Oxygen reduction on platinum electrodes in base: Theoretical study

Electrode-potential-dependent activation energies for electron transfer have been calculated using a local reaction center model and constrained variation theory for the oxygen reduction reaction on platinum in base. Results for four one-electron transfer steps are presented. For the first, O2(ads) is predicted to be reduced to adsorbed superoxide, O2−(ads), which dissociates with a low activation barrier to O(ads) + O−(ads). Then a proton transfer form H2O(ads) to O−(ads) takes place, forming OH(ads) + OH−(aq). The second electron transfer reacts O(ads) with H2O(aq) to form a second OH(ads) + OH−(aq). The third and fourth electron transfers react the two OH(ads) with two H2O(aq) to form two H2O(ads) + two OH−(aq). All three different surface reduction reactions are predicted to have reversible potentials in the −0.24 V(SHE) to −0.29 V(SHE) range for 0.1 M base and activation energies for the superoxide formation step are close to the experimentally observed range in 0.1 M base for the overall four-electron to water over the three low index (1 1 0) (1 0 0) and (1 1 1) surfaces: 0.38–0.49 eV at 0.35 eV respectively at 0.88 V(RHE). Predicted reversible potentials for forming O2−(ads) are compared with estimates from the experimental literature. The difference between the acid mechanism, where the peroxyl radical, OOH(ads) is the first reduction intermediate, and the base mechanism, where superoxide, O2−(ads) is the first reduction intermediate, is discussed.