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

Abstract

Electrochemical co‐reduction of CO2 and NO3− is a promising route for sustainable urea synthesis, but its efficiency is limited by kinetic mismatch between CO2RR and NO3RR, and unfavorable adsorption–migration of *CO for C─N coupling. Herein, we design a nickel single‐atom catalyst anchored on ZnO (NiSA/ZnO) to coordinate CO2RR and NO3RR kinetics by promoting C─N coupling for efficient urea electrosynthesis. At −0.8 V versus the reversible hydrogen electrode, NiSA/ZnO achieves urea yield rate of 41.38 mmol h−1 gcat−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 CO2 activation toward *CO formation, while neighboring Zn sites facilitate NO3− reduction to *NH2. 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.