The interplay between transition metal d-electrons and anion p-electrons drives reactivity and structural trends not only in molecular compounds, but also in extended solids. Here, in honor of his 90th birthday, we related the foundational work by Prof. Harry B. Gray on the oxo wall in molecular compounds to the layered-to-pyrite transition observed in metal chalcogenide extended solids. In both cases, we can consider a ligand-to-metal charge transfer process as the mechanism for producing reduced metal centers with relatively oxidized ligands/anions. We focus the review on this process and the inability to stabilize high valent metals in specific anion frameworks — namely Fe in a sulfide. Such concepts are critical for understanding our ability to electrochemically oxidize metal sulfides to yield high valent Fe, which in sulfides is Fe3+, and/or oxidized sulfide anions as persulfides, S²\u207b\u2082. Happy, happy birthday, Harry!
", "doi": "10.1016/j.ccr.2025.217070", "issn": "0010-8545", "publisher": "Elsevier", "publication": "Coordination Chemistry Reviews", "publication_date": "2026-01-15", "volume": "547", "pages": "217070" }, { "id": "authors:eaqz9-6t339", "collection": "authors", "collection_id": "eaqz9-6t339", "cite_using_url": "https://authors.library.caltech.edu/records/eaqz9-6t339", "type": "article", "title": "Cooperative effects associated with high electrolyte concentrations in driving the conversion of CO\u2082 to C\u2082H\u2084 on copper", "author": [ { "family_name": "Lin", "given_name": "Shaoyang", "orcid": "0000-0003-4108-7299" }, { "family_name": "Fishler", "given_name": "Yuval", "orcid": "0000-0001-7764-9455" }, { "family_name": "Kwon", "given_name": "Soonho", "orcid": "0000-0002-9225-3018" }, { "family_name": "B\u00f6hme", "given_name": "Annette E." }, { "family_name": "Nie", "given_name": "Weixuan", "orcid": "0000-0003-2094-6840" }, { "family_name": "Richter", "given_name": "Matthias H.", "orcid": "0000-0003-0091-2045" }, { "family_name": "Yang", "given_name": "Moon Young", "orcid": "0000-0003-4436-8010" }, { "family_name": "Matthews", "given_name": "Jesse E.", "orcid": "0009-0001-2733-3679" }, { "family_name": "Iton", "given_name": "Zachery W.B.", "orcid": "0000-0002-2226-9006" }, { "family_name": "Lee", "given_name": "Brian C.", "orcid": "0000-0002-0898-0838" }, { "family_name": "Jaramillo", "given_name": "Thomas F.", "orcid": "0000-0001-9900-0622" }, { "family_name": "Atwater", "given_name": "Harry A.", "orcid": "0000-0001-9435-0201", "clpid": "Atwater-H-A" }, { "family_name": "Goddard", "given_name": "William A.", "orcid": "0000-0003-0097-5716", "clpid": "Goddard-W-A-III" }, { "family_name": "Smith", "given_name": "Wilson A.", "orcid": "0000-0001-7757-5281" }, { "family_name": "See", "given_name": "Kimberly A.", "orcid": "0000-0002-0133-9693", "clpid": "See-Kimberly" } ], "abstract": "Compared to a conventional electrolyte concentration of 1 M HCOOK, the use of a highly concentrated 7.1 M HCOOK electrolyte increases the Faradaic efficiency (FE) ratio of C2H4/CO from 2.2 ± 0.3 to 18.3 ± 4.8 at −1.08 V vs. reversible hydrogen electrode (RHE) on a Cu gas-diffusion electrode. Based on electrochemical analysis and ab initio molecular dynamics (AIMD) simulation, the identity and concentration of the cation and anion play more important roles in controlling the CO2R reaction pathway than the bulk CO2 solubility and the bulk pH of electrolytes. In situ attenuated reflectance surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) suggests that, unlike 1 M HCOOK, the ∗CO-bridge-binding mode on Cu is dominant in 7.1 M HCOOK electrolyte, which potentially results in less CO release and higher yield of C2H4. This study demonstrates that although we can tailor the electrolyte composition to shift product selectivity, the factors that control the product selectivity are numerous and cannot be distilled down into one correlated property-reactivity relationship.
