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Lookup NU author(s): Professor Paul ChristensenORCiD,
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC 4.0).
The electrochemical oxidation of ethanol at a polycrystalline Pt electrode was studied using in situ Fourier transform infrared (FTIR) spectroscopy in 0.1 M KOH at 25 and 50 degrees C. It was found that the equilibrium between Pt and reversibly adsorbed OH shifts to favor the latter at 50 degrees C compared to 25 degrees C, and this was reflected in the higher oxidation currents observed in the voltammetry as well as increased production of acetate in the FTIR spectra. Acetate is the only product observed at lower potentials. Above the transition potential, where at least some of the areas of the thin layer in the spectroelectrochemical cell become acidic, acetaldehyde, acetic acid, and a small amount of CO2 are produced. This transition potential depends strongly on temperature: -0.1 V at 25 degrees C and -0.4 V at 50 degrees C. The temperature dependence of the production of acetaldehyde and acetic acid strongly suggests that the rate-determining step is the removal of the first proton from the initially adsorbed ethoxide species, and we tentatively suggest that this is also the rate-determining step under alkaline conditions. Overall, our data provide additional support for the mechanism we have developed over a number of publications concerning the oxidation of small alcohols at polycrystalline Pt in alkaline electrolyte.
Author(s): Christensen PA, Jones SWM
Publication type: Article
Publication status: Published
Journal: Journal of Physical Chemistry C
Print publication date: 26/12/2014
Online publication date: 24/11/2014
Acceptance date: 21/11/2014
Date deposited: 11/02/2015
ISSN (print): 1932-7447
ISSN (electronic): 1932-7455
Publisher: American Chemical Society
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