. We are enormously grateful to the National Science Foundation for steadfast support of our work in the 1960s. We are still working with the NSF, now as PI (H.B.G.) and advisor (R.E.) in the CCI Solar Fuels Program (CHE-0802907).", "abstract": "Noninnocence in inorganic chemistry traces its roots back half a century to work that was done on metal complexes containing unsaturated dithiolate ligands. In a flurry of activity in the early 1960s by three different research groups, homoleptic bis and tris complexes of these ligands, which came to be known as dithiolenes, were synthesized, and their structural, electrochemical, spectroscopic, and magnetic properties were investigated. The complexes were notable for facile one-electron transfers and intense colors in solution, and conventional oxidation-state descriptions could not account for their electronic structures. The bis complexes were, in general, found to be square-planar, including the first examples of this geometry for paramagnetic complexes and different formal dn configurations. Several of the neutral and monoanionic tris complexes were found to have trigonal-prismatic coordination, the first time that this geometry had been observed in molecular metal complexes. Electronic structural calculations employing extended H\u00fcckel and other semiempirical computational methods revealed extensive ligand\u2013metal mixing in the frontier orbitals of these systems, including the observation of structures in which filled metal-based orbitals were more stable than ligand-based orbitals of the same type, suggesting that the one-electron changes upon oxidation or reduction were occurring on the ligand rather than on the metal center. A summary of this early work is followed with a brief section on the current interpretations of these systems based on more advanced spectroscopic and computational methods. The take home message is that the early work did indeed provide a solid foundation for what was to follow in investigations of metal complexes containing redox-active ligands.", "date": "2011-10-17", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "50", "number": "20", "publisher": "American Chemical Society", "pagerange": "9741-9751", "id_number": "CaltechAUTHORS:20111116-071608250", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20111116-071608250", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "NSF CCI Solar Fuels Program", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ic2011748", "pub_year": "2011", "author_list": "Eisenberg, Richard and Gray, Harry B." }, { "id": "https://authors.library.caltech.edu/records/vkq8f-2tp33", "eprint_id": 34821, "eprint_status": "archive", "datestamp": "2023-08-22 03:55:02", "lastmod": "2024-01-13 05:55:55", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Electronic Structures of Oxo-Metal Ions", "ispublished": "unpub", "full_text_status": "restricted", "keywords": "Ferryl; Ligand field theory; Oxo wall; Vanadyl", "note": "\u00a9 2011 Springer-Verlag Berlin Heidelberg. Published online: 6 October 2011.\nWe dedicate this paper to the memory of Carl Ballhausen, a great scientist\nand a dear friend (Fig. 5). We note in closing that the B&G model is providing a firm foundation for structure/reactivity correlations in our current work on oxo-metal complexes [oxidative enzymes P450 and nitric oxide synthase (NIH DK019038, GM068461): water oxidation catalysts (NSF CCI Solar Program, CHE-0947829): and trans-dioxo osmium(VI) electrochemistry and\nphotochemistry (BP)]. We thank the Gordon and Betty Moore Foundation and the Arnold and Mabel Beckman Foundation for support of our research programs.", "abstract": "The dianionic oxo ligand occupies a very special place in coordination\nchemistry, owing to its ability to donate \u03c0 electrons to stabilize high oxidation states\nof metals. The ligand field theory of multiple bonding in oxo-metal ions, which was\nformulated in Copenhagen 50 years ago, predicts that there must be an \"oxo wall\"\nbetween Fe-Ru-Os and Co-Rh-Ir in the periodic table. In this tribute to Carl\nBallhausen, we review this early work as well as new developments in the field.\nIn particular, we discuss the electronic structures of beyond-the-wall (groups 9 and\n10) complexes containing metals multiply bonded to O- and N-donor ligands.", "date": "2011-10-06", "date_type": "published", "publisher": "Springer", "place_of_pub": "New York", "pagerange": "17-28", "id_number": "CaltechAUTHORS:20121010-111127266", "isbn": "9783642273704", "book_title": "Molecular Eectronic Sructures of Tansition Metal Complexes I", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20121010-111127266", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "DK019038" }, { "agency": "NIH", "grant_number": "GM068461" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "contributors": { "items": [ { "id": "Mingos-D-M-P", "name": { "family": "Mingos", "given": "D. M. P." } }, { "id": "Day-P", "name": { "family": "Day", "given": "P." } }, { "id": "Dahl-J-P", "name": { "family": "Dahl", "given": "Jens Peder" } } ] }, "doi": "10.1007/430_2011_55", "pub_year": "2011", "author_list": "Winkler, Jay R. and Gray, Harry B." }, { "id": "https://authors.library.caltech.edu/records/gvbez-y4017", "eprint_id": 25490, "eprint_status": "archive", "datestamp": "2023-08-19 07:52:06", "lastmod": "2023-10-24 15:54:52", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "McKone-J-R", "name": { "family": "McKone", "given": "James R." }, "orcid": "0000-0001-6445-7884" }, { "id": "Warren-E-L", "name": { "family": "Warren", "given": "Emily L." }, "orcid": "0000-0001-8568-7881" }, { "id": "Bierman-M-J", "name": { "family": "Bierman", "given": "Matthew J." } }, { "id": "Boettcher-S-W", "name": { "family": "Boettcher", "given": "Shannon W." }, "orcid": "0000-0001-8971-9123" }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Evaluation of Pt, Ni, and Ni\u2013Mo electrocatalysts for hydrogen evolution on crystalline Si electrodes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 The Royal Society of Chemistry. \n\nReceived 19 Apr 2011, Accepted 22 Jun 2011. First published on the web 01 Aug 2011. \n\nThis work was supported by the National Science Foundation (NSF) Powering the Planet Center for Chemical Innovation (CCI), Grants CHE-0802907 and CHE-0947829, and by the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology. The authors would like to acknowledge Joseph Beardslee for assistance with XPS analysis. JRM would like to thank the Department of Energy, Office of Science, for a graduate research fellowship. SWB gratefully acknowledges fellowship support from the Kavli Nanoscience Institute.\n\nPublished - McKone2011p15897Energ_Environ_Sci.pdf
Supplemental Material - c1ee01488a.pdf
", "abstract": "The dark electrocatalytic and light photocathodic hydrogen evolution properties of Ni, Ni\u2013Mo alloys, and Pt on Si electrodes have been measured, to assess the viability of earth-abundant electrocatalysts for integrated, semiconductor coupled fuel formation. In the dark, the activities of these catalysts deposited on degenerately doped p^+-Si electrodes increased in the order Ni < Ni\u2013Mo \u2264 Pt. Ni\u2013Mo deposited on degenerately doped Si microwires exhibited activity that was very similar to that of Pt deposited by metal evaporation on planar Si electrodes. Under 100 mW cm^(\u22122) of Air Mass 1.5 solar simulation, the energy conversion efficiencies of p-type Si/catalyst photoelectrodes ranged from 0.2\u20131%, and increased in the order Ni \u2248 Ni\u2013Mo < Pt, due to somewhat lower photovoltages and photocurrents for p-Si/Ni\u2013Mo relative to p-Si/Ni and p-Si/Pt photoelectrodes. Deposition of the catalysts onto microwire arrays resulted in higher apparent catalytic activities and similar photoelectrode efficiencies than were observed on planar p-Si photocathodes, despite lower light absorption by p-Si in the microwire structures.", "date": "2011-09", "date_type": "published", "publication": "Energy and Environmental Science", "volume": "4", "number": "9", "publisher": "Royal Society of Chemistry", "pagerange": "3573-3583", "id_number": "CaltechAUTHORS:20110929-104011152", "issn": "1754-5692", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110929-104011152", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Caltech Beckman Institute" }, { "agency": "Kavli Nanoscience Institute" } ] }, "local_group": { "items": [ { "id": "Kavli-Nanoscience-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c1ee01488a", "primary_object": { "basename": "McKone2011p15897Energ_Environ_Sci.pdf", "url": "https://authors.library.caltech.edu/records/gvbez-y4017/files/McKone2011p15897Energ_Environ_Sci.pdf" }, "related_objects": [ { "basename": "c1ee01488a.pdf", "url": "https://authors.library.caltech.edu/records/gvbez-y4017/files/c1ee01488a.pdf" } ], "pub_year": "2011", "author_list": "McKone, James R.; Warren, Emily L.; et el." }, { "id": "https://authors.library.caltech.edu/records/3jysn-xet46", "eprint_id": 23698, "eprint_status": "archive", "datestamp": "2023-08-19 06:19:38", "lastmod": "2023-10-23 19:52:09", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "MacFarlane-S-L", "name": { "family": "MacFarlane", "given": "Shaune L." } }, { "id": "Day-B-A", "name": { "family": "Day", "given": "Brittney A." } }, { "id": "McEleney-K", "name": { "family": "McEleney", "given": "Kevin" } }, { "id": "Freund-M-S", "name": { "family": "Freund", "given": "Michael S." }, "orcid": "0000-0003-1104-2292" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Designing electronic/ionic conducting membranes for artificial photosynthesis", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 Royal Society of Chemistry. \n\nReceived 24 Aug 2010; Accepted 06 Dec 2010; First published on the web 10 Jan 2011. \n\nFinancial support from the following is gratefully acknowledged: The Natural Sciences and Engineering Research Council (NSERC) of Canada, the Canada Foundation for Innovation (CFI), the Manitoba Research and Innovation Fund, the University of Manitoba, and made use of the Manitoba Materials and Surface Characterization Facility. This work was also supported by the NSF through a Center for Chemical Innovation, by the Stanford Global Trust and Energy Program, and by Toyota, and made use of the Molecular Materials Research Center of the Beckman Institute at Caltech, and the Kavli Nanoscience Institute at Caltech. This research was undertaken, in part, thanks to funding from the Canada Research Chairs Program. We thank Michael McDonald for the artwork in Fig. 1.\n\nPublished - McFarlane2011p13840Energ_Environ_Sci.pdf
Supplemental Material - c0ee00384k.pdf
", "abstract": "We discuss the figures of merit for conducting membranes in artificial photosynthetic systems and describe an electronically and ionically conducting polymer composite with attractive performance characteristics.", "date": "2011-05", "date_type": "published", "publication": "Energy and Environmental Science", "volume": "4", "number": "5", "publisher": "Royal Society of Chemistry", "pagerange": "1700-1703", "id_number": "CaltechAUTHORS:20110517-152016582", "issn": "1754-5692", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110517-152016582", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "Canada Foundation for Innovation" }, { "agency": "Manitoba Research and Innovation Fund" }, { "agency": "University of Manitoba" }, { "agency": "NSF" }, { "agency": "Stanford Global Trust and Energy Program" }, { "agency": "Toyota" }, { "agency": "Canada Research Chairs Program" } ] }, "local_group": { "items": [ { "id": "Kavli-Nanoscience-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/c0ee00384k", "primary_object": { "basename": "McFarlane2011p13840Energ_Environ_Sci.pdf", "url": "https://authors.library.caltech.edu/records/3jysn-xet46/files/McFarlane2011p13840Energ_Environ_Sci.pdf" }, "related_objects": [ { "basename": "c0ee00384k.pdf", "url": "https://authors.library.caltech.edu/records/3jysn-xet46/files/c0ee00384k.pdf" } ], "pub_year": "2011", "author_list": "MacFarlane, Shaune L.; Day, Brittney A.; et el." }, { "id": "https://authors.library.caltech.edu/records/pxwt9-zsk69", "eprint_id": 23806, "eprint_status": "archive", "datestamp": "2023-08-22 02:39:10", "lastmod": "2023-10-23 20:02:01", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Blanco-Rodr\u00edguez-A-M", "name": { "family": "Blanco-Rodr\u00edguez", "given": "Ana Mar\u00eda" } }, { "id": "Di-Bilio-A-J", "name": { "family": "Di Bilio", "given": "Angel J." } }, { "id": "Shih-Crystal", "name": { "family": "Shih", "given": "Crystal" } }, { "id": "Museth-A-K", "name": { "family": "Museth", "given": "Anna Katrine" } }, { "id": "Clark-I-P", "name": { "family": "Clark", "given": "Ian P." } }, { "id": "Towrie-M", "name": { "family": "Towrie", "given": "Michael" } }, { "id": "Cannizzo-A", "name": { "family": "Cannizzo", "given": "Andrea" } }, { "id": "Sudhamsu-J", "name": { "family": "Sudhamsu", "given": "Jawahar" } }, { "id": "Crane-B-R", "name": { "family": "Crane", "given": "Brian R." } }, { "id": "S\u00fdkora-J", "name": { "family": "S\u00fdkora", "given": "Jan" }, "orcid": "0000-0003-0936-9368" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Z\u00e1li\u0161-S", "name": { "family": "Z\u00e1li\u0161", "given": "Stanislav" } }, { "id": "Vl\u010dek-A-Jr", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn, Jr." } } ] }, "title": "Phototriggering Electron Flow through Re^I-modified Pseudomonas aeruginosa Azurins", "ispublished": "pub", "full_text_status": "public", "keywords": "density functional calculations; electron transfer; IR spectroscopy; peptides; pi interactions", "note": "\u00a9 2011 Wiley VCH Verlag GmbH&Co. KGaA, Weinheim.\n\nReceived: July 28, 2010. Revised: December 12, 2010. Published online: April 5, 2011.\n\n\nWe thank Lucie Sokolov\u00e1 (J.W. Goethe University, Frankfurt am Main) for measuring and interpreting the solution LILBID mass spectra. Research at Caltech was supported by the NSF Center for Chemical Innovation (Powering the Planet CHE-0802907 and CHE-0947829) and by NIH (DK019038 to HBG, JRW). The crystallographic work was supported by the NSF-CHE-0749997(BRC). The TRIR and theoretical investigations were funded by the STFC Rutherford Appleton Laboratory, CMSD 43, Queen Mary University of London, European COST D35 and ESF-DYNA programs, and Ministry of Education of the Czech Republic grants ME10124 and OC09043.\n\nAccepted Version - nihms290610.pdf
