Interfacial Electronic Interactions Promoted Activation for Nitrate Electroreduction to Ammonia over Ag‐Modified Co3O4

Abstract Electrocatalytic nitrate (NO 3 − ) reduction to ammonia (NRA) offers a promising pathway for ammonia synthesis. The interfacial electronic interactions (IEIs) can regulate the physicochemical capabilities of catalysts in electrochemical applications, while the impact of IEIs on electrocatalytic NRA remains largely unexplored in current literature. In this study, the high‐efficiency electrode Ag‐modified Co 3 O 4 (Ag 1.5 Co/CC) is prepared for NRA in neutral media, exhibiting an impressive nitrate conversion rate of 96.86 %, ammonia Faradaic efficiency of 96.11 %, and ammonia selectivity of ~100 %. Notably, the intrinsic activity of Ag 1.5 Co/CC is ~81 times that of Ag nanoparticles (Ag/CC). Multiple characterizations and theoretical computations confirm the presence of IEIs between Ag and Co 3 O 4 , which stabilize the CoO 6 octahedrons within Co 3 O 4 and significantly promote the adsorption of reactants (NO 3 − ) as well as intermediates (NO 2 − and NO), while suppressing the Heyrovsky step, thereby improving nitrate electroreduction efficiency. Furthermore, our findings reveal a synergistic effect between different active sites that enables tandem catalysis for NRA: NO 3 − reduction to NO 2 − predominantly occurs at Ag sites while NO 2 − tends to hydrogenate to ammonia at Co sites. This study offers valuable insights for the development of high‐performance NRA electrocatalysts.