[ { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/w4qh6-j9e64", "eprint_id": 77479, "eprint_status": "archive", "datestamp": "2023-08-19 15:40:07", "lastmod": "2023-10-25 23:05:29", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kadish-K-M", "name": { "family": "Kadish", "given": "Karl M." } }, { "id": "Fr\u00e9mond-L", "name": { "family": "Fr\u00e9mond", "given": "Laurent" } }, { "id": "Ou-Zhongping", "name": { "family": "Ou", "given": "Zhongping" } }, { "id": "Shao-Jianguo", "name": { "family": "Shao", "given": "Jianguo" } }, { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } }, { "id": "Burdet-F", "name": { "family": "Burdet", "given": "Fabien" } }, { "id": "Gros-C-P", "name": { "family": "Gros", "given": "Claude P." } }, { "id": "Barbe-J-M", "name": { "family": "Barbe", "given": "Jean-Michel" } }, { "id": "Guilard-R", "name": { "family": "Guilard", "given": "Roger" } } ] }, "title": "Cobalt(III) Corroles as Electrocatalysts for the Reduction of Dioxygen: Reactivity of a Monocorrole, Biscorroles, and Porphyrin\u2212Corrole Dyads", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2005 American Chemical Society. \n\nReceived 7 January 2005. Published online 26 March 2005. Published in print 1 April 2005. \n\nK.M.K. is grateful to the Robert A. Welch Foundation (Grant E-680) for support of this research as is L.K. for a predoctoral fellowship. The R\u00e9gion Bourgogne and CNRS are also acknowledged for financial support and for a BDI fellowship (F.B.).", "abstract": "Three series of cobalt(III) corroles were tested as catalysts for the electroreduction of dioxygen to water. One was a simple monocorrole represented as (Me_4Ph_5Cor)Co, one a face-to-face biscorrole linked by an anthracene (A), biphenylene (B), 9,9-dimethylxanthene (X), dibenzofuran (O) or dibenzothiophene (S) bridge, (BCY)Co_2 (with Y = A, B, X, O or S), and one a face-to-face bismacrocyclic complex, (PCY)Co_2, containing a Co(II) porphyrin and a Co(III) corrole also linked by one of the above rigid spacers (Y = A, B, X, or O). Cyclic voltammetry and rotating ring\u2212disk electrode voltammetry were both used to examine the catalytic activity of the cobalt complexes in acid media. The mixed valent Co(II)/Co(III) complexes, (PCY)Co_2, and the biscorrole complexes, (BCY)Co_2, which contain two Co(III) ions in their air-stable forms, all provide a direct four-electron pathway for the reduction of O_2 to H_2O in aqueous acidic electrolyte when adsorbed on a graphite electrode, with the most efficient process being observed in the case of the complexes having an anthracene spacer. A relatively small amount of hydrogen peroxide was detected at the ring electrode in the vicinity of E_(1/2) which was located at 0.47 V vs SCE for (PCA)Co_2 and 0.39 V vs SCE for (BCA)Co_2. The cobalt(III) monocorrole (Me_4Ph_5Cor)Co also catalyzes the electroreduction of dioxygen at E_(1/2) = 0.38 V with the final products being an approximate 50% mixture of H_2O_2 and H_2O.", "date": "2005-04-20", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "127", "number": "15", "publisher": "American Chemical Society", "pagerange": "5625-5631", "id_number": "CaltechAUTHORS:20170516-072216755", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170516-072216755", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Robert A. Welch Foundation", "grant_number": "E-680" }, { "agency": "R\u00e9gion Bourgogne" }, { "agency": "Centre National de la Recherche Scientifique (CNRS)" } ] }, "doi": "10.1021/ja0501060", "resource_type": "article", "pub_year": "2005", "author_list": "Kadish, Karl M.; Fr\u00e9mond, Laurent; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/qz4e9-f9z91", "eprint_id": 76766, "eprint_status": "archive", "datestamp": "2023-08-19 14:07:09", "lastmod": "2023-10-25 16:50:30", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Chang-Christopher-J", "name": { "family": "Chang", "given": "Christopher J." } }, { "id": "Loh-Zhi-Heng", "name": { "family": "Loh", "given": "Zhi-Heng" } }, { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } }, { "id": "Nocera-D-G", "name": { "family": "Nocera", "given": "Daniel G." }, "orcid": "0000-0001-5055-320X" } ] }, "title": "Targeted Proton Delivery in the Catalyzed Reduction of Oxygen to Water by Bimetallic Pacman Porphyrins", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2004 American Chemical Society. \n\nReceived 17 February 2004. Published online 14 July 2004. Published in print 1 August 2004. \n\nC.J.C. thanks the National Science Foundation and the MIT/Merck Foundation for predoctoral fellowships. Z.-H.L. gratefully acknowledges the benefits of the M.I.T. Undergraduate Research Opportunities Program (UROP) and the National Science and Technology Board (Singapore) for an undergraduate scholarship. The National Institutes of Health (GM 47274) and the National Computational Science Alliance (CHE020041N) provided funding for this work.\n\n
Supplemental Material - ja049115jsi20040217_032825.cif
Supplemental Material - ja049115jsi20040521_090652.tif
", "abstract": "A combined experimental and theoretical investigation of the role of proton delivery in determining O_2 reduction pathways catalyzed by cofacial bisporphyrins is presented. A homologous family of dicobalt(II) Pacman porphyrins anchored by xanthene [Co_2(DPX) (1) and Co_2(DPXM) (3)] and dibenzofuran [Co_2(DPD) (2) and Co_2(DPDM) (4)] have been synthesized, characterized, and evaluated as catalysts for the direct four-proton, four-electron reduction of O_2 to H_2O. Structural analysis of the intramolecular diiron(III) \u03bc-oxo complex Fe_2O(DPXM) (5) and electrochemical measurements of 1\u22124 establish that Pacman derivatives bearing an aryl group trans to the spacer possess structural flexibilities and redox properties similar to those of their parent counterparts; however, these trans-aryl catalysts exhibit markedly reduced selectivities for the direct reduction of O_2 to H_2O over the two-proton, two-electron pathway to H_2O_2. Density functional theory calculations reveal that trans-aryl substitution results in inefficient proton delivery to O_2-bound catalysts compared to unsubstituted congeners. In particular, the HOMO of [Co_2(DPXM)(O_2)]+ disfavors proton transfer to the bound oxygen species, funneling the O\u2212O activation pathway to single-electron chemistry and the production of H_2O_2, whereas the HOMO of [Co_2(DPX)(O_2)]+ directs protonation to the [Co_2O_2] core to facilitate subsequent multielectron O\u2212O bond activation to generate two molecules of H_2O. Our findings highlight the importance of controlling both proton and electron inventories for specific O\u2212O bond activation and offer a unified model for O\u2212O bond activation within the clefts of bimetallic porphyrins.", "date": "2004-08-18", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "126", "number": "32", "publisher": "American Chemical Society", "pagerange": "10013-10020", "id_number": "CaltechAUTHORS:20170420-115314999", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170420-115314999", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Predoctoral Fellowship" }, { "agency": "Merck Foundation" }, { "agency": "NIH", "grant_number": "GM 47274" }, { "agency": "National Computational Science Alliance", "grant_number": "CHE020041N" }, { "agency": "Massachusetts Institute of Technology (MIT)" } ] }, "doi": "10.1021/ja049115j", "primary_object": { "basename": "ja049115jsi20040521_090652.tif", "url": "https://authors.library.caltech.edu/records/qz4e9-f9z91/files/ja049115jsi20040521_090652.tif" }, "related_objects": [ { "basename": "ja049115jsi20040217_032825.cif", "url": "https://authors.library.caltech.edu/records/qz4e9-f9z91/files/ja049115jsi20040217_032825.cif" } ], "resource_type": "article", "pub_year": "2004", "author_list": "Chang, Christopher J.; Loh, Zhi-Heng; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/tgh0n-6et57", "eprint_id": 76998, "eprint_status": "archive", "datestamp": "2023-08-19 09:21:11", "lastmod": "2023-10-25 17:04:30", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Zou-Shouzhong", "name": { "family": "Zou", "given": "Shouzhong" } }, { "id": "Clegg-R-S", "name": { "family": "Clegg", "given": "Robert S." } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Attachment of Cobalt \"Picket Fence\" Porphyrin to the Surface of Gold Electrodes Coated with 1-(10-Mercaptodecyl)imidazole", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2002 American Chemical Society. \n\nReceived 17 September 2001. Published online 22 March 2002. Published in print 1 April 2002. \n\nThis work was supported by the National Science Foundation via Grant CHE-9816329 and by the Laboratory for Molecular Science, an NSF-supported facility at Caltech. Helpful discussions with Dr. Beat Steiger, Professor Ahmed Zewail, and Professor Jim Hutchinson are acknowledged with pleasure as is the assistance of Dr. Robert Rossi and Joseph Nemanick in the preparation of gold film electrodes.\n\nSupplemental Material - la011444r_s.pdf
", "abstract": "Self-assembled monolayers of 1-(10-mercaptodecyl)imidazole on Au electrodes were used to bind cobalt \"picket fence\" porphyrin (cobalt 5,10,15,20-tetrakis(\u03b1,\u03b1,\u03b1,\u03b1-2-pivalamidophenyl)porphyrin) to the electrode surface. The binding involved coordination of the cobalt center of the porphyrin to the pendant imidazole groups in the monolayer coating. Attempts to coordinate the Co(II) oxidation state of the porphyrin to the coatings were not successful. However, with the Co(III) oxidation state, substantial binding was achieved which persisted even when the Co(III) was reduced to Co(II). Absorption spectra of the attached porphyrin were obtained for both oxidation states of the cobalt center. The remaining axial coordination site on the attached cobalt porphyrin is accessible to ligands, for example, imidazole, in aqueous solution.", "date": "2002-04-16", "date_type": "published", "publication": "Langmuir", "volume": "18", "number": "8", "publisher": "American Chemical Society", "pagerange": "3241-3246", "id_number": "CaltechAUTHORS:20170427-103551816", "issn": "0743-7463", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170427-103551816", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF", "grant_number": "CHE-9816329" } ] }, "doi": "10.1021/la011444r", "primary_object": { "basename": "la011444r_s.pdf", "url": "https://authors.library.caltech.edu/records/tgh0n-6et57/files/la011444r_s.pdf" }, "resource_type": "article", "pub_year": "2002", "author_list": "Zou, Shouzhong; Clegg, Robert S.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/jmyy1-xgp60", "eprint_id": 75154, "eprint_status": "archive", "datestamp": "2023-08-19 08:31:11", "lastmod": "2023-10-25 14:47:33", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Catalysis of the Electro-Oxidation of Carbon Monoxide by Cobalt Octaethylporphyrin", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2001 American Chemical Society. \n\nReceived May 21, 2001. Publication Date (Web): September 26, 2001. \n\nThis work was supported by the National Science Foundation. We are grateful to Prof. Karl Kadish for calling our attention to the reaction between Co(III) porphyrins and CO.\n\nSupplemental Material - ic010530b_s.pdf
", "abstract": "The electro-oxidation of cobalt (II) octaethylporphyrin adsorbed on graphite electrodes, Co^(II)(OEP)_(ads') to Co^(III)(OEP) ^+_(ads), in the presence of aqueous solutions of CO leads to catalytic oxidation of CO to CO_2. No such oxidation occurs with Co^(II)(OEP) and CO dissolved in nonaqueous solvents. Coordination of the CO to Co^(III)(OEP)^+ is the first step in the catalytic mechanism. Nucleophilic attack on the coordinated CO by H_2O is the probable rate-limiting step in the catalytic oxidation. A pseudo first-order rate constant of 0.3 s^(-1) was estimated for this reaction.", "date": "2001-11-05", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "40", "number": "23", "publisher": "American Chemical Society", "pagerange": "5829-5833", "id_number": "CaltechAUTHORS:20170315-150552429", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170315-150552429", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/ic010530b", "primary_object": { "basename": "ic010530b_s.pdf", "url": "https://authors.library.caltech.edu/records/jmyy1-xgp60/files/ic010530b_s.pdf" }, "resource_type": "article", "pub_year": "2001", "author_list": "Shi, Chunnian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/gy0j0-1xf64", "eprint_id": 77484, "eprint_status": "archive", "datestamp": "2023-08-19 08:18:17", "lastmod": "2023-10-25 23:05:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Rates of Electron-Transfer Across Liquid/Liquid Interfaces. Effects of Changes in Driving Force and Reaction Reversibility", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2001 American Chemical Society. \n\nReceived: February 7, 2001; In Final Form: May 13, 2001.\nPublication Date (Web): June 23, 2001. \n\nThis work was supported by the National Science Foundation. We appreciated receiving a pre-print of reference 26 prior to its publication.", "abstract": "Rates of electron-transfer between redox reactants located on opposite sides of the interface between thin layers of organic solvents on graphite electrode and aqueous solutions were measured by means of steady-state electrochemistry. Changes in the overall driving forces for irreversible reactions produced changes in rate that fit no simple behavioral pattern. For reversible reactions, a regular increase in rate with driving force was obtained. Evidence for a significant effect of diffuse-layer potentials on reaction rates was not found.", "date": "2001-09-20", "date_type": "published", "publication": "Journal of Physical Chemistry B", "volume": "105", "number": "37", "publisher": "American Chemical Society", "pagerange": "8963-8969", "id_number": "CaltechAUTHORS:20170516-073937933", "issn": "1520-6106", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170516-073937933", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/jp010465r", "resource_type": "article", "pub_year": "2001", "author_list": "Shi, Chunnian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/ecwhk-m7713", "eprint_id": 76858, "eprint_status": "archive", "datestamp": "2023-08-19 07:26:50", "lastmod": "2023-10-25 16:55:56", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Liu-Zenghe", "name": { "family": "Liu", "given": "Zenghe" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Schiff Base Complexes of Vanadium(III, IV, V) as Catalysts for the Electroreduction of O_2 to H_2O in Acetonitrile", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2001 American Chemical Society. \n\nReceived 13 September 2000. Published online 13 February 2001. Published in print 1 March 2001. \n\nThis work was supported by the National Science Foundation. Z.L. was the grateful recipient of a 2000 Energy Research Summer Fellowship of The Electrochemical Society.\n\nSupplemental Material - ic0010407_s.pdf
