Effects of the anion adsorption and pH on the formic acid oxidation reaction on Pt(111) electrodes

The effects of solution pH and anion adsorption for the formic acid oxidation reaction on the Pt(111) electrode have been examined using electrochemical techniques. Regarding the pH effects, it has been found that oxidation currents for this reaction increase with pH, which indicates that solution formate is involved in the reaction mechanism. Unexpectedly, the adsorption of sulfate on the Pt(111) electrode has a positive effect on the oxidation of formic acid, which also suggests that adsorbed anions are also involved in the mechanism. The activation energy calculated from temperature dependent measurements diminishes with the solution pH and also in the presence of adsorbed sulfate. These measurements corroborate the involvement of solution formate and anions in the oxidation mechanism. Using these results, a rate equation for the oxidation of formic acid is proposed. The current values calculated from this equation are in very good agreement with the experimental currents in perchloric acid solutions.