Abstract

Methanol oxidation on a supported Pt fuel cell catalyst was investigated by on-line differential electrochemical mass spectrometry (DEMS) at continuous electrolyte flow and defined catalyst utilization, employing a thin-film electrode setup and a thin-layer flow-through cell. The active surface of the Pt/Vulcan (E-TEK) high surface area catalyst was characterized quantitatively by Hupd and preadsorbed CO monolayer stripping. Methanol stripping DEMS experiments, oxidizing the adsorbed dehydrogenation products formed upon methanol adsorption at potentials in the hydrogen adsorption region, show that the coverage of these products and hence the methanol uptake depend on the electrode potential, in contrast to the potential-independent COad coverage. The dehydrogenation products cannot be displaced by Hupd. The number of close to two electrons used per oxidation of one adsorbed dehydrogenation product identifies this as COad species. Further methanol dehydrogenation is hindered when the CO adlayer reaches a d...

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