", "abstract": "Fifteen Schiff base ligands were synthesized and used to form complexes with vanadium in oxidation states III, IV, and V. Electrochemical and spectral characteristics of the complexes were evaluated and compared. In acidified solutions in acetonitrile the vanadium(IV) complexes undergo reversible disproportionation to form V(III) and V(V) complexes. With several of the ligands the V(III) complexes are much more stable in the presence of acid than is the previously studied complex with salen, an unelaborated Schiff base ligand (H_2 salen = N,N'-ethylenebis(salicylideneamine)). Equilibrium constants for the disproportionation were evaluated. The vanadium(III) complexes reduce dioxygen to form two oxo ligands. The reaction is stoichiometric in the absence of acid, and second-order rate constants were evaluated. In the presence of acid some of the complexes investigated participate in a catalytic electroreduction of dioxygen.", "date": "2001-03-12", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "40", "number": "6", "publisher": "American Chemical Society", "pagerange": "1329-1333", "id_number": "CaltechAUTHORS:20170424-125035745", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170424-125035745", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "The Electrochemical Society" } ] }, "doi": "10.1021/ic0010407", "primary_object": { "basename": "ic0010407_s.pdf", "url": "https://authors.library.caltech.edu/records/ecwhk-m7713/files/ic0010407_s.pdf" }, "resource_type": "article", "pub_year": "2001", "author_list": "Liu, Zenghe and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/a5m7e-gdh90", "eprint_id": 75160, "eprint_status": "archive", "datestamp": "2023-08-19 07:18:48", "lastmod": "2023-10-25 14:47:58", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Selecting Experimental Conditions for Measurement of Rates of Electron-Transfer at Liquid/Liquid Interfaces by Thin-Layer Electrochemistry", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2001 American Chemical Society. \n\nReceived: October 12, 2000; In Final Form: November 28, 2000.\nPublication Date (Web): January 11, 2001. \n\nThis work was supported by the National Science Foundation. Helpful comments from Prof. Carl Koval are acknowledged with appreciation.", "abstract": "The use of thin layers of water-immiscible organic solvents on electrode surfaces to evaluate rates of electron-transfer across liquid/liquid interfaces requires that reactant concentrations in the two adjacent phases be selected to minimize the effects of mass transfer on the measured currents. A general inequality is derived which provides a guide to the selection of suitable concentrations of the coreactants. Experimental tests of the inequality demonstrated its utility and should allay recently expressed concerns about the reliability of the thin-layer methodology.", "date": "2001-02-08", "date_type": "published", "publication": "Journal of Physical Chemistry B", "volume": "105", "number": "5", "publisher": "American Chemical Society", "pagerange": "1047-1049", "id_number": "CaltechAUTHORS:20170315-154112820", "issn": "1520-6106", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170315-154112820", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/jp003741v", "resource_type": "article", "pub_year": "2001", "author_list": "Shi, Chunnian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/gwrta-zrc20", "eprint_id": 69244, "eprint_status": "archive", "datestamp": "2023-08-19 07:13:24", "lastmod": "2023-10-20 16:42:41", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Chung-Taek-Dong", "name": { "family": "Chung", "given": "Taek Dong" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Electrochemical Monitoring of Proton Transfer across Liquid/Liquid Interfaces on the Surface of Graphite Electrodes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2001 American Chemical Society. \n\nReceived for review August 10, 2000. Accepted October 30, 2000. Publication Date (Web): December 14, 2000. \n\nThis work was supported by the National Science Foundation. T.D.C. acknowledges partial support from the Korea Science and Engineering Foundation. Dr. Chunnian Shi provided essential expertise and helpful discussions. We are grateful to Prof. Steven Strauss of Colorado University for the generous gift of the hydrophobic ferrocene, HMFc.", "abstract": "Equilibrium partitioning of HClO_4 between aqueous solutions and benzonitrile (BN) or nitrobenzene (NB) was measured and used to evaluate the pKa of the acid in the two organic solvents. The potential drop across the BN/H_2O interface was evaluated from the known potential drop across the NB/H_2O interface and the voltammetrically measured formal potential of a ferrocenium/ferrocene redox couple confined within thin layers of the two organic solvents. The voltammetric reduction of tetrachloro-1, 4-benzoquinone in thin layers of BN was used to monitor changes in the concentration of protons in the layer during proton-consuming faradaic reactions. The rate of proton transfer from the aqueous to the nonaqueous phase across the BN/H_2O interface was shown to be adequate to sustain proton-consuming reactions at the electrode/BN interface.", "date": "2001-01-15", "date_type": "published", "publication": "Analytical Chemistry", "volume": "73", "number": "2", "publisher": "American Chemical Society", "pagerange": "337-342", "id_number": "CaltechAUTHORS:20160727-100827075", "issn": "0003-2700", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160727-100827075", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Korea Science and Engineering Foundation" } ] }, "doi": "10.1021/ac0009447", "resource_type": "article", "pub_year": "2001", "author_list": "Chung, Taek Dong and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/n27t8-1n652", "eprint_id": 76890, "eprint_status": "archive", "datestamp": "2023-08-19 06:24:21", "lastmod": "2023-10-25 16:57:30", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Steiger-B", "name": { "family": "Steiger", "given": "Beat" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Examination of Cobalt \"Picket Fence\" Porphyrin and Its Complex with 1-Methylimidazole as Catalysts for the Electroreduction of Dioxygen", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2000 American Chemical Society. \n\nReceived 22 May 2000. Published online 7 September 2000. Published in print 1 October 2000. \n\nThis work was supported by the National Science Foundation through a grant to F.C.A. and by the Laboratory for Molecular Sciences, an NSF supported facility at Caltech. Helpful discussions with Drs. Taek Dong Chung, Chunnian Shi, and Shouzhong Zou and with Prof. Ahmed Zewail are acknowledged with pleasure.", "abstract": "The electrochemical behavior of cobalt 5,10,15,20-tetrakis(\u03b1,\u03b1,\u03b1,\u03b1-2-pivalamidophenyl)porphyrin (Co^(II)TpivPP) was examined in benzonitrile solutions. The electrochemical responses were changed significantly by the addition of 1-methylimidazole which coordinates once to the Co(II) and twice to the Co(III) porphyrin. The corresponding equilibrium binding constants were estimated as 2.9 \u00d7 10^3 M^(-1) and 1.7 \u00d7 10^(20) M^(-2). The cyclic voltammetric responses were affected by the rates of the ligand association/dissociation reactions. Formation of the O_2 adduct of the Co(II) porphyrin resulted in only small changes in the cyclic voltammetric pattern. Comparison between Co^(II)TpivPP and cobalt tetraphenylporphyrin (Co^(II)TPP) as catalysts for the electroreduction of O_2 showed the latter to be the superior catalyst both when adsorbed on graphite electrodes and when dissolved in thin layers of acidified benzonitrile where Co^(II)TpivPP exhibited unimpressive catalytic activity compared with Co^(II)TPP, which appeared to catalyze the reduction of O_2 by significantly more than 2 electrons per molecule.", "date": "2000-10-02", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "39", "number": "20", "publisher": "American Chemical Society", "pagerange": "4579-4585", "id_number": "CaltechAUTHORS:20170425-063336725", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170425-063336725", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/ic000537d", "resource_type": "article", "pub_year": "2000", "author_list": "Steiger, Beat and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/ztzc8-dtf25", "eprint_id": 3790, "eprint_status": "archive", "datestamp": "2023-08-21 21:27:34", "lastmod": "2023-10-16 16:09:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Chang-Christopher-J", "name": { "family": "Chang", "given": "Christopher J." } }, { "id": "Deng-Yongqi", "name": { "family": "Deng", "given": "Yongqi" } }, { "id": "Nocera-D-G", "name": { "family": "Nocera", "given": "Daniel G." }, "orcid": "0000-0001-5055-320X" }, { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } }, { "id": "Chang-C-K", "name": { "family": "Chang", "given": "C. K." } } ] }, "title": "Electrocatalytic four-electron reduction of oxygen to water by a highly flexible cofacial cobalt bisporphyrin", "ispublished": "pub", "full_text_status": "public", "keywords": "CYTOCHROME-C-OXIDASE; TERMINAL OXIDASES; ELECTROREDUCTION; PORPHYRINS; CATALYSTS; DIOXYGEN; ANALOGS; MODEL", "note": "\u00a9 The Royal Society of Chemistry 2000. \n\nReceived (in Bloomington, IN, USA) 16th February 2000; accepted 11th April 2000. Published on the Web 5th July 2000. \n\nC. J. C. gratefully acknowledges the National Science Foundation for a predoctoral fellowship. We thank A. Heyduk for help with the X-ray crystallography. This work was supported by the National Institutes of Health GM 47274.\n\nPublished - CHAcc00.pdf
", "abstract": "Dicobalt(II) cofacial bisporphyrins anchored by dibenzofuran (DPD) and xanthene (DPX) are efficient electrocatalysts for the four-electron reduction of oxygen to water despite their ca. 4 \u00c5 difference in metal\u2013metal distances, suggesting that the considerable longitudinal Pac-Man flexibility of the pillared platforms is the origin for the similar catalytic reactivity of these structurally disparate systems.", "date": "2000-08-01", "date_type": "published", "publication": "Chemical Communications", "volume": "2000", "number": "15", "publisher": "Royal Society of Chemistry", "pagerange": "1355-1356", "id_number": "CaltechAUTHORS:CHAcc00", "issn": "1359-7345", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:CHAcc00", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Predoctoral Fellowship" }, { "agency": "NIH", "grant_number": "GM 47274" } ] }, "doi": "10.1039/b001620i", "primary_object": { "basename": "CHAcc00.pdf", "url": "https://authors.library.caltech.edu/records/ztzc8-dtf25/files/CHAcc00.pdf" }, "resource_type": "article", "pub_year": "2000", "author_list": "Chang, Christopher J.; Deng, Yongqi; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/0y2y2-bvb61", "eprint_id": 79922, "eprint_status": "archive", "datestamp": "2023-08-19 05:18:49", "lastmod": "2023-10-26 17:26:15", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Liu-Zenghe", "name": { "family": "Liu", "given": "Zenghe" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Electrochemical Properties of Vanadium(III,IV,V)\u2212Salen Complexes in Acetonitrile. Four-Electron Reduction of O_2 by V(III)\u2212Salen", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2000 American Chemical Society. \n\nReceived August 10, 1999. Publication Date (Web): December 18, 1999. \n\nThis work was supported by the National Science Foundation. Our interest in V(salen) complexes resulted from extensive discussions and collaborations with Prof. Eishun Tsuchida and his group for which we are most grateful.\n\nSupplemental Material - ic990958z_s.pdf
", "abstract": "The coordination chemistry and electrochemistry of complexes of vanadium(III,IV,V) with salen (H_2 salen = N,N'-ethylenebis(salicylideneamine) were reexamined in an attempt to uncover the origin of puzzling results reported in a previous study (Inorg. Chem. 1994, 33, 1056). Microelectrodes were utilized to allow measurements in the absence of supporting electrolyte. The source of the puzzling results was identified and the modifications required in the previous interpretations are specified. Corrected values of formal potentials and diffusion coefficients are also given. The acid-induced disproportionation of V^(IV)O(salen), as originally proposed by Bonadies et al. (J. Chem. Soc., Chem. Commun. 1986, 1218; Inorg. Chem. 1987, 26, 1218), was largely supported by the present results. The equilibrium constant for this disproportionation reaction was measured. The stoichiometry and kinetics of the reaction between O_2 and the V(III)\u2212salen complex were examined, and a possible mechanism for this four-electron reduction of O_2 is suggested.", "date": "2000-01-24", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "39", "number": "2", "publisher": "American Chemical Society", "pagerange": "274-280", "id_number": "CaltechAUTHORS:20170808-094651903", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170808-094651903", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/ic990958z", "primary_object": { "basename": "ic990958z_s.pdf", "url": "https://authors.library.caltech.edu/records/0y2y2-bvb61/files/ic990958z_s.pdf" }, "resource_type": "article", "pub_year": "2000", "author_list": "Liu, Zenghe and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/g3kh2-n2c10", "eprint_id": 69800, "eprint_status": "archive", "datestamp": "2023-08-21 20:50:36", "lastmod": "2023-10-20 20:38:09", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Steiger-B", "name": { "family": "Steiger", "given": "Beat" } }, { "id": "Baskin-J-S", "name": { "family": "Baskin", "given": "J. Spencer" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } }, { "id": "Zewail-A-H", "name": { "family": "Zewail", "given": "Ahmed H." } } ] }, "title": "Femtosecond Dynamics of Dioxygen - Picket-Fence Cobalt Porphyrins: Ultrafast Release of O_2 and the Nature of Dative Bonding", "ispublished": "pub", "full_text_status": "restricted", "keywords": "cobalt; femtochemistry; laser spectroscopy; O\u2212O activation; porphyrinoids", "note": "\u00a9 2000 Wiley-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany. \n\nReceived: September 23, 1999. Version of Record online: 12 Jan 2000. \n\nThis work was supported by the US National Science Foundation (Laboratory for Molecular Sciences).", "abstract": "The ultrafast release of O_2 from the O_2 adduct of picket-fence cobalt porphyrin (see picture) has been probed in real time, and has a total reaction time of 2 ps, without subsequent recombination over several nanoseconds. The dynamics of this ultrafast release of O_2 shows that relaxation within the porphyrin system (200 fs) precedes porphyrin-to-metal electron transfer, but the latter occurs at an enhanced rate (500 fs as opposed to the more usual 1\u2009\u2013\u20092 ps) because of the dative bonding of cobalt and O_2, which gives the adduct ground state significant Co^(III)\u2212O_2^\u2212 character.", "date": "2000-01-03", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "39", "number": "1", "publisher": "Wiley", "pagerange": "257-260", "id_number": "CaltechAUTHORS:20160819-142157037", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160819-142157037", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1002/(SICI)1521-3773(20000103)39:1<257::AID-ANIE257>3.0.CO;2-3", "resource_type": "article", "pub_year": "2000", "author_list": "Steiger, Beat; Baskin, J. Spencer; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/s4m9f-w8k08", "eprint_id": 69855, "eprint_status": "archive", "datestamp": "2023-08-19 03:57:51", "lastmod": "2023-10-20 20:41:29", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Yu-Hua-Zhong", "name": { "family": "Yu", "given": "Hua-Zhong" } }, { "id": "Baskin-J-S", "name": { "family": "Baskin", "given": "J. Spencer" } }, { "id": "Steiger-B", "name": { "family": "Steiger", "given": "Beat" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } }, { "id": "Zewail-A-H", "name": { "family": "Zewail", "given": "Ahmed H." } } ] }, "title": "Femtosecond Dynamics and Electrocatalysis of the Reduction of O_2: Tetraruthenated Cobalt Porphyrins", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1999 American Chemical Society. \n\nReceived October 6, 1998. Publication Date (Web): December 31, 1998. \n\nThis work was supported by the National Science Foundation (Laboratory for Molecular Sciences). We wish to thank Mr.