Dual-Native Vacancy Activated Basal Plane and Conductivity of MoSe2 with High-Efficiency Hydrogen Evolution Reaction

Abstract

Although transition metal dichalcogenide MoSe₂ is recognized as one of the low-cost and efficient electrocatalysts for the hydrogen evolution reaction (HER), its thermodynamically stable basal plane and semiconducting property still hamper the electrocatalytic activity. Here, it is demonstrated that the basal plane and edges of 2H-MoSe₂ toward HER can be activated by introducing dual-native vacancy. The first-principle calculations indicate that both the Se and Mo vacancies together activate the electrocatalytic sites in the basal plane and edges of MoSe₂ with the optimal hydrogen adsorption free energy (ΔG_H* ) of 0 eV. Experimentally, 2D MoSe₂ nanosheet arrays with a large amount of dual-native vacancies are fabricated as a catalytic working electrode, which possesses an overpotential of 126 mV at a current density of 100 mV cm^-2 , a Tafel slope of 38 mV dec^-1 , and an excellent long-term durability. The findings pave a rational pathway to trigger the activity of inert MoSe₂ toward HER and also can be extended to other layered dichalcogenide.

Keywords: CVD; HER; MoSe2; catalysis; dual vacancies; first-principles calculations.