", "abstract": "The [Re^I(CO)_3(4,7-dimethyl-1,10-phenanthroline)(histidine-124)(tryptophan-122)] complex, denoted [Re^I(dmp)(W122)], of Pseudomonas aeruginosa azurin behaves as a single photoactive unit that triggers very fast electron transfer (ET) from a distant (2\u2005nm) Cu^I center in the protein. Analysis of time-resolved (ps\u2013\u03bcs) IR spectroscopic and kinetics data collected on [Re^I(dmp)(W122)AzM] (in which M=Zn^(II), Cu^(II), Cu^I; Az=azurin) and position-122 tyrosine (Y), phenylalanine (F), and lysine (K) mutants, together with excited-state DFT/time-dependent (TD)DFT calculations and X-ray structural characterization, reveal the character, energetics, and dynamics of the relevant electronic states of the [Re^I(dmp)(W122)] unit and a cascade of photoinduced ET and relaxation steps in the corresponding Re\u2013azurins. Optical population of [Re^I(imidazole-H124)(CO)_3]\u2192dmp ^1CT states (CT=charge transfer) is followed by around 110\u2005fs intersystem crossing and about 600\u2005ps structural relaxation to a ^3CT state. The IR spectrum indicates a mixed Re^I(CO)_3,A\u2192dmp/\u03c0\u2192\u03c0^*(dmp) character for aromatic amino acids A122 (A=W, Y, F) and Re^I(CO)_3\u2192dmp metal\u2013ligand charge transfer (MLCT) for [Re^I(dmp)(K122)AzCu^(II)]. In a few ns, the ^3CT state of [Re^I(dmp)(W122)AzM] establishes an equilibrium with the [Re^I(dmp.^\u2212)(W122.^+)AzM] charge-separated state, ^3CS, whereas the ^3CT state of the other Y, F, and K122 proteins decays to the ground state. In addition to this main pathway, ^3CS is populated by fs- and ps-W(indole)\u2192Re^(II) ET from ^1CT and the initially \"hot\" ^3CT states, respectively. The ^3CS state undergoes a tens-of-ns dmp.^\u2212\u2192W122.^+ ET recombination leading to the ground state or, in the case of the Cu^I azurin, a competitively fast (\u224830\u2005ns over 1.12\u2005nm) Cu^I\u2192W.^+ ET, to give [Re^I(dmp.^\u2212)(W122)AzCu^(II)]. The overall photoinduced CuI\u2192Re(dmp) ET through [Re^I(dmp)(W122)AzCu^I] occurs over a 2\u2005nm distance in <50\u2005ns after excitation, with the intervening fast ^3CT\u2013^3CS equilibrium being the principal accelerating factor. No reaction was observed for the three Y, F, and K122 analogues. Although the presence of [Re(dmp)(W122)AzCu^(II)] oligomers in solution was documented by mass spectrometry and phosphorescence anisotropy, the kinetics data do not indicate any significant interference from the intermolecular ET steps. The ground-state dmp\u2013indole \u03c0\u2013\u03c0 interaction together with well-matched W/W.^+ and excited-state [Re^II(CO)_3(dmp.^\u2212)]/[Re^I(CO)_3(dmp.^\u2212)] potentials that result in very rapid electron interchange and ^3CT\u2013^3CS energetic proximity, are the main factors responsible for the unique ET behavior of [Re^I(dmp)(W122)]-containing azurins.", "date": "2011-05", "date_type": "published", "publication": "Chemistry: a European Journal", "volume": "17", "number": "19", "publisher": "John Wiley & Sons", "pagerange": "5350-5361", "id_number": "CaltechAUTHORS:20110526-090614868", "issn": "0947-6539", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110526-090614868", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "NIH", "grant_number": "DK019038" }, { "agency": "NSF", "grant_number": "CHE-0749997" }, { "agency": "Queen Mary University of London" }, { "agency": "European COST", "grant_number": "D35" }, { "agency": "ESF-DYNA programs" }, { "agency": "Ministry of Education of the Czech Republic", "grant_number": "ME10124" }, { "agency": "Ministry of Education of the Czech Republic", "grant_number": "OC09043" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1002/chem.201002162", "pmcid": "PMC3108028", "primary_object": { "basename": "nihms290610.pdf", "url": "https://authors.library.caltech.edu/records/pxwt9-zsk69/files/nihms290610.pdf" }, "pub_year": "2011", "author_list": "Blanco-Rodr\u00edguez, Ana Mar\u00eda; Di Bilio, Angel J.; et el." }, { "id": "https://authors.library.caltech.edu/records/h4f38-k0660", "eprint_id": 23331, "eprint_status": "archive", "datestamp": "2023-08-19 05:53:27", "lastmod": "2023-10-23 19:00:55", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Yahyaie-I", "name": { "family": "Yahyaie", "given": "Iman" } }, { "id": "McEleney-K", "name": { "family": "McEleney", "given": "Kevin" } }, { "id": "Walter-M", "name": { "family": "Walter", "given": "Michael" } }, { "id": "Oliver-D-R", "name": { "family": "Oliver", "given": "Derek R." } }, { "id": "Thomson-D-J", "name": { "family": "Thomson", "given": "Douglas J." } }, { "id": "Freund-M-S", "name": { "family": "Freund", "given": "Michael S." }, "orcid": "0000-0003-1104-2292" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Electrical Characterization of Si Microwires and of Si Microwire/Conducting Polymer Composite Junctions", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 American Chemical Society. \n\nReceived: January 28, 2011; Accepted: February 25, 2011. \n\nFinancial support from the following is gratefully acknowledged: The Technology International Collaboration Fund of Manitoba Innovation Energy and Mines, the Natural Sciences and Engineering Research Council (NSERC) of Canada, the Canada Foundation for Innovation (CFI), the Manitoba Research and Innovation Fund, and the University of Manitoba. The work reported made use of the Manitoba Institute for Materials. This work was also supported by the NSF through a Center for Chemical Innovation, by the Stanford Global Trust and Energy Program, and by Toyota and made use of the Molecular Materials Research Center of the Beckman Institute at Caltech and the Kavli Nanoscience Institute at Caltech. This research was undertaken, in part, thanks to funding from the Canada Research Chairs Program.\n\nSupplemental Material - jz2001375_si_001.pdf
", "abstract": "The electrical (DC) behavior of single silicon microwires has been determined by the use of tungsten probes to make ohmic contact to the silicon microwires. The basic electrical properties of the microwires, such as their DC resistivity and the doping distribution along the length of the microwires, were investigated using this approach. The technique was also used to characterize the junction between silicon microwires and conducting polymers to assess the suitability of such contacts for use in a proposed artificial photosynthesis system.", "date": "2011-03-17", "date_type": "published", "publication": "Journal of Physical Chemistry Letters", "volume": "2", "number": "6", "publisher": "American Chemical Society", "pagerange": "675-680", "id_number": "CaltechAUTHORS:20110414-091143113", "issn": "1948-7185", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110414-091143113", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Technology International Collaboration Fund of Manitoba Innovation Energy and Mines" }, { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "Canada Foundation for Innovation" }, { "agency": "Manitoba Research and Innovation Fund" }, { "agency": "University of Manitoba" }, { "agency": "NSF" }, { "agency": "Stanford Global Trust and Energy Program" }, { "agency": "Toyota" }, { "agency": "Canada Research Chairs Program" } ] }, "local_group": { "items": [ { "id": "Kavli-Nanoscience-Institute" }, { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/jz2001375", "primary_object": { "basename": "jz2001375_si_001.pdf", "url": "https://authors.library.caltech.edu/records/h4f38-k0660/files/jz2001375_si_001.pdf" }, "pub_year": "2011", "author_list": "Yahyaie, Iman; McEleney, Kevin; et el." }, { "id": "https://authors.library.caltech.edu/records/0vcvf-sx493", "eprint_id": 23227, "eprint_status": "archive", "datestamp": "2023-08-19 05:30:31", "lastmod": "2023-10-23 18:04:55", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dong-Sijia-S", "name": { "family": "Dong", "given": "Sijia S." }, "orcid": "0000-0002-5811-9333" }, { "id": "Nielsen-R-J", "name": { "family": "Nielsen", "given": "Robert J." }, "orcid": "0000-0002-7962-0186" }, { "id": "Palmer-J-H", "name": { "family": "Palmer", "given": "Joshua H." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Gross-Z", "name": { "family": "Gross", "given": "Zeev" } }, { "id": "Dasgupta-S", "name": { "family": "Dasgupta", "given": "Siddharth" }, "orcid": "0000-0002-9161-7457" }, { "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "orcid": "0000-0003-0097-5716" } ] }, "title": "Electronic Structures of Group 9 Metallocorroles with Axial Ammines", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 American Chemical Society. Published In Issue February 07, 2011. Article ASAP January 07, 2011. Received March 29, 2010. This work was supported by an NSF Center for Chemical Innovation (CCI Powering the Planet, Grants CHE-0802907 and CHE-0947829), the U.S.-Israel BSF (Z.G. and H.B.G.), CCSER (Gordon and Betty Moore Foundation), and the Arnold and Mabel Beckman Foundation. W.A.G. and R.S.N. and\nthe quantum mechanicals calculations were supported as\npart of the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center funded\nby the U.S. Department of Energy, Office of Science,\nOffice of Basic Energy Sciences under Award Number\nDE-SC0001298. S.S.D. was also supported by the Overseas\nResearch Fellowship Scheme from the Faculty of\nScience, University of Hong Kong.\n\nSupplemental Material - ic1005902_si_001.pdf
", "abstract": "The electronic structures of metallocorroles (tpfc)M(NH_3)_2 and (tfc)M(NH_3)_2 (tpfc is the trianion of 5,10,15-(tris)pentafluorophenylcorrole, tfc is the trianion of 5,10,15-trifluorocorrole, and M = Co, Rh, Ir) have been computed using first principles quantum mechanics [B3LYP flavor of Density Functional Theory (DFT) with Poisson\u2212Boltzmann continuum solvation]. The geometry was optimized for both the neutral systems (formal M^(III) oxidation state) and the one-electron oxidized systems (formally M^(IV)). As expected, the M^(III) systems have a closed shell d^6 configuration; for all three metals, the one-electron oxidation was calculated to occur from a ligand-based orbital (highest occupied molecular orbital (HOMO) of B_1 symmetry). The ground state of the formal M^(IV) system has M^(III)-C\u03c0 character, indicating that the metal remains d^6, with the hole in the corrole \u03c0 system. As a result the calculated M^(IV/III) reduction potentials are quite similar (0.64, 0.67, and 0.56 V vs SCE for M = Ir, Rh and Co, respectively), whereas the differences would have been large for purely metal-based oxidations. Vertically excited states with substantial metal character are well separated from the ground state in one-electron-oxidized cobalt (0.27 eV) and rhodium (0.24 eV) corroles, but become closer in energy in the iridium (0.15 eV) analogues. The exact splittings depend on the chosen functional and basis set combination and vary by ~0.1 eV.", "date": "2011-02-07", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "50", "number": "3", "publisher": "American Chemical Society", "pagerange": "764-770", "id_number": "CaltechAUTHORS:20110404-100258063", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110404-100258063", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Binational Science Foundation (USA-Israel)" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-SC000-1298" }, { "agency": "University of Hong Kong" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ic1005902", "primary_object": { "basename": "ic1005902_si_001.pdf", "url": "https://authors.library.caltech.edu/records/0vcvf-sx493/files/ic1005902_si_001.pdf" }, "pub_year": "2011", "author_list": "Dong, Sijia S.; Nielsen, Robert J.; et el." }, { "id": "https://authors.library.caltech.edu/records/gxp92-c2g14", "eprint_id": 23014, "eprint_status": "archive", "datestamp": "2023-08-22 01:51:46", "lastmod": "2023-10-23 17:49:08", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Urie-K-G", "name": { "family": "Urie", "given": "Kristopher G." } }, { "id": "Pletneva-E-V", "name": { "family": "Pletneva", "given": "Ekaterina" } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Kozak-J-J", "name": { "family": "Kozak", "given": "John J." } } ] }, "title": "Geometrical analysis of cytochrome c unfolding", "ispublished": "pub", "full_text_status": "public", "keywords": "protein folding; cytochrome c; Monte Carlo simulations", "note": "\u00a9 2011 Taylor & Francis.\n\nReceived 14 July 2010; final version received 31 August 2010. \nFirst Published on: 22 December 2010.\n\nResearch at Caltech is supported by the National Institutes\nof Health (DKOI9038, GM068461), the National Science\nFoundation (CHE-0802907), and the Arnold and Mabel\nBeckman Foundation.\n\nAccepted Version - nihms240528.pdf
", "abstract": "A geometrical model has been developed to study the unfolding of iso-1 cytochrome c. The model draws on the crystallographic data reported for this protein. These data were used to calculate the distance between specific residues in the folded state, and in a sequence of extended states defined by n = 3, 5, 7, 9, 11, 13, and 15 residue units. Exact calculations carried out for each of the 103 residues in the polypeptide chain demonstrate that different regions of the chain have different unfolding histories. Regions where there is a persistence of compact structures can be identified, and this geometrical characterization is fully consistent with analyses of time-resolved fluorescence energy-transfer (TrFET) data using dansyl-derivatized cysteine side-chain probes at positions 39, 50, 66, 85, and 99. The calculations were carried out assuming that different regions of the polypeptide chain unfold synchronously. To test this assumption, lattice Monte Carlo simulations were performed to study systematically the possible importance of asynchronicity. Calculations show that small departures from synchronous dynamics can arise if displacements of residues in the main body of the chain are much more sluggish than near-terminal residues.", "date": "2011-01-20", "date_type": "published", "publication": "Molecular Physics", "volume": "109", "number": "2", "publisher": "Taylor & Francis", "pagerange": "301-313", "id_number": "CaltechAUTHORS:20110321-142051991", "issn": "0026-8976", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110321-142051991", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "DK019038" }, { "agency": "NIH", "grant_number": "GM068461" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1080/00268976.2010.521202", "pmcid": "PMC3046399", "primary_object": { "basename": "nihms240528.pdf", "url": "https://authors.library.caltech.edu/records/gxp92-c2g14/files/nihms240528.pdf" }, "pub_year": "2011", "author_list": "Urie, Kristopher G.; Pletneva, Ekaterina; et el." }, { "id": "https://authors.library.caltech.edu/records/fsckm-dns66", "eprint_id": 44654, "eprint_status": "archive", "datestamp": "2023-08-19 05:16:06", "lastmod": "2023-10-26 14:51:00", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Whited-M-T", "name": { "family": "Whited", "given": "Matthew T." } }, { "id": "Djurovich-P-I", "name": { "family": "Djurovich", "given": "Peter I." } }, { "id": "Roberts-S-T", "name": { "family": "Roberts", "given": "Sean T." } }, { "id": "Durrell-A-C", "name": { "family": "Durrell", "given": "Alec C." } }, { "id": "Schlenker-C-W", "name": { "family": "Schlenker", "given": "Cody W." } }, { "id": "Bradforth-S-E", "name": { "family": "Bradforth", "given": "Stephen E." } }, { "id": "Thompson-M-E", "name": { "family": "Thompson", "given": "Mark E." }, "orcid": "0000-0002-7764-4096" } ] }, "title": "Singlet and Triplet Excitation Management in a Bichromophoric Near-Infrared-Phosphorescent BODIPY-Benzoporphyrin Platinum Complex", "ispublished": "pub", "full_text_status": "public", "note": "Copyright \u00a9 2010 American Chemical Society. \n\nReceived September 20, 2010. \n\nPublication Date (Web): December 10, 2010.\n\nFunding for this research was provided by the Center for Advanced Molecular Photovoltaics (CAMP) (KUS-C1-015-21) of the King Abdullah University of Science and Technology (KAUST) and the Global Photonic Corporation. The quantification of absorbance at AM1.5G illumination and femtosecond transient absorption measurements were carried out with support from the Department of Energy's Energy Frontier Research Center program (Center for Energy Nanoscience, Award DE-SC0001011). S.T.R. acknowledges support from the National Science Foundation in the form of an ACC-F fellowship (CHE-0937015), and A.C.D. acknowledges support from the NSF Center for Chemical Innovation (CCI Powering the Planet, Grants CHE-0802907 and CHE-0947829). We are also grateful to Dr. Jay Winkler and the Beckman Institute Laser Resource Center at the California Institute of Technology for assistance with nanosecond transient absorption measurements. We dedicate this manuscript to Professor Harry B. Gray, pioneer of inorganic photochemistry, on the occasion of his 75th birthday.\n\nSupporting Information: Derivation of eq 1; 1H NMR spectrum of 4; absorption and photoluminescence spectra for 3, 4, and model complexes; femtosecond-resolved transient absorption spectra for 3. This material is available free of charge via the Internet at http://pubs.acs.org.\n\nSupplemental Material - ja108493b_si_001.pdf
