The Role of COad in the Oxidation of Methanol at a Platinum Electrode in an Acid Solution

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Abstract
The role of the adsorbate COad in the oxidation of methanol was studied under a variety of experimental conditions on the basis of the rate-ratio of the path of CO2 formation via COad to the overall oxidation of methanol at a platinum electrode in 0.5 mol dm−3 of H2SO4. The results: (a) At potentials below 0.55 V and with a short time of oxidation, COad inhibited its own formation; (b) at 0.60–0.75 V and with a long time of oxidation, COad was a poison to parallel reactions; (c) at above 0.8 V and at θ1>0.15, the formation of CO2 via COad was predominant, and the COad never hindered parallel reactions. There was no difference between the role of the COad formed from dissolved CO and that of the COad formed from methanol, though, in the absence of dissolved CO, the oxidation of methanol was, for some reason, inhibited at small coverages close to the respective limiting values. When the coverage was larger than about 0.85, COad remarkably inhibited all the parallel reactions in the methanol oxidation.

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