Efficient industrial-current-density H2O2 production in neutral medium via external-shell boron regulation on single-atom VN4 sites

•An external shell B regulated nitrogen coordinated single atom vanadium sites catalyst is reasonably designed through sacrificial template strategy.•VN4B/NC showcases superior 2e− ORR performance in neutral electrolyte, with a high H2O2 selectivity of 96.6 %.•Excellent H2O2 production rate of 16.23 mmol cm−1 h−1 and nearly 90 % Faradaic efficiency are achieved at 1.1 A cm−2 in flow cell.•VN4B/NC exhibits outstanding production rate of 10.18 mmol cm−2 h−1 and durability for 100 h in solid electrolyte reactor.•Mechanism study suggests that the external shell B regulated V-N4 site optimizes the adsorption energy of pivotal intermediates (OOH*) for producing H2O2. The unamiable electrolyte environment and insufficient kinetics of electrochemical two-electron oxygen reduction reaction (2e− ORR) hinders its application in producing H2O2. To address this issue, nitrogen-coordinated single atom vanadium with external shell boron regulation is designed for efficient H2O2 production in neutral medium. The optimal catalyst VN4B/NC showcase a 2e− ORR pathway selectivity of 96.6 % in 0.1 M Na2SO4. And the high current density (1.1 A cm−2) and excellent production rate (16.23 mmol cm−1 h−1) in flow cell further confirm its superior activity. Moreover, VN4B/NC exhibits potential application in solid electrolyte reactor, which is demonstrated by the production rate of 10.18 mmol cm−1 h−1 and long-term stability up to 100 h. Mechanism study suggest the external shell B regulation optimize the adsorption of OOH* intermediates on V sites, boosting the 2e− ORR pathway. This work provides novel insights to rational design of electrocatalysts for commodity chemicals production.