Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex

Song, Na; Concepcion, Javier J.; Binstead, Robert A.; Rudd, Jennifer A.; Vannucci, Aaron K.; Dares, Christopher J.; Coggins, Michael K.; Meyer, Thomas J.

doi:10.1073/pnas.1500245112

Title: Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex

Journal Article · Mon Apr 06 00:00:00 EDT 2015 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1500245112· OSTI ID:1210509

Song, Na ^[1]; Concepcion, Javier J. ^[2]; Binstead, Robert A. ^[2]; Rudd, Jennifer A. ^[2]; Vannucci, Aaron K. ^[3]; Dares, Christopher J. ^[2]; Coggins, Michael K. ^[2]; Meyer, Thomas J. ^[2]

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

In aqueous solution above pH 2.4 with 4% (vol/vol) CH₃CN, the complex [Ru^II(bda)(isoq)₂] (bda is 2,2'-bipyridine-6,6'-dicarboxylate; isoq is isoquinoline) exists as the open-arm chelate, [Ru^II(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 PO₄^3–, 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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Contributing Organization:: 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

Grant/Contract Number:: SC0001011; CHE-0957215

OSTI ID:: 1210509

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 112, Issue 16; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 108 works

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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
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water splitting

Title: Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex

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