\nBj\u00f6rn \u00d6nfelt for his assistance with some of the experiments.", "abstract": "Recently we reported the femtosecond dynamics of some porphyrin molecules. These studies elucidated the elementary steps involved in intramolecular relaxation and charge transfer (CT) in cobalt tetraphenylporphyrin (CoTPP) from the porphyrin \u03c0 (a_(2u)) system to the Co(d_z^2). Our interest in the dynamics of intramolecular electron transfer stems from recent studies of cobalt porphyrins that were modified by attachment of Ru(II) or Os(II) complexes to the periphery of the porphyrin ring. These modified cobalt porphyrins exhibit high catalytic activity for the electroreduction of O_2 directly to H_2O, a process that most monomeric cobalt porphyrins are unable to accomplish. The mechanism by which the modified cobalt porphyrins achieve the direct, four-electron reduction of O_2 has been suggested to involve back-bonding interactions among the attached Ru(II) and Os(II) centers, the porphyrin ring, and the Co(II) ion at its center.", "date": "1999-01-20", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "121", "number": "2", "publisher": "American Chemical Society", "pagerange": "484-485", "id_number": "CaltechAUTHORS:20160823-144513594", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160823-144513594", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/ja983532c", "resource_type": "article", "pub_year": "1999", "author_list": "Yu, Hua-Zhong; Baskin, J. Spencer; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/qrp0m-dnp64", "eprint_id": 69858, "eprint_status": "archive", "datestamp": "2023-08-19 03:15:03", "lastmod": "2023-10-20 20:41:48", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Yu-H-Z", "name": { "family": "Yu", "given": "H. Z." } }, { "id": "Baskin-J-S", "name": { "family": "Baskin", "given": "J. S." } }, { "id": "Steiger-B", "name": { "family": "Steiger", "given": "B." } }, { "id": "Wang-C-Z", "name": { "family": "Wan", "given": "C. Z." } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "F. C." } }, { "id": "Zewail-A-H", "name": { "family": "Zewail", "given": "A. H." } } ] }, "title": "Femtosecond dynamics of metalloporphyrins: electron transfer and energy redistribution", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1998 Elsevier Science B.V. \n\nReceived 25 May 1998. Available online 16 September 1998. \n\nThis work was supported by the National Science Foundation (Laboratory for Molecular Sciences).", "abstract": "Femtosecond-resolved, real-time dynamics of the low-lying excited state ^2Q(\u03c0,\u03c0^*) of cobalt(II) tetraphenylporphyrin are reported in different solvents of varying polarity and structure. The dependence of the dynamics on the probing wavelength and on the metal and porphyrin substitution was also investigated. The decay in the \u03c0 system of the porphyrin occurs with a lifetime of 220 fs in benzene, while a second process with a lifetime of 1.8 ps is consistent with a proposed model for intramolecular charge separation: porphyrin a_(2u)(\u03c0)\u2192Co(d_z^2). The dynamics of the charge transfer state is influenced by the solvents' polarity and coordination ability.", "date": "1998-08-21", "date_type": "published", "publication": "Chemical Physics Letters", "volume": "293", "number": "1-2", "publisher": "Elsevier", "pagerange": "1-8", "id_number": "CaltechAUTHORS:20160823-144514367", "issn": "0009-2614", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160823-144514367", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1016/S0009-2614(98)00753-2", "resource_type": "article", "pub_year": "1998", "author_list": "Yu, H. Z.; Baskin, J. S.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/2845h-nte07", "eprint_id": 81480, "eprint_status": "archive", "datestamp": "2023-08-19 03:12:34", "lastmod": "2023-10-17 19:53:24", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "A Simple Method for Examining the Electrochemistry of Metalloporphyrins and Other Hydrophobic Reactants in Thin Layers of Organic Solvents Interposed between Graphite Electrodes and Aqueous Solutions", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1998 American Chemical Society. \n\nReceived for review April 22, 1998. Accepted June 10, 1998. Publication Date (Web): July 3, 1998. \n\nThis work was supported by the U.S. National Science Foundation.", "abstract": "A method is described for the preparation of stable, adherent, thin layers of organic solvents interposed between the surfaces of graphite electrodes and aqueous supporting electrolytes in which they are immersed. The electrochemistry of reactants dissolved in the thin layers is examined and utilized to evaluate surface coverages and formal potentials for molecules, such as cobalt tetraphenylporphyrins, that do not exhibit useful electrochemical responses when adsorbed on graphite. The thin layers of organic solvent can be used to concentrate analytes by extracting them from dilute aqueous solutions to produce enhanced sensitivity in electroanalytical applications. Electron transfer across the liquid/liquid interface created by the presence of the thin layer of immiscible organic solvent is also demonstrated.", "date": "1998-08-01", "date_type": "published", "publication": "Analytical Chemistry", "volume": "70", "number": "15", "publisher": "American Chemical Society", "pagerange": "3114-3118", "id_number": "CaltechAUTHORS:20170915-082322991", "issn": "0003-2700", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170915-082322991", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/ac980426k", "resource_type": "article", "pub_year": "1998", "author_list": "Shi, Chunnian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/88prs-y2p61", "eprint_id": 88039, "eprint_status": "archive", "datestamp": "2023-08-19 03:08:32", "lastmod": "2023-10-18 21:39:01", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Song-Euihwan", "name": { "family": "Song", "given": "Euihwan" } }, { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Comparison of the Behavior of Several Cobalt Porphyrins as Electrocatalysts for the Reduction of O_2 at Graphite Electrodes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1998 American Chemical Society. \n\nReceived January 21, 1998. In Final Form: May 18, 1998. \n\nE.S. is grateful for a Fellowship provided by the Korea Science and Engineering Foundation. The work was also supported by the U. S. National Science Foundation.", "abstract": "Four cobalt porphyrins were adsorbed on graphite electrodes and used to catalyze the electroreduction of O_2. The two porphyrins without substituent groups in the meso positions of the porphyrin ring operated at the most positive potentials and catalyzed the reduction of O_2 to both H_2O_2 and H_2O, but the H_2O did not result from significant reduction of H_2O_2. The porphyrins containing meso substituents catalyzed only the reduction of O_2 to H_2O_2. The catalysts that accomplish the four-electron reduction of O_2 are argued to consist of dimeric (or higher oligomeric) forms of the adsorbed porphyrins. The present results and those of two recent related studies indicate that the presence of only hydrogen or small alkyl groups in the meso positions of porphyrin rings facilitates the spontaneous formation of van der Waals dimers with greater catalytic activity for the reduction of O_2 by four electrons. Such cobalt porphyrins were also found to be unusually active catalysts for the electro-oxidation of H_2O_2.", "date": "1998-07-21", "date_type": "published", "publication": "Langmuir", "volume": "14", "number": "15", "publisher": "American Chemical Society", "pagerange": "4315-4321", "id_number": "CaltechAUTHORS:20180719-161207344", "issn": "0743-7463", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180719-161207344", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Korea Science and Engineering Foundation" }, { "agency": "NSF" } ] }, "doi": "10.1021/la980084d", "resource_type": "article", "pub_year": "1998", "author_list": "Song, Euihwan; Shi, Chunnian; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/zdb09-9gw24", "eprint_id": 81400, "eprint_status": "archive", "datestamp": "2023-08-19 02:45:07", "lastmod": "2023-10-17 19:49:28", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Minglian", "name": { "family": "Shi", "given": "Minglian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Adsorption/Deposition of the Ligands 9,10-Phenanthroline-5,6-dione and 9,10-Phenanthroline-5,6-diol and Their Metal Complexes on Pyrolytic Graphite Electrodes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1998 American Chemical Society. \n\nReceived for review November 12, 1997. Accepted January 28, 1998. Publication Date (Web): March 13, 1998. \n\nThis work was supported by the National Science Foundation. We appreciated receiving a copy of ref 12 prior to publication and helpful discussions with Prof. E. Steckhan and Dr. G. Hilt.", "abstract": "Metal complexes of the electroactive ligand 9,10-phenanthroline-5,6-dione (pdon) are receiving extensive study because of their demonstrated potential as electrocatalysts for the oxidation of NADH and other substrates. In aqueous media, the reduced ligand, 9,10-phenanthroline-5,6-diol (pdol), and its complexes with transition metals are only slightly soluble and tend to accumulate on the surfaces of electrodes, where they are generated by reduction of pdon. The adsorbed (or precipitated) molecular layers can interfere with the continued electroreduction of the more soluble, oxidized precursors from which they are generated. The use of freshly cleaved basal plane pyrolytic graphite electrodes allowed the surface coordination chemistry and electrochemistry of pdon, pdol, and their complexes to be inspected in more detail than in previous studies. The results revealed several general trends:\u2009 (i) Coordination of pdon to transition metals shifts its reduction potential to more positive values. (ii) The affinity of the dipositive form of transition metal redox couples for pdon is greater than that of the tripositive form by a factor that exceeds the corresponding affinities for 9,10-phenanthroline. (iii) Pdol and its complexes are much less soluble in aqueous media than are pdon and its complexes. (iv) Complexes of pdon are much less strongly adsorbed on graphite than is the free ligand in both its protonated and unprotonated forms.", "date": "1998-04-15", "date_type": "published", "publication": "Analytical Chemistry", "volume": "70", "number": "8", "publisher": "American Chemical Society", "pagerange": "1489-1495", "id_number": "CaltechAUTHORS:20170913-084950345", "issn": "0003-2700", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170913-084950345", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/ac971234c", "resource_type": "article", "pub_year": "1998", "author_list": "Shi, Minglian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/e8ytp-qzq08", "eprint_id": 86639, "eprint_status": "archive", "datestamp": "2023-08-19 02:36:42", "lastmod": "2023-10-18 19:49:10", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "(5,10,15,20-Tetramethylporphyrinato)cobalt(II):\u2009 A Remarkably Active Catalyst for the Electroreduction of O_2 to H_2O", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 1998 American Chemical Society. \n\nReceived October 10, 1997. \n\nThis work was supported by the National Science Foundation. Dr. Beat Steiger contributed a number of very helpful suggestions.\n\nSupplemental Material - ic1037.pdf
", "abstract": "Unlike most simple, monomeric cobalt porphyrins, the cobalt tetramethylporphyrin identified in the title catalyzes the electroreduction of O_2 to H_2O instead of H_2O_2. On graphite electrodes, coatings of the porphyrin prepared by irreversible adsorption from chloroform solutions catalyze the electroreduction of O_2 in aqueous HClO_4 at unusually positive potentials. Both the title porphyrin and the corresponding unsubstituted cobalt porphine are argued to derive their activity as four-electron reduction catalysts from their propensity to form dimers (or higher aggregates) in solution and, presumptively, on the surface of graphite electrodes.", "date": "1998-03-09", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "37", "number": "5", "publisher": "American Chemical Society", "pagerange": "1037-1043", "id_number": "CaltechAUTHORS:20180525-140420261", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180525-140420261", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/ic971255p", "primary_object": { "basename": "ic1037.pdf", "url": "https://authors.library.caltech.edu/records/e8ytp-qzq08/files/ic1037.pdf" }, "resource_type": "article", "pub_year": "1998", "author_list": "Shi, Chunnian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/jhn9q-s4t68", "eprint_id": 83425, "eprint_status": "archive", "datestamp": "2023-08-19 02:00:02", "lastmod": "2023-10-17 23:06:59", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } }, { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Steiger-B", "name": { "family": "Steiger", "given": "Beat" } } ] }, "title": "Novel Multinuclear Catalysts for the Electroreduction of Dioxygen Directly to Water", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1997 American Chemical Society. \n\nReceived April 2, 1997. Publication Date (Web): November 13, 1997. \n\nThe research described in this Account was supported by the National Science Foundation and by ONR/DARPA.", "abstract": "The electroreduction of O_2 to H_2O in aqueous acid at\npotentials close to the thermodynamically permitted value\nremains a daunting challenge for designers of superior fuel\ncells and batteries that utilize dioxygen as the reducible\nreactant. The four-electron reduction of O_2, which involves\nthe rupture of the O-O bond and the formation of four O-H bonds, requires the use of catalysts to obtain useful rates at cathode potentials of interest in practical applications. The standard potential of the O_2/H_2O couple in solutions containing 1 M H^+ and saturated with O_2 at\n1 atm is ca. 1.0 V (vs the saturated calomel electrode, SCE), but the highest cathode potentials achievable with currently available catalysts are closer to 0.55 V. (Molecules, functional groups, or metallic deposits that accelerate the rates of electrode reactions when they are confined to the surfaces of electrodes are often called electrocatalysts, a terminology that will be adopted in this Account.) Finely divided platinum supported on high area carbon is the electrocatalyst employed most frequently to achieve the electroreduction of O_2 to H_2O in presently available fuel cells. However, this type of electrocatalyst suffers from the disadvantages of high cost and gradual loss in catalytic activity as the surface area of the active platinum particles decreases because of sintering, dissolution, physical dislodgment, and/or adsorption of impurities. Searches for superior electrocatalysts for the reduction of O2 have often focused on cobalt porphyrins which are well-known to exhibit electrocatalytic activity toward the reduction of O_2, although H_2O_2 instead of H_2O is the usual product. However, it was discovered in recent years that a variety of molecular catalysts consisting of dimeric cofacial cobalt porphyrins adsorbed on the surface of graphite electrodes are able to catalyze the direct four-electron electroreduction of O_2 without passing through H_2O_2 as an intermediate. Both dimeric and monomeric iridium por phyrins have also been found to accomplish the electroreduction of O_2 to H_2O at unusually positive potentials. The mechanisms through which dimeric electrocatalysts are believed to operate involve the simultaneous interaction of both metal centers with the two\noxygen atoms of the O_2 molecule as the O-O bond is severed. The ideas and strategies that underlay the\ndevelopment of these electrocatalysts have been described.", "date": "1997-11", "date_type": "published", "publication": "Accounts of Chemical Research", "volume": "30", "number": "11", "publisher": "American Chemical Society", "pagerange": "437-444", "id_number": "CaltechAUTHORS:20171122-083839178", "issn": "0001-4842", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20171122-083839178", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Office of Naval Research (ONR)" }, { "agency": "Defense Advanced Research Projects Agency (DARPA)" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/ar960264j", "resource_type": "article", "pub_year": "1997", "author_list": "Anson, Fred C.; Shi, Chunnian; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/59mgt-7b067", "eprint_id": 86565, "eprint_status": "archive", "datestamp": "2023-08-19 01:51:00", "lastmod": "2023-10-18 19:43:26", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Steiger-B", "name": { "family": "Steiger", "given": "Beat" } }, { "id": "Yuasa-Makoto", "name": { "family": "Yuasa", "given": "Makoto" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Electroreduction of O_2 to H_2O at Unusually Positive Potentials Catalyzed by the Simplest of the Cobalt Porphyrins", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 1997 American Chemical Society. \n\nReceived May 1, 1997. Publication Date (Web): September 24, 1997. \n\nThis work was supported by the National Science Foundation.\n\nSupplemental Material - ic4294.pdf
