The electrocatalytic nitrate reduction reaction (NO3RR) enables sustainable ammonia synthesis from nitrate waste, yet its complex mechanism and severe competition from the hydrogen evolution reaction (HER) demand precise control over interfacial electronic structures. This review provides a mechanistic overview of interfacial electron engineering for NO3RR via charge transfer, d-band center modulation, and d-p orbital coupling. We propose a reverse-engineering framework that starts from the three kinetic bottlenecks of NO3RR (nitrate activation, *H supply, and intermediate poisoning) and back-extracts the required electronic effects (charge transfer, d-band shift, and d-p orbital coupling). From this perspective, we cover the construction of built-in electric fields (BIEFs) in heterojunctions, engineering atomic-scale active sites (e.g., single-atom and dual-atom catalysts), and exploiting hydrogen spillover and reverse spillover for cross-spatial proton delivery. Given that rational interfaces dynamically evolve under operating conditions, we highlight that in situ/operando characterization captures the dynamic restructuring of valence states, coordination environments, and morphologies, establishing clear structure–electron–activity relationships. Finally, we discuss key challenges and outline future directions, including machine learning-accelerated screening, dynamic interface regulation, and synergistic integration of multiple electronic effects. This review offers a comprehensive framework for interfacial electron engineering, guiding rational design of next-generation NO3RR electrocatalysts.
Liu et al. (Sun,) studied this question.