Rapid Water Reduction to H_2 Catalyzed by a Cobalt Bis(iminopyridine) Complex
Abstract
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.
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).Attached Files
Supplemental Material - ja2078015_si_001.pdf
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Additional details
- Eprint ID
- 28696
- Resolver ID
- CaltechAUTHORS:20120106-104425949
- NSF
- CHE-0802907
- NSF
- CHE-0947829
- Stanford Global Climate and Energy Project (GCEP)
- Created
-
2012-01-06Created from EPrint's datestamp field
- Updated
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2021-11-09Created from EPrint's last_modified field
- Caltech groups
- CCI Solar Fuels