", "abstract": "Simple cobalt porphine, adsorbed on graphite electrodes, catalyzes the direct reduction of O_2 to H_2O, while most other monomeric cobalt porphyrins do not. The surprising behavior of cobalt porphine suggests possible new strategies for the design of electrocatalysts for the reduction of O_2 to H_2O using structurally similar but more oxidation-resistant analogs.", "date": "1997-09-24", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "36", "number": "20", "publisher": "American Chemical Society", "pagerange": "4294-4295", "id_number": "CaltechAUTHORS:20180523-110226758", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180523-110226758", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/ic970516s", "primary_object": { "basename": "ic4294.pdf", "url": "https://authors.library.caltech.edu/records/59mgt-7b067/files/ic4294.pdf" }, "resource_type": "article", "pub_year": "1997", "author_list": "Shi, Chunnian; Steiger, Beat; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/ez3vv-8ws48", "eprint_id": 86662, "eprint_status": "archive", "datestamp": "2023-08-19 01:45:14", "lastmod": "2023-10-18 19:50:40", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Steiger-B", "name": { "family": "Steiger", "given": "Beat" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "[5,10,15,20-Tetrakis(4-((pentaammineruthenio)- cyano)phenyl)porphyrinato]cobalt(II) Immobilized on Graphite Electrodes Catalyzes the Electroreduction of O_2 to H_2O, but the Corresponding 4-Cyano-2,6-dimethylphenyl Derivative Catalyzes the Reduction Only to H_2O_2", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1997 American Chemical Society. \n\nReceived March 7, 1997. \n\nThis work was supported by the U.S. National Science Foundation. The experienced advice and enthusiastic encouragement of Dr. Chunnian Shi are a pleasure to acknowledge.", "abstract": "Cobalt porphyrins in which Ru(NH_3)_5^(2+) groups are coordinated to four cyanophenyl ligands pendant to the porphyrin ring act as catalysts for the electroreduction of O_2 when adsorbed on the surface of graphite electrodes. The parent 4-cyanophenyl derivative catalyzes the four-electron reduction of O_2 to H_2O, but the 4-cyano-2,6-dimethylphenyl derivative catalyzes only the two-electron reduction of O_2 to H_2O_2.", "date": "1997-08-27", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "36", "number": "18", "publisher": "American Chemical Society", "pagerange": "4138-4140", "id_number": "CaltechAUTHORS:20180529-110358826", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180529-110358826", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/ic970275o", "resource_type": "article", "pub_year": "1997", "author_list": "Steiger, Beat and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/rstze-2js37", "eprint_id": 81127, "eprint_status": "archive", "datestamp": "2023-08-19 01:36:41", "lastmod": "2023-10-17 19:35:30", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Minglian", "name": { "family": "Shi", "given": "Minglian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Non-Steady-State Rotating Disk Voltammetry of Redox Couples Incorporated in Perfluorsulfonated Ionomer Coatings on Electrodes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1997 American Chemical Society. \n\nReceived for review February 5, 1997. Accepted April 30, 1997. Publication Date (Web): July 15, 1997. \n\nThis work was supported by the National Science Foundation. Dr. Iqbal Bhugun was a consistent source of insightful comments and helpful suggestions.", "abstract": "The differences in the affinity of Nafion coatings for Ru(NH_3)_6^(3+/2+) and Os(bpy)_3^(3+/2+) counterions and the difference in the mobilities of the two types of cations within Nafion are used to explain the differences in the voltammetric signatures that they exhibit. A new method is proposed with which to determine whether apparent diffusion coefficients of electroactive counterions in electrode coatings differ when they are evaluated in transient or in steady-state experiments. The utility of non-steady-state cyclic voltammetry with Nafion-coated rotating disk electrodes to separate the contribution to the observed current from dissolved and Nafion-confined reactants is demonstrated.", "date": "1997-07-15", "date_type": "published", "publication": "Analytical Chemistry", "volume": "69", "number": "14", "publisher": "American Chemical Society", "pagerange": "2661-2668", "id_number": "CaltechAUTHORS:20170905-092129135", "issn": "0003-2700", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170905-092129135", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/ac9701389", "resource_type": "article", "pub_year": "1997", "author_list": "Shi, Minglian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/mmxrb-s4597", "eprint_id": 83353, "eprint_status": "archive", "datestamp": "2023-08-19 01:36:49", "lastmod": "2023-10-17 23:03:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Minglian", "name": { "family": "Shi", "given": "Minglian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Some Consequences of the Significantly Different Mobilities of Hydrophilic and Hydrophobic Metal Complexes in Perfluorosulfonated Ionomer Coatings on Electrodes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1997 American Chemical Society. \n\nReceived for review February 5, 1997. Accepted April 30, 1997. Publication Date (Web): July 15, 1997. \n\nThis work was supported by the National Science Foundation.", "abstract": "Thin coatings of Nafion on glassy carbon rotating disk electrodes were saturated with hydrophilic [Ru(NH_3)_6^(3+), Co(NH_3)_6^(3+)] or hydrophobic [Ru(bpy)_3^(2+)] counterions. With both types of counterions, the plateau currents obtained when the electrodes were rotated in solutions of the cations matched the currents obtained with the uncoated electrodes in the same solutions at all accessible rotation rates. The high rates of cross-coating charge propagation demonstrated by these results involved physical diffusion of the hydrophilic complexes and electron hopping between adjacent, immobile pairs of the hydrophobic complexes. The approximate concentration profiles that develop within, and just outside of, Nafion coatings on disk electrodes that are rotated in solutions of electroactive counterions are depicted.", "date": "1997-07-15", "date_type": "published", "publication": "Analytical Chemistry", "volume": "69", "number": "14", "publisher": "American Chemical Society", "pagerange": "2653-2660", "id_number": "CaltechAUTHORS:20171120-141114122", "issn": "0003-2700", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20171120-141114122", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/ac970137g", "resource_type": "article", "pub_year": "1997", "author_list": "Shi, Minglian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/t7k0y-73h39", "eprint_id": 86663, "eprint_status": "archive", "datestamp": "2023-08-19 01:28:46", "lastmod": "2023-10-18 19:50:47", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Electrochemical Assessment of the Stability of [Os(NH_3)_5(OH_2)]^(2+) in Aqueous Solutions", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 1997 American Chemical Society. \n\nReceived December 27, 1996. \n\nThis work was supported by the National Science Foundation. Helpful suggestions and comments from Prof. W. D. Harman were greatly appreciated. Dr. Minglian Shi's assistance in the preparation and use of the microelectrode was invaluable.\n\nSupplemental Material - ic2682.pdf
", "abstract": "The [Os(NH_3)_5(OH_2)]^(2+) complex in aqueous acid has been widely regarded as short-lived on the basis of results reported in an early pioneering electrochemical study.1 More recently, a much longer-lived Os(II) species generated by reduction of [Os(NH)3))5(OH)2)]^(3+) but of uncertain composition has been reported. In the present study the lifetime of [Os(NH_3)_5(OH_2)]^(2+) in aqueous acid was determined by steady-state voltammetry at a carbon microelectrode and by comparing experimental with simulated cyclic voltammograms obtained for solutions of [Os(NH_3)_5(OH_2)]^(3+). Rate constants for the oxidation of [Os(NH_3)_5(OH_2)]^(2+) by H^+, CH_3COOH (HA), and H_2O were evaluated as k_H = 17 M^(-1) s^(-1), k_(HA) = 1.2 M^(-1) s^(-1), and k_(H_2O) = 4.1 \u00d7 10^(-4) s^(-1). These values are shown to be compatible with the data in ref 1 and come close to accounting for the long-lived species described in ref 6 which may be [Os(NH_3)_5(OH_2)]^(2+) itself. A revised value of 4.85 was measured for the pKA of [Os(NH_3)_5(OH_2)]^(3+). Adsorption of an Os complex on the surface of mercury, but not glassy carbon, electrodes is shown to enhance greatly the rate with which protons undergo direct electroreduction.", "date": "1997-06-04", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "36", "number": "12", "publisher": "American Chemical Society", "pagerange": "2682-2687", "id_number": "CaltechAUTHORS:20180529-110854891", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180529-110854891", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/ic961522b", "primary_object": { "basename": "ic2682.pdf", "url": "https://authors.library.caltech.edu/records/t7k0y-73h39/files/ic2682.pdf" }, "resource_type": "article", "pub_year": "1997", "author_list": "Shi, Chunnian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/q622r-6pz07", "eprint_id": 86634, "eprint_status": "archive", "datestamp": "2023-08-19 00:41:52", "lastmod": "2023-10-18 19:48:45", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Cobalt meso-Tetrakis(N-methyl-4-pyridiniumyl)porphyrin Becomes a Catalyst for the Electroreduction of O_2 by Four Electrons When [(NH_3)_5Os]^(n+) (n = 2, 3) Groups Are Coordinated to the Porphyrin Ring", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1996 American Chemical Society. \n\nReceived June 14, 1996. \n\nThis work was supported by the National Science Foundation. Helpful suggestions from Prof. W. D. Harmon were appreciated.", "abstract": "In a series of recent reports evidence has been offered to support the proposal that coordination of (NH_3)_5Ru^(2+) groups to ligand sites introduced on the meso positions of certain cobalt porphyrins enhances their abilities to act as electrocatalysts for the reduction of O_2 to H_2O. The enhancement is believed to be the result of back-bonding by the Ru(II) centers into the pendant ligands and the cobalt porphyrin to which they are linked. The catalytic mechanism that has been proposed leaves the coordinated Ru centers in their +2 oxidation state as the O_2 molecule coordinated to the Co(II) center of the porphyrin in the activated complex is reduced via electron-transfer from the electrode surface. Intramolecular electron-transfer from the Ru(II) centers to the coordinated O_2 is not consistent with the experimental data. To obtain additional information about the importance of back-bonding in enhancing the catalytic activity of these cobalt porphyrins, we sought to use Os(III) in place of Ru(II) as the source of the back-donation. Os(III), unlike Ru(III), exhibits substantial back-bonding capabilities, but Os(III) is a much weaker thermodynamic reductant than Ru(II). Thus, we reasoned that any increase in the catalytic activity of cobalt porphyrins that might result from the attachment of Os(III) centers to the porphyrin ring could be confidently attributed to back-bonding effects free of any contributions from intramolecular electron-transfer. The results of experiments designed to test this speculation are described in this report.", "date": "1996-12-18", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "35", "number": "26", "publisher": "American Chemical Society", "pagerange": "7928-7931", "id_number": "CaltechAUTHORS:20180525-133925688", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180525-133925688", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1021/ic9607189", "resource_type": "article", "pub_year": "1996", "author_list": "Shi, Chunnian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/r4nnn-79s79", "eprint_id": 86397, "eprint_status": "archive", "datestamp": "2023-08-19 00:40:26", "lastmod": "2023-10-18 19:33:08", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Bhugun-I", "name": { "family": "Bhugun", "given": "Iqbal" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Enhancement of the Catalytic Activity of a Macrocyclic Cobalt(II) Complex for the Electroreduction of O_2 by Adsorption on Graphite", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1996 American Chemical Society. \n\nReceived July 17, 1996. Publication Date (Web): December 4, 1996. \n\nThis work was supported by the National Science Foundation. I.B. was the grateful recipient of an A. A. Noyes Postdoctoral Fellowship at Caltech. Discussions with Dr. Beat Steiger were stimulating and very helpful.", "abstract": "In solution, the [(tim)Co]^(2+) complex (tim = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) reacts only slowly with O_2, but upon adsorption on graphite electrodes it becomes an active catalyst for the reduction of O_2 to H_2O_2. The remarkable enhancement in catalytic activity is attributed to a higher affinity for O_2 of the adsorbed complex as a result of its interaction with functional groups on the surface of roughened or oxidized graphite. A possible catalytic mechanism is proposed.", "date": "1996-12-04", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "35", "number": "25", "publisher": "American Chemical Society", "pagerange": "7253-7259", "id_number": "CaltechAUTHORS:20180514-153140758", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180514-153140758", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Caltech" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/ic9608399", "resource_type": "article", "pub_year": "1996", "author_list": "Bhugun, Iqbal and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/5780t-p8n22", "eprint_id": 79978, "eprint_status": "archive", "datestamp": "2023-08-19 00:28:37", "lastmod": "2023-10-26 17:29:14", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kuhn-A", "name": { "family": "Kuhn", "given": "Alexander" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Adsorption of Monolayers of P_2Mo_(18)O_(62)^(6-) and Deposition of Multiple Layers of Os(bpy)_3^(2+)\u2212P_2Mo_(18)O_(62)^(6-) on Electrode Surfaces", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1996 American Chemical Society. \n\nReceived May 10, 1996. In Final Form: September 5, 1996. Publication Date (Web): October 30, 1996. \n\nThis work was supported by the National Science Foundation and the Alexander von Humboldt Foundation in the form of a Feodor Lynen Fellowship to A.K. We are very grateful to Dr. Minglian Shi for his construction of the quartz crystal microbalance and assistance with its operation and to Alan Rice for performing the XPS measurements. To Drs. Chunnian Shi and Beat Steiger we are grateful for invaluable assistance and helpful discussions.", "abstract": "The unusually strong, irreversible adsorption of monolayer quantities of the P_2Mo_(18)O_(62)^(6-) anion on glassy carbon, highly ordered pyrolytic graphite, indium tin oxide, and gold-coated quartz electrodes was examined by electrochemical, spectroelectrochemical, and quartz crystal microgravimetric techniques. A very simple method was developed to deposit multiple layers of composites consisting of alternating layers of the P_2Mo_(18)O_(62)^(6-) anion and large, multiply-charged cations such as Os(bpy)_3^(2+). The resulting deposit is stable and exhibits electroactivity from both of the components that reflects the structure and ionic conductivity of the solid multilayer.", "date": "1996-10-30", "date_type": "published", "publication": "Langmuir", "volume": "12", "number": "22", "publisher": "American Chemical Society", "pagerange": "5481-5488", "id_number": "CaltechAUTHORS:20170808-160245451", "issn": "0743-7463", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170808-160245451", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Alexander von Humboldt Foundation" } ] }, "doi": "10.1021/la960461r", "resource_type": "article", "pub_year": "1996", "author_list": "Kuhn, Alexander and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/k5snm-9xp72", "eprint_id": 29225, "eprint_status": "archive", "datestamp": "2023-08-19 00:27:53", "lastmod": "2023-10-24 22:00:44", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Xie-Y", "name": { "family": "Xie", "given": "Yuanwu" } }, { "id": "Kang-C", "name": { "family": "Kang", "given": "Chang" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Calculation of cyclic voltammetric responses for the reductive\n formation of catalyst-substrate adducts on electrode surfaces", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 1996 Royal Society of Chemistry. Received 6th March, 1996.\nThis work was supported by the U.S. National Science Foundation.\n\nPublished - XIEjcsft96.pdf