", "doi": "10.1016/j.checat.2025.101338", "issn": "2667-1093", "publisher": "Cell Press", "publication": "Chem Catalysis", "publication_date": "2025-06-19", "series_number": "6", "volume": "5", "issue": "6", "pages": "101338" }, { "id": "authors:tmyjq-tsm95", "collection": "authors", "collection_id": "tmyjq-tsm95", "cite_using_url": "https://authors.library.caltech.edu/records/tmyjq-tsm95", "type": "article", "title": "High-Energy Density Li-Ion Battery Cathode Using Only Industrial Elements", "author": [ { "family_name": "Patheria", "given_name": "Eshaan S.", "orcid": "0000-0002-2761-8498", "clpid": "Patheria-Eshaan-S" }, { "family_name": "Guzman", "given_name": "Pedro", "orcid": "0000-0002-9726-8315", "clpid": "Guzman-Pedro" }, { "family_name": "Soldner", "given_name": "Leah S.", "orcid": "0009-0009-9355-5761", "clpid": "Soldner-Leah-S" }, { "family_name": "Qian", "given_name": "Michelle D.", "orcid": "0000-0002-4815-1014", "clpid": "Qian-Michelle-D" }, { "family_name": "Morrell", "given_name": "Colin T.", "orcid": "0000-0002-8010-2474", "clpid": "Morrell-Colin-T" }, { "family_name": "Kim", "given_name": "Seong Shik", "orcid": "0000-0003-2604-6392", "clpid": "Kim-Seong-Shik" }, { "family_name": "Hunady", "given_name": "Kyle", "orcid": "0000-0001-8364-786X", "clpid": "Hunady-Kyle" }, { "family_name": "Priesen Reis", "given_name": "Elena R.", "orcid": "0009-0000-5385-9466", "clpid": "Priesen-Reis-Elena-R" }, { "family_name": "Dulock", "given_name": "Nicholas V.", "orcid": "0009-0008-6616-4039", "clpid": "Dulock-Nicholas-V" }, { "family_name": "Neilson", "given_name": "James R.", "orcid": "0000-0001-9282-5752" }, { "family_name": "Nelson Weker", "given_name": "Johanna", "orcid": "0000-0001-6856-3203" }, { "family_name": "Fultz", "given_name": "Brent", "orcid": "0000-0002-6364-8782", "clpid": "Fultz-B" }, { "family_name": "See", "given_name": "Kimberly A.", "orcid": "0000-0002-0133-9693", "clpid": "See-Kimberly" } ], "abstract": "Li-ion batteries are crucial for the global energy transition to renewables; however, their scalability is limited by the supply of key elements used in commercial cathodes (e.g., Ni, Mn, Co, P). Therefore, there is an urgent need for next-generation cathodes composed of widely available and industrially scalable elements. Here, we introduce a Li-rich cathode based on the known material Li2FeS2, composed of low-cost elements (Al, Fe, S) that are globally mined and refined at an industrial scale. The substitution of redox-inactive Al3+ for Fe2+ achieves remarkably high degrees of anion redox, which, in turn, yields high gravimetric capacity (≈450 mAh·g-1) and energy density (\u22731000 Wh·kg-1). We show that Al3+ enables high degrees of delithiation by stabilizing the delithiated state, suppressing phase transformations that would otherwise prevent deep delithiation and extensive anion redox. This mechanistic insight offers new possibilities for developing scalable, next-generation Li-ion battery cathodes to meet pressing societal needs.
