Tuning Proton Affinity on Co−N−C Atomic Interface to Disentangle Activity‐Selectivity Trade‐off in Acidic Oxygen Reduction to H₂O₂

In oxygen reduction reaction to H₂O₂ via two-electron pathway (2e^- ORR), adsorption strength of oxygen-containing intermediates determines both catalytic activity and selectivity. However, it also causes activity-selectivity trade-off. Herein, we propose a novel strategy through modulating the interaction between protons and *OOH intermediates to break the activity-selectivity trade-off for highly active and selective 2e^- ORR. Taking the typical cobalt-nitrogen-carbon single-atom catalyst as an example, boron heteroatoms doped into second coordination sphere of CoN₄ (Co₁-NBC) increase proton affinity on catalyst surface, facilitating proton attack on the former oxygen of *OOH and thereby promoting H₂O₂ formation. As a result, Co₁-NBC simultaneously achieves prominent 2e^- ORR activity and selectivity in acid with onset potential of 0.724 V vs. RHE and H₂O₂ selectivity of 94 %, surpassing most reported catalysts. Furthermore, Co₁-NBC exhibits a remarkable H₂O₂ productivity of 202.7 mg cm^-2 h^-1 and a remarkable stability of 60 h at 200 mA cm^-2 in flow cell. This work provides new insights into resolving activity-selectivity trade-off in electrocatalysis.