Theoretical analysis of oxygen reduction reaction and H2O2 formation and the impact of CF3SO3H coverage on Pt (111)

Theoretical analysis of ORR on Pt (111) was carried out with the combined technique of DFT calculation and the UBI-QEP method in order to understand the overall ORR pathways, behavior of H2O2 formation, and the impact of trifluoromethane sulfonic acid (CF3SO3H and TfOH) coverage, the alternative material of Nafion®, on the reactivity on the Pt surface. The ORR scheme consisting of elementary reactions was then modeled to determine the dominant path and the limiting step based on their activation energies. The results showed that the dominant ORR path included the H2O2 formation step and OOH formation step was limiting. When TfOH covered the Pt surface, it was revealed that the adsorption energy of an O2 molecule on Pt (111) was decreased due to the lower Fermi level and the d-band center, resulting in decreasing the activation energy of the limiting step. TfOH, however, could suppress the O2 adsorption on the Pt surface. In addition, with the TfOH coverage, it was indicated that the limiting step of ORR was shifted to H2O-production step which was after the H2O2 production, resulting in the enhancement of the H2O2 formation.