The quest for sustainable urea production has directed attention toward electrocatalytic methods that bypass the energy-intensive traditional Haber-Bosch process. This study introduces an approach to urea synthesis through the coreduction of CO2 and NO3- using copper-doped molybdenum diselenide (Cu-MoSe2) with Cu-Mo dual sites as electrocatalysts. The electrocatalytic activity of the Cu-MoSe2 electrode is characterized by a urea yield rate of 1235 μg h-1 mgcat.-1 at -0.7 V versus the reversible hydrogen electrode and a maximum Faradaic efficiency of 23.43% at -0.6 V versus RHE. Besides, a continuous urea production with an enhanced average yield rate of 9145 μg h-1 mgcat.-1 can be achieved in a flow cell. These figures represent a substantial advancement over that of the baseline MoSe2 electrode. Density functional theory (DFT) calculations elucidate that Cu doping accelerates *NO2 deoxygenation and significantly decreases the energy barriers for C-N bond formation. Consequently, Cu-MoSe2 demonstrates a more favorable pathway for urea production, enhancing both the efficiency and feasibility of the process. This study offers valuable insights into electrode design and understanding of the facilitated electrochemical pathways.
Keywords: C−N coupling; dual sites; heteroatom-doping; transition metal dichalcogenides; urea synthesis.