Charge Transfer Modulation in g-C3N4/CeO2 Composites: Electrocatalytic Oxygen Reduction for H2O2 Production

The electrocatalytic two-electron oxygen reduction reaction (2e-ORR) represents one of the most prospective avenues for the in situ synthesis of hydrogen peroxide (H2O2). However, the four-electron competition reaction constrains the efficiency of H2O2 synthesis. Therefore, there is an urgent need to develop superior catalysts to facilitate the H2O2 synthesis. In this study, graphite-phase carbon nitride and cerium dioxide composites (g-C3N4/CeO2) with varying CeO2 loadings were prepared with favorable 2e-ORR electrocatalysts. The optimized composite, containing 20 wt % CeO2 (g-C3N4/CeO2-20%) exhibited the highest Faradaic efficiency (FE) of 97% and notable H2O2 yielding of 9.84 mol gcat.-1 h-1 at the potential of 0.3 V (vs RHE) in a 0.1 M KOH electrolyte. Density functional theory calculations revealed that the improvement of the selectivity and yield of H2O2 for the composites were attributed to the charge transfer between g-C3N4 and CeO2, which causes the active site C atom donating electrons to form C+, thereby enhancing the adsorption and desorption of *OOH intermediates. Additionally, the g-C3N4/CeO2-20% composite exhibits excellent 2e-ORR performance in neutral and acidic electrolytes and demonstrates superior capability in electro-Fenton degradation of organic pollutants. This study not only provides new insights into the electrocatalytic mechanism of g-C3N4/CeO2 composites but also demonstrates an effective method for designing 2e-ORR catalysts. © 2025 American Chemical Society.