Abstract
Molybdenum disulfide (MoS(2)) has been demonstrated as a promising non-precious metal electrocatalyst for the hydrogen evolution reaction (HER). However the efficiency of the HER falls short of expectations due to the large inert basal plane and poor electrical conductivity. In order to activate the MoS(2) basal plane and enhance the hydrogen evolution reaction (HER) activity, two strategies on the hybrid MoS(2)/graphene, including intrinsic defects and simultaneous strain engineering, have been systematically investigated based on density functional theory calculations. We firstly investigated the HER activity of a MoS(2)/graphene hybrid material with seven types of point defect sites, V (S), V(S2), V (Mo), V (MoS3), V (MoS6), Mo(S2) and S2(Mo). Using the hydrogen adsorption free energy (ΔG (H)) as the descriptor, results demonstrate that four of these seven defects (V (S), V (S2), Mo(S2), V (MoS3)) act as a catalytic active site for the HER and exhibited superior electrocatalytic activity. More importantly, we found that ΔG (H) can be further tuned to an ideal value (0 eV) with proper tensile strain, which effectively optimizes and boosts the HER activity, especially for the V (S), V (S2), V (MoS3) defects and Mo(S2) antisite defects. Our results demonstrated that a proper combination of tensile strain and defect structure is an effective approach to achieve more catalytic active sites and further tune and boost the intrinsic activity of the active sites for HER performance. Furthermore, the emendatory d-band center of metal proves to be an excellent descriptor for determining H adsorption strength on defective MoS(2)/graphene hybrid material under different strain conditions. In addition, the low kinetic barrier of H(2) evolution indicated that the defective MoS(2)/graphene system exhibited favorable kinetic activity in both the Volmer-Heyrovsky and the Volmer-Tafel mechanism. These results may pave a new way to design novel ultrahigh-performance MoS(2)-based HER catalysts.