Methanol electrooxidation on supported Pt and Pt-Ru catalysts in acid and alkaline solutions

The kinetics of methanol oxidation on supported 47.5 wt.% Pt and 54 wt.% PtRu (with nominal Pt:Ru ratios of 2:3) catalysts are measured in 0.5 M H2SO4 and 0.1 NaOH at 295 and 333 K using thin-film rotating disk electrode (RDE) method. It was found that the activity of Pt and PtRu for methanol oxidation is a strong function of pH of solution and temperature. The kinetics are much higher in alkaline than in acid solution; at 333 K, a factor of 30 for Pt and a factor of 20 for Pt2Ru3 at 0.5 V. The pH effect is attributed to the pH competitive adsorption of oxygenated species with anions from supporting electrolytes. The activity of Pt and Pt2Ru3 catalysts at 333 K is higher (a factor of 5) than at 295 K. Irrespective of pH, only negligible differences in the kinetics are observed between Pt and on high Ru content Pt alloys, presumably owing to a slow rate of methanol dehydrogenation on the Ru-rich surface and insufficient number of Pt sites required for dissociative chemisorption of methanol