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

Abstract

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.

Authors:
 [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
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1378349
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 8; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Pham, Hieu H., Cheng, Mu-Jeng, Frei, Heinz, and Wang, Lin-Wang. Surface Proton Hopping and Fast-Kinetics Pathway of Water Oxidation on Co3O4 (001) Surface. United States: N. p., 2016. Web. doi:10.1021/acscatal.6b00713.
Pham, Hieu H., Cheng, Mu-Jeng, Frei, Heinz, & Wang, Lin-Wang. Surface Proton Hopping and Fast-Kinetics Pathway of Water Oxidation on Co3O4 (001) Surface. United States. https://doi.org/10.1021/acscatal.6b00713
Pham, Hieu H., Cheng, Mu-Jeng, Frei, Heinz, and Wang, Lin-Wang. 2016. "Surface Proton Hopping and Fast-Kinetics Pathway of Water Oxidation on Co3O4 (001) Surface". United States. https://doi.org/10.1021/acscatal.6b00713. https://www.osti.gov/servlets/purl/1378349.
@article{osti_1378349,
title = {Surface Proton Hopping and Fast-Kinetics Pathway of Water Oxidation on Co3O4 (001) Surface},
author = {Pham, Hieu H. and Cheng, Mu-Jeng and Frei, Heinz and Wang, Lin-Wang},
abstractNote = {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.},
doi = {10.1021/acscatal.6b00713},
url = {https://www.osti.gov/biblio/1378349}, journal = {ACS Catalysis},
issn = {2155-5435},
number = 8,
volume = 6,
place = {United States},
year = {Mon Jul 18 00:00:00 EDT 2016},
month = {Mon Jul 18 00:00:00 EDT 2016}
}

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