Dual Electron Donating Metal‐Boron Reaction Center Boosts Electrocatalytic Urea Synthesis from N2 and CO2

Abstract Urea (NH 2 CONH 2 ) production by electrosynthesis at mild conditions has been hampered due to the lack of systematic evaluation of pathways in effectively activating inert N 2 and CO 2 molecules and facilitating the formation of C−N bonds. In this work, we evaluated 16 transition metal (M) atoms anchored on carbon nitride nanosheet with boron (B) doping (M−B@C 2 N) for boosting urea production by theoretical calculations. All possible urea synthesis pathways, ( i ) CO 2 pathway, ( ii ) OCOH pathway, ( iii ) CO pathway, and ( iv ) NCON pathway, were comparatively studied on Cu, Fe, Co, Ni−B@C 2 N. This systematic calculation identified that the first reduction of *N 2 is the key step for urea synthesis. We found that the bond index of *N 2 shows a strong correlation with ΔG *N2→*NNH , so they are promising descriptors for screening. Through the screening, we found that Nb‐ and Mo−B@C 2 N show a low limiting potential of −0.56 and −0.53 V. Although previous studies found that spin could promote C−C bond formation on M−B@C 2 N, we found that for C−N coupling, such effects by spin were only active for Nb−B@C 2 N. Combining boron and early transition metal atoms allows for neighboring reaction sites that simultaneously donate electrons to activate inert N 2 and CO 2 for efficient urea synthesis.