Amorphous palladium-silicon alloys for the oxidation of formic acid and formaldehyde. A voltammetric investigation

The electrocatalytic oxidation of formic acid and formaldehyde on Pd and on amorphous Pd(Si) was studied by cyclic voltammetry and the results compared with the literature for similar systems. The oxidation of HCOOH on Pd occurs through direct catalytic dehydrogenation via (:C(OH)(2))(ads) while on Pd(Si) this intermediate does not appear to be formed. This is a consequence of the presence of inert Si on the surface that diminishes the probability of adjacent free sites. At high HCOOH concentrations, that intermediate undergoes dehydration on the Pd surface and COads oxidation peak is observed. For HCHO, the oxidation mechanism on both electrode materials appears similar to that previously proposed for Pt. However, the oxides formed on the amorphous Pd(Si) allay are more reactive than those on Pd thus affecting the overall kinetics of the process for both organic molecules, a fact revealed by the increase in anodic currents observed in the voltammograms.