Promoting the Intermediates Hydrogenation for Urea Electrosynthesis over an “Active Hydrogen Pump” Catalyst

Electrocatalytic coupling of CO2 and NO3− offers a sustainable approach for urea production. However, the limited supply of active hydrogen (*H) hinders the formation of the key carbon‐ and nitrogen‐containing intermediates, thus impeding the selective C‒N coupling. Herein, we developed copper molybdate (Cu3Mo2O9) nanorods, which could serve as “active hydrogen pump” catalysts by regulating the water dissociation and hydrogen adsorption. Such electrocatalyst would guarantee a steady *H supply for intermediates hydrogenation, hence boosting the generation of *CO and *NH2 intermediates for selective C‒N coupling and urea production. In a CO2‐saturated 0.1 M KNO3 solution, Cu3Mo2O9 achieved a maximum urea yield rate of 177 mmol h−1 g−1 with a urea‐producing FE of 40% in a flow cell configuration, outperforming most reported electrocatalysts. This study underscores the crucial role of *H, which may guide the exploration of advanced catalysts for expediting the sustainable synthesis of indispensable chemicals requiring rapid intermediates hydrogenation.