Boosting Active Hydrogen Supply via Pyridinic/Pyrrolic‐N Coordination Zn‐N 4 Sites on Ultrathin Porous N‐Doped Carbon for Scalable and Salt‐Free Neutral H 2 O 2 Electrosynthesis

Abstract Neutral H 2 O 2 electrosynthesis via a two‐electron oxygen reduction reaction (2e − ‐ORR) provides a green and sustainable production avenue. However, it remains the scarcity of efficient electrocatalysts with rapid kinetics of neutral 2e − ‐ORR and well‐matched H 2 O 2 production process. Here, a Zinc‐vapor escape strategy is developed to construct pyridinic/pyrrolic‐N (Py/Pr‐N) coordinated Zn‐N 4 sites on ultrathin porous graphitic‐N‐doped carbon. The resultant catalyst achieves a record current density of 4.96 mA cm −2 at 0 V vs RHE and ≈100% selectivity of H 2 O 2 from 0 to 0.50 V vs RHE. Systematical analysis suggests that both Zn‐N 4 sites and carbon support synergistically accelerate the kinetics of water dissociation at positive potential to optimize free energy of *OOH formation due to electron transfer from Py/Pr‐N to Zn in Zn‐N 4 moieties. Integration of this catalyst into the coupled electrolysis system achieved a record H 2 O 2 yield rate of 88.97 mol g cat −1 h −1 and formic acid (FA) yield rate of 5.29 mol g cat −1 h −1 at 350 mA cm −2 . Moreover, it presents a record real‐time continuous and neutral salt‐free H 2 O 2 production concentration of 44.4 m m at 300 mA cm −2 , suggesting positive techno‐economic potential for this system. This work provides a new strategy to develop electrocatalysts and a feasible process for neutral salt‐free H 2 O 2 production, coupling with high‐added value chemicals production.