", "abstract": "Multichromophoric arrays provide one strategy for assembling molecules with intense absorptions across the visible spectrum but are generally focused on systems that efficiently produce and manipulate singlet excitations and therefore are burdened by the restrictions of (a) unidirectional energy transfer and (b) limited tunability of the lowest molecular excited state. In contrast, we present here a multichromophoric array based on four boron dipyrrins (BODIPY) bound to a platinum benzoporphyrin scaffold that exhibits intense panchromatic absorption and efficiently generates triplets. The spectral complementarity of the BODIPY and porphryin units allows the direct observation of fast bidirectional singlet and triplet energy transfer processes (k_(ST)(^1BDP\u2192^1Por) = 7.8 \u00d7 10^(11) s^(\u22121), k_(TT)(^3Por\u2192^3BDP) = 1.0 \u00d7 10^(10) s^(\u22121), k_(TT)(^3BDP\u2192^3Por) = 1.6 \u00d7 10^(10) s^(\u22121)), leading to a long-lived equilibrated [^3BDP][Por]\u21d4[BDP][^3Por] state. This equilibrated state contains approximately isoenergetic porphyrin and BODIPY triplets and exhibits efficient near-infrared phosphorescence (\u03bb_(em) = 772 nm, \u03a6 = 0.26). Taken together, these studies show that appropriately designed triplet-utilizing arrays may overcome fundamental limitations typically associated with core\u2212shell chromophores by tunable redistribution of energy from the core back onto the antennae.", "date": "2011-01-12", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "133", "number": "1", "publisher": "American Chemical Society", "pagerange": "88-96", "id_number": "CaltechAUTHORS:20140403-163634083", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140403-163634083", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Center for Advanced Molecular Photovoltaics (CAMP) of the King Abdullah University of Science and Technology (KAUST)", "grant_number": "KUS-C1-015-21" }, { "agency": "Global Photonic Corporation" }, { "agency": "Center for Energy Nanoscience", "grant_number": "DE-SC0001011" }, { "agency": "NSF", "grant_number": "CHE-0937015" }, { "agency": "NSF Center for Chemical Innovation Powering the Planet", "grant_number": "CHE-0802907" }, { "agency": "NSF Center for Chemical Innovation Powering the Planet", "grant_number": "CHE-0947829" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja108493b", "primary_object": { "basename": "ja108493b_si_001.pdf", "url": "https://authors.library.caltech.edu/records/fsckm-dns66/files/ja108493b_si_001.pdf" }, "pub_year": "2011", "author_list": "Whited, Matthew T.; Djurovich, Peter I.; et el." }, { "id": "https://authors.library.caltech.edu/records/ws34c-5ew07", "eprint_id": 23151, "eprint_status": "archive", "datestamp": "2023-08-19 04:49:09", "lastmod": "2023-10-23 17:59:22", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Johnson-J-A", "name": { "family": "Johnson", "given": "Jeremiah A." }, "orcid": "0000-0001-9808-7172" }, { "id": "Lu-Ying-Yu", "name": { "family": "Lu", "given": "Ying Y." } }, { "id": "Burts-A-O", "name": { "family": "Burts", "given": "Alan O." } }, { "id": "Xia-Yan", "name": { "family": "Xia", "given": "Yan" } }, { "id": "Durrell-A-C", "name": { "family": "Durrell", "given": "Alec C." } }, { "id": "Tirrell-D-A", "name": { "family": "Tirrell", "given": "David A." }, "orcid": "0000-0003-3175-4596" }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817" } ] }, "title": "Drug-Loaded, Bivalent-Bottle-Brush Polymers by Graft-through ROMP", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nReceived: September 15, 2010; Revised: November 08, 2010. Article ASAP December 02, 2010. Published In Issue December 28, 2010. \n\nWe thank Dr. S. Virgil for helpful discussion and advice. We also thank the Beckman Institute for a postdoctoral fellowship for JAJ. UV-vis experiments were performed in the Beckman Institute Laser Center. This work was supported by the National Institutes of Health (NIH, R01-GM31332), the MRSEC program of the National Science Foundation (NSF) under award number DMR-0520565, and the NSF Center for Chemical Innovation (Powering the Planet, CHE-0802907 and CHE-0947829).\n\nAccepted Version - nihms255854.pdf
Supplemental Material - ma1021506_si_001.pdf
", "abstract": "Graft through ring-opening metathesis polymerization (ROMP) using ruthenium N heterocyclic carbene catalysts has enabled the synthesis of bottle-brush polymers with unprecedented ease and control Here we report the first bivalent-brush polymers, these materials were prepared by graft through ROMP of drug-loaded poly(ethylene glycol) (PEG) based macromonomers (MMs) Anticancer drugs doxorubicin (DOX) and camptothecin (CT) were attached to a norbornene alkyne-PEG MM via a photocleavable linker ROMP of either or both drug loaded MMs generated brush homo and copolymers with low polydispersities and defined molecular weights. Release of free DOX and CT from these materials was initiated by exposure to 365 nm light All of the CT and DOX polymers were at least 10 fold more toxic to human cancer cells after photoinitiated drug release while a copolymer carrying both CT and DOX displayed 30-fold increased toxicity upon irradiation Graft through ROMP of drug loaded macromonomers provides a general method for the systematic study of structure function relationships for stimuli responsive polymers in biological systems.", "date": "2010-12-28", "date_type": "published", "publication": "Macromolecules", "volume": "43", "number": "24", "publisher": "American Chemical Society", "pagerange": "10326-10335", "id_number": "CaltechAUTHORS:20110329-095607608", "issn": "0024-9297", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110329-095607608", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Caltech Beckman Institute" }, { "agency": "NIH", "grant_number": "R01-GM31332" }, { "agency": "NSF", "grant_number": "DMR-0520565" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ma1021506", "pmcid": "PMC3083120", "primary_object": { "basename": "nihms255854.pdf", "url": "https://authors.library.caltech.edu/records/ws34c-5ew07/files/nihms255854.pdf" }, "related_objects": [ { "basename": "ma1021506_si_001.pdf", "url": "https://authors.library.caltech.edu/records/ws34c-5ew07/files/ma1021506_si_001.pdf" } ], "pub_year": "2010", "author_list": "Johnson, Jeremiah A.; Lu, Ying Y.; et el." }, { "id": "https://authors.library.caltech.edu/records/q9ycn-wk039", "eprint_id": 21660, "eprint_status": "archive", "datestamp": "2023-08-19 04:45:40", "lastmod": "2023-10-21 00:13:03", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Coe-B-J", "name": { "family": "Coe", "given": "Benjamin J." }, "orcid": "0000-0002-5998-3895" }, { "id": "Fielden-J", "name": { "family": "Fielden", "given": "John" }, "orcid": "0000-0001-5963-7792" }, { "id": "Foxon-S-P", "name": { "family": "Foxon", "given": "Simon P." } }, { "id": "Helliwell-M", "name": { "family": "Helliwell", "given": "Madeleine" } }, { "id": "Asselberghs-I", "name": { "family": "Asselberghs", "given": "Inge" } }, { "id": "Clays-K", "name": { "family": "Clays", "given": "Koen" } }, { "id": "De-Mey-K", "name": { "family": "De Mey", "given": "Kurt" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" } ] }, "title": "Syntheses and Properties of Two-Dimensional, Dicationic Nonlinear Optical Chromophores Based on Pyrazinyl Cores", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nReceived October 5, 2010. Publication Date (Web): November 16, 2010. \n\nWe thank the EPSRC for support (grants EP/E000738 and EP/D070732) and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08), the University of Leuven (GOA/2006/3), and the NSF (grant CHE-0802907, Powering the Planet: an NSF Center for Chemical Innovation). I.A. is a postdoctoral fellow of the FWO-V. We thank Dr. Daniela Rusanova-Naydenova for obtaining some of the data presented in Figure 4, and are grateful to Dr Robin Pritchard of the University of Manchester for assistance with solving the crystal structure of salt [2][PF6]2.\n\nSupplemental Material - jo101966r_si_001.cif
Supplemental Material - jo101966r_si_002.pdf
", "abstract": "Six new dicationic 2D nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by nucleophilic substitutions of 2,6-dichloropyrazine with pyridyl derivatives. These compounds have been characterized as their PF_6^\u2212 salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Large red shifts in the intense, \u03c0 \u2192 \u03c0* intramolecular charge-transfer (ICT) transitions on replacing \u2212OMe with \u2013Nme_2 substituents arise from the stronger \u03c0-electron donor ability of the latter. Each compound shows a number of redox processes which are largely irreversible. Single crystal X-ray structures have been determined for five salts, including two nitrates, all of which adopt centrosymmetric packing arrangements. Molecular first hyperpolarizabilities \u03b2 have been determined by using femtosecond hyper-Rayleigh scattering at 880 and 800 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly 2D, with dominant \"off-diagonal\" \u03b2_(zyy) components. Stark (electroabsorption) spectroscopic measurements on the ICT bands afford estimated static first hyperpolarizabilities \u03b2_0. The directly and indirectly derived \u03b2 values are large, and the Stark-derived \u03b2_0 response for one of the new salts is several times greater than that determined for (E)-4\u2032-(dimethylamino)-N-methyl-4-stilbazolium hexafluorophosphate. These Stark spectroscopic studies also permit quantitative comparisons with related 2D, binuclear RuII ammine complex salts.", "date": "2010-12-17", "date_type": "published", "publication": "Journal of Organic Chemistry", "volume": "75", "number": "24", "publisher": "American Chemical Society", "pagerange": "8550-8563", "id_number": "CaltechAUTHORS:20110110-090253636", "issn": "0022-3263", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110110-090253636", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/E000738" }, { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/D070732" }, { "agency": "Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)", "grant_number": "FWO-V G.0312.08" }, { "agency": "University of Leuven", "grant_number": "GOA/2006/3" }, { "agency": "NSF", "grant_number": "CHE-0802907" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1021/jo101966r", "primary_object": { "basename": "jo101966r_si_002.pdf", "url": "https://authors.library.caltech.edu/records/q9ycn-wk039/files/jo101966r_si_002.pdf" }, "related_objects": [ { "basename": "jo101966r_si_001.cif", "url": "https://authors.library.caltech.edu/records/q9ycn-wk039/files/jo101966r_si_001.cif" } ], "pub_year": "2010", "author_list": "Coe, Benjamin J.; Fielden, John; et el." }, { "id": "https://authors.library.caltech.edu/records/r3a8j-9de91", "eprint_id": 21675, "eprint_status": "archive", "datestamp": "2023-08-19 04:41:11", "lastmod": "2023-10-21 00:13:54", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dempsey-J-L", "name": { "family": "Dempsey", "given": "Jillian L." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Mechanism of H_2 Evolution from a Photogenerated Hydridocobaloxime", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society.\n\nReceived October 17, 2010. Publication Date (Web): November 10, 2010. \n\nWe thank Bruce Brunschwig, Alec Durrell, Maraia Ener, Jonas Peters, and Jeff Warren for helpful discussions and experimental advice. Charles McCrory and Jacob Good are acknowledged for generous assistance with GC measurements. This work was supported by an NSF Center for Chemical Innovation (Powering the Planet, CHE-0947829), the Arnold and Mabel Beckman Foundation, and CCSER (Gordon and Betty Moore Foundation). J.L.D. was supported by an NSF Graduate Research Fellowship.\n\nSupplemental Material - ja109351h_si_001.pdf
", "abstract": "Proton transfer from the triplet excited state of brominated naphthol to a difluoroboryl bridged Co^I-diglyoxime complex, forming Co^(III)H, was monitored via transient absorption. The second-order rate constant for Co^(III)H formation is in the range (3.5\u22124.7) \u00d7 10^9 M^(\u22121) s^(\u22121), with proton transfer coupled to excited-state deactivation of the photoacid. Co^(III)H is subsequently reduced by excess Co^I-diglyoxime in solution to produce Co^(II)H (k_(red) = 9.2 \u00d7 10^6 M^(\u22121) s^(\u22121)), which is then protonated to yield Co^(II)-diglyoxime and H_2.", "date": "2010-12-01", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "47", "publisher": "American Chemical Society", "pagerange": "16774-1677", "id_number": "CaltechAUTHORS:20110110-150437628", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110110-150437628", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Caltech Center for Sustainable Energy Research" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja109351h", "primary_object": { "basename": "ja109351h_si_001.pdf", "url": "https://authors.library.caltech.edu/records/r3a8j-9de91/files/ja109351h_si_001.pdf" }, "pub_year": "2010", "author_list": "Dempsey, Jillian L.; Winkler, Jay R.; et el." }, { "id": "https://authors.library.caltech.edu/records/td45z-y4f62", "eprint_id": 21864, "eprint_status": "archive", "datestamp": "2023-08-19 04:32:28", "lastmod": "2023-10-23 15:27:00", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dempsey-J-L", "name": { "family": "Dempsey", "given": "Jillian L." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Proton-Coupled Electron Flow in Protein Redox Machines", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society.\n\nReceived June 11, 2010.\nPublication Date (Web): November 17, 2010.\nThis article is part of the 2010 Proton-Coupled Electron Transfer special issue.\n\nOur work is supported by the NIH (DK019038, GM068461),\nan NSF Center for Chemical Innovation Grant (CHE-0802907), GCEP (Stanford), CCSER (Gordon and Betty\nMoore Foundation), and the Arnold and Mabel Beckman\nFoundation.\n\nAccepted Version - nihms253731.pdf
", "abstract": "Electron transfer (ET) reactions are fundamental steps in biological redox processes. Respiration is a case in point: at least 15 ET reactions are required to take reducing equivalents from NADH, deposit them in O_2, and generate the electrochemical proton gradient that drives ATP synthesis. Most of these reactions involve quantum tunneling between weakly coupled redox cofactors (ET distances > 10 \u00c5) embedded in the interiors of folded proteins. Here we review experimental findings that have shed light on the factors controlling these distant ET events. We also review work on a sensitizer-modified copper protein photosystem in which multistep electron tunneling (hopping) through an intervening tryptophan is orders of magnitude faster than the corresponding single-step ET reaction.If proton transfers are coupled to ET events, we refer to the processes as proton coupled ET, or PCET, a term introduced by Huynh and Meyer in 1981. Here we focus on two protein redox machines, photosystem II and ribonucleotide reductase, where PCET processes involving tyrosines are believed to be critical for function. Relevant tyrosine model systems also will be discussed.", "date": "2010-12", "date_type": "published", "publication": "Chemical Reviews", "volume": "110", "number": "12", "publisher": "American Chemical Society", "pagerange": "7024-7039", "id_number": "CaltechAUTHORS:20110124-105132769", "issn": "0009-2665", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20110124-105132769", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "DK019038" }, { "agency": "NIH", "grant_number": "GM068461" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Stanford Global Climate and Energy Project (GCEP)" }, { "agency": "Caltech Center for Sustainable Energy Research" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/cr100182b", "pmcid": "PMC3005815", "primary_object": { "basename": "nihms253731.pdf", "url": "https://authors.library.caltech.edu/records/td45z-y4f62/files/nihms253731.pdf" }, "pub_year": "2010", "author_list": "Dempsey, Jillian L.; Winkler, Jay R.; et el." }, { "id": "https://authors.library.caltech.edu/records/hf1dh-20413", "eprint_id": 21249, "eprint_status": "archive", "datestamp": "2023-08-19 04:25:53", "lastmod": "2023-10-20 23:52:54", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Coe-B-J", "name": { "family": "Coe", "given": "Benjamin J." }, "orcid": "0000-0002-5998-3895" }, { "id": "Fielden-J", "name": { "family": "Fielden", "given": "John" }, "orcid": "0000-0001-5963-7792" }, { "id": "Foxon-S-P", "name": { "family": "Foxon", "given": "Simon P." } }, { "id": "Helliwell-M", "name": { "family": "Helliwell", "given": "Madeleine" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Asselberghs-I", "name": { "family": "Asselberghs", "given": "Inge" } }, { "id": "Clays-K", "name": { "family": "Clays", "given": "Koen" } }, { "id": "Olesiak-J", "name": { "family": "Olesiak", "given": "Joanna" } }, { "id": "Matczyszyn-K", "name": { "family": "Matczyszyn", "given": "Katarzyna" } }, { "id": "Samoc-M", "name": { "family": "Samoc", "given": "Marek" } } ] }, "title": "Quadratic and Cubic Nonlinear Optical Properties of Salts of Diquat-Based Chromophores with Diphenylamino Substituents", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nReceived: July 13, 2010. Publication Date (Web): October 26, 2010. \n\nWe thank the EPSRC for support (grants EP/E000738 and EP/D070732) and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08), the University of Leuven (GOA/2006/3), the NSF (grant CHE-0802907, \"Powering the Planet: an NSF Center for Chemical Innovation\"), and the Foundation for Polish Science. I. A. is a postdoctoral fellow of the FWO-V, and M. S. is a Laureate and J. O. is a Ph.D. scholar of the FNP Welcome programme.\n\nSupplemental Material - jp106473e_si_001.pdf
Supplemental Material - jp106473e_si_002.cif
