TY - JOUR
T1 - Solution structures of highly active molecular ir water-oxidation catalysts from density functional theory combined with high-energy X-ray scattering and EXAFS spectroscopy
AU - Yang, Ke R.
AU - Matula, Adam J.
AU - Kwon, Gihan
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.
PY - 2016/5/4
Y1 - 2016/5/4
N2 - 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.
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-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.
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U2 - 10.1021/jacs.6b01750
DO - 10.1021/jacs.6b01750
M3 - Article
AN - SCOPUS:84968902236
VL - 138
SP - 5511
EP - 5514
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 17
ER -