Mechanism of di(methyl)ether (DME) electrooxidation at platinum electrodes in acid medium
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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.
Keywordsdimethylether electrooxidation fuel cell in situ Infrared Reflectance Spectroscopy platinum
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- 7.Y. Tsutsumi, T. Moriyama and S. Kajitani, in V. W. Wong (MIT) (Ed.), Proceeding of the 2000 Spring Technical Conference of The ASME Internal Combustion Engine Division, ICE Vol. 34–3 (2000), pp 58–63Google Scholar
- 9.Tsutsumi Y., Nakano Y., Kajitani S. and Yamasita S.(2002). Electrochemistry 70: 984Google Scholar
- 20.Piersma B.J. and Gileadi E.(1966). In: Bockris JO’M. (eds), Modern Aspects of Electrochemistry, Vol. 4, Ch. 2. Butterworths, London, pp. 102Google Scholar
- 21.J.-M. Léger, PhD thesis (University of Poitiers, France, 1982).Google Scholar
- 25.J.Müller, P. Urban, R. Wezel, K.M. Colbow and J. Zhang, US Patent no US 6,777,116 B1, Aug. 17. 2004.Google Scholar
- 28.Beden B., Lamy C., Bewick A. and Kunimatsu K.(1981). J. Electroanal. Chem. 121: 343Google Scholar
- 30.B. Beden, F. Hahn, S. Juanto, C. Lamy and J.-M. Léger, ␣J.␣Electroanal. Chem. 225 (1987)Google Scholar