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Rapid Water Reduction to H_2 Catalyzed by a Cobalt Bis(iminopyridine) Complex

Stubbert, Bryand D. and Peters, Jonas C. and Gray, Harry B. (2011) Rapid Water Reduction to H_2 Catalyzed by a Cobalt Bis(iminopyridine) Complex. Journal of the American Chemical Society, 133 (45). pp. 18070-18073. ISSN 0002-7863.

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A cobalt bis(iminopyridine) complex is a highly active electrocatalyst for water reduction, with an estimated apparent second order rate constant k_(app) ≤ 10^7 M^(–1)s^(–1) over a range of buffer/salt concentrations. Scan rate dependence data are consistent with freely diffusing electroactive species over pH 4–9 at room temperature for each of two catalytic reduction events, one of which is believed to be ligand based. Faradaic H_2 yields up to 87 ± 10% measured in constant potential electrolyses (−1.4 V vs SCE) confirm high reactivity and high fidelity in a catalyst supported by the noninnocent bis(iminopyridine) ligand. A mechanism involving initial reduction of Co^(2+) and subsequent protonation is proposed.

Item Type:Article
Related URLs:
URLURL TypeDescription
Peters, Jonas C.0000-0002-6610-4414
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2011 American Chemical Society. Received: August 17, 2011. Publication Date (Web): October 24, 2011. We thank Charles C. L. McCrory, Christopher Uyeda, and James R. McKone for helpful discussions. Our work was supported by the NSF Center for Chemical Innovation on Solar Fuels (CCI Solar, CHE-0802907 and CHE-0947829) and the Stanford Global Climate and Energy Project (GCEP).
Group:CCI Solar Fuels
Funding AgencyGrant Number
Stanford Global Climate and Energy Project (GCEP)UNSPECIFIED
Issue or Number:45
Record Number:CaltechAUTHORS:20120106-104425949
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Official Citation:Rapid Water Reduction to H2 Catalyzed by a Cobalt Bis(iminopyridine) Complex Bryan D. Stubbert, Jonas C. Peters, and Harry B. Gray Journal of the American Chemical Society 2011 133 (45), 18070-18073
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:28696
Deposited By: Ruth Sustaita
Deposited On:06 Jan 2012 19:02
Last Modified:10 Jun 2020 23:26

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