Single Atom Catalysis for Hydrogen Evolution Reaction using Transition‐metal Atoms Doped g‐C3N3: A Density Functional Theory Study

Abstract Single transition‐metal atom coordinated graphite carbon nitride, including the metal atom doped g‐C 3 N 4 system, displays catalytic activity comparable to that of the noble metal Pt catalyst with outstanding performance. Herein, we investigate the single atom catalytic performance of g‐C 3 N 3 embedded by a single transition metal atom (M−C 3 N 3 ; M=Mn, Fe, Co, Ni, Cu, Rh, Pd, Ag, and Pt) for hydrogen evolution reaction (HER) using density functional theory (DFT) calculations. The results indicate that all the M−C 3 N 3 catalysts are thermally and dynamically stable systems. By comparing the Gibbs free energies, we found that the Rh−C 3 N 3 catalyst exhibits the best HER electrocatalytic performance among the investigated systems. Subsequently, analysis of electronic structure indicates that the Rh−C 3 N 3 system displays a metallic behavior, which is a beneficial feature for an adequate HER electrocatalyst. Finally, the charge density difference of the Rh−C 3 N 3 structure further supports the rationality of our results. This study provides a new candidate of low‐cost, high‐performance, and highly active non‐noble metal electrocatalysts.