Electrocatalytic urea synthesis has emerged as a promising green strategy for sustainable urea production. This review focuses on the recent research advances in urea electrosynthesis from CO₂ with small nitrogenous molecules. The catalyst design strategies, reaction mechanisms, and performance optimization are discussed, future challenges and opportunities are also highlighted.

Abstract

Electrocatalytic urea synthesis has emerged as a promising green strategy for sustainable nitrogen and carbon utilization, which is achieved by coupling CO₂ with small nitrogenous molecules (e.g., N₂, NO₃⁻, NO₂⁻) to form C─N bonds under mild conditions. This review systematically summarizes recent research advances in electrocatalytic urea synthesis, with a focus on catalyst design strategies, reaction mechanisms, and performance optimization. First, diverse catalytic synthesis approaches, such as vacancy engineering, heteroatom doping, crystal facet engineering, atomic-scale modulation, alloying, and heterostructure construction are analyzed to assess their impact on catalytic activity, selectivity, and stability. Then, mechanistic insights into C─N coupling reactions are discussed, including key reaction intermediates, proton-coupled electron transfer processes, and the influence of catalytic active sites on product selectivity. Next, advanced characterization techniques and detection methods for the precise quantification of urea are reviewed. Finally, future challenges and opportunities in electrocatalytic urea synthesis are highlighted. This review aims to provide a comprehensive understanding of electrocatalytic urea synthesis and to guide the rational design of efficient catalysts, thereby accelerating the development of sustainable urea production.