", "abstract": "A series of chromophoric salts has been prepared in which 4-(diphenylamino)phenyl (Dpap) electron donor groups are connected to electron-accepting diquaternized 2,2\u2032-bipyridyl (diquat) units. The main aim is to combine large quadratic and cubic nonlinear optical (NLO) effects in potentially redox-switchable molecules with 2D structures. The chromophores have been characterized as their PF_6^\u2212 salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible absorption spectra are dominated by intense \u03c0 \u2192 \u03c0* intramolecular charge-transfer (ICT) bands, and all of the compounds show two reversible or quasireversible diquat-based reductions and partially reversible Dpap oxidations. Single crystal X-ray structures have been obtained for one salt and for the precursor compound (E)-4-(diphenylamino)cinnamaldehyde, both of which adopt centrosymmetric space groups. First hyperpolarizabilities \u03b2 have been measured by using hyper-Rayleigh scattering (HRS) with a 800 nm laser, and Stark (electroabsorption) spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities \u03b2_0. The directly and indirectly derived \u03b2 values are large and generally increased substantially for the bis-Dpap derivatives when compared with their monosubstituted analogues. Polarized HRS studies show that the NLO responses of the disubstituted species are dominated by \"off-diagonal\" \u03b2_(zyy) components. Lengthening the diquaternizing alkyl unit lowers the electron-acceptor strength and therefore increases the ICT energies and decreases the E_(1/2) values for diquat reduction. However, compensating increases in the ICT intensity prevent significant decreases in the Stark-based \u03b2_0 responses. Cubic NLO properties have been measured by using the Z-scan technique over a wavelength range of 520\u22121600 nm, revealing relatively high two-photon absorption cross-sections of up to 730 GM at 620 nm for one of the disubstituted chromophores.", "date": "2010-11-18", "date_type": "published", "publication": "Journal of Physical Chemistry A", "volume": "114", "number": "45", "publisher": "American Chemical Society", "pagerange": "12028-12041", "id_number": "CaltechAUTHORS:20101208-133020453", "issn": "1089-5639", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20101208-133020453", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/E000738" }, { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/D070732" }, { "agency": "Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)", "grant_number": "G.0312.08" }, { "agency": "University of Leuven", "grant_number": "GOA/2006/3" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Foundation for Polish Science" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/jp106473e", "primary_object": { "basename": "jp106473e_si_001.pdf", "url": "https://authors.library.caltech.edu/records/hf1dh-20413/files/jp106473e_si_001.pdf" }, "related_objects": [ { "basename": "jp106473e_si_002.cif", "url": "https://authors.library.caltech.edu/records/hf1dh-20413/files/jp106473e_si_002.cif" } ], "pub_year": "2010", "author_list": "Coe, Benjamin J.; Fielden, John; et el." }, { "id": "https://authors.library.caltech.edu/records/1a6kf-4ks08", "eprint_id": 21428, "eprint_status": "archive", "datestamp": "2023-08-19 04:25:29", "lastmod": "2023-10-21 00:01:51", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Coe-B-J", "name": { "family": "Coe", "given": "Benjamin J." }, "orcid": "0000-0002-5998-3895" }, { "id": "Fielden-J", "name": { "family": "Fielden", "given": "John" }, "orcid": "0000-0001-5963-7792" }, { "id": "Foxon-S-P", "name": { "family": "Foxon", "given": "Simon P." } }, { "id": "Asselberghs-I", "name": { "family": "Asselberghs", "given": "Inge" } }, { "id": "Clays-K", "name": { "family": "Clays", "given": "Koen" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" } ] }, "title": "Two-Dimensional, Pyrazine-Based Nonlinear Optical Chromophores with Ruthenium(II) Ammine Electron Donors", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2010 American Chemical Society. \n\nReceived September 20, 2010. Publication Date (Web): October 20, 2010. \n\nWe thank the EPSRC for support (Grants EP/E000738 and EP/D070732) and also the Fund for ScientificResearch-Flanders (FWO-V, G.0312.08), the University of Leuven (GOA/2006/3), and the NSF (Grant CHE-0802907, \"Powering the Planet: an NSF Center for Chemical Innovation\"). I.A. is a postdoctoral fellow of the FWO-V.", "abstract": "Six new nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by complexing a known pro-ligand with electron donating {Ru^(II)(NH_3)_5}^(2+) or trans-{Ru^(II)(NH_3)_4(py)}^(2+) (py = pyridine) centers. These cationic complexes have been characterized as their PF_6^\u2212 salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible d \u2192 \u03c0* metal-to-ligand charge-transfer (MLCT) absorptions gain intensity on increasing the number of Ru^(II) centers from one to two, but remain at constant energy. One or two Ru^(III/II) redox processes are observed which are reversible, quasi-reversible, or irreversible, while all of the ligand-based reductions are irreversible. Molecular first hyperpolarizabilities \u03b2 have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly two-dimensional (2D) in character, with dominant \"off-diagonal\" \u03b2_(zyy) components. Stark (electroabsorption) spectroscopic measurements on the MLCT bands also allow the indirect determination of estimated static first hyperpolarizabilities \u03b2_0. Both the HRS and the Stark-derived \u03b2_0 values increase on moving from mono- to bimetallic complexes, and substantial enhancements in NLO response are achieved when compared with one-dimensional (1D) and 2D monometallic Ru^(II) ammine complexes reported previously.", "date": "2010-11-15", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "49", "number": "22", "publisher": "American Chemical Society", "pagerange": "10718-10726", "id_number": "CaltechAUTHORS:20101220-094653213", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20101220-094653213", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/E000738" }, { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/D070732" }, { "agency": "Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)", "grant_number": "G.0312.08" }, { "agency": "University of Leuven", "grant_number": "GOA/2006/3" }, { "agency": "NSF", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ic1019197", "pub_year": "2010", "author_list": "Coe, Benjamin J.; Fielden, John; et el." }, { "id": "https://authors.library.caltech.edu/records/93k21-0nz61", "eprint_id": 21330, "eprint_status": "archive", "datestamp": "2023-08-19 04:14:19", "lastmod": "2023-10-20 23:56:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Walter-M-G", "name": { "family": "Walter", "given": "Michael G." } }, { "id": "Warren-E-L", "name": { "family": "Warren", "given": "Emily L." }, "orcid": "0000-0001-8568-7881" }, { "id": "McKone-J-R", "name": { "family": "McKone", "given": "James R." }, "orcid": "0000-0001-6445-7884" }, { "id": "Boettcher-S-W", "name": { "family": "Boettcher", "given": "Shannon W." }, "orcid": "0000-0001-8971-9123" }, { "id": "Mi-Qixi", "name": { "family": "Mi", "given": "Qixi" } }, { "id": "Santori-E-A", "name": { "family": "Santori", "given": "Elizabeth A." } }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Solar Water Splitting Cells", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2010 American Chemical Society. \n\nReceived July 23, 2010. Publication Date (Web): November 10, 2010. \n\nThis work was supported by a National Science Foundation (NSF) Center for Chemical Innovation (CCI) Powering the Planet, Grants (CHE-0802907, CHE-0947829) and (NSFACCF) support for MGW (CHE-0937048). The authors would also like to thank Dr. Nick Strandwitz and Dr. Bruce Brunschwig for help reviewing the manuscript.", "abstract": "No abstract.", "date": "2010-11", "date_type": "published", "publication": "Chemical Reviews", "volume": "110", "number": "11", "publisher": "American Chemical Society", "pagerange": "6446-6473", "id_number": "CaltechAUTHORS:20101213-121533554", "issn": "0009-2665", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20101213-121533554", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "NSF Postdoctoral Fellowship", "grant_number": "CHE-0937048" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/cr1002326", "pub_year": "2010", "author_list": "Walter, Michael G.; Warren, Emily L.; et el." }, { "id": "https://authors.library.caltech.edu/records/nw4y3-a2d82", "eprint_id": 19895, "eprint_status": "archive", "datestamp": "2023-08-22 00:34:40", "lastmod": "2023-10-20 22:01:28", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Spurgeon-J-M", "name": { "family": "Spurgeon", "given": "Joshua M." }, "orcid": "0000-0002-2987-0865" }, { "id": "Boettcher-S-W", "name": { "family": "Boettcher", "given": "Shannon W." }, "orcid": "0000-0001-8971-9123" }, { "id": "Kelzenberg-M-D", "name": { "family": "Kelzenberg", "given": "Michael D." }, "orcid": "0000-0002-6249-2827" }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Atwater-H-A", "name": { "family": "Atwater", "given": "Harry A." }, "orcid": "0000-0001-9435-0201" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Flexible, Polymer-Supported, Si Wire Array Photoelectrodes", "ispublished": "pub", "full_text_status": "restricted", "keywords": "solar cells; microstructures; silicon nanowires; flexible electronics; photochemistry", "note": "\u00a9 2010 Wiley-Blackwell. \n\nReceived: February 16, 2010; Published online: June 29, 2010. \n\nThis work was financially supported by BP plc and by the Department of Energy, Office of Basic Energy Sciences, DE-FG02-07ER46405. BSB acknowledges support from the NSF Center for Chemical Innovation Grant No. 0802907 (Powering the Planet). We acknowledge use of facilities supported by the Caltech Center for Science and Engineering of Materials, an NSF MRSEC, and the Caltech Center for Sustainable Energy Research.", "abstract": "Arrays of oriented, crystalline Si wires are transferred into flexible, transparent polymer films. The polymer-supported Si wire arrays in liquid-junction photoelectrochemical cells yield current-potential behavior similar to the Si wires attached to the brittle growth substrate. These systems offer the potential for attaining high solar energy-conversion efficiencies using modest diffusion length, readily grown, crystalline Si in a flexible, processable form.", "date": "2010-08-10", "date_type": "published", "publication": "Advanced Materials", "volume": "22", "number": "30", "publisher": "Wiley", "pagerange": "3277-3281", "id_number": "CaltechAUTHORS:20100913-100004178", "issn": "0935-9648", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100913-100004178", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "BP" }, { "agency": "Department of Energy (DOE)", "grant_number": "DE-FG02-07ER46405" }, { "agency": "NSF", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1002/adma.201000602", "pub_year": "2010", "author_list": "Spurgeon, Joshua M.; Boettcher, Shannon W.; et el." }, { "id": "https://authors.library.caltech.edu/records/j5mc7-b3q86", "eprint_id": 19485, "eprint_status": "archive", "datestamp": "2023-08-19 03:27:13", "lastmod": "2023-10-20 20:44:59", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Coe-B-J", "name": { "family": "Coe", "given": "Benjamin J." }, "orcid": "0000-0002-5998-3895" }, { "id": "Fielden-J", "name": { "family": "Fielden", "given": "John" }, "orcid": "0000-0001-5963-7792" }, { "id": "Foxon-S-P", "name": { "family": "Foxon", "given": "Simon P." } }, { "id": "Harris-J-A", "name": { "family": "Harris", "given": "James A." } }, { "id": "Helliwell-M", "name": { "family": "Helliwell", "given": "Madeleine" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Asselberghs-I", "name": { "family": "Asselberghs", "given": "Inge" } }, { "id": "Clays-K", "name": { "family": "Clays", "given": "Koen" } }, { "id": "Gar\u00edn-J", "name": { "family": "Gar\u00edn", "given": "Javier" } }, { "id": "Orduna-J", "name": { "family": "Orduna", "given": "Jess" } } ] }, "title": "Diquat Derivatives: Highly Active, Two-Dimensional Nonlinear Optical Chromophores with Potential Redox Switchability", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nReceived April 19, 2010. Publication Date (Web): July 9, 2010. \n\nWe thank the EPSRC for support (Grants EP/E000738 and EP/D070732) and also the Fund for Scientific Research-Flanders (FWO-V, G.0297.04), the University of Leuven (GOA/2006/3), MCyT-FEDER (CTQ2005-01368, CTQ2008-02942), the NSF (Grant CHE-0802907, 'Powering the Planet: an NSF Center for Chemical Innovation') and Gobierno de Aragon-Fondo Social Europeo (E39). We thank Dr. Emma C. Fitzgerald for assistance with obtaining the data for Figure 4, Kurt De Mey for assistance with the HRS studies, and Dr. John E. Warren (Synchrotron Radiation Source, CCLRC, Daresbury Laboratory, Warrington WA4 4AD, U.K.) for assistance with the data collection for [16][NapSO3]2 \u00b72H2O and [18][PF6]2 \u00b72Me2CO.\n\nSupplemental Material - ja103289a_si_001.pdf
Supplemental Material - ja103289a_si_002.cif
", "abstract": "In this article, we present a detailed study of structure\u2212activity relationships in diquaternized 2,2\u2032-bipyridyl (diquat) derivatives. Sixteen new chromophores have been synthesized, with variations in the amino electron donor substituents, \u03c0-conjugated bridge, and alkyl diquaternizing unit. Our aim is to combine very large, two-dimensional (2D) quadratic nonlinear optical (NLO) responses with reversible redox chemistry. The chromophores have been characterized as their PF_6^\u2212 salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Their visible absorption spectra are dominated by intense \u03c0 \u2192 \u03c0^* intramolecular charge-transfer (ICT) bands, and all show two reversible diquat-based reductions. First hyperpolarizabilities \u03b2 have been measured by using hyper-Rayleigh scattering with an 800 nm laser, and Stark spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities \u03b2_0. The directly and indirectly derived \u03b2 values are large and increase with the extent of \u03c0-conjugation and electron donor strength. Extending the quaternizing alkyl linkage always increases the ICT energy and decreases the E_(1/2) values for diquat reduction, but a compensating increase in the ICT intensity prevents significant decreases in Stark-based \u03b2_0 responses. Nine single-crystal X-ray structures have also been obtained. Time-dependent density functional theory clarifies the molecular electronic/optical properties, and finite field calculations agree with polarized HRS data in that the NLO responses of the disubstituted species are dominated by 'off-diagonal' \u03b2_(zyy) components. The most significant findings of these studies are: (i) \u03b2_0 values as much as 6 times that of the chromophore in the technologically important material (E)-4\u2032-(dimethylamino)-N-methyl-4-stilbazolium tosylate; (ii) reversible electrochemistry that offers potential for redox-switching of optical properties over multiple states; (iii) strongly 2D NLO responses that may be exploited for novel practical applications; (iv) a new polar material, suitable for bulk NLO behavior.", "date": "2010-08-04", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "30", "publisher": "American Chemical Society", "pagerange": "10498-10512", "id_number": "CaltechAUTHORS:20100818-080217906", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100818-080217906", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/E000738" }, { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/D070732" }, { "agency": "Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)", "grant_number": "G.0297.04" }, { "agency": "University of Leuven", "grant_number": "GOA/2006/3" }, { "agency": "Ministerio de Ciencia y Tecnolog\u00eda (MCyT)", "grant_number": "CTQ2005-01368" }, { "agency": "Ministerio de Ciencia y Tecnolog\u00eda (MCyT)", "grant_number": "CTQ2008-029" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Gobierno de Aragon-Fondo Social Europeo", "grant_number": "E39" }, { "agency": "Fondo Europeo de Desarrollo Regional (FEDER)" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja103289a", "primary_object": { "basename": "ja103289a_si_001.pdf", "url": "https://authors.library.caltech.edu/records/j5mc7-b3q86/files/ja103289a_si_001.pdf" }, "related_objects": [ { "basename": "ja103289a_si_002.cif", "url": "https://authors.library.caltech.edu/records/j5mc7-b3q86/files/ja103289a_si_002.cif" } ], "pub_year": "2010", "author_list": "Coe, Benjamin J.; Fielden, John; et el." }, { "id": "https://authors.library.caltech.edu/records/4bzec-9rv51", "eprint_id": 19276, "eprint_status": "archive", "datestamp": "2023-08-22 00:26:14", "lastmod": "2023-10-20 20:29:39", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lancaster-K-M", "name": { "family": "Lancaster", "given": "Kyle M." }, "orcid": "0000-0001-7296-128X" }, { "id": "Gerken-J-B", "name": { "family": "Gerken", "given": "James B." } }, { "id": "Durrell-A-C", "name": { "family": "Durrell", "given": "Alec C." } }, { "id": "Palmer-J-H", "name": { "family": "Palmer", "given": "Joshua H." