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Title: Electrocatalytic Water Oxidation by Single Site and Small Nuclearity Clusters of Cobalt

Here, cobalt oxides are an earth abundant material that exhibits high electrocatalytic activity for the oxygen evolution reaction (OER) across a wide pH range. Recent studies suggest that OER catalysis can proceed through an active site comprised of one or two cobalt atoms but that multiple adjacent cobalt centers are preferred to stabilize high valent cobalt oxo-intermediates by delocalization. Utilizing molecular precursors to prepare single, isolated cobalt atoms (SS-Co) and small clusters of Co 3O 4 we find that OER proceeds more efficiently on Co 3O 4. Using electrochemical impedance spectroscopy (EIS), these results were rationalized at an atomic level. The EIS results support a hypothesis that charge transfer related to the formation of reaction intermediates proceeds more easily on Co 3O 4 than on SS-Co, which is attributed to the difficulty in forming Co(IV) = O and unlikely nucleophilic attack by water to form Co(II)-OOH.
Authors:
ORCiD logo [1] ;  [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Yale Univ., New Haven, CT (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 4; Related Information: © The Author(s) 2017.; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electrocatalysis; Electrochemical Impedance Spectroscopy; Oxygen Evolution Reaction
OSTI Identifier:
1466714

Swierk, John R., and Tilley, T. Don. Electrocatalytic Water Oxidation by Single Site and Small Nuclearity Clusters of Cobalt. United States: N. p., Web. doi:10.1149/2.0041804jes.
Swierk, John R., & Tilley, T. Don. Electrocatalytic Water Oxidation by Single Site and Small Nuclearity Clusters of Cobalt. United States. doi:10.1149/2.0041804jes.
Swierk, John R., and Tilley, T. Don. 2017. "Electrocatalytic Water Oxidation by Single Site and Small Nuclearity Clusters of Cobalt". United States. doi:10.1149/2.0041804jes. https://www.osti.gov/servlets/purl/1466714.
@article{osti_1466714,
title = {Electrocatalytic Water Oxidation by Single Site and Small Nuclearity Clusters of Cobalt},
author = {Swierk, John R. and Tilley, T. Don},
abstractNote = {Here, cobalt oxides are an earth abundant material that exhibits high electrocatalytic activity for the oxygen evolution reaction (OER) across a wide pH range. Recent studies suggest that OER catalysis can proceed through an active site comprised of one or two cobalt atoms but that multiple adjacent cobalt centers are preferred to stabilize high valent cobalt oxo-intermediates by delocalization. Utilizing molecular precursors to prepare single, isolated cobalt atoms (SS-Co) and small clusters of Co3O4 we find that OER proceeds more efficiently on Co3O4. Using electrochemical impedance spectroscopy (EIS), these results were rationalized at an atomic level. The EIS results support a hypothesis that charge transfer related to the formation of reaction intermediates proceeds more easily on Co3O4 than on SS-Co, which is attributed to the difficulty in forming Co(IV) = O and unlikely nucleophilic attack by water to form Co(II)-OOH.},
doi = {10.1149/2.0041804jes},
journal = {Journal of the Electrochemical Society},
number = 4,
volume = 165,
place = {United States},
year = {2017},
month = {11}
}

Works referenced in this record:

Solar Water Splitting Cells
journal, November 2010
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In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+
journal, August 2008