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

• Published in: ChemCatChem 2023-10, Vol.15 (20), p.n/a
• Main Authors: Jin, Mingzhu, Wu, Shuang, Du, Aijun, Fan, Jianfen, Sun, Qiao
• Format: Article
• Language: English
• Subjects: Adsorption; C-N coupling; Chemical synthesis; Coupling; Density functional theory; Electrocatalysis; Free energy; Metal clusters; Mo3@GDY; Porous materials; Substrates; Urea production; Ureas
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.202300836

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 (Mo3@GDY) stands out for efficient urea synthesis among several TM3@GDY (TM=Mo, Fe, Co, Ni and Cu), based on density functional theory (DFT) computations. The co‐adsorption of side‐on N2 and end‐on CO on Mo3@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. This study provides a new two‐dimensional C−N coupling catalyst for urea production by loading three Mo‐atoms on graphdiyne.