", "doi": "10.1021/jacs.4c18440", "issn": "0002-7863", "publisher": "American Chemical Society", "publication": "Journal of the American Chemical Society", "publication_date": "2025-03-19", "series_number": "11", "volume": "147", "issue": "11", "pages": "9786-9799" }, { "id": "authors:p8qt4-a4048", "collection": "authors", "collection_id": "p8qt4-a4048", "cite_using_url": "https://authors.library.caltech.edu/records/p8qt4-a4048", "type": "article", "title": "Multiscale approaches for optimizing the impact of strain on Na-ion battery cycle life", "author": [ { "family_name": "Brady", "given_name": "Michael J." }, { "family_name": "Andrews", "given_name": "Jessica L." }, { "family_name": "Zambotti", "given_name": "Andrea" }, { "family_name": "Zhang", "given_name": "Delin" }, { "family_name": "Yuan", "given_name": "Xintong" }, { "family_name": "Thurber", "given_name": "Kodi" }, { "family_name": "Duan", "given_name": "Xiangfeng" }, { "family_name": "Li", "given_name": "Yuzhang" }, { "family_name": "Nelson Weker", "given_name": "Johanna" }, { "family_name": "Renuka Balakrishna", "given_name": "Ananya" }, { "family_name": "See", "given_name": "Kimberly", "orcid": "0000-0002-0133-9693", "clpid": "See-Kimberly" }, { "family_name": "Seshadri", "given_name": "Ram" }, { "family_name": "Van der Ven", "given_name": "Anton" }, { "family_name": "Dunn", "given_name": "Bruce S." }, { "family_name": "Tolbert", "given_name": "Sarah H.", "orcid": "0000-0001-9969-1582" }, { "family_name": "Melot", "given_name": "Brent C." } ], "abstract": "The high costs and geopolitical challenges inherent to the lithium-ion (Li-ion) battery supply chain have driven a rising interest in the development of sodium-ion (Na-ion) batteries as a potential alternative. Unfortunately, the larger ionic radius of Na limits the reversibility of cycling because of the extensive atomic rearrangements that accompany Na-ion insertion, which in turn limit diffusion and charging speed, and lead to rapid degradation of the electrodes. The Center for Strain Optimization for Renewable Energy (STORE) was established to address these challenges and develop new electrode materials for Na-ion cells. This article discusses the current state-of-the-art materials used in Na-ion cells and several directions that STORE believes are critical to understand and control the structural and volumetric changes during the reversible (de)insertion of large cations.
", "doi": "10.1557/s43581-024-00118-x", "issn": "2329-2237", "publisher": "Springer Science and Business Media LLC", "publication": "MRS Energy and Sustainability", "publication_date": "2024-11-26" }, { "id": "authors:d5khf-jav88", "collection": "authors", "collection_id": "d5khf-jav88", "cite_using_url": "https://authors.library.caltech.edu/records/d5khf-jav88", "type": "publication_workingpaper", "title": "Transport characterization of solid-state Li2FeS2 cathodes from a porous electrode theory perspective", "author": [ { "family_name": "Bernges", "given_name": "Tim" }, { "family_name": "Ketter", "given_name": "Lukas" }, { "family_name": "Helm", "given_name": "Bianca" }, { "family_name": "Kraft", "given_name": "Marvin" }, { "family_name": "See", "given_name": "Kimberly", "orcid": "0000-0002-0133-9693", "clpid": "See-Kimberly" }, { "family_name": "Zeier", "given_name": "Wolfgang", "orcid": "0000-0001-7749-5089" } ], "abstract": "The abundance and cost of resources for current state-of-the-art cathode active materials makes the search for alternative cell chemistries inevitable. Nonetheless, especially in solid-state batteries, establishing new cell chemistries comes at the challenge of optimizing the transport of both charge carriers, electrons and ions, through the electrode. Limitations in transport of either species lead to underutilization of the electrode caused by insufficiently contacted particles and/or nonuniform reaction rates and state-of-charge gradients through the electrode. In this work, we investigate the capabilities of Li2FeS2 as alternative active material in all-solid-state cathodes by thorough investigation of the initial utilization and rate capability as a function of the cathode loading. The cathode loading is increased from 1.8 to 7.3 mAh\u00b7cm\u22122 by increasing the fraction of active material from 32 to 74 vol.