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Mechanism of di(methyl)ether (DME) electrooxidation at platinum electrodes in acid medium

Mechanism of di(methyl)ether (DME) electrooxidation at platinum electrodes in acid medium The electrooxidation of DME was studied at a bulk platinum electrode. It was shown that the DME adsorption was a slow step in the overall oxidation reaction. The DME adsorption is potential dependent in the hydrogen region of platinum and independent in the double layer region. From low potential scan rate voltammetry and DME stripping experiments, it was shown that the DME oxidation mechanism occurred via several reaction paths. At low potentials, DME oxidation leads to the existence of a positive current plateau. “In situ” Infrared Reflectance Spectroscopy experiments were carried out to identify the intermediate and reaction products of DME adsorption and oxidation at different potentials. COL (linearly bonded CO), COB (bridge bonded CO), adsorbed COOH species and CO2 were detected. From these electrochemical and spectro-electrochemical results, it was proposed that some adsorbed DME was hydrolysed and directly oxidized to CO2 or HCOOH species and some partially blocked platinum sites at the surface forming Pt–CHO and/or Pt–CO. Then, as soon as platinum becomes able to activate water, a bifunctionnal mechanism occurs to form either HCOOH or CO2 again following two different reaction paths. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Journal of Applied Electrochemistry Springer Journals

Mechanism of di(methyl)ether (DME) electrooxidation at platinum electrodes in acid medium

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References (36)

Publisher
Springer Journals
Copyright
Copyright © 2005 by Springer Science+Business Media, Inc.
Subject
Chemistry; Industrial Chemistry/Chemical Engineering; Physical Chemistry ; Electrochemistry
ISSN
0021-891X
eISSN
1572-8838
DOI
10.1007/s10800-005-9095-6
Publisher site
See Article on Publisher Site

Abstract

The electrooxidation of DME was studied at a bulk platinum electrode. It was shown that the DME adsorption was a slow step in the overall oxidation reaction. The DME adsorption is potential dependent in the hydrogen region of platinum and independent in the double layer region. From low potential scan rate voltammetry and DME stripping experiments, it was shown that the DME oxidation mechanism occurred via several reaction paths. At low potentials, DME oxidation leads to the existence of a positive current plateau. “In situ” Infrared Reflectance Spectroscopy experiments were carried out to identify the intermediate and reaction products of DME adsorption and oxidation at different potentials. COL (linearly bonded CO), COB (bridge bonded CO), adsorbed COOH species and CO2 were detected. From these electrochemical and spectro-electrochemical results, it was proposed that some adsorbed DME was hydrolysed and directly oxidized to CO2 or HCOOH species and some partially blocked platinum sites at the surface forming Pt–CHO and/or Pt–CO. Then, as soon as platinum becomes able to activate water, a bifunctionnal mechanism occurs to form either HCOOH or CO2 again following two different reaction paths.

Journal

Journal of Applied ElectrochemistrySpringer Journals

Published: Dec 17, 2005

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