Size effects on the electrochemical oxidation of oxalic acid on nanocrystalline platinum

The electrocatalytic activity of platinised platinum (Pt ∣ Pt) electrodes in the electrooxidation of oxalic acid was found to be dependent on the degree of ageing. Pt ∣ Pt electrodes prepared by electrodeposition were aged by cycling the potential with an upper positive potential limit corresponding to Pt surface oxidation. This procedure results in surface reconstruction with an increase of mean particle size. The changes of surface area and roughness of Pt ∣ Pt during ageing have been discussed in terms of sintering processes for supported catalysts or ceramic materials. An increase of mean particle size is accompanied by a decrease in oxygen adsorption, e.g. through changes in the surface concentration of defects on the particle surface. Two possible mechanisms for the electrooxidation of oxalic acid involving either an oxygen adsorbate species (CE mechanism) or direct electrode transfer can be distinguished. Changes of oxidation rate are related to changes of oxygen coverage with ageing.