Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 132, Issue 20, Pages 6882-+Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja1013344
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Funding
- NSF [CHE-0802907, CHE-0947829, CHE-0533150, CHE-0939178, EAR0814242]
- U.S. Department of Energy [DE-FG02-05ER15693]
- Chesonis Family Foundation
- U.S. Department of Energy (DOE) [DE-FG02-05ER15693] Funding Source: U.S. Department of Energy (DOE)
- Direct For Mathematical & Physical Scien [0939178] Funding Source: National Science Foundation
- Directorate For Geosciences
- Division Of Earth Sciences [0814242] Funding Source: National Science Foundation
- Division Of Chemistry [0939178] Funding Source: National Science Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0802907] Funding Source: National Science Foundation
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Thin-film water oxidation catalysts (Co-Pi) prepared by electrodeposition from phosphate electrolyte and Co(NO3)(2) 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.
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