Interfacial Electron Engineering for Nitrate-to-Ammonia Electrocatalysis: Mechanistic Insights and Design Strategies

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.