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

Abstract

Here, the observed water oxidation activity of the compound class Co 4O 4(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 Co 4O 4 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.

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [1];  [3];  [2];  [1]
  1. Harvard Univ., Cambridge, MA (United States)
  2. Cornell Univ., Ithaca, NY (United States)
  3. Providence College, Providence, RI (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Energy Materials Center at Cornell (EMC2)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1165631
Alternate Identifier(s):
OSTI ID: 1370465
Grant/Contract Number:  
SC0001086; SC0009565
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 136; Journal Issue: 50; Related Information: Emc2 partners with Cornell University (lead); Lawrence Berkeley National Laboratory; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ullman, Andrew M., Liu, Yi, Huynh, Michael, Bediako, D. Kwabena, Wang, Hongsen, Anderson, Bryce L., Powers, David C., Breen, John J., Abruna, Hector D., and Nocera, Daniel G. Water Oxidation Catalysis by Co(II) Impurities in Co(III)4O4 Cubanes. United States: N. p., 2014. Web. doi:10.1021/ja5110393.
Ullman, Andrew M., Liu, Yi, Huynh, Michael, Bediako, D. Kwabena, Wang, Hongsen, Anderson, Bryce L., Powers, David C., Breen, John J., Abruna, Hector D., & Nocera, Daniel G. Water Oxidation Catalysis by Co(II) Impurities in Co(III)4O4 Cubanes. United States. doi:10.1021/ja5110393.
Ullman, Andrew M., Liu, Yi, Huynh, Michael, Bediako, D. Kwabena, Wang, Hongsen, Anderson, Bryce L., Powers, David C., Breen, John J., Abruna, Hector D., and Nocera, Daniel G. Tue . "Water Oxidation Catalysis by Co(II) Impurities in Co(III)4O4 Cubanes". United States. doi:10.1021/ja5110393.
@article{osti_1165631,
title = {Water Oxidation Catalysis by Co(II) Impurities in Co(III)4O4 Cubanes},
author = {Ullman, Andrew M. and Liu, Yi and Huynh, Michael and Bediako, D. Kwabena and Wang, Hongsen and Anderson, Bryce L. and Powers, David C. and Breen, John J. and Abruna, Hector D. and Nocera, Daniel G.},
abstractNote = {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.},
doi = {10.1021/ja5110393},
journal = {Journal of the American Chemical Society},
number = 50,
volume = 136,
place = {United States},
year = {2014},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/ja5110393

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Cited by: 65 works
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