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 language | English |
|---|---|
| Pages (from-to) | 5511-5514 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 138 |
| Issue number | 17 |
| DOIs | |
| Publication status | Published - May 4 2016 |
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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 journal › Article
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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.
UR - http://www.scopus.com/inward/record.url?scp=84968902236&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84968902236&partnerID=8YFLogxK
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 -