%, and the thickness of the composite electrode from 73 to 145 \u03bcm. Careful characterization of the effective electronic and ionic transport, and consideration of the \u03b4-parameter from porous electrode theory, guides the understanding of the electrode performances. With that, this work shows that Li2FeS2 solid-state cathodes with high areal loadings and gravimetric energy densities can be realized.", "doi": "10.26434/chemrxiv-2024-2b0w3", "publisher": "ChemRxiv", "publication_date": "2024-11-26" }, { "id": "authors:sjez0-mxg64", "collection": "authors", "collection_id": "sjez0-mxg64", "cite_using_url": "https://authors.library.caltech.edu/records/sjez0-mxg64", "type": "article", "title": "Modular MPS\u2083-Based Frameworks for Superionic Conduction of Monovalent and Multivalent Ions", "author": [ { "family_name": "Iton", "given_name": "Zachery W. B.", "orcid": "0000-0002-2226-9006", "clpid": "Iton-Zachery-W-B" }, { "family_name": "Irving-Singh", "given_name": "Zion", "orcid": "0000-0002-6053-4763", "clpid": "Irving-Singh-Zion" }, { "family_name": "Hwang", "given_name": "Son-Jong", "orcid": "0000-0002-3210-466X", "clpid": "Hwang-Sonjong" }, { "family_name": "Bhattacharya", "given_name": "Amit", "orcid": "0000-0002-3104-9187" }, { "family_name": "Shaker", "given_name": "Sammy", "orcid": "0000-0003-1751-4908", "clpid": "Shaker-Sammy" }, { "family_name": "Das", "given_name": "Tridip", "orcid": "0000-0002-3320-2157", "clpid": "Das-Tridip" }, { "family_name": "Cl\u00e9ment", "given_name": "Rapha\u00eble J.", "orcid": "0000-0002-3611-1162" }, { "family_name": "Goddard", "given_name": "William A.", "orcid": "0000-0003-0097-5716", "clpid": "Goddard-W-A-III" }, { "family_name": "See", "given_name": "Kimberly", "orcid": "0000-0002-0133-9693", "clpid": "See-Kimberly" } ], "abstract": "Next-generation batteries based on more sustainable working ions could offer improved performance, safety, and capacity over lithium-ion batteries while also decreasing the cost. Development of next-generation battery technology using “beyond-Li” mobile ions, especially multivalent ions, is limited due to a lack of understanding of solid state conduction of these ions. Here, we introduce ligand-coordinated ions in MPS3-based (M = Mn, Cd) solid host crystals to simultaneously increase the size of the interlayer spacing, through which the ions can migrate, and screen the charge-dense ions. The ligand-assisted conduction mechanism enables ambient temperature superionic conductivity of various next-generation mobile ions in the electronically insulating MPS3-based solid. Without the coordinating ligands, all of the compounds show little to no ionic conductivity. Pulsed-field gradient nuclear magnetic resonance spectroscopy suggests that the ionic conduction occurs through a hopping mechanism, where the cations are moving between H2O molecules, instead of a vehicular mechanism which has been observed in other hydrated layered solids. This modular system not only facilitates tailoring to different potential applications but also enables us to probe the effect of different host structures, mobile ions, and coordinating ligands on the ionic conductivity. This research highlights the influence of cation charge density, diffusion channel size, and effective charge screening on ligand-assisted solid state ionic conductivity. The insights gained can be applied in the design of other ligand-assisted solid state ionic conductors, which will be especially impactful in realizing solid state multivalent ionic conductors. Additionally, the ion-intercalated MPS3-based frameworks could potentially serve as a universal solid state electrolyte for various next-generation battery chemistries.
