Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High- Energy X-ray Scattering and EXAFS Spectroscopy.

The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-p-O cores and termin...

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Publicado en:Journal of the American Chemical Society Vol. 138; no. 17; pp. 5511 - 5515
Autores principales: Yang, Ke R., Matula, Adam J., Gihan Kwon, Jiyun Hong, Sheehan, Stafford W., Thomsen, Julianne M., Brudvig, Gary W., Crabtree, Robert H., Tiede, David M., Chen, Lin X., Batista, Victor S.
Formato: Artículo
Publicado: American Chemical Society 5/4/2016
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 5/4/2016
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      pub: American Chemical Society
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        10.1021/jacs.6b01750
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        atl: Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High- Energy X-ray Scattering and EXAFS Spectroscopy.
      aug:
        au:
          Yang, Ke R.
          Matula, Adam J.
          Gihan Kwon
          Jiyun Hong
          Sheehan, Stafford W.
          Thomsen, Julianne M.
          Brudvig, Gary W.
          Crabtree, Robert H.
          Tiede, David M.
          Chen, Lin X.
          Batista, Victor S.
        affil:
          Yale Energy Sciences Institute and Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, United States
          Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
          Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States
          Catalytic Innovations LLC, 70 Crandall Road, PO Box 356, Adamsville, Rhode Island, 02801, United States
      su:
        Oxidation of water
        Iridium catalysts
        Density functional theory
        X-ray scattering
        Extended X-ray absorption fine structure
        Partial oxidation
      sug:
        subj:
          Oxidation of water
          Iridium catalysts
          Density functional theory
          X-ray scattering
          Extended X-ray absorption fine structure
          Partial oxidation
      ab: The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-p-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by H and O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFTEXAFS- HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2016
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