Emerging Atomistic Modeling Catalysts for C─N Electrocatalysis

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.