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Electronic structures, photophysical properties, and electrochemistry of ruthenium(II)(bpy)_2 pyridylimidazole complexes", "ispublished": "pub", "full_text_status": "restricted", "keywords": "Ruthenium; Pyridylimidazoles; Photophysics; Cyclic voltammetry", "note": "\u00a9 2010 Published by Elsevier B.V. \n\nReceived 20 August 2009; accepted 9 April 2010. Available online 24 April 2010. \n\nWe thank Jay Winkler and Theis Brock-Nannestad for discussions. We thank Tony Vl\u010dek for a critical reading of this manuscript. We also thank John D. Roberts and Brian Stoltz for the kind loan of reagents and equipment. This work was supported by the NSF Center for Chemical Innovation (Powering the Planet, CHE-0802907 and CHE-0947829), the Arnold and Mabel Beckman Foundation, and CCSER (Gordon and Betty Moore Foundation).", "abstract": "The properties of Ru^(II) complexes involving the imidazole moiety are discussed. Complexes [Ru(bpy)_2(L)]^(2+) [bpy = 2,2\u2032-bipyridine, L = 2-(2\u2032-pyridyl)imidazole (2-pimH) and 4-(2\u2032-pyridyl)imidazole (4-pimH)] have been synthesized and fully characterized. Reduction potentials are 0.76 V vs. Fc^+/Fc^0 for both complexes in acetonitrile solution, and the deprotonated complexes undergo irreversible electrochemical oxidation at 0.38 V vs. Fc^+/Fc^0. Density functional theory (DFT) calculations suggest that oxidation of the protonated complexes is primarily metal-based and that of the deprotonated complexes is ligand-centered. The pK_a of the 4-pimH complex was found to be 9.7 \u00b1 0.2; the pK_a of the 2-pimH complex is 7.9 \u00b1 0.2. Luminescence lifetimes (L = 4-pimH, 277 ns; 2-pimH, 224 ns; 4pim^\u2212, 40 ns; 2pim^\u2212, 34 ns in 5% methanol/water solution) combined with quantum yield data and acid\u2013base behavior suggest that the non-coordinated imidazole nitrogen tunes deactivation pathways.", "date": "2010-08", "date_type": "published", "publication": "Coordination Chemistry Reviews", "volume": "254", "number": "15-16", "publisher": "Elsevier", "pagerange": "1803-1811", "id_number": "CaltechAUTHORS:20100804-134627105", "issn": "0010-8545", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100804-134627105", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1016/j.ccr.2010.04.005", "pub_year": "2010", "author_list": "Lancaster, Kyle M.; Gerken, James B.; et el." }, { "id": "https://authors.library.caltech.edu/records/bzb47-vs884", "eprint_id": 19285, "eprint_status": "archive", "datestamp": "2023-08-19 03:10:23", "lastmod": "2023-10-20 20:30:25", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Palmer-J-H", "name": { "family": "Palmer", "given": "Joshua H." } }, { "id": "Durrell-A-C", "name": { "family": "Durrell", "given": "Alec C." } }, { "id": "Gross-Z", "name": { "family": "Gross", "given": "Zeev" } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Near-IR Phosphorescence of Iridium(III) Corroles at Ambient Temperature", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society.\nReceived March 2, 2010.\nPublication Date (Web): June 22, 2010.\n\nThis work was supported by the NSF Center\nfor Chemical Innovation (CCI Powering the Planet, Grants CHE-\n0802907 and CHE-0947829), the US-Israel BSF, CCSER (Gordon\nand Betty Moore Foundation), and the Arnold and Mabel Beckman\nFoundation.\n\nSupplemental Material - ja101647t_si_001.pdf
", "abstract": "The photophysical properties of Ir(III) corroles differ from those of phosphorescent porphyrin complexes, cyclometalated and polyimine Ir(III) compounds, and other luminescent metallocorroles. Ir(III) corrole phosphorescence is observed at ambient temperature at wavelengths much longer (>800 nm) than those of most Ir(III) phosphors. The solvatochromic behavior of Ir(III)-corrole Soret and Q absorption bands suggests that the lowest singlet excited states (S2 and S1) are substantially more polar than the ground state.", "date": "2010-07-14", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "27", "publisher": "American Chemical Society", "pagerange": "9230-9231", "id_number": "CaltechAUTHORS:20100805-082356637", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100805-082356637", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Binational Science Foundation (USA-Israel)" }, { "agency": "Caltech Center for Sustainable Energy Research" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja101647t", "primary_object": { "basename": "ja101647t_si_001.pdf", "url": "https://authors.library.caltech.edu/records/bzb47-vs884/files/ja101647t_si_001.pdf" }, "pub_year": "2010", "author_list": "Palmer, Joshua H.; Durrell, Alec C.; et el." }, { "id": "https://authors.library.caltech.edu/records/d1s69-86539", "eprint_id": 44651, "eprint_status": "archive", "datestamp": "2023-08-19 02:49:01", "lastmod": "2023-10-26 14:50:53", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lotito-K-J", "name": { "family": "Lotito", "given": "Kenneth J." } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Efficient luminescence from easily prepared three-coordinate copper(I) arylamidophosphines", "ispublished": "pub", "full_text_status": "public", "note": "This journal is \u00a9 The Royal Society of Chemistry 2010. \n\nReceived 13th January 2010, Accepted 30th March 2010, First published on the web 14th April 2010. \n\nThis work was supported by an NSF Center for Chemical Innovation (CHE-0802907). Luminescence measurements were carried out in the laboratory of T. M. Swager with assistance from T. L. Andrews. K. J. L. gratefully acknowledges a fellowship from the MIT Energy Initiative.\n\nElectronic supplementary information (ESI) available: Synthetic procedures and characterization, absorption spectrum of 6, excitation and emission spectra, electrochemical data, and solid state structures. CCDC 766167 (1), 766168 (2), 766169 (3), 766170 (7). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c000818d\n\nPublished - c000818d.pdf
Supplemental Material - c000818d__1_.pdf
Supplemental Material - c000818d.txt
", "abstract": "A series of brightly luminescent, three-coordinate copper(I) arylamidophosphine complexes have been prepared from readily available precursors in high yield. Emission maxima span 102 nm in the visible spectrum from 461 (blue) to 563 nm (yellow) while photoluminescence quantum yields range from 0.11 to 0.24 in fluid solution at room temperature.", "date": "2010-06-10", "date_type": "published", "publication": "Chemical Communications", "volume": "46", "number": "21", "publisher": "Royal Society of Chemistry", "pagerange": "3690-3692", "id_number": "CaltechAUTHORS:20140403-160228002", "issn": "1359-7345", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140403-160228002", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Center for Chemical Innovation", "grant_number": "CHE-0802907" }, { "agency": "MIT Energy Initiative" } ] }, "other_numbering_system": { "items": [ { "id": "766170", "name": "CCDC" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/C000818D", "primary_object": { "basename": "c000818d.pdf", "url": "https://authors.library.caltech.edu/records/d1s69-86539/files/c000818d.pdf" }, "related_objects": [ { "basename": "c000818d.txt", "url": "https://authors.library.caltech.edu/records/d1s69-86539/files/c000818d.txt" }, { "basename": "c000818d__1_.pdf", "url": "https://authors.library.caltech.edu/records/d1s69-86539/files/c000818d__1_.pdf" } ], "pub_year": "2010", "author_list": "Lotito, Kenneth J. and Peters, Jonas C." }, { "id": "https://authors.library.caltech.edu/records/9q8qw-mq606", "eprint_id": 18317, "eprint_status": "archive", "datestamp": "2023-08-19 02:05:15", "lastmod": "2023-10-20 16:06:25", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Durrell-A-C", "name": { "family": "Durrell", "given": "Alec C." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Hazari-N", "name": { "family": "Hazari", "given": "Nilay" } }, { "id": "Incarvito-C-D", "name": { "family": "Incarvito", "given": "Christopher D." } }, { "id": "Liu-Jian", "name": { "family": "Liu", "given": "Jian" }, "orcid": "0000-0001-8552-1400" }, { "id": "Yan-Elsa-C-Y", "name": { "family": "Yan", "given": "Elsa C. Y." } } ] }, "title": "Tris(hydroxypropyl)phosphine Oxide: A Chiral Three-Dimensional Material with Nonlinear Optical Properties", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society.\n\nReceived January 27, 2010. Publication Date (Web): March 17, 2010. \n\nWe thank Larry Henling for assistance with face indexing the crystal and George Rossman for assistance with single crystal Raman spectroscopy. This research was supported in part by the Starter Grant Award from the Spectroscopy Society of Pittsburgh (to E. C.Y.Y.) and the NSF Center for Chemical Innovation (CCI Powering the Plant, Grants CHE-0802907 and CHE-0947829 to H.B.G.).\n\nSupplemental Material - cg1001286_si_001.pdf
Supplemental Material - cg1001286_si_002.cif
", "abstract": "The achiral C_(3v) organic phosphine tris(hydroxypropyl)phosphine oxide (1) crystallizes in the unusual chiral hexagonal space group P6_3. The structure is highly ordered because each phosphine oxide moiety forms three hydrogen bonds with adjacent hydroxy groups from three different molecules. The properties of the crystals and the presence of hydrogen bonding interactions were investigated using single crystal Raman spectroscopy. The crystals show nonlinear optical properties and are capable of efficient second harmonic generation.", "date": "2010-04", "date_type": "published", "publication": "Crystal Growth and Design", "volume": "10", "number": "4", "publisher": "American Chemical Society", "pagerange": "1482-1485", "id_number": "CaltechAUTHORS:20100517-091141484", "issn": "1528-7483", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100517-091141484", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Spectroscopy Society of Pittsburgh" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1021/cg1001286", "primary_object": { "basename": "cg1001286_si_001.pdf", "url": "https://authors.library.caltech.edu/records/9q8qw-mq606/files/cg1001286_si_001.pdf" }, "related_objects": [ { "basename": "cg1001286_si_002.cif", "url": "https://authors.library.caltech.edu/records/9q8qw-mq606/files/cg1001286_si_002.cif" } ], "pub_year": "2010", "author_list": "Durrell, Alec C.; Gray, Harry B.; et el." }, { "id": "https://authors.library.caltech.edu/records/a6y9k-27464", "eprint_id": 17910, "eprint_status": "archive", "datestamp": "2023-08-19 01:59:02", "lastmod": "2023-10-20 15:24:34", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Coe-B-J", "name": { "family": "Coe", "given": "Benjamin J." }, "orcid": "0000-0002-5998-3895" }, { "id": "Fielden-J", "name": { "family": "Fielden", "given": "John" }, "orcid": "0000-0001-5963-7792" }, { "id": "Foxon-S-P", "name": { "family": "Foxon", "given": "Simon P." } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Asselberghs-I", "name": { "family": "Asselberghs", "given": "Inge" } }, { "id": "Clays-K", "name": { "family": "Clays", "given": "Koen" } }, { "id": "Samoc-A", "name": { "family": "Samoc", "given": "Anna" } }, { "id": "Samoc-M", "name": { "family": "Samoc", "given": "Marek" } } ] }, "title": "Combining Very Large Quadratic and Cubic Nonlinear Optical Responses in Extended, Tris-Chelate Metallochromophores with Six \u03c0-Conjugated Pyridinium Substituents", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nPublished In Issue March 17, 2010. Article ASAP February 18, 2010. Received: December 14, 2009. \n\nWe thank the EPSRC for support (grants EP/D070732 and EP/E000738) and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08), the University of Leuven (GOA/2006/3), the NSF (grant CHE-0802907, 'Powering the Planet: an NSF Center for Chemical Innovation') and the Foundation for Polish Science. I.A. is a postdoctoral fellow of the FWO-V and M.S. is a Laureate of the FNP Welcome programme.\n\nSupplemental Material - ja910538s_si_001.cif
Supplemental Material - ja910538s_si_002.cif
Supplemental Material - ja910538s_si_003.pdf
", "abstract": "We describe a series of nine new complex salts in which electron-rich Ru^(II) or Fe^(II) centers are\nconnected via \u03c0-conjugated bridges to six electron-accepting N-methyl-/N-arylpyridinium groups. This work\nbuilds upon our previous preliminary studies (Coe, B. J. J. Am. Chem. Soc. 2005, 127, 13399-13410; J.\nPhys. Chem. A 2007, 111, 472-478), with the aims of achieving greatly enhanced NLO properties and\nalso combining large quadratic and cubic effects in potentially redox-switchable molecules. Characterization\nhas involved various techniques, including electronic absorption spectroscopy and cyclic voltammetry. The\ncomplexes display intense, visible d \u2192 \u03c0^* metal-to-ligand charge-transfer (MLCT) bands, and their \u03c0 \u2192 \u03c0^*\nintraligand charge-transfer (ILCT) absorptions in the near-UV region show molar extinction coefficients as\nhigh as ca. 3.5 \u00d7 10^5 M^(-1) cm^(-1). Molecular quadratic nonlinear optical (NLO) responses \u03b2 have been\ndetermined by using hyper-Rayleigh scattering at 800 and 1064 nm and also via Stark (electroabsorption)\nspectroscopic studies. The directly and indirectly derived \u03b2 values are very large, with the Stark-based\nstatic first hyperpolarizabilities \u03b2_0 reaching as high as ca. 10^(-27) esu, and generally increase on extending\nthe \u03c0-conjugation and enhancing the electron-accepting strength of the ligands. Cubic NLO properties\nhave also been measured by using the Z-scan technique, revealing relatively high two-photon absorption\ncross sections of up to 2500 GM at 750 nm.", "date": "2010-03-17", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "10", "publisher": "American Chemical Society", "pagerange": "3496-3513", "id_number": "CaltechAUTHORS:20100408-153120348", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100408-153120348", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/D070732" }, { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/E000738" }, { "agency": "Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)", "grant_number": "G.0312.08" }, { "agency": "University of Leuven", "grant_number": "GOA/2006/3" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Foundation for Polish Science" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1021/ja910538s", "primary_object": { "basename": "ja910538s_si_003.pdf", "url": "https://authors.library.caltech.edu/records/a6y9k-27464/files/ja910538s_si_003.pdf" }, "related_objects": [ { "basename": "ja910538s_si_002.cif", "url": "https://authors.library.caltech.edu/records/a6y9k-27464/files/ja910538s_si_002.cif" }, { "basename": "ja910538s_si_001.cif", "url": "https://authors.library.caltech.edu/records/a6y9k-27464/files/ja910538s_si_001.cif" } ], "pub_year": "2010", "author_list": "Coe, Benjamin J.; Fielden, John; et el." }, { "id": "https://authors.library.caltech.edu/records/ny03t-byq66", "eprint_id": 17671, "eprint_status": "archive", "datestamp": "2023-08-19 01:38:45", "lastmod": "2023-10-20 00:08:15", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." } }, { "id": "Durrell-A-C", "name": { "family": "Durrell", "given": "Alec C." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Green-J-C", "name": { "family": "Green", "given": "Jennifer C." } }, { "id": "Hazari-N", "name": { "family": "Hazari", "given": "Nilay" } }, { "id": "Labinger-J-A", "name": { "family": "Labinger", "given": "Jay A." }, "orcid": "0000-0002-1942-9232" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" } ] }, "title": "Electronic Structures of Pd^(II) Dimers", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society.\nReceived November 5, 2009.\n\nPublication Date (Web): January 21, 2010\n\n\nWe thank George Rossman and Elizabeth\nMiura Boyd for assistance with single-crystal Raman\nspectroscopy and Larry Henling and Michael Day for assistance\nwith X-ray crystallography. This work was supported by BP\nthrough the MC2 program, the NSF Center for Chemical\nInnovation (Powering the Planet, CHE-0802907 and CHE-\n0947829), and CCSER (Gordon and Betty Moore Foundation).\nThe Bruker KAPPA APEXII X-ray diffractometer used in this\nwork was purchased via an NSF CRIF:MU CHE-0639094\naward to the California Institute of Technology.\n\nSupplemental Material - ic902189g_si_001.pdf
Supplemental Material - ic902189g_si_002.cif
