The rate of methanol adsorption and oxidation on carbon supported Pt nanoparticles and polycrystalline Pt has been studied by differential electrochemical mass spectrometry (DEMS) under continuous flow. At room temperature, the maximum adsorption rate at polycrystalline Pt is about 0.06 monolayer per second, whereas at Pt nanoparticles it is 0.04 monolayer per second. On polycrystalline Pt it amounts to 56% of a full CO monolayer, obtained by adsorbing CO from a CO saturated electrolyte. On the nanoparticles only 28% of a full CO monolayer can be obtained. The oxidation rate of the adsorbate is of zero order at polycrystalline Pt, whereas at nanoparticles it is of first order with respect to the coverage. Oxidation of methanol starts below the onset of CO2 formation. At polycrystalline Pt and Pt(111), the rate of CO2 formation is determined by the oxidation rate of the adsorbate. At Pt(332) and the nanoparticle electrodes, the rate of CO2 formation from bulk methanol is higher than that from methanol adsorbate, due to the heterogenity of these electrodes.Similarly to Ru modified Pt single crystal electrodes, Ru modified polycrystalline Pt and Pt nanoparticles offer different adsorption sites for CO, which can be selectively populated.
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