Cation Effects on the Acidic Oxygen Reduction Reaction at Carbon Surfaces

Hydrogen peroxide (H₂O₂) is a widely used green oxidant. Until now, research has focused on the development of efficient catalysts for the two-electron oxygen reduction reaction (2e^- ORR). However, electrolyte effects on the 2e^- ORR have remained little understood. We report a significant effect of alkali metal cations (AMCs) on carbons in acidic environments. The presence of AMCs at a glassy carbon electrode shifts the half wave potential from -0.48 to -0.22 V_RHE. This cation-induced enhancement effect exhibits a uniquely sensitive on/off switching behavior depending on the voltammetric protocol. Voltammetric and in situ X-ray photoemission spectroscopic evidence is presented, supporting a controlling role of the potential of zero charge of the catalytic enhancement. Density functional theory calculations associate the enhancement with stabilization of the *OOH key intermediate as a result of locally induced field effects from the AMCs. Finally, we developed a refined reaction mechanism for the H₂O₂ production in the presence of AMCs.