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Title: Surface Proton Hopping and Fast-Kinetics Pathway of Water Oxidation on Co3O4 (001) Surface

Journal Article · · ACS Catalysis
 [1];  [2];  [3];  [4]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis and Chemical Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis and Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis and Chemical Sciences Division; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
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A mechanism of water splitting on cobalt oxide surface is proposed, with atomistic thermodynamic and kinetic details. The density-functional theory studies suggest that the oxidation process could proceed with several nonelectrochemical (spontaneous) intermediate steps, following the initial electrochemical hydroxyl-to-oxo conversion. More specifically, the single oxo sites CoIV=O can hop (via surface proton/electron hopping) to form oxo pair CoIV(=O)-O-CoIV=O, which will undergo nucleophilic attack by a water molecule and form the hydroperoxide CoIII -OOH. Encounter with another oxo would generate a superoxo CoIII-OO, followed by the O2 release. Finally the addition and deprotonation of a fresh water molecule will restart the catalytic cycle by forming the hydroxyl CoIII-OH at this active site. Our theoretical investigations indicate that all nonelectrochemical reactions are kinetically fast and thermodynamically downhill. This hypothesis is supported by recent in situ spectroscopic observations of surface superoxo that is stabilized by hydrogen bonding to adjacent hydroxyl group as an intermediate on fast-kinetics Co catalytic site.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1378349
Journal Information:
ACS Catalysis, Vol. 6, Issue 8; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 68 works
Citation information provided by
Web of Science

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