Electrocatalytic Urea Synthesis via C–N Coupling from CO 2 and Nitrogenous Species

作者：Yujie Wang, Dawei Chen, Chen Chen, Shuangyin Wang · 发表于：Accounts of Chemical Research · 年份：2023 · DOI：10.1021/acs.accounts.3c00633 · 被引用次数：145 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、CO2 Reduction Techniques and Catalysts、Carbon dioxide utilization in catalysis

Conspectus Industrial urea synthesis consists of the Haber–Bosch process to produce ammonia and the subsequent Bosch–Meiser process to produce urea. Compared to the conventional energy-intensive urea synthetic protocol, electrocatalytic C–N coupling from CO 2 and nitrogenous species emerges as a promising alternative to construct a C–N bond under ambient conditions and to realize the direct synthesis of high-value urea products via skipping the intermediate step of ammonia production. The main challenges for electrocatalytic C–N coupling lie in the intrinsic inertness of molecules and the competition with parallel side reactions. In this Account, we give an overview of our recent progress toward electrocatalytic C–N coupling from CO 2 and nitrogenous species toward urea synthesis. To begin, we present the direct transformation of dinitrogen (N 2 ) to the C–N bond by coelectrolysis, verifying the feasibility of direct urea synthesis from N 2 and CO 2 under ambient conditions. In contrast to the highly endothermic step of proton coupling in conventional N 2 reduction, the N 2 activation and construction of the C–N bond arise from a thermodynamic spontaneous reaction between CO (derived from CO 2 reduction) and *N═N* (the asterisks represent the adsorption sites), and the crucial *NCON* species mediates the interconversion of N 2, CO 2, and urea. Based on theoretical guidance, the effect of N 2 adsorption configurations on C–N coupling is investigated on the model catalysts with...