Abstract
Electrocatalytic urea synthesis is an emerging alternative technology to the traditional energy-intensive industrial urea synthesis protocol. Novel strategies are urgently needed to promote the electrocatalytic C-N coupling process and inhibit the side reactions. Here, we report a CuWO(4) catalyst with native bimetallic sites that achieves a high urea production rate (98.5 ± 3.2 μg h(-1) mg(-1)(cat)) for the co-reduction of CO(2) and NO(3)(-) with a high Faradaic efficiency (70.1 ± 2.4%) at -0.2 V versus the reversible hydrogen electrode. Mechanistic studies demonstrated that the combination of stable intermediates of *NO(2) and *CO increases the probability of C-N coupling and reduces the potential barrier, resulting in high Faradaic efficiency and low overpotential. This study provides a new perspective on achieving efficient urea electrosynthesis by stabilizing the key reaction intermediates, which may guide the design of other electrochemical systems for high-value C-N bond-containing chemicals.