Uniting Synergistic Effect of Single‐Ni Site and Electric Field of B‐ Bridged‐N for Boosted Electrocatalytic Nitrate Reduction to Ammonia

Abstract Electrochemical conversion of nitrate, a prevalent water pollutant, to ammonia (NH 3 ) is a delocalized and green path for NH 3 production. Despite the existence of different nitrate reduction pathways, selectively directing the reaction pathway on the road to NH 3 is now hindered by the absence of efficient catalysts. Single‐atom catalysts (SACs) are extensively investigated in a wide range of catalytic processes. However, their application in electrocatalytic nitrate reduction reaction (NO 3 − RR) to NH 3 is infrequent, mostly due to their pronounced inclination toward hydrogen evolution reaction (HER). Here, Ni single atoms on the electrochemically active carrier boron, nitrogen doped‐graphene (BNG) matrix to modulate the atomic coordination structure through a boron‐spanning strategy to enhance the performance of NO 3 − RR is designed. Density functional theory (DFT) study proposes that BNG supports with ionic characteristics, offer a surplus electric field effect as compared to N‐doped graphene, which can ease the nitrate adsorption. Consistent with the theoretical studies, the as‐obtained NiSA@BNG shows higher catalytic activity with a maximal NH 3 yield rate of 168 µg h −1 cm −2 along with Faradaic efficiency of 95% and promising electrochemical stability. This study reveals novel ways to rationally fabricate SACs' atomic coordination structure with tunable electronic properties to enhance electrocatalytic performance.