Modifying microscopic structures of MoS2 by high pressure and high temperature used in hydrogen evolution reaction

•High pressure and high temperature were utilized to modify microscopic structures.•Stacking faults can sharply reduce the transfer resistance of electrons in MoS2.•Distortions were uncovered, which can activate the basal plane of MoS2.•Modifying the microscopic structures is an effective way to promote HER. MoS2 is a classical catalyst for hydrogen evolution reaction (HER), but the performance is limited by poor electrical transport in c axis, and absent of active sites in (001) planes (basal planes). Simultaneously enhance the layer's interaction and activate the basal plane in MoS2 is urgent. In this work, a new sight of high pressure and high temperature (HPHT) was presented to modify the microscopic structures, and finally promoting the connection among the layers and activate the basal planes in bulk MoS2. It is found that high pressure generates shear between grains, and results stacking faults in structures. The stacking faults can enhance interaction between MoS2 sandwich layers, and reduce the charge transfer resistance. An intermediate state was captured, which exhibits distortions in structure at 3 GPa, 200 °C. The distortions cause longer or shorter Mo-S bonds, which introduce strains to activate the basal plane. Density functional theory (DFT) calculations show that the distortions can effective reduced the adsorption free energy of H* in MoS2 basal plane from 1.92 eV to 0.33 eV. So the activity of MoS2 was modified by HPHT, which indicates better activity than commercial MoS2. This work is not only significant to activate catalyst by HPHT, but also important to promote the functional materials.