", "abstract": "The Pd^(II) dimers [(2-phenylpyridine)Pd(\u03bc-X)]_2 and [(2-p-tolylpyridine)Pd(\u03bc-X)]_2 (X = OAc or TFA) do not exhibit the expected planar geometry (of approximate D_(2h) symmetry) but instead resemble an open \"clamshell\" in which the acetate ligands are perpendicular to the plane containing the Pd atoms and 2-arylpyridine ligands, with the Pd atoms brought quite close to one another (approximate distance 2.85 \u00c5). The molecules adopt this unusual geometry in part because of a d^8\u2212d^8 bonding interaction between the two Pd centers. The Pd\u2212Pd dimers exhibit two successive one-electron oxidations: Pd^(II)\u2212Pd^(II) to Pd^(II)\u2212Pd^(III) to Pd^(III)\u2212Pd^(III). Photophysical measurements reveal clear differences in the UV\u2212visible and low-temperature fluorescence spectra between the clamshell dimers and related planar dimeric [(2-phenylpyridine)Pd(\u03bc-Cl)]_2 and monomeric [(2-phenylpyridine)Pd(en)][Cl] (en = ethylenediamine) complexes that do not have any close Pd\u2212Pd contacts. Density functional theory and atoms in molecules analyses confirm the presence of a Pd\u2212Pd bonding interaction in [(2-phenylpyridine)Pd(\u03bc-X)]_2 and show that the highest occupied molecular orbital is a d_(z2) \u03c3* Pd\u2212Pd antibonding orbital, while the lowest unoccupied molecular orbital and close-lying empty orbitals are mainly located on the 2-phenylpyridine rings. Computational analyses of other Pd^(II)\u2212Pd^(II) dimers that have short Pd\u2212Pd distances yield an orbital ordering similar to that of [(2-phenylpyridine)Pd(\u03bc-X)]_2, but quite different from that found for d^8\u2212d^8 dimers of Rh, Ir, and Pt. This difference in orbital ordering arises because of the unusually large energy gap between the 4d and 5p orbitals in Pd and may explain why Pd d^8\u2212d^8 dimers do not exhibit the distinctive photophysical properties of related Rh, Ir, and Pt species.", "date": "2010-02-15", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "49", "number": "4", "publisher": "American Chemical Society", "pagerange": "1801-1810", "id_number": "CaltechAUTHORS:20100305-091958620", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100305-091958620", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Caltech Center for Sustainable Energy Research" }, { "agency": "NSF", "grant_number": "CHE-0639094" }, { "agency": "BP MC2 program" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1021/ic902189g", "primary_object": { "basename": "ic902189g_si_002.cif", "url": "https://authors.library.caltech.edu/records/ny03t-byq66/files/ic902189g_si_002.cif" }, "related_objects": [ { "basename": "ic902189g_si_001.pdf", "url": "https://authors.library.caltech.edu/records/ny03t-byq66/files/ic902189g_si_001.pdf" } ], "pub_year": "2010", "author_list": "Bercaw, John E.; Durrell, Alec C.; et el." }, { "id": "https://authors.library.caltech.edu/records/f4tpb-wta85", "eprint_id": 17838, "eprint_status": "archive", "datestamp": "2023-08-19 01:37:29", "lastmod": "2023-10-20 15:19:36", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Coe-B-J", "name": { "family": "Coe", "given": "Benjamin J." }, "orcid": "0000-0002-5998-3895" }, { "id": "Foxon-S-P", "name": { "family": "Foxon", "given": "Simon P." } }, { "id": "Harper-E-C", "name": { "family": "Harper", "given": "Elizabeth C." } }, { "id": "Helliwell-M", "name": { "family": "Helliwell", "given": "Madeleine" } }, { "id": "Raftery-J", "name": { "family": "Raftery", "given": "James" } }, { "id": "Swanson-C-A", "name": { "family": "Swanson", "given": "Catherine A." } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Clays-K", "name": { "family": "Clays", "given": "Koen" } }, { "id": "Franz-E", "name": { "family": "Franz", "given": "Edith" } }, { "id": "Garin-J", "name": { "family": "Garin", "given": "Javier" } }, { "id": "Orduna-J", "name": { "family": "Orduna", "given": "Jes\u00fas" } }, { "id": "Horton-P-N", "name": { "family": "Horton", "given": "Peter N." } }, { "id": "Hursthouse-M-B", "name": { "family": "Hursthouse", "given": "Michael B." } } ] }, "title": "Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nReceived October 20, 2009. Publication Date (Web): January 15, 2010. \n\nWe thank the EPSRC for support (grant EP/D070732/1) and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08), the University of Leuven (GOA/2006/3), MCyT-FEDER (CTQ2005-01368, CTQ2008-02942), the NSF (grant CHE-0802907, \"Powering the Planet: an NSF Center for Chemical Innovation\") and Gobierno de Aragon-Fondo Social Europeo (E39). We are grateful to Dr. Inge Asselberghs for technical assistance with the analysis of the HRS data.\n\nSupplemental Material - ja908667p_si_001.pdf
Supplemental Material - ja908667p_si_002.cif
", "abstract": "In this article, we describe a series of complexes with electron-rich cis-{Ru^(II)(NH_3)_4}^(2+) centers coordinated to two pyridyl ligands bearing N-methyl/arylpyridinium electron-acceptor groups. These V-shaped dipolar species are new, extended members of a class of chromophores first reported by us (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845\u22124859). They have been isolated as their PF_6\u2212 salts and characterized by using various techniques including ^1H NMR and electronic absorption spectroscopies and cyclic voltammetry. Reversible Ru^(III/II) waves show that the new complexes are potentially redox-switchable chromophores. Single crystal X-ray structures have been obtained for four complex salts; three of these crystallize noncentrosymmetrically, but with the individual molecular dipoles aligned largely antiparallel. Very large molecular first hyperpolarizabilities \u03b2 have been determined by using hyper-Rayleigh scattering (HRS) with an 800 nm laser and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d \u2192 \u03c0^* metal-to-ligand charge-transfer (MLCT) and \u03c0 \u2192 \u03c0^* intraligand charge-transfer (ILCT) bands. The latter measurements afford total nonresonant \u03b2_0 responses as high as ca. 600 \u00d7 10^(\u221230) esu. These pseudo-C_(2v) chromophores show two substantial components of the \u03b2 tensor, \u03b2_(zzz) and \u03b2_(zyy), although the relative significance of these varies with the physical method applied. According to HRS, \u03b2_(zzz) dominates in all cases, whereas the Stark analyses indicate that \u03b2_(zyy) is dominant in the shorter chromophores, but \u03b2_(zzz) and \u03b2_(zyy) are similar for the extended species. In contrast, finite field calculations predict that \u03b2_(zyy) is always the major component. Time-dependent density functional theory calculations predict increasing ILCT character for the nominally MLCT transitions and accompanying blue-shifts of the visible absorptions, as the ligand \u03c0-systems are extended. Such unusual behavior has also been observed with related 1D complexes (Coe, B. J. et al. J. Am. Chem. Soc. 2004, 126, 3880\u22123891).", "date": "2010-02-10", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "5", "publisher": "American Chemical Society", "pagerange": "1706-1723", "id_number": "CaltechAUTHORS:20100401-105537118", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100401-105537118", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/D070732/1" }, { "agency": "Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)", "grant_number": "G.0312.08" }, { "agency": "University of Leuven", "grant_number": "GOA/2006/3" }, { "agency": "Ministerio de Ciencia y Tecnolog\u00eda (MCyT)", "grant_number": "CTQ2005-01368" }, { "agency": "Ministerio de Ciencia y Tecnolog\u00eda (MCyT)", "grant_number": "CTQ2008-02942" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Gobierno de Aragon-Fondo Social Europeo", "grant_number": "E39" }, { "agency": "Fondo Europeo de Desarrollo Regional (FEDER)" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1021/ja908667p", "primary_object": { "basename": "ja908667p_si_002.cif", "url": "https://authors.library.caltech.edu/records/f4tpb-wta85/files/ja908667p_si_002.cif" }, "related_objects": [ { "basename": "ja908667p_si_001.pdf", "url": "https://authors.library.caltech.edu/records/f4tpb-wta85/files/ja908667p_si_001.pdf" } ], "pub_year": "2010", "author_list": "Coe, Benjamin J.; Foxon, Simon P.; et el." }, { "id": "https://authors.library.caltech.edu/records/qm400-k3a64", "eprint_id": 17499, "eprint_status": "archive", "datestamp": "2023-08-21 23:17:27", "lastmod": "2023-10-19 23:57:04", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hartings-M-R", "name": { "family": "Hartings", "given": "Matthew R." } }, { "id": "Kurnikov-I-V", "name": { "family": "Kurnikov", "given": "Igor V." } }, { "id": "Dunn-Alexander-R", "name": { "family": "Dunn", "given": "Alexander R." }, "orcid": "0000-0001-6096-4600" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Ratner-M-A", "name": { "family": "Ratner", "given": "Mark A." } } ] }, "title": "Electron tunneling through sensitizer wires bound to proteins", "ispublished": "pub", "full_text_status": "public", "keywords": "Cytochrome P450; Protein electron transfer; Conformational dynamics electron transfer; Bridge effects electron transfer", "note": "\u00a9 2009 Elsevier B.V.\n\nReceived 23 June 2009; accepted 7 August 2009. Available online 15 August 2009. \n\nInorganic Reaction Mechanisms - A Tribute to Ralph Pearson on the occasion of his 90th birthday.\nWe thank David Beratan for helpful discussions. This work\nwas supported by NIH (GM078792 to MRH and DK019038 to\nHBG and GM068461 to JRW) and NSF (CHE-0802907 to HBG and\nJRW). MR thanks the MURI program of the AFOSR and the Chemistry\nDivision of the NSF for support. This paper is dedicated\nto Ralph Pearson\u2014friend, mentor, colleague, scientist and honest\nbroker.\n\nAccepted Version - nihms-138947.pdf
", "abstract": "We report a quantitative theoretical analysis of long-range electron transfer through sensitizer wires bound in the active-site channel of cytochrome P450cam. Each sensitizer wire consists of a substrate group with high binding affinity for the enzyme active site connected to a ruthenium-diimine through a bridging aliphatic or aromatic chain. Experiments have revealed a dramatic dependence of electron transfer rates on the chemical composition of both the bridging group and the substrate. Using combined molecular dynamics simulations and electronic coupling calculations, we show that electron tunneling through perfluorinated aromatic bridges is promoted by enhanced superexchange coupling through virtual reduced states. In contrast, electron flow through aliphatic bridges occurs by hole-mediated superexchange. We have found that a small number of wire conformations with strong donor\u2013acceptor couplings can account for the observed electron tunneling rates for sensitizer wires terminated with either ethylbenzene or adamantane. In these instances, the rate is dependent not only on electronic coupling of the donor and acceptor but also on the nuclear motion of the sensitizer wire, necessitating the calculation of average rates over the course of a molecular dynamics simulation. These calculations along with related recent findings have made it possible to analyze the results of many other sensitizer-wire experiments that in turn point to new directions in our attempts to observe reactive intermediates in the catalytic cycles of P450 and other heme enzymes.", "date": "2010-02", "date_type": "published", "publication": "Coordination Chemistry Reviews", "volume": "254", "number": "3-4", "publisher": "Elsevier", "pagerange": "248-253", "id_number": "CaltechAUTHORS:20100217-095253375", "issn": "0010-8545", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100217-095253375", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "GM078792" }, { "agency": "NIH", "grant_number": "DK019038" }, { "agency": "NIH", "grant_number": "GM068461" }, { "agency": "NSF", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1016/j.ccr.2009.08.008", "pmcid": "PMC2797321", "primary_object": { "basename": "nihms-138947.pdf", "url": "https://authors.library.caltech.edu/records/qm400-k3a64/files/nihms-138947.pdf" }, "pub_year": "2010", "author_list": "Hartings, Matthew R.; Kurnikov, Igor V.; et el." }, { "id": "https://authors.library.caltech.edu/records/5gghh-tc813", "eprint_id": 17867, "eprint_status": "archive", "datestamp": "2023-08-19 01:30:15", "lastmod": "2023-10-20 15:21:37", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dempsey-J-L", "name": { "family": "Dempsey", "given": "Jillian L." } }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Kinetics of Electron Transfer Reactions of H_2-Evolving Cobalt Diglyoxime Catalysts", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2009 American Chemical Society. Received September 21, 2009. Publication Date (Web): December 31, 2009. We thank Bruce Brunschwig, Xile Hu, Jay\nLabinger, and Jonas Peters for insightful discussions. We also thank\nEtsuko Fujita for generous assistance in obtaining in situ absorption\nspectra. This work was supported by the NSF Center for Chemical\nInnovation (Powering the Planet, CHE-0802907 and CHE-\n0947829), the Arnold and Mabel Beckman Foundation, CCSER\n(Gordon and Betty Moore Foundation), and the BP MC2 program.\nJLD is an NSF Graduate Research Fellow.\n\nSupplemental Material - ja9080259_si_001.pdf
", "abstract": "Co\u2212diglyoxime complexes catalyze H_2 evolution from protic solutions at modest overpotentials. Upon reduction to Co^I, a Co^(III)-hydride is formed by reaction with a proton donor. Two pathways for H_2 production are analyzed: one is a heterolytic route involving protonation of the hydride to release H_2 and generate Co^(III); the other is a homoytic pathway requiring association of two Co^(III)-hydrides. Rate constants and reorganization parameters were estimated from analyses of laser flash\u2212quench kinetics experiments (Co^(III)\u2212Co^(II) self-exchange k = 9.5 \u00d7 10^(\u22128) \u2212 2.6 \u00d7 10^(\u22125) M^(\u22121) s^(\u22121); \u03bb = 3.9 (\u00b10.3) eV: Co^(II)\u2212Co^(I) self-exchange k = 1.2 (\u00b10.5) \u00d7 10^5 M^(\u22121) s^(\u22121); \u03bb = 1.4 (\u00b10.05) eV). Examination of both the barriers and driving forces associated with the two pathways indicates that the homolytic reaction (Co^(III)H + Co^(III)H \u2192 2 Co^(II) + H_2) is favored over the route that goes through a Co^(III) intermediate (Co^(III)H + H+ \u2192 Co^(III) + H_2).", "date": "2010-01-27", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "3", "publisher": "American Chemical Society", "pagerange": "1060-1065", "id_number": "CaltechAUTHORS:20100406-102958526", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100406-102958526", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE- 0947829" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "BP MC2 program" }, { "agency": "Caltech Center for Sustainable Energy Research" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1021/ja9080259", "primary_object": { "basename": "ja9080259_si_001.pdf", "url": "https://authors.library.caltech.edu/records/5gghh-tc813/files/ja9080259_si_001.pdf" }, "pub_year": "2010", "author_list": "Dempsey, Jillian L.; Winkler, Jay R.; et el." }, { "id": "https://authors.library.caltech.edu/records/1932x-s9p76", "eprint_id": 44647, "eprint_status": "archive", "datestamp": "2023-08-19 01:28:32", "lastmod": "2023-10-26 14:50:45", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Berben-L-A", "name": { "family": "Berben", "given": "Louise A." } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Hydrogen evolution by cobalt tetraimine catalysts adsorbed on electrode surfaces", "ispublished": "pub", "full_text_status": "public", "note": "This journal is \u00a9 The Royal Society of Chemistry 2010. \n\nReceived (in Berkeley, CA, USA) 14th October 2009, Accepted 10th November 2009, First published on the web 25th November 2009. \n\nThis work was supported by an NSF Center for Chemical Innovation (CHE-0802907) and by the Chesonis Family Foundation. Grants from NSF provided instrument support to the DCIF at MIT (CHE-9808061, DBI-9729592). We thank Dr Bruce Parkinson for helpful comments. \n\nElectronic supplementary information (ESI) available: Syntheses and characterization of compounds, plots of electrochemical measurements, CIF files for solid-state structures. CCDC 735555\u2013735559. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/b921559j\n\nPublished - b921559j.pdf
Supplemental Material - b921559j__1_.pdf
Supplemental Material - b921559j.txt
