On the activation energy of the formic acid oxidation reaction on platinum electrodes

• Activation energy for the direct oxidation of formic acid is in the range of 50–60 kJ/mol.
• The potential dependence of the activation energy can be related to changes in anion or OH coverage.
• It is proposed that a preadsorbed anion is required for the oxidation of formic acid.

A temperature dependent study on the formic acid oxidation reaction has been carried out in order to determine the activation energy of this reaction on different platinum single crystal electrodes, namely Pt(1 0 0), Pt(1 1 1), Pt(5 5 4) and Pt(5 4 4) surfaces. The chronoamperometric transients obtained with pulsed voltammetry have been analyzed to determine the current densities through the active intermediate and the CO formation rate. From the temperature dependency of those parameters, the activation energy for the direct reaction and the CO formation step have been calculated. For the active intermediate path, the activation energy are in the range of 50–60 kJ/mol. On the other hand, a large dependence on the electrode potential is found for the activation energy of the CO formation reaction on the Pt(1 0 0) electrode, and the activation energy values for this process range between 20 and 100 kJ/mol. These results have been explained using a reaction mechanism in which the oxidation of formic acid requires the presence of a pre-adsorbed anion on the electrode surface.