EPR Evidence for Co(IV) Species Produced During Water Oxidation at Neutral pH

McAlpin, J. Gregory; Surendranath, Yogesh; Dincǎ, Mircea; Stich, Troy A.; Stoian, Sebastian A.; Casey, William H.; Nocera, Daniel G.; Britt, R. David

doi:10.1021/ja1013344

EPR Evidence for Co(IV) Species Produced During Water Oxidation at Neutral pH

Journal Article · Fri Apr 30 00:00:00 EDT 2010 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja1013344· OSTI ID:2507303

McAlpin, J. Gregory ^[1]; Surendranath, Yogesh ^[1]; Dincǎ, Mircea ^[1]; Stich, Troy A. ^[1]; Stoian, Sebastian A. ^[1]; Casey, William H. ^[1]; Nocera, Daniel G. ^[1]; Britt, R. David ^[1]

University of California, Davis, CA (United States); Massachusetts Institute of Technology (MIT), Cambridge, MA (United States)

Thin-film water oxidation catalysts (Co–Pi) have been characterized by electron paramagnetic resonance (EPR) spectroscopy. Co–Pi catalyst films exhibit EPR signals corresponding to populations of both Co(II) and Co(IV). As the deposition voltage is increased into the region where water oxidation prevails, the population of Co(IV) rises and the population of Co(II) decreases. The changes in the redox speciation of the film can also be induced, in part, by prolonged water oxidation catalysis in the absence of additional catalyst deposition. These results provide spectroscopic evidence for the formation of Co(IV) species during water oxidation catalysis at neutral pH. The films are x-ray amorphous but must have a structure similar to common layered minerals like hydrotalcite or birnessite.

View Accepted Manuscript (DOE)

Research Organization:: University of California, Davis, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG02-05ER15693

OSTI ID:: 2507303

Alternate ID(s):: OSTI ID: 2544379

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 20 Vol. 132; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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EPR Evidence for Co(IV) Species Produced During Water Oxidation at Neutral pH

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