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Title: In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen

Abstract

An in situ Raman spectroscopic investigation has been carried out to identify the composition of the active phase present on the surface of nickel electrodes used for the electrochemical evolution of oxygen. The electrolyte in all cases was 0.1 M KOH. A freshly polished Ni electrode oxidized upon immersion in the electrolyte and at potentials approaching the evolution of oxygen developed a layer of γ-NiOOH. Electrochemical cycling of this film transformed it into β-NiOOH, which was observed to be three times more active than γ-NiOOH. The higher activity of β-NiOOH is attributed to an unidentified Ni oxide formed at a potential above 0.52 V (vs Hg/HgO reference). We have also observed that a submonolayer of Ni oxide deposited on Au exhibits a turnover frequency (TOF) for oxygen evolution that is an order of magnitude higher than that for a freshly prepared γ-NiOOH surface and more than 2-fold higher than that for a β-NiOOH surface. By contrast, a similar film deposited on Pd exhibits a TOF that is similar to that of bulk γ-NiOOH. Furthermore it is proposed that the high activity of submonolayer deposits of Ni oxide on Au is due to charge transfer from the oxide to the highlymore » electronegative Au, leading to the possible formation of a mixed Ni/Au surface oxide.« less

Authors:
 [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1511336
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 116; Journal Issue: 15; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yeo, Boon Siang, and Bell, Alexis T. In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen. United States: N. p., 2012. Web. doi:10.1021/jp3007415.
Yeo, Boon Siang, & Bell, Alexis T. In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen. United States. doi:10.1021/jp3007415.
Yeo, Boon Siang, and Bell, Alexis T. Wed . "In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen". United States. doi:10.1021/jp3007415. https://www.osti.gov/servlets/purl/1511336.
@article{osti_1511336,
title = {In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen},
author = {Yeo, Boon Siang and Bell, Alexis T.},
abstractNote = {An in situ Raman spectroscopic investigation has been carried out to identify the composition of the active phase present on the surface of nickel electrodes used for the electrochemical evolution of oxygen. The electrolyte in all cases was 0.1 M KOH. A freshly polished Ni electrode oxidized upon immersion in the electrolyte and at potentials approaching the evolution of oxygen developed a layer of γ-NiOOH. Electrochemical cycling of this film transformed it into β-NiOOH, which was observed to be three times more active than γ-NiOOH. The higher activity of β-NiOOH is attributed to an unidentified Ni oxide formed at a potential above 0.52 V (vs Hg/HgO reference). We have also observed that a submonolayer of Ni oxide deposited on Au exhibits a turnover frequency (TOF) for oxygen evolution that is an order of magnitude higher than that for a freshly prepared γ-NiOOH surface and more than 2-fold higher than that for a β-NiOOH surface. By contrast, a similar film deposited on Pd exhibits a TOF that is similar to that of bulk γ-NiOOH. Furthermore it is proposed that the high activity of submonolayer deposits of Ni oxide on Au is due to charge transfer from the oxide to the highly electronegative Au, leading to the possible formation of a mixed Ni/Au surface oxide.},
doi = {10.1021/jp3007415},
journal = {Journal of Physical Chemistry. C},
number = 15,
volume = 116,
place = {United States},
year = {2012},
month = {4}
}

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Works referencing / citing this record:

Expansion of the urea electrocatalytic oxidation window by adsorbed nickel ions
journal, July 2019