Unveiling the Cationic Promotion Effect of H₂O₂ Electrosynthesis Activity of O-Doped Carbons

H₂O₂ electrosynthesis is an emerging clean chemical technology, whose efficiency critically depends on the activity and selectivity of electrocatalysts for two-electron oxygen reduction reaction (2e^- ORR). Here, we demonstrate that 2e^- ORR activity of oxygen-doped carbons, which have been one of the most promising catalysts for this reaction, can be substantially influenced by the types and concentrations of cations in electrolytes. Heat-treated carbon comprising active oxygen functional groups exhibits cation-dependent 2e^- ORR activity trends in alkaline media, following the order Cs⁺ > K⁺ > Li⁺. Importantly, an electrolyte with a high cation concentration (0.1 M KOH + 0.5 M KCl) afforded the highest 2e^- ORR mass activity (250 ± 30 A g_cat^-1 at 0.70 V vs reversible hydrogen electrode) ever reported. We have established that the cation promotion effect correlates with cation-dependent electron-transfer kinetics, which regulates the rate-determining first electron transfer to O₂.