Atomic Ni─O─Zn Bridge Engineering Enables Efficient C─N Coupling for Urea Electrosynthesis

ABSTRACT Electrochemical co‐reduction of CO 2 and NO 3 − is a promising route for sustainable urea synthesis, but its efficiency is limited by kinetic mismatch between CO 2 RR and NO 3 RR, and unfavorable adsorption–migration of *CO for C─N coupling. Herein, we design a nickel single‐atom catalyst anchored on ZnO (Ni SA /ZnO) to coordinate CO 2 RR and NO 3 RR kinetics by promoting C─N coupling for efficient urea electrosynthesis. At −0.8 V versus the reversible hydrogen electrode, Ni SA /ZnO achieves urea yield rate of 41.38 mmol h −1 g cat −1 and Faradaic efficiency of 31.47%. In situ spectroscopic characterizations and density functional theory (DFT) calculations collectively reveal the formation of atomically defined Ni─O─Zn interfacial bridges, inducing charge redistribution and intrinsic electronic gradient across adjacent metal sites. This electronic heterogeneity enables spatially differentiated reaction pathways, with Ni sites favoring for CO 2 activation toward *CO formation, while neighboring Zn sites facilitate NO 3 − reduction to *NH 2 . Meanwhile, DFT calculations suggest that the interfacial electronic gradient thermodynamically drives *CO migration from Ni to Zn sites, which co‐localizes the key intermediates with a lowered barrier for subsequent C─N coupling. This work demonstrates that atomic‐scale interfacial bridge engineering can overcome kinetic bottlenecks in sustainable urea electrosynthesis, providing a general principle for regulating intermediate spillover and coupling in multistep electrocatalysis.