Main‐Group Elements Enhance Electrochemical Nitrogen Reduction Reaction of Vanadium‐Based Single Atom Catalysts Through d‐p Orbital Hybridization

Developing active sites with flexibility and diversity is crucial for single atom catalysts (SACs) towards sustainable nitrogen fixation at ambient conditions. Herein, the effects of doping main group metal elements (MGM) on the stability, catalytic activity, and selectivity of vanadium‐based SACs is systematically investigated based on density functional theory calculations. It is found that the catalytic activity of V site can be significantly enhanced by the synergistic effect between MGM and vanadium atoms. More importantly, a volcano curve between the catalytic activity and the adsorption free energy of NNH* can be established, in which V−Pb dimer embedded on N‐coordinated graphene (VPb‐NG) exhibits optimal NRR activity due to its location at the top of volcano. Further analysis of electronic structures reveals that the unoccupancy ratio (e g /t 2 g) of V site is dramatically increased by the strong d‐p orbital hybridization between V and Pb atoms, subsequently, N 2 is activated to a larger extent. These interesting findings may provide a new path for designing active sites in SACs with excellent performance.