Defect and Doping Engineered Penta-graphene for Catalysis of Hydrogen Evolution Reaction

Abstract Water electrolysis is a sustainable and clean method to produce hydrogen fuel via hydrogen evolution reaction (HER). Using stable, effective and low-cost electrocatalysts for HER to substitute expensive noble metals is highly desired. In this paper, by using first-principles calculation, we designed a defect and N-, S-, P-doped penta-graphene (PG) as a two-dimensional (2D) electrocatalyst for HER, and its stability, electronic properties and catalytic performance were investigated. The Gibbs free energy (Δ G H ), which is the best descriptor for the HER, is calculated and optimized, the calculation results show that the Δ G H can be 0 eV with C2 vacancies and P doping at C1 active sites, which should be the optimal performance for a HER catalyst. Moreover, we reveal that the larger charge transfer from PG to H, the closer Δ G H is to zero according to the calculation of the electron charge density differences and Bader charges analysis. Ulteriorly, we demonstrated that the HER performance prefers the Volmer–Heyrovsky mechanism in this study.