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dc.contributor.authorGiordano, Livia
dc.contributor.authorØstergaard, Thomas M.
dc.contributor.authorMuy, Sokseiha
dc.contributor.authorYang, Yu
dc.contributor.authorCharles, Nenian
dc.contributor.authorKim, Soo
dc.contributor.authorZhang, Yirui
dc.contributor.authorMaglia, Filippo
dc.contributor.authorJung, Roland
dc.contributor.authorLund, Isaac
dc.contributor.authorRossmeisl, Jan
dc.contributor.authorShao-Horn, Yang
dc.date.accessioned2020-10-08T22:20:26Z
dc.date.available2020-10-08T22:20:26Z
dc.date.issued2019-07
dc.date.submitted2019-06
dc.identifier.issn0897-4756
dc.identifier.issn1520-5002
dc.identifier.urihttps://hdl.handle.net/1721.1/127938
dc.description.abstractThe hydrogen adsorption energetics on the surface of inorganic compounds can be used to predict electrolyte stability in Li-ion batteries and catalytic activity for selective oxidation of small molecules such as H₂ and CH₄. Using first-principles density functional theory (DFT), the hydrogen adsorption was found to be unfavorable on high-band-gap insulators, which could be attributed to a lower energy level associated with adsorbed hydrogen relative to the bottom of the conduction band. In contrast, the hydrogen adsorption was shown to be the most favorable on metallic and semiconducting compounds, which results from an electron transfer from adsorbed hydrogen to the Fermi level or the bottom of the conduction band. Of significance, computed hydrogen adsorption energetics on insulating, semiconducting, and metallic oxides; phosphates; fluorides; and sulfides were decreased by lowering the ligand p band center, while the energy penalty for ligand vacancy formation was increased, indicative of decreased surface reducibility. A statistical regression analysis, where 16 structural and electronic parameters such as metal–ligand distance, electronegativity difference, Bader charges, bulk and surface metal and ligand band centers, band gap, ligand band width, and work function were examined, further showed that the surface ligand p band center is the most accurate single descriptor that governs the hydrogen adsorption tendency, and additional considerations of the band gap and average metal–ligand distance further reconcile the differences among compounds with different ligands/structures, whose ligand bands are different in shape and width. We discuss the implications of these findings for passivating coatings and design of catalysts and the need for novel theoretical methods to accurately estimate these quantities from first principles. These results establish a universal design principle for future high-throughput studies aiming to design electrode surfaces to minimize electrolyte oxidation by dehydrogenation in Li-ion batteries and enhance the H–H and C–H activation for selective oxidation catalysis.en_US
dc.publisherAmerican Chemical Society (ACS)en_US
dc.relation.isversionofhttp://dx.doi.org/10.1021/acs.chemmater.9b00767en_US
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.en_US
dc.sourceProf. Shao-Hornen_US
dc.titleLigand-Dependent Energetics for Dehydrogenation: Implications in Li-Ion Battery Electrolyte Stability and Selective Oxidation Catalysis of Hydrogen-Containing Moleculesen_US
dc.typeArticleen_US
dc.identifier.citationGiordano, Livia et al. "Ligand-Dependent Energetics for Dehydrogenation: Implications in Li-Ion Battery Electrolyte Stability and Selective Oxidation Catalysis of Hydrogen-Containing Molecules." Chemistry of Materials (July 2019): 5464–5474 © 2019 American Chemical Societyen_US
dc.contributor.departmentMassachusetts Institute of Technology. Research Laboratory of Electronicsen_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Mechanical Engineeringen_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Materials Science and Engineeringen_US
dc.relation.journalChemistry of Materialsen_US
dc.eprint.versionAuthor's final manuscripten_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/PeerRevieweden_US
dspace.date.submission2020-09-21T13:20:50Z
mit.journal.volume31en_US
mit.journal.issue15en_US
mit.licensePUBLISHER_POLICY


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