", "doi": "10.1021/jacs.4c06263", "issn": "0002-7863", "publisher": "American Chemical Society", "publication": "Journal of the American Chemical Society", "publication_date": "2024-09-04", "series_number": "35", "volume": "146", "issue": "35", "pages": "24398\u201324414" }, { "id": "authors:dz4t2-sjg26", "collection": "authors", "collection_id": "dz4t2-sjg26", "cite_using_url": "https://authors.library.caltech.edu/records/dz4t2-sjg26", "type": "article", "title": "Effect of Metal d Band Position on Anion Redox in Alkali-Rich Sulfides", "author": [ { "family_name": "Kim", "given_name": "Seong Shik", "orcid": "0000-0003-2604-6392", "clpid": "Kim-Seong-Shik" }, { "family_name": "Agyeman-Budu", "given_name": "David N.", "orcid": "0000-0002-3461-8373", "clpid": "Agyeman-Budu-David-N" }, { "family_name": "Zak", "given_name": "Joshua J.", "orcid": "0000-0003-3793-7254", "clpid": "Zak-Joshua-J" }, { "family_name": "Andrews", "given_name": "Jessica L.", "orcid": "0000-0001-9794-8903", "clpid": "Andrews-Jessica-L" }, { "family_name": "Li", "given_name": "Jonathan", "orcid": "0000-0003-2632-0080", "clpid": "Li-Jonathan" }, { "family_name": "Melot", "given_name": "Brent C.", "orcid": "0000-0002-7078-8206", "clpid": "Melot-Brent-C" }, { "family_name": "Nelson Weker", "given_name": "Johanna", "orcid": "0000-0001-6856-3203", "clpid": "Nelson-Weker-Johanna" }, { "family_name": "See", "given_name": "Kimberly A.", "orcid": "0000-0002-0133-9693", "clpid": "See-Kimberly" } ], "abstract": "New energy storage methods are emerging to increase the energy density of state-of-the-art battery systems beyond conventional intercalation electrode materials. For instance, employing anion redox can yield higher capacities compared with transition metal redox alone. Anion redox in sulfides has been recognized since the early days of rechargeable battery research. Here, we study the effect of d–p overlap in controlling anion redox by shifting the metal d band position relative to the S p band. We aim to determine the effect of shifting the d band position on the electronic structure and, ultimately, on charge compensation. Two isostructural sulfides LiNaFeS2 and LiNaCoS2 are directly compared to the hypothesis that the Co material should yield more covalent metal–anion bonds. LiNaCoS2 exhibits a multielectron capacity of ≥1.7 electrons per formula unit, but despite the lowered Co d band, the voltage of anion redox is close to that of LiNaFeS2. Interestingly, the material suffers from rapid capacity fade. Through a combination of solid-state nuclear magnetic resonance spectroscopy, Co and S X-ray absorption spectroscopy, X-ray diffraction, and partial density of states calculations, we demonstrate that oxidation of S nonbonding p states to S22– occurs in early states of charge, which leads to an irreversible phase transition. We conclude that the lower energy of Co d bands increases their overlap with S p bands while maintaining S nonbonding p states at the same higher energy level, thus causing no alteration in the oxidation potential. Further, the higher crystal field stabilization energy for octahedral coordination over tetrahedral coordination is proposed to cause the irreversible phase transition in LiNaCoS2.
\nConventional intercalation-based cathode materials in Li-ion batteries are based on charge compensation of the redox-active cation and can only intercalate one mole of electron per formula unit. Anion redox, which employs the anion sublattice to compensate charge, is a promising way to achieve multielectron cathode materials. Most anion redox materials still face the problems of slow kinetics and large voltage hysteresis. One potential solution to reduce voltage hysteresis is to increase the covalency of the metal–ligand bonds. By substituting Mn into the electrochemically inert Li1.33Ti0.67S2 (Li2TiS3), anion redox can be activated in the Li1.33–2y/3Ti0.67–y/3MnyS2 (y = 0–0.5) series. Not only do we observe substantial anion redox, but the voltage hysteresis is significantly reduced, and the rate capability is dramatically enhanced. The y = 0.3 phase exhibits excellent rate and cycling performance, maintaining 90% of the C/10 capacity at 1C, which indicates fast kinetics for anion redox. X-ray absorption spectroscopy (XAS) shows that both the cation and anion redox processes contribute to the charge compensation. We attribute the drop in hysteresis and increase in rate performance to the increased covalency between the metal and the anion. Electrochemical signatures suggest the anion redox mechanism resembles holes on the anion, but the S K-edge XAS data confirm persulfide formation. The mechanism of anion redox shows that forming persulfides can be a low hysteresis, high rate capability mechanism enabled by the appropriate metal–ligand covalency. This work provides insights into how to design cathode materials with anion redox to achieve fast kinetics and low voltage hysteresis.
