Interface-engineered PBA-derived Cu/Co/Fe oxide heterostructures for d-band-center-regulated ampere-level tandem nitrate-to-ammonia electrosynthesis

Electrochemical nitrate reduction reaction (NO 3 − RR) offers a sustainable route for ammonia production while simultaneously mitigating nitrate pollution. However, the simultaneous realization of near-unity selectivity and industrially relevant current density remains challenging because it requires precise regulation of multistep intermediate conversion and interfacial electronic structure. Here, we report a family of Prussian blue analogue-derived Cu/Co/Fe oxide heterostructures as compositionally programmable hybrid materials for high-rate nitrate-to-ammonia electrosynthesis. By tuning the Cu/Co ratio, the heterointerface coupling and associated d-band-center modulation can be rationally regulated to optimize *NO x adsorption and sequential hydrogenation. Among them, the Cu 1 Co 1 FeO catalyst demonstrates exceptional performance, achieving a Faradaic efficiency toward NH 3 of 99.1%, a yield rate of 0.89 mmol h − 1 cm − 2 at − 0.25 V vs. RHE, while sustaining stable operation for 90 h at 2 A cm − 2 . Operando Raman and FTIR spectroscopy reveal the dynamic evolution of surface Cu–OH and Co(OH) 2 interfacial species under working conditions, which synergistically promote NO 3 − activation and *NO 2 − hydrogenation, respectively. Density-functional-theory calculations further indicate that heterostructure coupling together with Co incorporation shifts the d-band center to an optimal regime, balancing *NO x adsorption, lowering the barrier for nitrate reduction, and suppressing poisoning and competitive hydrogen evolution under high-flux operation. This work establishes a structure-property-performance relationship for Cu–Co cooperative catalysis in multicomponent oxide heterostructures and highlights PBA-derived hybrid materials as a scalable platform for interface-engineered electrocatalysis and sustainable ammonia synthesis under industrially relevant current-density regime. A Prussian blue analogue-derived ternary oxide heterostructure enables ampere-level tandem nitrate-to-ammonia electrosynthesis through cooperative Cu–Co catalysis. Heterointerface coupling modulates the d-band center to optimize*NO x adsorption, while dynamically reconstructed Cu- and Co--associated surface species selectively promote NO 3 − activation and *NO 2 − hydrogenation, respectively, thereby accelerating nitrate-to-ammonia conversion at high current densities with sustained stability. This work highlights interface- and composition-engineered hybrid oxide heterostructures as a viable platform for high-rate, selective nitrate electroreduction