", "abstract": "Electrocatalysts based on monolayers of transition-metal complexes attached to electrode surfaces frequently follow mechanisms in which a chemical step is interposed between the first and subsequent electron-transfer steps. The cyclic voltammetric responses to be anticipated for such systems were calculated using finite difference procedures to solve the relevant differential equation. The calculated variation of the peak currents and peak potentials with the kinetic parameters governing the three steps in the mechanistic scheme are presented in graphical form. Application of the results to a specific experimental system, the catalysis of the electroreduction of O_2 by a macrocyclic complex of Co^(III) adsorbed on graphite electrodes, produced reasonable agreement between calculated and observed cyclic voltammograms.", "date": "1996-10-21", "date_type": "published", "publication": "Journal of the Chemical Society. Faraday Transactions", "volume": "92", "number": "20", "publisher": "Royal Society of Chemistry", "pagerange": "3917-3923", "id_number": "CaltechAUTHORS:20120209-110217213", "issn": "0956-5000", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120209-110217213", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1039/ft9969203917", "primary_object": { "basename": "XIEjcsft96.pdf", "url": "https://authors.library.caltech.edu/records/k5snm-9xp72/files/XIEjcsft96.pdf" }, "resource_type": "article", "pub_year": "1996", "author_list": "Xie, Yuanwu; Kang, Chang; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/prw36-0nz75", "eprint_id": 88042, "eprint_status": "archive", "datestamp": "2023-08-19 00:12:29", "lastmod": "2023-10-18 21:39:16", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Campbell-J-L-E", "name": { "family": "Campbell", "given": "John L. E." } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Factors Responsible for the Unusually Strong Adsorption of [Os(bpy)_2(Cl)L_1]^+ (L_1 = 1,2-bis(4-pyridyl)ethane) and Related Complexes on Metal and Graphite Electrode Surfaces", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1996 American Chemical Society. \n\nReceived March 22, 1996. \n\nThis work was supported by the U.S. National Science Foundation. J.L.E.C. was the grateful recipient of a Fellowship from the Natural Sciences and Engineering Research Council of Canada. Englightening discussions with Drs. Iqbal Bhugun and Beat Steiger are a pleasure to acknowledge.", "abstract": "The extent and dynamics of the adsorption on gold and pyrolytic graphite electrodes of four complexes of Os(II) were compared with the previously reported adsorption of similar complexes on Pt (Acevedo, D.; Abru\u00f1a, H. D. J. Phys. Chem. 1991, 95, 9590). The complexes investigated were [Os(bpy)_2(Cl)L]^+ with bpy = 2,2'-bipyridine and L = 1,2-bis(4-pyridyl)ethane, 4-phenylpyridine, 4-(1-n-butylpentyl)pyridine, and pyridine. Spontaneous, strong adsorption of all four complexes occurred on graphite electrodes and, except for the complex with L = pyridine, on gold electrodes. The presence of a pendant pyridine site on ligand L is not required for strong adsorption to occur. Replacement of the [Os(bpy)_2(Cl)]^+ center by Ru(NH_3)_5^(2+) also led to a strongly adsorbing complex. The adsorption appears to be driven by hydrophobic interactions of the organic ligands with the electrode surface and with each other as well as specific surface\u2212ligand bond formation when a pendant pyridine group is present. Although the concentration dependence of the quantities of the complexes adsorbed could be fit to a Langmuir isotherm, the dynamics of the adsorption and desorption reactions were not consistent with Langmuirian adsorption. Stabilizing intermolecular electronic interactions among the adsorbed molecules are suggested as a possible explanation for the observed behavior.", "date": "1996-08-07", "date_type": "published", "publication": "Langmuir", "volume": "12", "number": "16", "publisher": "American Chemical Society", "pagerange": "4008-4014", "id_number": "CaltechAUTHORS:20180719-162726781", "issn": "0743-7463", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180719-162726781", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" } ] }, "doi": "10.1021/la960278y", "resource_type": "article", "pub_year": "1996", "author_list": "Campbell, John L. E. and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/jvxbw-50w68", "eprint_id": 88086, "eprint_status": "archive", "datestamp": "2023-08-18 23:53:46", "lastmod": "2023-10-18 21:44:46", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hatozaki-Osamu", "name": { "family": "Hatozaki", "given": "Osamu" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Diffusion Coefficients of Intrinsically Electroactive Polyelectrolytes and of Counterions Bound to Them", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1996 American Chemical Society. \n\nReceived: December 15, 1995; In Final Form: March 4, 1996. \n\nThis work was supported in part by the U.S. Army Research Office (Durham).", "abstract": "An electroactive label was attached to poly(acrylic acid) (molecular weight = 5000) by reaction with ferrocenylethanol. The resulting ferrocene label was stable when the polymer was dissolved in aqueous solutions, and the diffusion coefficient of the labeled polymer was estimated from the currents obtained as the ferrocene was oxidized at a rotating disk electrode. Although strong adsorption of the polymer on the electrode surfaces depressed the oxidation currents below the convection\u2212diffusion controlled values at rotating disk electrodes, it was still possible to estimate diffusion coefficients by appropriate analysis of the rotation rate dependences of the measured currents. At pH values where the labeled polymer became a polyanion, its diffusion coefficient was also estimated from the reduction currents for Ru(NH_3)_6^(3+) or Co(NH_3)_6^(3+) counterions bound electrostatically to the polyelectrolyte. Good agreement was obtained between the diffusion coefficients estimated by the two independent routes.", "date": "1996-05-16", "date_type": "published", "publication": "Journal of Physical Chemistry", "volume": "100", "number": "20", "publisher": "American Chemical Society", "pagerange": "8448-8453", "id_number": "CaltechAUTHORS:20180720-144653154", "issn": "0022-3654", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180720-144653154", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Army Research Office (ARO)" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/jp953740g", "resource_type": "article", "pub_year": "1996", "author_list": "Hatozaki, Osamu and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/5k6v0-05w84", "eprint_id": 86671, "eprint_status": "archive", "datestamp": "2023-08-18 23:52:45", "lastmod": "2023-10-18 19:51:52", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lei-Yanbin", "name": { "family": "Lei", "given": "Yanbin" } }, { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Effects of Coordination to Transition Metals on the Hydration and Electroactivity of the Chelating Ligand 1,10-Phenanthroline-5,6-dione", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1996 American Chemical Society. \n\nReceived December 8, 1995. \n\nThis work was supported by the National Science Foundation.", "abstract": "The intrinsically electroactive ligand in the title was coordinated to Co^(2+), Fe^(2+), Ni^(2+), Zn^(2+), and Cu^+, and the resulting hydration of the carbonyl groups of a portion of the coordinated ligand eliminated its electroactivity. The extent of hydration of the coordinated ligand was evaluated by means of rotating disk voltammetry. Estimates were obtained for the equilibrium constants governing the hydration reaction. The hydration induced by coordination of the ligand to the metal cations varied in parallel with the magnitude of the first association constant for the metal\u2212ligand coordination.", "date": "1996-05-08", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "35", "number": "10", "publisher": "American Chemical Society", "pagerange": "3044-3049", "id_number": "CaltechAUTHORS:20180529-115958777", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180529-115958777", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "9165", "name": "Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "doi": "10.1021/ic951569h", "resource_type": "article", "pub_year": "1996", "author_list": "Lei, Yanbin; Shi, Chunnian; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/4smbf-j6d97", "eprint_id": 88043, "eprint_status": "archive", "datestamp": "2023-08-20 07:29:32", "lastmod": "2023-10-18 21:39:19", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Minglian", "name": { "family": "Shi", "given": "Minglian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Rapid Oxidation of Ru(NH_3)_6^(3+) by Os(bpy)_3^(3+) within Nafion Coatings on Electrodes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1996 American Chemical Society. \n\nReceived October 12, 1995. In Final Form: January 9, 1996. \n\nThis work was supported by the National Science Foundation.", "abstract": "The oxidation of Ru(NH_3)_6^(3+) by Os(bpy)_3^(3+) is a very slow process in aqueous acid. The rate increases with pH but the reaction remains slow at pH 7. However, when the two reactants are incorporated in Nafion coatings on electrodes the oxidation can proceed much more rapidly, especially with Nafion coatings that are not fully hydrated. Rotating disk and cyclic voltammetry were employed to determine the stoichiometry of the reaction and to measure its kinetics both in solution and in Nafion coatings. The Ru(NH_3)_6^(3+) is oxidized to Ru(VII) at a rate that is first order in Ru(NH_3)_6^(3+) and Os(bpy)_3^(3+) and inverse first order in H^+. The reaction rate constant evaluated in solution was similar to that evaluated in Nafion. The higher reaction rate obtained when the reactants are incorporated in Nafion results from their higher concentrations, not from significant enhancement of their reactivities. The higher reaction rate obtained from partially dehydrated Nafion coatings is believed to result from a breakdown in cation permselectivity that permits the ionic current inside the coating during anodic current flow to be carried by anions instead of by the ejection of Ru(NH_3)_6^(3+) cations from the Nafion.", "date": "1996-04-17", "date_type": "published", "publication": "Langmuir", "volume": "12", "number": "8", "publisher": "American Chemical Society", "pagerange": "2068-2075", "id_number": "CaltechAUTHORS:20180719-163135834", "issn": "0743-7463", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180719-163135834", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "9147", "name": "Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "doi": "10.1021/la950863j", "resource_type": "article", "pub_year": "1996", "author_list": "Shi, Minglian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/mfdmq-zx575", "eprint_id": 88091, "eprint_status": "archive", "datestamp": "2023-08-20 07:22:40", "lastmod": "2023-10-18 21:45:37", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Yoshikawa-Masaki", "name": { "family": "Yoshikawa", "given": "Masaki" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Association of Electroactive Counterions with Polyelectrolytes. 6. Electrostatic and Coordinative Binding of Ru^(3+/2+) Centers to a Copolymer of Acrylic Acid and Acrylonitrile", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1996 American Chemical Society. \n\nReceived: September 25, 1995; In Final Form: NoVember 28, 1995. \n\nThis work was supported by the U. S. Army Research Office (Durham) and by Unitika, Ltd. (Osaka). Discussions with Drs. Osamu Hatozaki, Chunnian Shi, and Beat Steiger were most helpful.", "abstract": "A random copolymer of acrylic acid and acrylonitrile was prepared in which the functionality on the polymer chain consisted of 93% carboxylic acid groups, 4.1% nitrile groups, and 2.9% acid anhydride groups. The nitrile groups were used to coordinate Ru(NH_3)_5^(2+) centers to the copolymer. The anionic carboxylate groups produced at pH values above \u223c3.5 were used to bind Ru(NH_3)_6^(3+) counterions to the resulting polyanionic copolymer. The electrochemical oxidation or reduction of the two redox centers bound to the copolymer were used to estimate diffusion coefficients for the copolymer. Reasonable agreement was obtained between the values obtained from both electroactive redox groups. The diffusion coefficient exhibited a strong dependence on pH that reflected changes in the structure of the copolymer as it was converted from its neutral to its polyanionic form. The rate of the reaction between the Ru(NH_3)_5OH_2^(2+) complex and the nitrile groups of the copolymer increased significantly with pH because electrostatic binding of the cation to the polyanionic copolymer increased the concentration of the complex in the vicinity of the nitrile groups. Adsorption of the copolymer on the surface of the electrodes interfered with the oxidation of Ru(NH_3)_5^(2+) groups coordinated to the dissolved copolymer but not with Ru(NH_3)_6^(3+) counterions electrostatically bound to the polyanion. A possible explanation for the contrasting behavior is suggested.", "date": "1996-03-07", "date_type": "published", "publication": "Journal of Physical Chemistry", "volume": "100", "number": "10", "publisher": "American Chemical Society", "pagerange": "4199-4204", "id_number": "CaltechAUTHORS:20180720-151111313", "issn": "0022-3654", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180720-151111313", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Army Research Office (ARO)" }, { "agency": "Unitika, Ltd." } ] }, "other_numbering_system": { "items": [ { "id": "9142", "name": "Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "doi": "10.1021/jp952831a", "resource_type": "article", "pub_year": "1996", "author_list": "Yoshikawa, Masaki and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/nbrw4-hdh64", "eprint_id": 32234, "eprint_status": "archive", "datestamp": "2023-09-14 19:26:54", "lastmod": "2023-10-23 20:50:57", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-M", "name": { "family": "Shi", "given": "Minglian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "High Sensitivity of Electron Transfer Rates within Nafion\n Coatings Saturated with Os(bpy)^(2+)_3 to the Extent of\n Hydration of the Coating", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 1995 The Electrochemical Society, Inc.\nSubmitted May 22, 1995; revised July 18, 1995.\nThis work was supported by the National Science Foundation.\nWe appreciated receiving a copy of Ref. 15 from Dr.\nI.-C. Jeon prior to publication.\nManuscript submitted May 22, 1995:, revised manuscript\nreceived July 18, 1995.\nCalifornia Institute of Technology assisted in meeting the\npublication costs of this article.\n\nPublished - SHIjes84.pdf
", "abstract": "The sensitivity of the electrochemical responses obtained from electroactive counterions incorporated in Nafion coatings to the extent of hydration of the coatings^(27-38) is shown to be enhanced significantly when the electroactive ion is the only counterion present in the coating. Nafion coatings fully saturated with Os(bpy)^(2+)_3 exhibit unusually narrow and sharply peaked anodic currents in first-scan oxidative voltammograms. This voltammetric feature is accompanied by the\nexpulsion of one-third of the Os complex from the coating. The counterion actually ejected is primarily Os(bpy)^(3+)_3. As the Os(bpy)^(3+)_3 counterions are ejected, H_2O molecules enter the coatings. The quantity of H_2O molecules incorporated is so large that the mass of the coating (monitored with a quartz crystal microbalance) increases despite the ejection of the heavy Os(bpy)^(3+)_3 cations. After several voltammetric cycles, normally shaped voltammograms are obtained that are relatively\ninsensitive to the initial state of hydration of the coatings. The contrasting behaviors of hydrated and unhydrated coatings are compared, and possible explanations are offered for the differences observed.", "date": "1995-12", "date_type": "published", "publication": "Journal of the Electrochemical Society", "volume": "142", "number": "12", "publisher": "The Electrochemical Society, Inc.", "pagerange": "4205-4214", "id_number": "CaltechAUTHORS:20120702-110414259", "issn": "0013-4651", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120702-110414259", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Caltech" } ] }, "doi": "10.1149/1.2048485", "primary_object": { "basename": "SHIjes84.pdf", "url": "https://authors.library.caltech.edu/records/nbrw4-hdh64/files/SHIjes84.pdf" }, "resource_type": "article", "pub_year": "1995", "author_list": "Shi, Minglian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/kq2cw-7fp26", "eprint_id": 88442, "eprint_status": "archive", "datestamp": "2023-08-20 06:14:12", "lastmod": "2023-10-18 22:03:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Comparison of the catalytic reduction of oxygen by [5,10,15,20-tetrakis((pentaammineruthenio(II)-4-pyridyl)porphyrinato]cobalt(II) in solution and on graphite electrode surfaces", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1995 American Chemical Society. \n\nReceived April 14, 1995. \n\nThis work was supported by the National Science Foundation. Dr. Beat Steiger was a source of continuing, reliable, and