Water Oxidation Catalysis by Co(II) Impurities in Co(III) 4 O 4 Cubanes

Ullman, Andrew M.; Liu, Yi; Huynh, Michael; Bediako, D. Kwabena; Wang, Hongsen; Anderson, Bryce L.; Powers, David C.; Breen, John J.; Abruña, Héctor D.; Nocera, Daniel G.

doi:10.1021/ja5110393

Title: Water Oxidation Catalysis by Co(II) Impurities in Co(III) ₄ O ₄ Cubanes

Journal Article · Thu Dec 04 00:00:00 EST 2014 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja5110393· OSTI ID:1165631

Ullman, Andrew M. ^[1]; Liu, Yi ^[1]; Huynh, Michael ^[1]; Bediako, D. Kwabena ^[1]; Wang, Hongsen ^[2]; Anderson, Bryce L. ^[1]; Powers, David C. ^[1]; Breen, John J. ^[3]; Abruña, Héctor D. ^[2]; Nocera, Daniel G. ^[1]

Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States
Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States
Department of Chemistry and Biochemistry, Providence College, 1 Cunningham Square, Providence, Rhode Island 02918, United States

Here, the observed water oxidation activity of the compound class Co₄O₄(OAc)₄(Py–X)₄ emanates from a Co(II) impurity. This impurity is oxidized to produce the well-known Co-OEC heterogeneous cobaltate catalyst, which is an active water oxidation catalyst. We present results from electron paramagnetic resonance spectroscopy, nuclear magnetic resonance line broadening analysis, and electrochemical titrations to establish the existence of the Co(II) impurity as the major source of water oxidation activity that has been reported for Co₄O₄ molecular cubanes. Differential electrochemical mass spectrometry is used to characterize the fate of glassy carbon at water oxidizing potentials and demonstrate that such electrode materials should be used with caution for the study of water oxidation catalysis.

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Research Organization:: Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Energy Materials Center at Cornell (EMC2)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001086; SC0009565

OSTI ID:: 1165631

Alternate ID(s):: OSTI ID: 1370465

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 136 Journal Issue: 50; ISSN 0002-7863

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 146 works

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