EPR evidence for Co(IV) species produced during water oxidation at neutral pH

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

doi:10.1021/ja1013344

EPR evidence for Co(IV) species produced during water oxidation at neutral pH

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

Research output: Contribution to journal › Article › peer-review

499 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	6882-6883
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	132
Issue number	20
DOIs	https://doi.org/10.1021/ja1013344
State	Published - May 26 2010
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja1013344

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title = "EPR evidence for Co(IV) species produced during water oxidation at neutral pH",

abstract = "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.",

author = "McAlpin, {J. Gregory} and Yogesh Surendranath and Mircea Dinc{\~a} and Stich, {Troy A.} and Stoian, {Sebastian A.} and Casey, {William H.} and Nocera, {Daniel G.} and Britt, {R. David}",

year = "2010",

month = may,

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doi = "10.1021/ja1013344",

language = "English (US)",

volume = "132",

pages = "6882--6883",

journal = "Journal of the American Chemical Society",

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TY - JOUR

T1 - EPR evidence for Co(IV) species produced during water oxidation at neutral pH

AU - McAlpin, J. Gregory

AU - Surendranath, Yogesh

AU - Dincã, Mircea

AU - Stich, Troy A.

AU - Stoian, Sebastian A.

AU - Casey, William H.

AU - Nocera, Daniel G.

AU - Britt, R. David

PY - 2010/5/26

Y1 - 2010/5/26

N2 - 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.

AB - 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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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 20

ER -

EPR evidence for Co(IV) species produced during water oxidation at neutral pH

Abstract

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