\nAbstract Mg batteries are a promising alternative to Li-based chemistries due to the high abundance, low cost, and high volumetric capacity of Mg relative to Li. Mg is also less prone to dendritic plating morphologies, promising safer operation. Mg plating and stripping is highly efficient in chloride-containing electrolytes; however, chloride is incompatible with many candidate cathode materials. In this work, we capitalize on the positive effect of chloride by using transition metal chloride cathodes with a focus on low cost, Earth-abundant metals. Both soluble and sparingly soluble chlorides show capacity fade upon cycling. Active material dissolution and subsequent crossover to the Mg anode are the primary drivers of capacity fade in highly soluble metal chloride cathodes. We hypothesize that incomplete conversion and chemical reduction by the Grignard-based electrolyte are major promoters of capacity fade in sparingly soluble metal chlorides. Modifications to the electrolyte can improve capacity retention, suggesting that future work in this system may yield low cost, high retention Mg-MCl\u2093 batteries.
", "doi": "10.1149/1945-7111/ad4fe4", "issn": "0013-4651", "publisher": "Electrochemical Society", "publication": "Journal of The Electrochemical Society", "publication_date": "2024-06", "series_number": "06", "volume": "171", "issue": "06", "pages": "060501" }, { "id": "authors:99r1w-t2230", "collection": "authors", "collection_id": "99r1w-t2230", "cite_using_url": "https://authors.library.caltech.edu/records/99r1w-t2230", "type": "article", "title": "A guide to troubleshooting metal sacrificial anodes for organic electrosynthesis", "author": [ { "family_name": "Ware", "given_name": "Skyler D.", "orcid": "0000-0002-3249-1946", "clpid": "Ware-Skyler-D" }, { "family_name": "Zhang", "given_name": "Wendy", "orcid": "0000-0002-6895-9598", "clpid": "Zhang-Wendy" }, { "family_name": "Guan", "given_name": "Weiyang", "orcid": "0000-0002-3590-921X", "clpid": "Guan-Weiyang" }, { "family_name": "Lin", "given_name": "Song", "orcid": "0000-0002-8880-6476", "clpid": "Lin-Song" }, { "family_name": "See", "given_name": "Kimberly A.", "orcid": "0000-0002-0133-9693", "clpid": "See-Kimberly" } ], "abstract": "The development of reductive electrosynthetic reactions is often enabled by the oxidation of a sacrificial metal anode, which charge-balances the reductive reaction of interest occurring at the cathode. The metal oxidation is frequently assumed to be straightforward and innocent relative to the chemistry of interest, but several processes can interfere with ideal sacrificial anode behavior, thereby limiting the success of reductive electrosynthetic reactions. These issues are compounded by a lack of reported observations and characterization of the anodes themselves, even when a failure at the anode is observed. Here, we weave lessons from electrochemistry, interfacial characterization, and organic synthesis to share strategies for overcoming issues related to sacrificial anodes in electrosynthesis. We highlight common but underexplored challenges with sacrificial anodes that cause reactions to fail, including detrimental side reactions between the anode or its cations and the components of the organic reaction, passivation of the anode surface by an insulating native surface film, accumulation of insulating byproducts at the anode surface during the reaction, and competitive reduction of sacrificial metal cations at the cathode. For each case, we propose experiments to diagnose and characterize the anode and explore troubleshooting strategies to overcome the challenge. We conclude by highlighting open questions in the field of sacrificial-anode-driven electrosynthesis and by indicating alternatives to traditional sacrificial anodes that could streamline reaction optimization.
