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.
Keywords: activity and selectivity; hydrogen peroxide electrosynthesis; oxygen reduction; proton affinity; single atom catalyst.
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