stimulating advice. We are most grateful to Prof. James Espenson for insightful comments and assistance with implementation of the Kinsim program.", "abstract": "The [5, 10, 15,20-tetrakis((pentaammineruthenio(II))-4-pyridylporphinato ]cobalt(II) complex that catalyzes the fourelectron reduction of O_2 at graphite electrode surfaces on which it has been assembled has now been prepared in homogeneous solution. The preparative procedure for the catalyst is described, and the kinetics of its catalysis of the reduction of O_2 by chemical reductants in homogeneous solution are reported. In solution, only twoelectron reductions of O_2 are obtained and the rate of intramolecular electron-transfer from the four Ru(NH_3)_(5-)py^(2+) centers on the periphery of the catalyst molecule to an O_2 molecule coordinated to the Co(II) center in the porphyrin ring is shown to be quite slow. Possible reasons for the contrasting mechanistic behavior of the catalyst in solution and on graphite electrodes are suggested.", "date": "1995-08-30", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "34", "number": "18", "publisher": "American Chemical Society", "pagerange": "4554-4561", "id_number": "CaltechAUTHORS:20180801-112457194", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180801-112457194", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "9083", "name": "Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "doi": "10.1021/ic00122a010", "resource_type": "article", "pub_year": "1995", "author_list": "Shi, Chunnian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/z47z1-bht69", "eprint_id": 43553, "eprint_status": "archive", "datestamp": "2023-08-20 05:42:17", "lastmod": "2023-10-25 23:39:30", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Linus Pauling Teaching at Caltech", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1995 American Chemical Society.", "abstract": "Throughout several decades Linus Pauling gave two lectures per week in the Chemistry Course\nrequired of all Caltech freshman. His style was unique and contrasted with that employed by the\nlecturers in the simultaneously required courses in Physics and Mathematics. A typical lecture by\nPauling was stimulating and entertaining and often seemed to be impromptu. The reactions of the\nfreshmen to the Pauling style were overwhelmingly positive and lasting. Some recollections by a former\nfreshman student, professorial colleague and personal friend of Linus Pauling will be offered.", "date": "1995-04-02", "date_type": "published", "publication": "Abstracts of Papers of the American Chemical Society", "volume": "209", "publisher": "American Chemical Society", "pagerange": "477-CHED", "id_number": "CaltechAUTHORS:20140129-132432696", "issn": "0065-7727", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140129-132432696", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "resource_type": "article", "pub_year": "1995", "author_list": "Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/862zz-7rd38", "eprint_id": 88717, "eprint_status": "archive", "datestamp": "2023-08-20 05:29:58", "lastmod": "2023-10-18 22:15:44", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Steiger-B", "name": { "family": "Steiger", "given": "Beat" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Coordination chemistry in electrocatalysis", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 1995 IUPAC. \n\nThis work was supported by the National Science Foundation and the Office of Naval Research/DARPA.\n\nPublished - _Pure_and_Applied_Chemistry__Coordination_chemistry_in_electrocatalysis.pdf
", "abstract": "Superior electrocatalysts for the reduction of O_2 by four-electrons in one step have been prepared by coordinating ammine complexes of Ru(II) to the pyridine ligand sites in cobalt tetrakis(4-pyridyl) porphyrin. At least three coordinated Ru(II) centers appear to be required to obtain the four-electron reduction. When fac-Ru(NH_3)_3(OH_2)_3^(2+) was used to ruthenate the porphyrin, a network structure was obtained in which both terminal and bridging ruthenium centers were present.", "date": "1995-02", "date_type": "published", "publication": "Pure and Applied Chemistry", "volume": "67", "number": "2", "publisher": "International Union of Pure and Applied Chemistry", "pagerange": "319-322", "id_number": "CaltechAUTHORS:20180809-152106160", "issn": "0033-4545", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180809-152106160", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Office of Naval Research (ONR)" }, { "agency": "Defense Advanced Research Projects Agency (DARPA)" } ] }, "doi": "10.1351/pac199567020319", "primary_object": { "basename": "_Pure_and_Applied_Chemistry__Coordination_chemistry_in_electrocatalysis.pdf", "url": "https://authors.library.caltech.edu/records/862zz-7rd38/files/_Pure_and_Applied_Chemistry__Coordination_chemistry_in_electrocatalysis.pdf" }, "resource_type": "article", "pub_year": "1995", "author_list": "Shi, Chunnian; Steiger, Beat; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/9e6nc-0ap35", "eprint_id": 86687, "eprint_status": "archive", "datestamp": "2023-08-20 04:05:08", "lastmod": "2023-10-18 19:53:24", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Rong-Chaoying", "name": { "family": "Rong", "given": "Chaoying" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Simplified Preparations and Electrochemical Behavior of Two Chromium-Substituted Heteropolytungstate Anions", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1994 American Chemical Society. \n\nReceived August 27, 1993. \n\nThis work was supported by a grant from the ONR/DARPA.", "abstract": "Simplified preparative procedures are described for the generation of \u03b1-[PW_(11)O_(39)Cr^(III)(OH_2)]^(4-) and \u03b12-[P_2W_(11)O_(61)Cr^(III)(OH_2)]^(7-) anions which can be readily oxidized, chemically or electrochemically, to \u03b1-[PW_(11)O_(39)Cr^(V)O]^(4-) and \u03b12-[P_2W_(17)O_(61)Cr^(V)O]^(7-). The oxidized complexes are stable in aqueous solutions. They react with benzyl or ethyl\nalcohol, but the rates of the oxidations are too slow to make the Cr(V) derivatives attractive as electrocatalysts. The voltammetry of the Cr^(V)/Cr^(III) couples is only quasi-reversible, but approximate formal potentials with their pH\ndependencies are reported. Diffusion coefficients evaluated for the polyanions show the larger anion to diffuse more\nslowly and neither anion to be highly hydrated.", "date": "1994-03-16", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "33", "number": "6", "publisher": "American Chemical Society", "pagerange": "1064-1070", "id_number": "CaltechAUTHORS:20180529-153402798", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180529-153402798", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" }, { "agency": "Defense Advanced Research Projects Agency (DARPA)" } ] }, "other_numbering_system": { "items": [ { "id": "8827", "name": "Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "doi": "10.1021/ic00084a016", "resource_type": "article", "pub_year": "1994", "author_list": "Rong, Chaoying and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/agr5s-3xv98", "eprint_id": 85367, "eprint_status": "archive", "datestamp": "2023-08-20 01:53:28", "lastmod": "2023-10-18 18:09:29", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Shi-Chunnian", "name": { "family": "Shi", "given": "Chunnian" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Electrocatalysis of the reduction of O_2 to H_2O by tetraruthenated cobalt meso-tetrakis(4-pyridyl)porphyrin adsorbed on graphite electrodes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1992 American Chemical Society. \n\nReceived June 25, 1992. \n\nNumerous enlightening discussions with Dr. Beat Steiger were very helpful to us. This work was supported by ONR/DARPA and by the National Science Foundation.", "abstract": "Coordination of Ru(NH_3)_5 groups to the four pyridine sites in cobalt meso-tetrakis(4-pyridyl)porphyrin adsorbed\non pyrolytic graphite electrodes produces the tetraruthenated complex which acts as a catalyst for the four-electron reduction of O_2 to H_2O. The adsorbed catalyst, prepared by this heterogeneous coordination reaction, yields higher catalytic reduction rates than those obtained previously when the same catalyst was prepared within Nafion coatings on electrodes. The coordination chemistry used in the preparation of the adsorbed catalyst and its behavior as an electrocatalyst are described.", "date": "1992-11-01", "date_type": "published", "publication": "Inorganic Chemistry", "volume": "31", "number": "24", "publisher": "American Chemical Society", "pagerange": "5078-5083", "id_number": "CaltechAUTHORS:20180319-154249507", "issn": "0020-1669", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180319-154249507", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" }, { "agency": "Defense Advanced Research Projects Agency (DARPA)" }, { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "8656", "name": "Caltech Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "doi": "10.1021/ic00050a029", "resource_type": "article", "pub_year": "1992", "author_list": "Shi, Chunnian and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/w1sb7-d3v39", "eprint_id": 81482, "eprint_status": "archive", "datestamp": "2023-08-20 01:43:37", "lastmod": "2023-10-17 19:53:35", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Jeon-Il-Cheol", "name": { "family": "Jeon", "given": "Il Cheol" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Application of scanning electrochemical microscopy to studies of charge propagation within polyelectrolyte coatings on electrodes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1992 American Chemical Society. \n\nReceived for review February 10, 1992. Accepted June\n18, 1992. \n\nThis work was supported by the National Science Foundation and the U.S. Army Research Office. I.C.J. was grateful for partial support provided by the Korean Science and Engineering Foundation. Numerous enlightening discussions with Dr. Chongmok Lee are a pleasure to acknowledge.", "abstract": "The technique of scanning electrochemical microscopy is used\nto examine the properties of polyelectrolyte coatings on\nelectrodes. Coatings of protonated poly(4-vinytpyridine)\nexhibit time dependences of their redox conductivities with\nFe(CN)_6^(3-) or IrCl_6^(2-) as counterions incorporated in the coatings. By contrast, responses obtained from coatings of Nafion show no comparable time dependence. A possible reason for the difference is suggested. Images of the two types of coatings obtained with the scanning electrochemical microscope include apparent topological features in the poly(4-vinytpyridine) coatings which are shown to arise from significant variations in redox conductivity across the surface of aged coatings\nrather than from true changes in the coating's dimension. In\nthe case of Nafion coatings, only smooth surfaces are observed in scanning electrochemical microscope images whether they are recorded under conditions of positive or negative feedback. The absence of significant spatial variations in redox conductivity is believed to be responsible for the featureless images obtained with Nafion coatings.", "date": "1992-09-15", "date_type": "published", "publication": "Analytical Chemistry", "volume": "64", "number": "18", "publisher": "American Chemical Society", "pagerange": "2021-2028", "id_number": "CaltechAUTHORS:20170915-084856218", "issn": "0003-2700", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170915-084856218", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Army Research Office (ARO)" }, { "agency": "Korean Science and Engineering Foundation" } ] }, "doi": "10.1021/ac00042a003", "resource_type": "article", "pub_year": "1992", "author_list": "Jeon, Il Cheol and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/kah5a-sn720", "eprint_id": 84571, "eprint_status": "archive", "datestamp": "2023-08-20 01:09:00", "lastmod": "2023-10-18 16:22:18", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lee-Chongmok", "name": { "family": "Lee", "given": "Chongmok" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Use of Electrochemical Microscopy to Examine Counterion Ejection from Nafion Coatings on Electrodes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1992 American Chemical Soclety. \n\nReceived for review September 19,1991. Accepted November 26, 1991. Published in print 1 March 1992. \n\nThis work was supported by the National Science Foundation\nand the U.S. Army Research Office. This paper is contribution no. 8510 from the Division of Chemistry and Chemical Engineering.", "abstract": "The ideal cation permselectivity exhibited by electrode\ncoatings prepared from the polyelectrolyte Nafion leads to\nejection of countercatlons from the coatings during electrochemical oxidation of Os(bpy)_3^(2+) counterions incorporated in the coatings. If the coatings are saturated with Os(bpy)_3^(2+) so that these are the only counterions present, one-third of the incorporated cations are ejected during the oxidation of Os(bpy)_3^(2+) to Os(bpy)_3^(3+). The cyclic voltammetry of the incorporated Os(bpy)_3^(3+/2+) couple is altered substantially in the absence of additional counterions. The changes are attributed to contributions to the voltammetric potentials from the free energy of transfer of these strongly bound counterions. Microtip electrodes positioned just above Nafion-coated electrodes were used to monitor the ejection of both Os(bpy)_3^(3+) and Os(bpy)_3^(2+) from Nafion coatings. Much more of the former complex lo ejected from saturated coatings which is believed to be the result of electric field-assisted ejection.", "date": "1992-03-01", "date_type": "published", "publication": "Analytical Chemistry", "volume": "64", "number": "5", "publisher": "American Chemical Society", "pagerange": "528-533", "id_number": "CaltechAUTHORS:20180130-090151012", "issn": "0003-2700", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180130-090151012", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Army Research Office (ARO)" } ] }, "other_numbering_system": { "items": [ { "id": "8510", "name": "Caltech Division of Chemistry and Chemical Engineering" } ] }, "doi": "10.1021/ac00029a015", "resource_type": "article", "pub_year": "1992", "author_list": "Lee, Chongmok and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/r3d0x-wjb14", "eprint_id": 84570, "eprint_status": "archive", "datestamp": "2023-08-20 01:04:23", "lastmod": "2023-10-18 16:22:12", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kwak-Juhyoun", "name": { "family": "Kwak", "given": "Juhyoun" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Monitoring the Ejection and Incorporation of Ferricyanide Fe(CN)_6^(3-) and Ferrocyanide Fe(CN)_6^(4-) Counterions at Protonated Poly(4-vinylpyridine) Coatings on Electrodes with the Scanning Electrochemical Microscope", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1992 American Chemical Society. \n\nPublished in print 1 February 1992. Publication Date: February 1992. \n\nThis work was supported by the National Science Foundation.