Solution structures of highly active molecular ir water-oxidation catalysts from density functional theory combined with high-energy X-ray scattering and EXAFS spectroscopy

Ke R. Yang, Adam J. Matula, Gihan Kwon, Jiyun Hong, Stafford W. Sheehan, Julianne M. Thomsen, Gary W Brudvig, Robert H. Crabtree, David M. Tiede, Lin X. Chen, Victor S. Batista

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

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-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by 1H and 17O 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.

Original languageEnglish
Pages (from-to)5511-5514
Number of pages4
JournalJournal of the American Chemical Society
Volume138
Issue number17
DOIs
Publication statusPublished - May 4 2016

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Extended X ray absorption fine structure spectroscopy
X ray scattering
Density functional theory
Spectrum Analysis
X-Rays
Oxidation
Catalysts
Water
Electrophoresis
Dimers
Ligands
Paramagnetic resonance
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Solution structures of highly active molecular ir water-oxidation catalysts from density functional theory combined with high-energy X-ray scattering and EXAFS spectroscopy. / Yang, Ke R.; Matula, Adam J.; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W.; Thomsen, Julianne M.; Brudvig, Gary W; Crabtree, Robert H.; Tiede, David M.; Chen, Lin X.; Batista, Victor S.

In: Journal of the American Chemical Society, Vol. 138, No. 17, 04.05.2016, p. 5511-5514.

Research output: Contribution to journalArticle

Yang, Ke R. ; Matula, Adam J. ; Kwon, Gihan ; Hong, Jiyun ; Sheehan, Stafford W. ; Thomsen, Julianne M. ; Brudvig, Gary W ; Crabtree, Robert H. ; Tiede, David M. ; Chen, Lin X. ; Batista, Victor S. / Solution structures of highly active molecular ir water-oxidation catalysts from density functional theory combined with high-energy X-ray scattering and EXAFS spectroscopy. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 17. pp. 5511-5514.
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AU - Hong, Jiyun

AU - Sheehan, Stafford W.

AU - Thomsen, Julianne M.

AU - Brudvig, Gary W

AU - Crabtree, Robert H.

AU - Tiede, David M.

AU - Chen, Lin X.

AU - Batista, Victor S.

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