Balancing Intermediates Formation on Atomically Pd‐Bridged Cu/Cu 2 O Interfaces for Kinetics‐Matching Electrocatalytic C─N Coupling Reaction

Abstract The electrochemical C─N coupling of CO 2 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/Cu 2 O (Pd 1 –Cu/Cu 2 O) catalyst, synthesized through the in situ electrochemical reconstruction of Pd 1 –Cu 2 Te nanosheets. This catalyst features Pd–Cu dual sites that significantly enhance C─N coupling both thermodynamically and kinetically. The reconstructed Pd 1 –Cu/Cu 2 O achieves a urea yield rate of 31.8 mmol h −1 g cat. −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 Pd 1 –Cu/Cu 2 O modulate the reduction kinetics of CO 2 and NO 3 − , balance the formation of crucial *CO and *NH 2 intermediates, and lower the energy barrier for C─N coupling, thereby facilitating urea synthesis. Furthermore, the Pd 1 –Cu/Cu 2 O enables the unprecedented C─N coupling of aniline with CO, resulting in a remarkable acetanilide yield rate of 1021.2 mmol h −1 g cat. −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.