\nThis is Contribution No. 8492 from the Division of Chemistry and Chemical Engineering, California Institute of Technology.", "abstract": "The precise positioning of microtlp electrodes close to the\nsurface of substrate electrodes, as practiced in scanning\nelectrochemlcal microscopy, was exploited to monitor the\nconcentrations of Fe(CN)_6^(-3) and Fe(CN)_6^(-4) anions at the surfaces of protonated poly(4-vinylpyridine) coatings on glassy-carbon electrodes. Positive feedback, which enhanced the magnitude of currents at the monitoring tip electrode, gave way to negative feedback when reactant concentrations were increased to the point that electron propagation through the polyectrolyte coatings became the curent-limiting step. The election of counterions when cathodic currents were passed through coatings which were saturated with Fe(CN)_6^(3-) was readily detected, especially when current steps were applied to the coated substrate electrode. Delayed arrival of counterions at the monitoring tip could be associated with the time required for the ions to traverse the coatings before they were ejected. Reincorporation of multiply-charged counterions inmediately following their ejection appeared to be favored over the incorporation of singly charged anions present at much higher concentrations.", "date": "1992-02-02", "date_type": "published", "publication": "Analytical Chemistry", "volume": "64", "number": "3", "publisher": "American Chemical Society", "pagerange": "250-256", "id_number": "CaltechAUTHORS:20180130-083252099", "issn": "0003-2700", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180130-083252099", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "8492", "name": "Caltech Division of Chemistry and Chemical Engineering" } ] }, "doi": "10.1021/ac00027a003", "resource_type": "article", "pub_year": "1992", "author_list": "Kwak, Juhyoun and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/6prqf-sa826", "eprint_id": 80987, "eprint_status": "archive", "datestamp": "2023-08-20 00:13:15", "lastmod": "2023-10-17 19:19:37", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lee-Chongmok", "name": { "family": "Lee", "given": "Chongmok" } }, { "id": "Kwak-Juhyoun", "name": { "family": "Kwak", "given": "Juhyoun" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Application of scanning electrochemical microscopy to generation/collection experiments with high collection efficiency", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1991 American Chemical Society. \n\nReceived for review January 14, 1991. Accepted April 18, 1991. \n\nThis work was supported by the National Science Foundation. This is Contribution No. 8379 from the Division of Chemistry and Chemical Engineering.", "abstract": "The technique of scanning electrochemical microscopy (SECM) was introduced by Bard and co-workers (1) who have utilized it in a variety of experiments (2). The use of a microelectrode placed close to a substrate electrode to detect electroactive products generated at the latter, as described by Engstrom and co-workers (3,4),is one attractive application of the SECM technique (1). In previous studies, this type of generation/detection experiment has usually been carried out with the microelectrode used as the detector electrode (1-5).\nIn the present study, a larger (100 \u00b5m diameter) substrate electrode is used to detect and collect electrode reaction\nproducts generated at a microtip electrode positioned at\nvarious distances above the substrate electrode. The collection efficiency (in the sense employed for rotating ring-disk electrodes (6)) of such an arrangement is virtually 100% at easily achievable separation distances. The advantages of carrying out generation/collection experiments with the present apparatus are exemplified with some simple experimental systems. Comparisons with similar recent experiments in which arrays of microband electrodes are utilized (7,8) are also provided.", "date": "1991-07", "date_type": "published", "publication": "Analytical Chemistry", "volume": "63", "number": "14", "publisher": "American Chemical Society", "pagerange": "1501-1504", "id_number": "CaltechAUTHORS:20170830-144806113", "issn": "0003-2700", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170830-144806113", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "8379", "name": "Caltech Division of Chemistry and Chemical Engineering" } ] }, "doi": "10.1021/ac00014a030", "resource_type": "article", "pub_year": "1991", "author_list": "Lee, Chongmok; Kwak, Juhyoun; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/1py12-j4p95", "eprint_id": 88061, "eprint_status": "archive", "datestamp": "2023-08-20 00:02:03", "lastmod": "2023-10-18 21:40:54", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Montgomery-D-D", "name": { "family": "Montgomery", "given": "Donald D." } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Time-resolved measurement of equilibrium surface tensions at the electrified mercury-aqueous sodium fluoride interphase by the method of Wilhelmy", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1991 American Chemical Society. \n\nReceived May 25, 1990. In Final Form: October 17, 1990. \n\nThis work was supported by the National Science Foundation and the US. Army Research Office.", "abstract": "The Wilhelmy plate technique for measuring static and dynamic surface tensions was extended to the electrified mercury-aqueous electrolyte interphase. Several modifications to a conventional Wilhelmy plate are described, which were necessary to implement the technique within an electrochemical environment. Proper isolation of the Wilhelmy plate and associated instrument from vibration allowed sensitivities to be reached that were about 5 times greater than those attainable with maximum bubble pressure measurements. The surface tensions at the electrified mercury-aqueous NaF interphase measured with the modified Wilhelmy plate instrument agreed well with literature values. The capability of the instrument described for making rapid measurements of surface tensions was exploited to observe intrinsic fluctuations in the equilibrium surface tensions. The importance of intrinsic fluctuations and time-averaging for precise evaluation of the equilibrium surface tension are discussed.", "date": "1991-05", "date_type": "published", "publication": "Langmuir", "volume": "7", "number": "5", "publisher": "American Chemical Society", "pagerange": "1000-1004", "id_number": "CaltechAUTHORS:20180720-112442312", "issn": "0743-7463", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180720-112442312", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Army Research Office (ARO)" } ] }, "other_numbering_system": { "items": [ { "id": "8150", "name": "Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "doi": "10.1021/la00053a031", "resource_type": "article", "pub_year": "1991", "author_list": "Montgomery, Donald D. and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/hbw2w-ant22", "eprint_id": 85347, "eprint_status": "archive", "datestamp": "2023-08-19 23:48:40", "lastmod": "2023-10-18 18:08:15", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kobayashi-Junya", "name": { "family": "Kobayashi", "given": "Junya" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Association of electroactive counterions with polyelectrolytes. 2. Comparison of electrostatic and coordinative bonding to a mixed polycation-polypyridine", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1991 American Chemical Society. \n\nThis work was supported in part by the National Science Foundation and the U.S. Army Research Office. J.K. received support from the Shimadzu Corp. (Kyoto). Discussions with Dr. Manshi Ohyanagi were helpful during the initial stages of this work.", "abstract": "A soluble polysiloxane containing 4,4'-bipyridine as a singly quaternized pendant group was synthesized and allowed to interact with Fe(CN)_6^(4-), Fe(CN)_5(OH_2)^(3-), and Ru(edta)OH_2^- as counterions. The electrochemical responses (formal potentials and mass-transfer-limited oxidation or reduction currents) of the electroactive counterions were utilized to evaluate diffusion coefficients and equilibrium binding constants. The latter were also measured by equilibrium dialysis. The moderate agreement between the equilibrium constants obtained by the two independent methods lent support to the general procedures employed in analyzing the electrochemical data, although some of the assumptions required for the data analysis may not be fully\njustified. The results obtained indicate that the polyelectrolyte-counterion binding equilibrium is static rather than dynamic on the electrochemical time scale of a few hundred milliseconds.", "date": "1991-03-01", "date_type": "published", "publication": "Journal of Physical Chemistry", "volume": "95", "number": "6", "publisher": "American Chemical Society", "pagerange": "2595-2601", "id_number": "CaltechAUTHORS:20180316-141224548", "issn": "0022-3654", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180316-141224548", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Army Research Office (ARO)" }, { "agency": "Shimadzu Corporation" } ] }, "other_numbering_system": { "items": [ { "id": "8170", "name": "Caltech Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "doi": "10.1021/j100159a089", "resource_type": "article", "pub_year": "1991", "author_list": "Kobayashi, Junya and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/rmfze-1fk61", "eprint_id": 4934, "eprint_status": "archive", "datestamp": "2023-08-22 03:49:37", "lastmod": "2023-10-16 18:00:34", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Tsou-Y-M", "name": { "family": "Tsou", "given": "Yu-Min" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Shifts in Redox Formal Potentials Accompanying the Incorporation of Cationic Complexes in Perfluoro Polycarboxylate and Polysulfonate Coatings on Graphite Electrodes", "ispublished": "pub", "full_text_status": "public", "keywords": "polymer electrolytes; polymer films; graphite; electrochemical electrodes; positive ions; reduction (chemical); oxidation; electric potential", "note": "\u00a91984 The Electrochemical Society, Inc. \n\nManuscript submitted May 20, 1983; revised manuscript received Sept. 23, 1983. \n\nThis work was supported by the U.S. Army Research Office. Dr. H. Zumbrunnen offered many helpful suggestions during early stages of this work. We thank Asahi Glass Company, Tokyo, for a sample of polyelectrolyte II.", "abstract": "The formal potentials of several redox couples incorporated in coatings of a perfluoropolycarboxylate on graphite electrodes were measured and compared with the formal potentials of the same couples in homogeneous solution. The differences observed agreed with those calculated from the Nernst equation with the independently measured incorporationcoefficients for both halves of the redox couples. The dependences of the shifts in formal potentials on the nature of theincorporating complex ion, the ionic strength, and the temperature were determined and indicated that the incorporationequilibrium is governed by electrostatic and hydrophobic interactions that act in opposite directions. The incorporation ofmost cations examined was driven by large increases in entropy which overcame the usually unfavorable enthalpy changes.", "date": "1984-03-01", "date_type": "published", "publication": "Journal of the Electrochemical Society", "volume": "131", "number": "3", "publisher": "Journal of the Electrochemical Society", "pagerange": "595-601", "id_number": "CaltechAUTHORS:TSOjes84", "issn": "0013-4651", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:TSOjes84", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "doi": "10.1149/1.2115632", "primary_object": { "basename": "TSOjes84.pdf", "url": "https://authors.library.caltech.edu/records/rmfze-1fk61/files/TSOjes84.pdf" }, "resource_type": "article", "pub_year": "1984", "author_list": "Tsou, Yu-Min and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/rqfv1-rsg83", "eprint_id": 70517, "eprint_status": "archive", "datestamp": "2023-08-19 15:56:41", "lastmod": "2023-10-20 23:03:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Perry-J-W", "name": { "family": "Perry", "given": "Joseph W." } }, { "id": "McQuillan-A-J", "name": { "family": "McQuillan", "given": "A. James" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } }, { "id": "Zewail-A-H", "name": { "family": "Zewail", "given": "Ahmed H." } } ] }, "title": "Laser Spectroelectrochemistry of a Ruthenium(II) Tris(bipyridyl) Derivative Adsorbed on Graphite Electrodes", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1983 American Chemical Society. \n\nReceived: February 4, 1983. \n\nThis work was supported by the U.S. Army Research Office and by the National Science Foundation. We thank Daniel Buttry for the sample of [Ru(bpy)_2(pbpy)]Cl_2 and helpful discussions. A.J.M. acknowledges a Fullbright-Hays Travel Grant.", "abstract": "The luminescence spectra of laser-excited films of [Ru(bpy)_2pbpy]Cl_2 (bpy = 2,2'-bipyridine; pbpy = 4 4'bis(2-(diphenylamino)ethyl)-2,2'-bipyridine) adsorbed on pyrolytic graphite electrode surfaces are reported. The graphite electrode surface is shown to be effective in quenching the excited state and the resulting decay of the luminescence ls analyzed. The intensity of the luminescence from the molecules in the film can be modulated by controlling the potential of the underlying electrode. It is shown that the emitting molecules are in electronic contact with the electrode.", "date": "1983-04-28", "date_type": "published", "publication": "Journal of Physical Chemistry", "volume": "87", "number": "9", "publisher": "American Chemical Society", "pagerange": "1480-1483", "id_number": "CaltechAUTHORS:20160921-131026889", "issn": "0022-3654", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160921-131026889", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Army Research Office (ARO)" }, { "agency": "NSF" }, { "agency": "Fulbright Foundation" } ] }, "other_numbering_system": { "items": [ { "id": "6792", "name": "Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "doi": "10.1021/j100232a005", "resource_type": "article", "pub_year": "1983", "author_list": "Perry, Joseph W.; McQuillan, A. James; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/7c0gs-5zm43", "eprint_id": 1447, "eprint_status": "archive", "datestamp": "2023-08-22 03:04:40", "lastmod": "2023-10-23 16:11:53", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Taniguchi-Vernon-T", "name": { "family": "Taniguchi", "given": "Vernon T." } }, { "id": "Malmstr\u00f6m-B-G", "name": { "family": "Malmstr\u00f6m", "given": "Bo G." } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } }, { "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876" } ] }, "title": "Temperature dependence of the reduction potential of blue copper in fungal laccase", "ispublished": "pub", "full_text_status": "public", "keywords": "spectroelectrochemistry, thermodynamic parameters", "note": "\u00a9 1982 by the National Academy of Sciences. \n\nContributed by Harry B. Gray, February 22, 1982. \n\nWe thank Grant Mauk for providing a sample of potassium octacyanomolybdate(IV) dihydrate and Ann-Cathrine Carlsson for preparing the fungal laccase. This research was supported by National Institutes of Health Grant AM19038 and the Swedish Natural Science Research Council. B.G.M. was a Sherman Fairchild Distinguished Scholar at the California Institute of Technology during 1980-1981. This is contribution no. 6607 from the Arthur Amos Noyes Laboratory. \n\nThe publication costs of this article were defrayed in part by page charge payment. This article must therefore be hereby marked \"advertisement\" in accordance with 18 U. S. C. \u00a71734 solely to indicate this fact.\n\nPublished - TANpnas82.pdf
", "abstract": "Thin-layer spectroelectrochemical methods have\nbeen employed to measure the reduction potentials of the blue copper in Polypors veruicolor laccase (EC 1.10.3.2) between 7\u00b0C and 41\u00b0C (0.2 M sodium phosphate, pH 5.4). Thermodynamic parameters are: \u0394S\u00b0 = -13.9 \u00b1 2 cal/mol-K; \u0394H\u00b0 = -22.1 \u00b1 0.5 kcal/mol; E\u00b0 (25\u00b0C) = 780 \u00b1 3 mV vs. the normal hydrogen electrode. Comparison of the \u0394S\u00b0 and \u0394H\u00b0 values with those for single-site proteins suggests that the high potential of the blue copper in fungal laccase is attributable mainly to stabilization of the copper (I) center by enhanced ligand binding interactions and that protein solvation effects play a lesser role.", "date": "1982-05-15", "date_type": "published", "publication": "Proceedings of the National Academy of Sciences of the United States of America", "volume": "79", "number": "10", "publisher": "National Academy of Sciences", "pagerange": "3387-3389", "id_number": "CaltechAUTHORS:TANpnas82.968", "issn": "0027-8424", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:TANpnas82.968", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "AM19038" }, { "agency": "Swedish Natural Science Research Council" }, { "agency": "Sherman Fairchild Foundation" } ] }, "other_numbering_system": { "items": [ { "id": "6607", "name": "Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "pmcid": "PMC346421", "primary_object": { "basename": "TANpnas82.pdf", "url": "https://authors.library.caltech.edu/records/7c0gs-5zm43/files/TANpnas82.pdf" }, "resource_type": "article", "pub_year": "1982", "author_list": "Taniguchi, Vernon T.; Malmstr\u00f6m, Bo G.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/pkqxp-j2g83", "eprint_id": 32521, "eprint_status": "archive", "datestamp": "2023-08-22 02:53:18", "lastmod": "2023-10-18 14:31:40", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Willett-B-C", "name": { "family": "Willett", "given": "Brian C." } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Electrochemistry and Adsorption of Bis 2,2\u2032\u2010Bipyridinecobalt(I) and Bis 6,6\u2032\u2010Dimethyl\u20102,2\u2032\u2010Bipyridinecobalt(I) in Acetonitrile", "ispublished": "pub", "full_text_status": "public", "keywords": "reduction (chemical); surface chemistry; catalysis; adsorption; electrochemistry; organometallic compounds; cobalt compounds; reaction kinetics; electrochemical analysis; coulometry; chronocoulometry; electroreduction", "note": "\u00a9 1982 The Electrochemical Society.\n\nManuscript received October 5, 1981; Revised manuscript received December 14, 1981.\n\nThis work was supported by the National Science Foundation. Helpful discussions with Professor Duane Bartak are a pleasure to acknowledge. Initial exploratory experiments by Dr. Roger Sperline aided and guided us in portions of the work described here. Any discussion of this paper will appear in a Discussion Section be published in the December 1982 JOURNAL. All discussions tor the December 1982 Discussion Section should be submitted by Aug. 1, 1982.\nPublication costs of this article were assisted by the\nCalifornia Institute of Technology.\n\nPublished - WILjes82.pdf