", "abstract": "Aryl-substituted tetraimine complexes related to Co(dmgBF_2)_2(MeCN)_2 (dmg = dimethylglyoxime) were synthesized and are active for hydrogen evolution. Co(dmgBF_2)_2(MeCN)_2 can be adsorbed to a glassy carbon electrode. The chemically modified electrode is active for hydrogen evolution in aqueous solution at pH < 4.5, with an overpotential of only 100 mV.", "date": "2010-01-21", "date_type": "published", "publication": "Chemical Communications", "volume": "46", "number": "3", "publisher": "Royal Society of Chemistry", "pagerange": "398-400", "id_number": "CaltechAUTHORS:20140403-153248105", "issn": "1359-7345", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140403-153248105", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Center for Chemical Innovation", "grant_number": "CHE-0802907" }, { "agency": "Chesonis Family Foundation" }, { "agency": "NSF", "grant_number": "CHE-9808061" }, { "agency": "NSF", "grant_number": "DBI-9729592" } ] }, "collection": "CaltechAUTHORS", "other_numbering_system": { "items": [ { "id": "735555\u2013735559", "name": "CCDC" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1039/B921559J", "primary_object": { "basename": "b921559j.pdf", "url": "https://authors.library.caltech.edu/records/1932x-s9p76/files/b921559j.pdf" }, "related_objects": [ { "basename": "b921559j__1_.pdf", "url": "https://authors.library.caltech.edu/records/1932x-s9p76/files/b921559j__1_.pdf" }, { "basename": "b921559j.txt", "url": "https://authors.library.caltech.edu/records/1932x-s9p76/files/b921559j.txt" } ], "pub_year": "2010", "author_list": "Berben, Louise A. and Peters, Jonas C." }, { "id": "https://authors.library.caltech.edu/records/pe2st-hmr23", "eprint_id": 17186, "eprint_status": "archive", "datestamp": "2023-08-19 00:55:41", "lastmod": "2023-10-19 23:37:38", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Coe-B-J", "name": { "family": "Coe", "given": "Benjamin J." }, "orcid": "0000-0002-5998-3895" }, { "id": "Docherty-R-J", "name": { "family": "Docherty", "given": "Rebecca J." } }, { "id": "Foxon-S-P", "name": { "family": "Foxon", "given": "Simon P." } }, { "id": "Harper-E-C", "name": { "family": "Harper", "given": "Elizabeth C." } }, { "id": "Helliwell-M", "name": { "family": "Helliwell", "given": "Madeleine" } }, { "id": "Raftery-J", "name": { "family": "Raftery", "given": "James" } }, { "id": "Clays-K", "name": { "family": "Clays", "given": "Koen" } }, { "id": "Franz-E", "name": { "family": "Franz", "given": "Edith" } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" } ] }, "title": "Syntheses and Properties of Salts of Chromophores with Ferrocenyl Electron Donor Groups and Quaternary Nitrogen Acceptors", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2009 American Chemical Society. \n\nReceived September 11, 2009. Publication Date (Web): November 12, 2009. \n\nWe thank the EPSRC for support in the form of a Ph.D. studentship (E.C.H.) and a postdoctoral grant (S.P.F., EP/D070732), and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08) and the University of Leuven (GOA/2006/3). B.S.B. acknowledges support from the NSF (CHE-0802907, 'Powering the Planet: an NSF Center for Chemical Innovation').\n\nSupplemental Material - om9007955_si_001.cif
", "abstract": "A series of five new dipolar cations has been synthesized with ferrocenyl (Fc) electron donor groups connected to N-arylpyridinium, N-methylquinolinium, N-methylbenzothiazolium, or N-methylacridinium acceptors. Together with their known N-methylpyridinium analogue, these chromophores have been characterized as their PF_6^\u2212 salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Nine single-crystal X-ray structures have been determined, including two polymorphs of one salt obtained from a single crystallization experiment, and two of these are polar materials. A highly favorable degree of dipolar alignment for bulk NLO effects is observed in one case. Molecular quadratic nonlinear optical (NLO) responses have been determined by using femtosecond hyper-Rayleigh scattering (HRS) at 1300 nm and also via Stark (electroabsorption) spectroscopic studies on the intense \u03c0 \u2192 \u03c0^* intraligand and d \u2192 \u03c0^* metal-to-ligand charge-transfer bands. A broad correlation between the electron acceptor strength and the HRS-derived first hyperpolarizabilities \u03b2 and the static first hyperpolarizabilities \u03b20 estimated from the Stark data is evident. This is the first time that meaningful (albeit indirectly determined) \u03b2_0 data have been reported for Fc compounds, allowing quantitative comparisons with the chromophore in the technologically important material (E)-4\u2032-(dimethylamino)-N-methyl-4-stilbazolium (DAS) tosylate. The observed \u03b2_0 values are in several cases similar to that of [DAS]PF_6, and possibly even larger in one instance.", "date": "2009-12-28", "date_type": "published", "publication": "Organometallics", "volume": "28", "number": "24", "publisher": "American Chemical Society", "pagerange": "6880-6892", "id_number": "CaltechAUTHORS:20100114-133116831", "issn": "0276-7333", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100114-133116831", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Engineering and Physical Sciences Research Council (EPSRC)", "grant_number": "EP/D070732" }, { "agency": "Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)", "grant_number": "G.0312.08" }, { "agency": "University of Leuven", "grant_number": "GOA/2006/3" }, { "agency": "NSF", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/om9007955", "primary_object": { "basename": "om9007955_si_001.cif", "url": "https://authors.library.caltech.edu/records/pe2st-hmr23/files/om9007955_si_001.cif" }, "pub_year": "2009", "author_list": "Coe, Benjamin J.; Docherty, Rebecca J.; et el." }, { "id": "https://authors.library.caltech.edu/records/nvaeq-ny258", "eprint_id": 17228, "eprint_status": "archive", "datestamp": "2023-08-19 00:40:52", "lastmod": "2023-10-19 23:40:14", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dempsey-J-L", "name": { "family": "Dempsey", "given": "Jillian L." } }, { "id": "Brunschwig-B-S", "name": { "family": "Brunschwig", "given": "Bruce S." }, "orcid": "0000-0002-6135-6727" }, { "id": "Winkler-J-R", "name": { "family": "Winkler", "given": "Jay R." }, "orcid": "0000-0002-4453-9716" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Hydrogen Evolution Catalyzed by Cobaloximes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2009 American Chemical Society. \n\nReceived on September 30, 2009. Publication Date (Web): November 23, 2009. \n\nWe thank Xile Hu, Louise Berben, Brandi Cossairt, and Jonas Peters for discussions and their important contributions to cobaloxime chemistry. This work was supported by an NSF Center for Chemical Innovation (CCI Powering the Planet, Grants CHE-0802907 and CHE-0947829), the Arnold and Mabel Beckman Foundation, CCSER (Gordon and Betty Moore Foundation), and the BP MC2 program. J.L.D. is an NSF Graduate Research Fellow.", "abstract": "Natural photosynthesis uses sunlight to drive the conversion\nof energy-poor molecules (H_2O, CO_2) to energyrich\nones (O_2, (CH_2O)_n). Scientists are working hard to develop\nefficient artificial photosynthetic systems toward the \"Holy\nGrail\" of solar-driven water splitting. High on the list of challenges\nis the discovery of molecules that efficiently catalyze\nthe reduction of protons to H_2. In this Account, we report on\none promising class of molecules: cobalt complexes with diglyoxime\nligands (cobaloximes).\nChemical, electrochemical, and photochemical methods all\nhave been utilized to explore proton reduction catalysis by\ncobaloxime complexes. Reduction of a Co^(II)-diglyoxime generates\na Co^I species that reacts with a proton source to produce\na Co^(III)-hydride. Then, in a homolytic pathway, two Co^(III) hydrides\nreact in a bimolecular step to eliminate H_2.\nAlternatively, in a heterolytic pathway, protonation of the\nCo^(III)-hydride produces H_2 and Co^(III).\nA thermodynamic analysis of H_2 evolution pathways sheds\nnew light on the barriers and driving forces of the elementary\nreaction steps involved in proton reduction by Co^I-diglyoximes.\nIn combination with experimental results, this\nanalysis shows that the barriers to H_2 evolution along the heterolytic\npathway are, in most cases, substantially greater than those of the homolytic route. In particular, a formidable barrier\nis associated with Co^(III)-diglyoxime formation along the heterolytic pathway.\nOur investigations of cobaloxime-catalyzed H_2 evolution, coupled with the thermodynamic preference for a homolytic route,\nsuggest that the rate-limiting step is associated with formation of the hydride. An efficient water splitting device may require\nthe tethering of catalysts to an electrode surface in a fashion that does not inhibit association of Co^(III)-hydrides.", "date": "2009-12", "date_type": "published", "publication": "Accounts of Chemical Research", "volume": "42", "number": "12", "publisher": "American Chemical Society", "pagerange": "1995-2004", "id_number": "CaltechAUTHORS:20100120-084526967", "issn": "0001-4842", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100120-084526967", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0947829" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "BP MC2 program" }, { "agency": "NSF Graduate Research Fellowship" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1021/ar900253e", "pub_year": "2009", "author_list": "Dempsey, Jillian L.; Brunschwig, Bruce S.; et el." }, { "id": "https://authors.library.caltech.edu/records/rnvdr-mnv33", "eprint_id": 17086, "eprint_status": "archive", "datestamp": "2023-08-21 22:46:45", "lastmod": "2023-10-19 22:48:07", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lancaster-K-M", "name": { "family": "Lancaster", "given": "Kyle M." }, "orcid": "0000-0001-7296-128X" }, { "id": "George-S-D", "name": { "family": "George", "given": "Serena DeBeer" } }, { "id": "Yokoyama-Keiko", "name": { "family": "Yokoyama", "given": "Keiko" } }, { "id": "Richards-J-H", "name": { "family": "Richards", "given": "John H." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Type-zero copper proteins", "ispublished": "pub", "full_text_status": "public", "keywords": "Chemical biology; Inorganic chemistry", "note": "\u00a9 2009 Macmillan Publishers Limited. \n\nReceived 5 May 2009; Accepted 15 September 2009; Published online 1 November 2009. \n \nWe thank B. Brunschwig for assistance with Fourier transform infrared spectroscopy, Z. Gates and L. Thomas for assistance with X-ray diffraction data collection, and M. Day and J. Kaiser for discussions of crystal structural analyses. We thank E. Solomon for helpful comments on electronic structural formulations, and Y. Sheng for assistance with protein expression and purification. Stanford Synchrotron Radiation Lightsource operations are funded by DOE(BES). The Structural Molecular Biology program is supported by NIH (NCRR BMTP) (Grant Number 5 P41 RR001209)N and DOE(BER). This work was supported by NIH DK019038(HBG), Stanford GCEP, and NSF CHE-0802907. The Caltech Molecular Observatory is supported by the Gordon and Betty Moore Foundation. \n\nAuthor Contributions: K.M.L. and H.B.G. conceived and designed the experiments; K.M.L., S.D.G., and K.Y. performed the experiments; K.M.L., S.D.G., K.Y., and H.B.G. analysed the data, K.M.L., S.D.G., J.H.R., and H.B.G. co-wrote the paper.\n\nAccepted Version - nihms146123.pdf
Supplemental Material - Lancaster2009p6499Nat_Chem_supp.pdf
", "abstract": "Many proteins contain copper in a range of coordination environments, where it has various biological roles, such as transferring electrons or activating dioxygen. These copper sites can be classified by their function or spectroscopic properties. Those with a single copper atom are either type 1, with an intense absorption band near 600 nm, or type 2, with weak absorption in the visible region. We have built a novel copper(ii) binding site within structurally modified Pseudomonas aeruginosa azurins that does not resemble either existing type, which we therefore call 'type zero'. X-ray crystallographic analysis shows that these sites adopt distorted tetrahedral geometries, with an unusually short Cu\u2013O (G45 carbonyl) bond. Relatively weak absorption near 800 nm and narrow parallel hyperfine splittings in electron paramagnetic resonance spectra are the spectroscopic signatures of type zero copper. Cyclic voltammetric experiments demonstrate that the electron transfer reactivities of type-zero azurins are enhanced relative to that of the corresponding type 2 (C112D) protein.", "date": "2009-12", "date_type": "published", "publication": "Nature Chemistry", "volume": "1", "number": "9", "publisher": "Nature Publishing Group", "pagerange": "711-715", "id_number": "CaltechAUTHORS:20100107-092654651", "issn": "1755-4330", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20100107-092654651", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "5 P41 RR001209" }, { "agency": "Department of Energy (DOE)" }, { "agency": "NIH", "grant_number": "DK019038" }, { "agency": "Stanford Global Climate and Energy Project (GCEP)" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1038/NCHEM.412", "pmcid": "PMC2841405", "primary_object": { "basename": "Lancaster2009p6499Nat_Chem_supp.pdf", "url": "https://authors.library.caltech.edu/records/rnvdr-mnv33/files/Lancaster2009p6499Nat_Chem_supp.pdf" }, "related_objects": [ { "basename": "nihms146123.pdf", "url": "https://authors.library.caltech.edu/records/rnvdr-mnv33/files/nihms146123.pdf" } ], "pub_year": "2009", "author_list": "Lancaster, Kyle M.; George, Serena DeBeer; et el." }, { "id": "https://authors.library.caltech.edu/records/exy60-kxc11", "eprint_id": 44646, "eprint_status": "archive", "datestamp": "2023-08-19 00:37:12", "lastmod": "2023-10-26 14:50:43", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Szymczak-N-K", "name": { "family": "Szymczak", "given": "Nathaniel K." }, "orcid": "0000-0002-1296-1445" }, { "id": "Berben-L-A", "name": { "family": "Berben", "given": "Louise A." } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Redox rich dicobalt macrocycles as templates for multi-electron transformations", "ispublished": "pub", "full_text_status": "public", "note": "This journal is \u00a9 The Royal Society of Chemistry 2009. \n\nReceived 13 Jul 2009, Accepted 17 Sep 2009, First published online 06 Oct 2009. \n\nThis work was generously supported by BP and an NSF Center for Chemical Innovation grant (Grant CHE-0802907). We thank Dr Yunho Lee and Dr Sebastian Stoian for EPR assistance, and Dr Bruce Brunschwig for helpful discussions. \n\nElectronic supplementary information (ESI) available: Complete experimental details and crystal structures. CCDC 740044\u2013740052. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/b913946j\n\nPublished - b913946j.pdf
Supplemental Material - b913946j__1_.pdf
Supplemental Material - b913946j.txt
", "abstract": "Pyridazine-templated dicobalt macrocycles reversibly support five oxidation states with unusually positive Co^(II)/Co^I redox couples, and are also active proton reduction electrocatalysts.", "date": "2009-11-28", "date_type": "published", "publication": "Chemical Communications", "volume": "2009", "number": "44", "publisher": "Royal Society of Chemistry", "pagerange": "6729-6731", "id_number": "CaltechAUTHORS:20140403-151953405", "issn": "1359-7345", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140403-151953405", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "BP" }, { "agency": "NSF Center for Chemical Innovation", "grant_number": "CHE-0802907" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1039/B913946J", "primary_object": { "basename": "b913946j.pdf", "url": "https://authors.library.caltech.edu/records/exy60-kxc11/files/b913946j.pdf" }, "related_objects": [ { "basename": "b913946j.txt", "url": "https://authors.library.caltech.edu/records/exy60-kxc11/files/b913946j.txt" }, { "basename": "b913946j__1_.pdf", "url": "https://authors.library.caltech.edu/records/exy60-kxc11/files/b913946j__1_.pdf" } ], "pub_year": "2009", "author_list": "Szymczak, Nathaniel K.; Berben, Louise A.; et el." }, { "id": "https://authors.library.caltech.edu/records/a2mhd-mp244", "eprint_id": 16309, "eprint_status": "archive", "datestamp": "2023-08-19 00:16:40", "lastmod": "2023-10-19 22:05:41", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Palmer-J-H", "name": { "family": "Palmer", "given": "Joshua H." } }, { "id": "Mahammed-Atif", "name": { "family": "Mahammed", "given": "Atif" } }, { "id": "Lancaster-K-M", "name": { "family": "Lancaster", "given": "Kyle M." }, "orcid": "0000-0001-7296-128X" }, { "id": "Gross-Z", "name": { "family": "Gross", "given": "Zeev" }, "orcid": "0000-0003-1170-2115" }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Structures and Reactivity Patterns of Group 9 Metallocorroles", "ispublished": "pub", "full_text_status": "public", "note": "Copyright \u00a9 2009 American Chemical Society. \n\nReceived June 17, 2009. Publication Date (Web): September 8, 2009. \n\nThis work was supported by the Center for Chemical Innovation Grant NSF CHE-0802907, U.S.\u2212Israel BSF (Z.G. and H.B.G.), BP, CCSER (Gordon and Betty Moore Foundation), and the Arnold and Mabel Beckman Foundation. We thank Dr. Angelo Di Bilio for help with measurements of low-temperature EPR spectra; and Drs. Lawrence M. Henling and Michael W. Day for assistance with the acquisition and analysis of crystallographic data. \n\nSupporting Information: Additional information as noted in the text. This material is available free of charge via the Internet at http://pubs.acs.org.\n\nSupplemental Material - ic901164r_si_001.pdf
Supplemental Material - ic901164r_si_002.pdf
