Computational investigation of hydrogen evolution reaction on transition metal-doped monolayer VSe₂: A DFT approach

Density functional theory (DFT) was used to investigate the hydrogen evolution reaction (HER) on monolayer VSe₂ doped by transition metal (TM) (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rh, Ir), in which Se or V is replaced by TM atoms (denoted as TM@Se or TM@V). Introducing transition metals (TMs) into the VSe₂ monolayer can alter its electronic structure and catalytic properties. The choice of transition metal dopants and their configurations can significantly impact the catalytic performance of the material. It is illustrated that the TM@V systems are more stable than TM@Se configurations. Moreover, Co@V, Cu@V, Fe@V Zn@V and Cu@Se exhibit the lower ΔG_H* values of 0.07, 0.09, 0.10, 0.12 and −0.1 eV, respectively, and ΔG_H* values are very close to the ideal value of zero and are superior to precious metal Pt (ΔG_H* = −0.1eV). Based on the scaling relationship of ΔG_H* of H* intermediate, the volcano diagram and exchange current density diagram are established. It is predicted that Cu@V, Co@V, Fe@V, Zn@V structures could provide large exchange current of −1.6, −1.22, −1.7, −2 i₀/(Acm⁻²), respectively.