", "abstract": "Cyclic voltammetry, coulometry, and chronocoulometry were used to examine the reduction of \nbis\u20102,2\u2032\u2010bipyridinecobalt(II), Co(bipy)^(2+)_2 , and \nbis\u20106,6\u2032\u2010dimethyl\u20102,2\u2032\u2010bipyridinecobalt(II), Co(dmbp)^(2+)_2 in acetonitrile solution. Both of the cobalt(I) reduction products, Co(bipy)^(+)_2 and Co(dmbp)^(+)_2 , adsorb on mercury but not on graphite or platinum electrodes. Formula decomposes at a modest rate while Formula is much more stable. Neither reduced complex proved effective as a catalyst for the electroreduction of nitrous oxide or alkyl halides.", "date": "1982", "date_type": "published", "publication": "Journal of the Electrochemical Society", "volume": "129", "number": "6", "publisher": "The Electrochemical Society", "pagerange": "1260-1266", "id_number": "CaltechAUTHORS:20120717-132826689", "issn": "0013-4651", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120717-132826689", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "doi": "10.1149/1.2124098", "primary_object": { "basename": "WILjes82.pdf", "url": "https://authors.library.caltech.edu/records/pkqxp-j2g83/files/WILjes82.pdf" }, "resource_type": "article", "pub_year": "1982", "author_list": "Willett, Brian C. and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/vgez6-2vk65", "eprint_id": 4932, "eprint_status": "archive", "datestamp": "2023-08-22 02:19:20", "lastmod": "2023-10-16 18:00:30", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Anson-F-C", "name": { "family": "Anson", "given": "F. C." } } ] }, "title": "Roger Parsons\u2014Olin Palladium Award Medalist", "ispublished": "pub", "full_text_status": "public", "keywords": "electrochemistry; research and development management", "note": "\u00a91980 The Electrochemical Society, Inc. \n\nIntroductory remarks by F. C. Anson, Arthur A. Noyes Laboratory, California Institute of Technology, on the occasion of the presentation of the Olin Palladium Medal Award to Roger Parsons on October 16, 1979, at the Los Angeles Meeting of the Society.", "abstract": "The Olin Palladium Medal of this Society has such a distinguished set of former awardees that I suspect the person who has been asked to introduce each of the medal winners has probably felt as superfluous as I do today. \n\nRoger Parsons has played so prominent a role in the development of fundamental electrochemistry in the last thirty years that his name and his ideas constantly pop up in discussions among electrochemists in Moscow and Buenos Aires, Delhi and Paris, College Station and Pasadena.", "date": "1980-04-01", "date_type": "published", "publication": "Journal of the Electrochemical Society", "volume": "127", "number": "5", "publisher": "Journal of the Electrochemical Society", "pagerange": "175C", "id_number": "CaltechAUTHORS:ANSjes80", "issn": "0013-4651", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:ANSjes80", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "doi": "10.1149/1.2129754", "primary_object": { "basename": "ANSjes80.pdf", "url": "https://authors.library.caltech.edu/records/vgez6-2vk65/files/ANSjes80.pdf" }, "resource_type": "article", "pub_year": "1980", "author_list": "Anson, F. C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/9mbrn-kjp34", "eprint_id": 5671, "eprint_status": "archive", "datestamp": "2023-08-22 02:18:12", "lastmod": "2023-10-16 19:20:58", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Oyama-N", "name": { "family": "Oyama", "given": "Noboru" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Factors Affecting the Electrochemical Responses of Metal Complexes at Pyrolytic Graphite Electrodes Coated with Films of Poly(4-Vinylpyridine)", "ispublished": "pub", "full_text_status": "public", "keywords": "electrochemical electrodes; polymer films; graphite; electrochemistry; metals", "note": "\u00a91980 The Electrochemical Society, Inc. \n\nManuscript submitted July 23, 1979; revised manuscript received Oct. 15, 1979. \n\nThe assistance of Prof. J. P. Revel and Pat Cohen in obtaining electron micrographs is acknowledged gratefully. Drs. Alan Rembaum and Roger Williams kindly provided the samples of fractionated PVP that were used to obtain the data for Fig. 2. Several perceptive comments and criticisms by the reviewers of an earlier version of this manuscript helped us to formulate our speculations more clearly. \n\nThis work was supported by the National Science Foundation and the U.S. Army Research Office. \n\nPublication costs oS this article were assisted by the California Institute of Technology.", "abstract": "Electrochemical responses from the reduction of RuIII (edta) coordinatedto films of high molecular weight poly(4-vinylpyridine) on pyrolytic graphiteelectrodes were studied as functions of film thickness, temperature, supportingelectrolyte composition, and solvent. Responses at filmed electrodes from metalcomplexes that do not coordinate to the films were also examined. With filmsthicker than ca. 1000\u00c5, the current responses are limited by the rates of molecularmotions within the films. Penetration of counterions, segmental motion ofsections of the polymer chains, and juxtapositioning of pairs of attached metalcomplexes to facilitate intercomplex electron transfer within the film or combinationsof the three are suggested as likely current limiting processes.", "date": "1980-03-01", "date_type": "published", "publication": "Journal of the Electrochemical Society", "volume": "127", "number": "3", "publisher": "Journal of the Electrochemical Society", "pagerange": "640-647", "id_number": "CaltechAUTHORS:OYAjes80c", "issn": "0013-4651", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:OYAjes80c", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "doi": "10.1149/1.2129725", "primary_object": { "basename": "OYAjes80c.pdf", "url": "https://authors.library.caltech.edu/records/9mbrn-kjp34/files/OYAjes80c.pdf" }, "resource_type": "article", "pub_year": "1980", "author_list": "Oyama, Noboru and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/1c493-67h85", "eprint_id": 5672, "eprint_status": "archive", "datestamp": "2023-08-22 02:14:05", "lastmod": "2023-10-23 17:02:01", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Oyama-N", "name": { "family": "Oyama", "given": "Noboru" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Electrostatic Binding of Metal Complexes to Electrode Surfaces Coated with Highly Charged Polymeric Films", "ispublished": "pub", "full_text_status": "public", "keywords": "electrochemical electrodes; graphite; polymer films; polymer electrolytes; voltammetry (chemical analysis); metals", "note": "\u00a91980 The Electrochemical Society, Inc.\nManuscript submitted July 31, 1979;\nrevised manuscript received Oct. 22, 1979.\nPublication costs of this article were assisted by the California Institute of Technology.\nThis work was supported by the National Science Foundation and the U. S. Army Research Office.\n\nPublished - OYAjes80a.pdf
Updated - JES000249.pdf
", "abstract": "Previous reports in which metal complexes have been attached to electrode surfaces coated with polymeric molecules have depended upon the formation of covalent or coordination bonds in the attachment procedure (1-4). Such schemes can be quite successful but depending, as they do, on rather specific surface chemistry, they are not applicable to as wide a variety of metal complexes as might be desirable. We have observed that coating graphite electrodes with polymers bearing charged ionic groups produces surfaces which strongly bind multiply-charged metal complexes bearing charges opposite to that on the attached ionic polymer. By exploiting this observation it is entirely possible that virtually any desired metal ion can be attached in large quantities to electrode surfaces by coordinating the metal ion with ligands that produce a multiply-charged complex ion.", "date": "1980-01", "date_type": "published", "publication": "Journal of the Electrochemical Society", "volume": "127", "number": "1", "publisher": "Ellectrochemical Society", "pagerange": "247-250", "id_number": "CaltechAUTHORS:OYAjes80a", "issn": "0013-4651", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:OYAjes80a", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "U. S. Army Research Office" } ] }, "primary_object": { "basename": "JES000249.pdf", "url": "https://authors.library.caltech.edu/records/1c493-67h85/files/JES000249.pdf" }, "related_objects": [ { "basename": "OYAjes80a.pdf", "url": "https://authors.library.caltech.edu/records/1c493-67h85/files/OYAjes80a.pdf" } ], "resource_type": "article", "pub_year": "1980", "author_list": "Oyama, Noboru and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/kpgw9-sbk58", "eprint_id": 32859, "eprint_status": "archive", "datestamp": "2023-09-14 19:27:28", "lastmod": "2023-10-23 20:51:50", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Margel-S", "name": { "family": "Margel", "given": "Shlomo" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Catalysis of the Electroreduction of Allyl Chloride by\n Cobalt 2,2'-Bipyridine Complexes", "ispublished": "pub", "full_text_status": "public", "keywords": "catalysis; electrochemical analysis; cobalt compounds; organic compounds; electrolytes; \u03c0\u2010coordination; intramolecular", "note": "\u00a9 1978 Electrochemical Society. This work was supported by the National Science Foundation. A Chaim Weizmann Fellowship supplied partial support for S.M. Manuscript submitted Sept. 12, 1977; revised manuscript received ca. March 25, 1978.\nAny discussion of this paper will appear in a Discussion\nSection to be published in the June 1979 Journal.\nAll discussions for the June 1979 Discussion Section\nshould be submitted by Feb. 1, 1979.\n\nPublished - MARjes78b.pdf
", "abstract": "The electrochemical reduction of allyl chloride is strongly catalyzed in the presence of cobalt complexes of 2,2\u2032\u2010bipyridine. A prominent reaction product of the catalyzed reduction is 1,5\u2010hexadiene. Voltammetry, coulometry, and gas chromatographic data are presented and analyzed and a mechanistic scheme proposed to account for the catalytic action of the cobalt\u20102,2\u2032\u2010bipyridine complexes.", "date": "1978-08", "date_type": "published", "publication": "Journal of the Electrochemical Society", "volume": "125", "number": "8", "publisher": "Electrochemical Society", "pagerange": "1232-1235", "id_number": "CaltechAUTHORS:20120802-082030036", "issn": "0013-4651", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120802-082030036", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Chaim Weizmann Fellowship" } ] }, "doi": "10.1149/1.2131655", "primary_object": { "basename": "MARjes78b.pdf", "url": "https://authors.library.caltech.edu/records/kpgw9-sbk58/files/MARjes78b.pdf" }, "resource_type": "article", "pub_year": "1978", "author_list": "Margel, Shlomo and Anson, Fred C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/g6wfp-xfj67", "eprint_id": 32857, "eprint_status": "archive", "datestamp": "2023-08-22 01:40:20", "lastmod": "2023-10-18 16:24:48", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Margel-S", "name": { "family": "Margel", "given": "Shlomo" } }, { "id": "Smith-W", "name": { "family": "Smith", "given": "Wayne" } }, { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Electrochemistry of 2,2'-Bipyridine Complexes of Cobalt in the Presence of Acrylonitrile", "ispublished": "pub", "full_text_status": "public", "keywords": "electrochemical analysis; electrochemical electrodes; mercury compounds; modelling; cobalt compounds; catalysis; mixed complexes; vinyl monomers", "note": "\u00a9 1978 Electrochemical Society. This work was supported by the National Science Foundation. Shlomo Margel gratefully acknowledges a Chaim Weizmann Fellowship. Manuscript received July 12, 1977. Revised manuscript received September 19, 1977. Any discussion of this paper will appear in a Discussion Section to be published in the December 1978 Journal. All discussions for the December 1978 Discussion Section should be submitted by Aug. 1, 1978. Publication costs of this article were assisted by the California Institute of Technology.\n\nPublished - MARjes78a.pdf
", "abstract": "The previously claimed (1) catalysis of the electroreduction of acrylonitrile by means of a complex of Co(I) and 2,2\u2032\u2010bipyridine is shown to be erroneous. The \"catalytic currents\" result instead from the two\u2010electron reduction of a mixed complex of Co(I) acrylonitrile and 2,2\u2032\u2010bipyridine. The equilibrium and forward rate constants for the formation of the mixed complex have been estimated and its spectrum is given. The behavior of a number of other vinyl monomers, which mimic acrylonitrile, is described.", "date": "1978-02", "date_type": "published", "publication": "Journal of the Electrochemical Society", "volume": "125", "number": "2", "publisher": "Electrochemical Society", "pagerange": "241-246", "id_number": "CaltechAUTHORS:20120802-075025406", "issn": "0013-4651", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20120802-075025406", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Chaim Weizmann Fellowship" } ] }, "doi": "10.1149/1.2131421", "primary_object": { "basename": "MARjes78a.pdf", "url": "https://authors.library.caltech.edu/records/g6wfp-xfj67/files/MARjes78a.pdf" }, "resource_type": "article", "pub_year": "1978", "author_list": "Margel, Shlomo; Smith, Wayne; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/3nw80-j7f38", "eprint_id": 65092, "eprint_status": "archive", "datestamp": "2023-08-19 09:49:57", "lastmod": "2023-10-17 23:11:11", "type": "teaching_resource", "metadata_visibility": "show", "creators": { "items": [ { "id": "Anson-F-C", "name": { "family": "Anson", "given": "Fred C." } } ] }, "title": "Electroanalytical Chemistry", "ispublished": "unpub", "full_text_status": "public", "note": "\u00a9 1976 American Chemical Society. Permission granted by the American Chemical Society to add workbook and audio files to CaltechAUTHORS. \n\nThe final form of this manual and the course content benefitted considerably from extensive criticism by the reviewers of preliminary versions. Although the reviewers' identities were not revealed to me, I had little difficulty in recognizing the style of at least two of them whose comments were particularly helpful. I am extremely grateful to Lou, Don and the other reviewers for their careful, thorough reviews and thoughtful suggestions, most of which were incorporated into the course. I must also record the enormously important contribution of Mrs. Harue Bierce who not only typed countless revisions of the manual but prepared most of the figures and layouts.\n\nPublished - AnsonElectroanal1976.pdf
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", "abstract": "[no abstract]", "date": "1976", "date_type": "published", "publisher": "American Chemical Society", "id_number": "CaltechAUTHORS:20160305-125750662", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160305-125750662", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided", "primary_object": { "basename": "disc-5-01-part-9.wav", "url": "https://authors.library.caltech.edu/records/3nw80-j7f38/files/disc-5-01-part-9.wav" }, "related_objects": [ { "basename": "disc-1-01-part-1.flac", "url": "https://authors.library.caltech.edu/records/3nw80-j7f38/files/disc-1-01-part-1.flac" }, { "basename": "disc-1-01-part-1.wav", "url": "https://authors.library.caltech.edu/records/3nw80-j7f38/files/disc-1-01-part-1.wav" }, { "basename": "disc-3-02-part-6.flac", "url": "https://authors.library.caltech.edu/records/3nw80-j7f38/files/disc-3-02-part-6.flac" }, { "basename": "disc-5-02-part-10.wav", "url": 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