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

Abstract

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.

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [1];  [3];  [2];  [1]
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  1. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States
  2. Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States
  3. Department of Chemistry and Biochemistry, Providence College, 1 Cunningham Square, Providence, Rhode Island 02918, 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)
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 Name: Journal of the American Chemical Society Journal Volume: 136 Journal Issue: 50; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
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., Abruña, Héctor D., and Nocera, Daniel G. Water Oxidation Catalysis by Co(II) Impurities in Co(III) 4 O 4 Cubanes. United States: N. p., 2014. Web. doi:10.1021/ja5110393.
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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. Water Oxidation Catalysis by Co(II) Impurities in Co(III) 4 O 4 Cubanes. United States. https://doi.org/10.1021/ja5110393
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Ullman, Andrew M., Liu, Yi, Huynh, Michael, Bediako, D. Kwabena, Wang, Hongsen, Anderson, Bryce L., Powers, David C., Breen, John J., Abruña, Héctor D., and Nocera, Daniel G. Thu . "Water Oxidation Catalysis by Co(II) Impurities in Co(III) 4 O 4 Cubanes". United States. https://doi.org/10.1021/ja5110393.
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@article{osti_1165631,
title = {Water Oxidation Catalysis by Co(II) Impurities in Co(III) 4 O 4 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 Abruña, Héctor 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 = {Thu Dec 04 00:00:00 EST 2014},
month = {Thu Dec 04 00:00:00 EST 2014}
}
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https://doi.org/10.1021/ja5110393
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Figures / Tables:

Figure 1 Figure 1: (left) Molecular structure of Co4O4 cubane structure 1 and (right) thermal ellipsoid representation at the 50% probability level of the one-electron oxidized cubane, 1[PF6]. Hydrogen atoms and an acetonitrile molecule have been omitted for clarity. Atoms are colorcoded: gray (carbon), blue (nitrogen), red (oxygen), dark blue (cobalt), greenmore » (fluorine), and yellow (phosphorus).« less
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