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The electrochemical oxidation of methanol was investigated by using various ad-layer modified Au(111) electrodes in alkaline media in comparison to Au(111), polycrystalline Pd, and polycrystalline Pt electrodes. Catalytic activity of gold toward methanol oxidation has tended to increase in more alkaline media, as reflected in the oxidation peak in the concentration range of NaOH (0.1-3.0 M) studied here. The oxidation peak potential of methanol shifted to more negative potentials, indicating a pH-dependent surface reaction. Among the electrodes studied, single-crystal gold electrode surfaces modified with Pd and Pt ad-layers displayed the highest catalytic activity for methanol oxidation. Additional shifts of about 350 mV in the oxidation peak potential of methanol was observed for both ad-layer modified electrodes to more negative potentials compared to that of bare electrodes. The Pd and Pt ad-layer modified Au(111) electrode surfaces did not only supply a superior electrical contact, but also accelerated electron transfer, as shown by the increase in peak current and the positive shift in peak potential. This effect was supported by the doublelayer capacitance measurements of bare Au(111) and Pd ad-layer modified singlecrystal electrodes where the potential of zero charge changed from 15 to 5 mV.

Electrocatalytic oxidation of methanol at Pd and Pt ad-layer modified Au(111) electrodes in alkaline solution