Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy
Abstract
The solution structures of highly active Ir water-oxidation catalysts are elucidated herein 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 DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.
- Authors:
-
- Yale Univ., New Haven, CT (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Northwestern Univ., Evanston, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1387676
- Grant/Contract Number:
- SC0001059; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 138; Journal Issue: 17; Related Information: ANSER partners with Northwestern University (lead); Argonne National Laboratory; University of Chicago; University of Illinois, Urbana-Champaign; Yale University; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); solar (photovoltaic); solar (fuels); photosynthesis (natural and artificial); bio-inspired; hydrogen and fuel cells; electrodes - solar; defects; charge transport; spin dynamics; membrane; materials and chemistry by design; optics; synthesis (novel materials); synthesis (self-assembly); ligands; oligomers; catalysts; extended X-ray absorption fine structure; transition metals
Citation Formats
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., and 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. United States: N. p., 2016.
Web. doi:10.1021/jacs.6b01750.
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. United States. https://doi.org/10.1021/jacs.6b01750
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., and Batista, Victor S. Mon .
"Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy". United States. https://doi.org/10.1021/jacs.6b01750. https://www.osti.gov/servlets/purl/1387676.
@article{osti_1387676,
title = {Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy},
author = {Yang, Ke R. and Matula, Adam J. and Kwon, Gihan and Hong, Jiyun and Sheehan, Stafford W. and Thomsen, Julianne M. and Brudvig, Gary W. and Crabtree, Robert H. and Tiede, David M. and Chen, Lin X. and Batista, Victor S.},
abstractNote = {The solution structures of highly active Ir water-oxidation catalysts are elucidated herein 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 DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.},
doi = {10.1021/jacs.6b01750},
journal = {Journal of the American Chemical Society},
number = 17,
volume = 138,
place = {United States},
year = {Mon Apr 18 00:00:00 EDT 2016},
month = {Mon Apr 18 00:00:00 EDT 2016}
}
Web of Science
Figures / Tables:
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