Oscillatory electrocatalytic oxidation of methanol on an Ni(OH)2 film electrode |
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| Authors: | W. Huang Z. L. Li Y. D. Peng S. Chen J. F. Zheng Z. J. Niu |
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| Affiliation: | (1) Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, 321004, China;(2) Department of Chemistry, Hunan Normal University, Changsha, 410081, China |
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| Abstract: | A film of Ni(OH)2 deposited cathodically on a roughened nickel substrate consists of even nanoparticles, which were characterized by atomic-force microscopy (AFM). The mechanism of potential oscillations in the electrocatalytic oxidation of methanol on this film electrode in alkaline medium was studied in situ by means of Raman spectroscopy in combination with electrochemical measurements. The redox change of the nickel hydroxide film, the concentration distribution of methanol in the diffusion layer, and the oxidation products of methanol were characterized in situ by time-resolved, spatial-resolved, and potential-dependent Raman spectroscopy, respectively. Electrochemical reactions, i.e. methanol oxidation and periodic oxygen evolution, coupling with alternately predominant diffusion and convection mass transfer of methanol, account for the potential oscillations that occur during oxidation of methanol above its limiting diffusion current. This mechanism is totally different from that of methanol oxidation on platinum electrodes, for which surface steps, i.e. formation and removal of COad, are essential.This work is dedicated to Professor Gyorgy Horanyi on the occasion of his 70th birthday in recognition of his numerous contributions to field of electrochemical oscillations and electrocatalysis at Ni-hydroxide electrodes. |
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| Keywords: | Nano-structured nickel hydroxide film In-situ Raman spectroscopy Potential oscillations Methanol Mechanism |
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