", "abstract": "Group 9 metallocorroles 1-M(PPh_3) and 1-M(py)_2 [M = Co(III), Rh(III), Ir(III); 1 denotes the trianion of 5,10,15-tris-pentafluorophenylcorrole] have been fully characterized by structural, spectroscopic, and electrochemical methods. Crystal structure analyses reveal that average metal\u2212N(pyrrole) bond lengths of the bis-pyridine metal(III) complexes increase from Co (1.886 \u00c5) to Rh (1.957 \u00c5)/Ir (1.963 \u00c5); and the average metal\u2212N(pyridine) bond lengths also increase from Co (1.995 \u00c5) to Rh (2.065 \u00c5)/Ir (2.059 \u00c5). Ligand affinities for 1-M(PPh_3) axial coordination sites increase dramatically in the order 1-Co(PPh_3) < 1-Rh(PPh_3) < 1-Ir(PPh_3). There is a surprising invariance in the M(+/0) reduction potentials within the five- and six-coordinate corrole series, and even between them; the average M(+/0) potential of 1-M(PPh_3) is 0.78 V vs Ag/AgCl in CH_2Cl_2 solution, whereas that of 1-M(py)_2 is 0.70 V under the same conditions. Electronic structures of one-electron-oxidized 1-M(py)_2 complexes have been assigned by analysis of electron paramagnetic resonance spectroscopic measurements: oxidation is corrole-centered for 1-Co(py)_2 (g = 2.008) and 1-Rh(py)_2 (g = 2.003), and metal-centered for 1-Ir(tma)_2 (g_(zz) = 2.489, g_(yy) = 2.010, g_(xx) = 1.884, g_(av) = 2.128) and 1-Ir(py)_2 (g_(zz) = 2.401, g_(yy) = 2.000, g_(xx) = 1.937, g_(av) = 2.113).", "date": "2009-10-05", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "48", "number": "19", "publisher": "American Chemical Society", "pagerange": "9308-9315", "id_number": "CaltechAUTHORS:20091013-093451813", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20091013-093451813", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "Binational Science Foundation (USA-Israel)" }, { "agency": "BP" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "collection": "CaltechAUTHORS", "local_group": { "items": [ { "id": "CCI-Solar-Fuels", "value": "CCI Solar Fuels" } ] }, "doi": "10.1021/ic901164r", "primary_object": { "basename": "ic901164r_si_002.pdf", "url": "https://authors.library.caltech.edu/records/a2mhd-mp244/files/ic901164r_si_002.pdf" }, "related_objects": [ { "basename": "ic901164r_si_001.pdf", "url": "https://authors.library.caltech.edu/records/a2mhd-mp244/files/ic901164r_si_001.pdf" } ], "pub_year": "2009", "author_list": "Palmer, Joshua H.; Mahammed, Atif; et el." }, { "id": "https://authors.library.caltech.edu/records/gqzs2-63037", "eprint_id": 15805, "eprint_status": "archive", "datestamp": "2023-08-20 02:39:43", "lastmod": "2023-10-19 17:16:00", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Blanco-Rodr\u00edguez-A-M", "name": { "family": "Blanco-Rodr\u00edguez", "given": "Ana Mar\u00eda" } }, { "id": "Busby-M", "name": { "family": "Busby", "given": "Michael" } }, { "id": "Ronayne-K", "name": { "family": "Ronayne", "given": "Kate" } }, { "id": "Towrie-M", "name": { "family": "Towrie", "given": "Michael" } }, { "id": "Gr\u0103dinaru-C", "name": { "family": "Gr\u0103dinaru", "given": "Cristian" } }, { "id": "Sudhamsu-J", "name": { "family": "Sudhamsu", "given": "Jawahar" } }, { "id": "S\u00fdkora-J", "name": { "family": "S\u00fdkora", "given": "Jan" }, "orcid": "0000-0003-0936-9368" }, { "id": "Hof-M", "name": { "family": "Hof", "given": "Martin" }, "orcid": "0000-0003-2884-3037" }, { "id": "Z\u00e1li\u0161-S", "name": { "family": "Z\u00e1li\u0161", "given": "Stanislav" } }, { "id": "Di-Bilio-A-J", "name": { "family": "Di Bilio", "given": "Angel J." } }, { "id": "Crane-B-R", "name": { "family": "Crane", "given": "Brian R." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" }, { "id": "Vl\u010dek-A-Jr", "name": { "family": "Vl\u010dek", "given": "Anton\u00edn, Jr." } } ] }, "title": "Relaxation Dynamics of Pseudomonas aeruginosa Re^I(C)O_3(\u03b1-diimine)(HisX)^+ (X=83, 107, 109, 124, 126)Cu-^(II) Azurins", "ispublished": "pub", "full_text_status": "public", "note": "Copyright \u00a9 2009 American Chemical Society. \n\nReceived April 10, 2009; Publication Date (Web): July 29, 2009. \n\nThis work was supported by EPSRC (EP/E060544), STFC (CMSD43), COST D35, Ministry of Education of the Czech Republic (OC09043 and LC06063), NSF (CHE-0802907 and CHE-0749997), and NIH (DK019038). \n\nSupporting Information: Tables of experimentally determined orientation of the histidine imidazole ligand relative to the Re(CO)_3(phen) unit in the five proteins, DFT-calculated frontier Kohn\u2212Sham orbitals and electronic transitions of Re(Etim) in two conformations, comparison of calculated and experimental ground- and excited-state \u03bd(CO) IR wavenumbers of Re(Etim), and results of stretched-exponential fitting of the A\u2032(1) \u03bd(CO) band shift kinetics at different concentrations. Figures of DFT-calculated structures of Re(Etim) in several ground- and excited-state conformations and time traces of the peak energy of the A\u2032(1) \u03bd(CO) band of 107-dmp, 124-phen, and 126-phen measured at different concentrations. Full text of ref 33 (Gaussian 03 software) is provided. This material is available free of charge via the Internet at http://pubs.acs.org.\n\nSupplemental Material - Blancoja902744s_si_001.pdf
", "abstract": "Photoinduced relaxation processes of five structurally characterized Pseudomonas aeruginosa Re^I(CO)_3(\u03b1-diimine)(HisX) (X = 83, 107, 109, 124, 126)Cu^(II) azurins have been investigated by time-resolved (ps\u2212ns) IR spectroscopy and emission spectroscopy. Crystal structures reveal the presence of Re-azurin dimers and trimers that in two cases (X = 107, 124) involve van der Waals interactions between interdigitated diimine aromatic rings. Time-dependent emission anisotropy measurements confirm that the proteins aggregate in mM solutions (D2O, KPi buffer, pD = 7.1). Excited-state DFT calculations show that extensive charge redistribution in the ReI(CO)_3 \u2192 diimine ^3MLCT state occurs: excitation of this ^3MLCT state triggers several relaxation processes in Re-azurins whose kinetics strongly depend on the location of the metallolabel on the protein surface. Relaxation is manifested by dynamic blue shifts of excited-state \u03bd(CO) IR bands that occur with triexponential kinetics: intramolecular vibrational redistribution together with vibrational and solvent relaxation give rise to subps, 2, and 8\u221220 ps components, while the ~10^2 ps kinetics are attributed to displacement (reorientation) of the Re^I(CO)_3(phen)(im) unit relative to the peptide chain, which optimizes Coulombic interactions of the Re^I excited-state electron density with solvated peptide groups. Evidence also suggests that additional segmental movements of Re-bearing \u03b2-strands occur without perturbing the reaction field or interactions with the peptide. Our work demonstrates that time-resolved IR spectroscopy and emission anisotropy of Re^I carbonyl\u2212diimine complexes are powerful probes of molecular dynamics at or around the surfaces of proteins and protein\u2212protein interfacial regions.", "date": "2009-08-26", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "131", "number": "33", "publisher": "American Chemical Society", "pagerange": "11788-11800", "id_number": "CaltechAUTHORS:20090911-153601363", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20090911-153601363", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Engineering and Physical Sciences Research Council", "grant_number": "EP/E060544" }, { "agency": "Science and Technology Facilities Council", "grant_number": "CMSD43" }, { "agency": "Engineering and Physical Sciences Research Council", "grant_number": "COST D35" }, { "agency": "Ministry of Education of the Czech Republic", "grant_number": "OC09043" }, { "agency": "Ministry of Education of the Czech Republic", "grant_number": "LC06063" }, { "agency": "NSF", "grant_number": "CHE-0802907" }, { "agency": "NSF", "grant_number": "CHE-0749997" }, { "agency": "NIH", "grant_number": "DK019038" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ja902744s", "primary_object": { "basename": "Blancoja902744s_si_001.pdf", "url": "https://authors.library.caltech.edu/records/gqzs2-63037/files/Blancoja902744s_si_001.pdf" }, "pub_year": "2009", "author_list": "Blanco-Rodr\u00edguez, Ana Mar\u00eda; Busby, Michael; et el." }, { "id": "https://authors.library.caltech.edu/records/ga5yt-q6496", "eprint_id": 88058, "eprint_status": "archive", "datestamp": "2023-08-20 02:38:00", "lastmod": "2024-01-14 20:28:53", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Reyes-Gil-K-R", "name": { "family": "Reyes Gil", "given": "Karla R." } }, { "id": "Spurgeon-J-M", "name": { "family": "Spurgeon", "given": "Joshua M." }, "orcid": "0000-0002-2987-0865" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan S." }, "orcid": "0000-0001-5245-0538" } ] }, "title": "Silicon and tungsten oxide nanostructures for water splitting", "ispublished": "unpub", "full_text_status": "public", "keywords": "water splitting, silicon, tungsten oxide, solar cell, membrane, hydrogen production, semiconductor", "note": "\u00a9 2009 Society of Photo-Optical Instrumentation Engineers (SPIE). \n\nWe acknowledge every former and current member of the Lewis group for their contribution to this work. We also acknowledge all members of the Powering the Planet Center for Chemical Innovation (CCI Solar) for their valuable contribution to this project. In addition, we acknowledge the DOE, NSF and BP plc for financial support that has made this work possible.\n\nPublished - 74080S.pdf
", "abstract": "Inorganic semiconductors are promising materials for driving photoelectrochemical water-splitting reactions. However, there is not a single semiconductor material that can sustain the unassisted splitting of water into H_2 and O_2. Instead, we are developing a three part cell design where individual catalysts for water reduction and oxidation will be attached to the ends of a membrane. The job of splitting water is therefore divided into separate reduction and oxidation reactions, and each catalyst can be optimized independently for a single reaction. Silicon might be suitable to drive the water reduction. Inexpensive highly ordered Si wire arrays were grown on a single crystal wafer and transferred into a transparent, flexible polymer matrix. In this array, light would be absorbed along the longer axial dimension while the resulting electrons or holes would be collected along the much shorter radial dimension in a massively parallel array resembling carpet fibers on a microscale, hence the term \"solar carpet\". Tungsten oxide is a good candidate to drive the water oxidation. Self-organized porous tungsten oxide was successfully synthesized on the tungsten foil by anodization. This sponge-like structure absorbs light efficiently due to its high surface area; hence we called it \"solar sponge\".", "date": "2009-08-20", "date_type": "published", "publisher": "Society of Photo-optical Instrumentation Engineers (SPIE)", "place_of_pub": "Bellingham, WA", "pagerange": "Art. No. 74080S", "id_number": "CaltechAUTHORS:20180720-110313872", "isbn": "9780819476982", "book_title": "Solar Hydrogen and Nanotechnology IV", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180720-110313872", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)" }, { "agency": "NSF" }, { "agency": "BP plc" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "contributors": { "items": [ { "id": "Osterloh-F-E", "name": { "family": "Osterloh", "given": "Frank E." } } ] }, "doi": "10.1117/12.825545", "primary_object": { "basename": "74080S.pdf", "url": "https://authors.library.caltech.edu/records/ga5yt-q6496/files/74080S.pdf" }, "pub_year": "2009", "author_list": "Reyes Gil, Karla R.; Spurgeon, Joshua M.; et el." }, { "id": "https://authors.library.caltech.edu/records/jn06r-67n34", "eprint_id": 15445, "eprint_status": "archive", "datestamp": "2023-08-20 01:20:52", "lastmod": "2023-10-18 21:47:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Powering the planet with solar fuel", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2009 Nature Publishing Group. \n\nI would like to thank my colleagues Jay R. Winkler, Bruce S. Brunschwig and Douglas L. Smith for their contributions to this article. \n\nCorrected: 19 March 2009.", "abstract": "With energy swiftly rising to the top of the world's agenda, Harry B. Gray at the California Institute of Technology looks at how chemistry can help to harness the power of the Sun to meet the world's energy needs.", "date": "2009-04", "date_type": "published", "publication": "Nature Chemistry", "volume": "1", "number": "1", "publisher": "Nature Publishing Group", "pagerange": "7", "id_number": "CaltechAUTHORS:20090828-231032888", "issn": "1755-4330", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20090828-231032888", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1038/nchem.141", "pub_year": "2009", "author_list": "Gray, Harry B." }, { "id": "https://authors.library.caltech.edu/records/1fxgk-8he80", "eprint_id": 44655, "eprint_status": "archive", "datestamp": "2023-08-20 00:12:46", "lastmod": "2023-10-26 14:51:04", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Berben-L-A", "name": { "family": "Berben", "given": "Louise A." } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Dimanganese and Diiron Complexes of a Binucleating Cyclam Ligand: Four-Electron, Reversible Oxidation Chemistry at High Potentials", "ispublished": "pub", "full_text_status": "public", "note": "Copyright \u00a9 2008 American Chemical Society. \n\nPublished In Issue December 15, 2008. Article ASAP November 13, 2008. Received: July 11, 2008. \n\nWe acknowledge support from an NSF Chemical Bonding Center (Grant CHE-0533150). L.A.B. was partially supported by a Dow Chemical Co. postdoctoral fellowship from the American Australian Association.\n\nSupporting Information:\n\nCIF files for the structures of 4\u22126, EPR spectra of 4 in MeCN and MeCN/H2O (8:2). UV\u2212vis and EPR spectra of the reaction solutions of 4 and 6 with PhIO, cyclic voltammetry data for 6 and 7, and plot of V(O2)/mL vs t/s for catalase measurements of 4. This material is available free of charge via the Internet at http://pubs.acs.org.\n\nSupplemental Material - ic801289x_si_001.pdf
Supplemental Material - ic801289x_si_002.cif
", "abstract": "The reaction of a binucleating biscyclam ligand cyclam_2^iPrO [where cyclam_2^iPrO = (1,3-bis[1,4,8,11-tetraazacyclododecane]-2-hydroxypropane] with Mn(CF_3SO_3)_2 or Fe(CF_3SO_3)_2\u20222MeCN gives [(cyclam_2^iPrO)Mn_2(\u03bc-CF_3SO_3)](CF_3SO_3)_2 (4) and [(cyclam_2^iPrO)Fe_2(\u03bc-CF_3SO_3)](CF_3SO_3)_2 (6), respectively. [(cyclam_2^iPrO)Mn_2(\u03bc-N_3)](CF_3SO_3)_2 (5) is obtained by the reaction of 4 with NaN_3. Single-crystal X-ray structural characterization indicates that in each of the bimetallic complexes the two metal centers are facially coordinated by a cyclam ligand and bridged by the isopropoxide linker of the ligand in addition to a triflate counteranion. Upon replacement of the triflate bridge with the single-atom bridge of an end-bound azide ligand in 5, the Mn\u2014Mn distance decreases by 0.38 \u00c5. All of the complexes are high-spin and colorless and were characterized by magnetic susceptibility measurements, electron paramagnetic resonance spectroscopy, and electrochemical methods. Magnetic susceptibility measurements indicate that 4 and 6 are weakly antiferromagnetically coupled while 5 is weakly ferromagnetically coupled. Cyclic voltammetry measurements indicate that the hard donor amine ligands impart high oxidation potentials to the metal centers and that four-electron redox activity can be accessed with a narrow potential range of 0.72 V. Upon inclusion of water in the cyclic voltammetry experiment, the oxidative waves shift to higher potentials, which is consistent with water binding the manganese centers. The diiron complex 6 displays four one-electron redox couples, of which the final two are irreversible. Inclusion of water in the cyclic voltammetry measurement for compound 6 resulted in two sets of shifted peaks, which suggests that two molecules of water bind the diiron core. In accordance with the observed reversibility of the electrochemical results, the dimanganese complex is more efficient than the diiron complex for mediating O-atom transfer to organic substrates and is an excellent hydrogen peroxide disproportionation catalyst, with the reaction proceeding for over 20\u2009000 turnovers.", "date": "2008-12-15", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "47", "number": "24", "publisher": "American Chemical Society", "pagerange": "11669-11679", "id_number": "CaltechAUTHORS:20140403-192533870", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140403-192533870", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Chemical Bonding Center", "grant_number": "CHE-0533150" }, { "agency": "Dow Chemical Company" }, { "agency": "American Australian Association" } ] }, "local_group": { "items": [ { "id": "CCI-Solar-Fuels" } ] }, "doi": "10.1021/ic801289x", "primary_object": { "basename": "ic801289x_si_001.pdf", "url": "https://authors.library.caltech.edu/records/1fxgk-8he80/files/ic801289x_si_001.pdf" }, "related_objects": [ { "basename": "ic801289x_si_002.cif", "url": "https://authors.library.caltech.edu/records/1fxgk-8he80/files/ic801289x_si_002.cif" } ], "pub_year": "2008", "author_list": "Berben, Louise A. and Peters, Jonas C." } ]