Emerging Atomistic Modeling Catalysts for C─N Electrocatalysis

Abstract Electrochemical C─N coupling for the synthesis of high‐value chemicals, such as urea and amides, offers a significant advantage over traditional chemical methods. The latter are characterized by high energy consumption and pollution. However, the complexity of reaction intermediates and competing reactions in electrochemical C─N coupling leads to low product selectivity. In addition, Faradaic efficiency is typically below 50%. Therefore, studying intermediates and designing catalysts are crucial for improving selectivity. Atomic‐level dispersed catalysts modify the structure and composition around the central metal atoms. This results in higher atomic efficiency and catalytic selectivity. This review systematically examines the C─N coupling mechanism, from single‐step reactions to intermediate coupling processes. It then discusses the design of atomic‐level catalysts with multiple active sites from three perspectives: 1) dual‐nucleus single‐atom catalyst, 2) dual‐nucleus heterogeneous dual‐atom catalysts, and 3) dual‐nucleus heteroatomic dual‐atom catalyst. Additionally, the review highlights the applications of characterization techniques and theoretical calculations in C─N electrocatalysis. Finally, it identifies future challenges and opportunities for development in this field. The review aims to provide theoretical guidance for designing atomic‐level catalysts for electrochemical C─N coupling reactions.