Bridging Electronic Structure and C─N Coupling Mechanisms in Electrochemical Urea Synthesis

ABSTRACT Electrochemical urea synthesis (EUS) is a sustainable route for carbon‐nitrogen co‐utilization, offering an energy‐saving alternative to the Haber‐Bosch process. Recent catalyst strategies (e.g., coordination tuning, heteroatom doping, heterointerfaces) improve kinetics and selectivity by regulating active‐site electronic structures to tune adsorption strength, intermediate distribution, and electronic coupling. However, there is no unified mechanistic framework that integrates multiscale electronic‐structure modulation with the reaction pathways and electrochemical behaviors that govern urea formation. This review aims to bridge this gap by establishing a comprehensive framework that links electronic‐structure regulation to the reaction mechanisms in EUS. We first summarize representative pathways for the co‐reduction of CO 2 with various nitrogen feedstocks, highlighting how adsorption configurations, binding strengths, and intermediate distributions influence electrochemical performances. We then discuss how key energy‐level electronic descriptors govern adsorption strength, activation barriers, and catalytic stability. Furthermore, we examine how charge‐distribution characteristics regulate interfacial interactions and dynamic reaction kinetics. Finally, we outline key challenges and opportunities for integrating theoretical predictions, operando characterization, and electronic‐structure engineering to achieve efficient, selective, and scalable urea electrosynthesis. Overall, this review provides a cohesive framework that links electronic‐structure design to the fundamental chemistry of EUS, offering mechanistic insights and guidance for the rational development of next‐generation urea electrocatalysts.