Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex
Abstract
In aqueous solution above pH 2.4 with 4% (vol/vol) CH3CN, the complex [RuII(bda)(isoq)2] (bda is 2,2'-bipyridine-6,6'-dicarboxylate; isoq is isoquinoline) exists as the open-arm chelate, [RuII(CO2-bpy-CO2$$-$$)(isoq)2(NCCH3)], as shown by 1H and 13C-NMR, X-ray crystallography, and pH titrations. Rates of water oxidation with the open-arm chelate are remarkably enhanced by added proton acceptor bases, as measured by cyclic voltammetry (CV). In 1.0 M PO43–, the calculated half-time for water oxidation is ~7 μs. In conclusion, the key to the rate accelerations with added bases is direct involvement of the buffer base in either atom–proton transfer (APT) or concerted electron–proton transfer (EPT) pathways.
- Authors:
-
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States)
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Contributing Org.:
- UNC partners with University of North Carolina (lead); Duke University; University of Florida; Georgia Institute of Technology; University; North Carolina Central University; Research Triangle Institute
- OSTI Identifier:
- 1210509
- Grant/Contract Number:
- SC0001011; CHE-0957215
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Volume: 112; Journal Issue: 16; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences, Washington, DC (United States)
- 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); hydrogen and fuel cells; electrodes - solar, charge transport; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); Ru polypyridyl complexes; electrocatalysis; solar energy; water oxidation catalysis; water splitting
Citation Formats
Song, Na, Concepcion, Javier J., Binstead, Robert A., Rudd, Jennifer A., Vannucci, Aaron K., Dares, Christopher J., Coggins, Michael K., and Meyer, Thomas J. Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex. United States: N. p., 2015.
Web. doi:10.1073/pnas.1500245112.
Song, Na, Concepcion, Javier J., Binstead, Robert A., Rudd, Jennifer A., Vannucci, Aaron K., Dares, Christopher J., Coggins, Michael K., & Meyer, Thomas J. Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex. United States. https://doi.org/10.1073/pnas.1500245112
Song, Na, Concepcion, Javier J., Binstead, Robert A., Rudd, Jennifer A., Vannucci, Aaron K., Dares, Christopher J., Coggins, Michael K., and Meyer, Thomas J. Mon .
"Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex". United States. https://doi.org/10.1073/pnas.1500245112. https://www.osti.gov/servlets/purl/1210509.
@article{osti_1210509,
title = {Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex},
author = {Song, Na and Concepcion, Javier J. and Binstead, Robert A. and Rudd, Jennifer A. and Vannucci, Aaron K. and Dares, Christopher J. and Coggins, Michael K. and Meyer, Thomas J.},
abstractNote = {In aqueous solution above pH 2.4 with 4% (vol/vol) CH3CN, the complex [RuII(bda)(isoq)2] (bda is 2,2'-bipyridine-6,6'-dicarboxylate; isoq is isoquinoline) exists as the open-arm chelate, [RuII(CO2-bpy-CO2$-$)(isoq)2(NCCH3)], as shown by 1H and 13C-NMR, X-ray crystallography, and pH titrations. Rates of water oxidation with the open-arm chelate are remarkably enhanced by added proton acceptor bases, as measured by cyclic voltammetry (CV). In 1.0 M PO43–, the calculated half-time for water oxidation is ~7 μs. In conclusion, the key to the rate accelerations with added bases is direct involvement of the buffer base in either atom–proton transfer (APT) or concerted electron–proton transfer (EPT) pathways.},
doi = {10.1073/pnas.1500245112},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 16,
volume = 112,
place = {United States},
year = {Mon Apr 06 00:00:00 EDT 2015},
month = {Mon Apr 06 00:00:00 EDT 2015}
}
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