Cation Effects on Hydrogen Oxidation Reaction on Pt Single-Crystal Electrodes in Alkaline Media

The exact mechanism behind the cation-assisted hydrogen oxidation reaction (HOR) on platinum electrodes in alkaline media remains disputed. We show that the cation effects at platinum display a remarkable structure sensitivity: not only the H adsorption but also the HOR activity on (111) terrace sites are independent of the nature of cation and cation concentration. On (110) step sites, at low cation concentration and mildly alkaline media, cations promote the HOR, whereas at more alkaline pH and consequently higher near-surface cation concentrations, the HOR is inhibition by the cations. Moreover, the role of the cation on terrace–OHad is different from that on step–OHad, as can also be observed from the inhibition of the HOR current by terrace–OHad at higher potentials. These results suggest that near the onset potential, HOR mainly takes place on steps, but under diffusion-limited conditions at higher overpotential, HOR mainly takes place on terraces.