Efficient urea electrosynthesis from carbon dioxide and nitrate via alternating Cu–W bimetallic C–N coupling sites

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. Electrocatalytic urea synthesis is an emerging alternative technology to the traditional urea synthesis protocol. Here, a CuWO 4 catalyst with native bimetallic sites achieves efficient co-reduction of carbon dioxide and nitrate to urea by stabilizing intermediates of *NO 2 and *CO for C–N coupling.