Balancing Intermediates Formation on Atomically Pd‐Bridged Cu/Cu2O Interfaces for Kinetics‐Matching Electrocatalytic C‐N Coupling Reaction

The electrochemical C‐N coupling of CO2 and nitrogenous species provides a promising approach for synthesizing valuable chemicals such as urea, amides, and other C‐N compounds. However, the unbalanced formation of C‐ and N‐intermediates results in slow C‐N coupling kinetics. Herein, we report an atomically Pd‐bridged Cu/Cu2O (Pd1‐Cu/Cu2O) catalyst, synthesized through the in situ electrochemical reconstruction of Pd1‐Cu2Te nanosheets. This catalyst features Pd‐Cu dual sites that significantly enhance C‐N coupling both thermodynamically and kinetically. The reconstructed Pd1‐Cu/Cu2O achieves a urea yield rate of 31.8 mmol h‐1 gcat.‐1 and a Faradaic efficiency (FE) of 42.2%, along with excellent stability over 100 h. In situ spectroscopic examinations and theoretical calculations disclose that the Pd‐Cu dual sites on Pd1‐Cu/Cu2O modulate the reduction kinetics of CO2 and NO3‐, balance the formation of crucial *CO and *NH2 intermediates, and lower the energy barrier for C‐N coupling, thereby facilitating urea synthesis. Furthermore, the Pd1‐Cu/Cu2O enables the unprecedented C‐N coupling of aniline with CO, resulting in a remarkable acetanilide yield rate of 1021.2 mmol h‐1 gcat.‐1 with an FE of 23.7%. This heteroatom bridging strategy offers a new pathway for designing efficient electrocatalyst for the synthesis of C‐N coupled compounds.