Suppression of Hydrogen Evolution Reaction in Electrochemical N2 Reduction Using Single-Atom Catalysts: A Computational Guideline

We studied electrochemical nitrogen reduction reactions (NRR) to ammonia on single atom catalysts (SACs) anchored on defective graphene derivatives by density functional calculations. We find significantly improved NRR selectivity on SACs compared to that on the existing bulk metal surface due to the great suppression of the hydrogen evolution reaction (HER) on SACs with the help of the ensemble effect. In addition, several SACs, including Ti@N 4 (0.69 eV) and V@N 4 (0.87 eV), are shown to exhibit lower free energy for NRR than that of the Ru(0001) stepped surface (0.98 eV) due to a strong back-bonding between the hybridized d-orbital metal atom in SAC and π* orbital in *N 2 . Formation energies as a function of nitrogen chemical potential suggest that Ti@N 4 and V@N 4 are also synthesizable under experimental conditions.