\nThe cross-electrophile dialkylation of alkenes enables the formation of two C(sp\u00b3)\u2013C(sp\u00b3) bonds from readily available starting materials in a single transformation, thereby providing a modular and expedient approach to building structural complexity in organic synthesis. Herein, we exploit the disparate electronic and steric properties of alkyl halides with varying degrees of substitution to accomplish their selective activation and addition to alkenes under electrochemical conditions. This method enables regioselective dialkylation of alkenes without the use of a transition-metal catalyst and provides access to a diverse range of synthetically useful compounds.
", "doi": "10.1021/jacs.3c06794", "pmcid": "PMC10625357", "issn": "0002-7863", "publisher": "American Chemical Society", "publication": "Journal of the American Chemical Society", "publication_date": "2023-10-18", "series_number": "41", "volume": "145", "issue": "41", "pages": "22298-22304" }, { "id": "authors:rf941-tk874", "collection": "authors", "collection_id": "rf941-tk874", "cite_using_url": "https://authors.library.caltech.edu/records/rf941-tk874", "type": "article", "title": "Improving the Mg Sacrificial Anode in Tetrahydrofuran for Synthetic Electrochemistry by Tailoring Electrolyte Composition", "author": [ { "family_name": "Zhang", "given_name": "Wendy", "orcid": "0000-0002-6895-9598", "clpid": "Zhang-Wanji-Wendy" }, { "family_name": "Gu", "given_name": "Chaoxuan", "orcid": "0000-0002-2118-9805", "clpid": "Gu-Chaoxuan" }, { "family_name": "Wang", "given_name": "Yi", "orcid": "0000-0001-5762-5958", "clpid": "Wang-Yi" }, { "family_name": "Ware", "given_name": "Skyler D.", "orcid": "0000-0002-3249-1946", "clpid": "Ware-Skyler-D" }, { "family_name": "Lu", "given_name": "Lingxiang", "orcid": "0000-0001-9168-6121", "clpid": "Lu-Lingxiang" }, { "family_name": "Lin", "given_name": "Song", "orcid": "0000-0002-8880-6476", "clpid": "Lin-Song" }, { "family_name": "Qi", "given_name": "Yue", "orcid": "0000-0001-5331-1193", "clpid": "Qi-Yue" }, { "family_name": "See", "given_name": "Kimberly A.", "orcid": "0000-0002-0133-9693", "clpid": "See-Kimberly" } ], "abstract": "Mg\u2070 is commonly used as a sacrificial anode in reductive electrosynthesis. While numerous methodologies using a Mg sacrificial anode have been successfully developed, the optimization of the electrochemistry at the anode, i.e., Mg stripping, remains empirical. In practice, electrolytes and organic substrates often passivate the Mg electrode surface, which leads to high overall cell potential causing poor energy efficiency and limiting reaction scale-up. In this study, we seek to understand and manipulate the Mg metal interfaces for a more effective counter electrode in tetrahydrofuran. Our results suggest that the ionic interactions between the cation and the anion of a supporting electrolyte can influence the electrical double layer, which impacts the Mg stripping efficiency. We find halide salt additives can prevent passivation on the Mg electrode by influencing the composition of the solid electrolyte interphase. This study demonstrates that, by tailoring the electrolyte composition, we can modify the Mg stripping process and enable a streamlined optimization process for the development of new electrosynthetic methodologies.
", "doi": "10.1021/jacsau.3c00305", "pmcid": "PMC10466324", "issn": "2691-3704", "publisher": "American Chemical Society", "publication": "JACS Au", "publication_date": "2023-07-28", "series_number": "8", "volume": "3", "issue": "8", "pages": "2280-2290" } ]