Electrochemical C‐N Coupling on Tri‐metallic Mo‐embedded Graphdiyne towards Efficient Urea Synthesis

Abstract Synthesis of urea by electrochemical C−N coupling is a promising alternative to the conventional approaches. A metal‐cluster catalyst generally possesses multi‐atomic active sites and can achieve co‐adsorption and activation of several species. As a two‐dimensional porous material, graphdiyne (GDY) is predicated to be a good substrate for loading a metal cluster. In this study, tri‐metallic Mo‐embedded graphdiyne (Mo 3 @GDY) stands out for efficient urea synthesis among several TM 3 @GDY (TM=Mo, Fe, Co, Ni and Cu), based on density functional theory (DFT) computations. The co‐adsorption of side‐on N 2 and end‐on CO on Mo 3 @GDY is benefit to the formation of the urea precursor *NCON with a negative free energy change (−0.66 eV). The final hydrogenation step is the potential‐determining step (PDS) with a medium onset potential (‐0.71 V). This work extends the application of GDY and first provides a new approach for the electrochemical synthesis of urea by loading tri‐metallic atoms on GDY.