Engineering Lewis‐Acidic Fields to Couple Proton Supply With Nitrate Activation: Boosting Neutral Kinetics

ABSTRACT The inadequate coordination at the solid–liquid interface imposes a fundamental limitation on nitrate electroreduction under neutral conditions, highlighting the urgent need for deliberate interfacial reorganization. Herein, a Lewis‐acidic field is constructed within spinel Co 3 O 4 by doping Zr via a lattice‐confined pyrolysis strategy, enabling synergistic coupling of proton dynamics with nitrate activation. The high‐valent Zr 4+ centers enrich nitrate electrostatically and reorganize the interfacial hydrogen‐bond network to accelerate water dissociation, while Zr‐induced lattice strain further activates Co sites, jointly elevating the turnover frequency. As a result, the optimized Zr‐Co 3 O 4 catalyst achieves a near‐unity ammonia Faradaic efficiency of 99.5% at −0.7 V vs. RHE and an impressive yield rate of 15.7 mg h −1 cm −2 at −0.9 V vs. RHE in a neutral electrolyte. This work establishes localized acidic‐field engineering as a general strategy to overcome intrinsic kinetic limitations in neutral‐pH electrosynthesis.