Computational screening of nonmetal dopants to active MoS2 basal-plane for hydrogen evolution reaction via structural descriptor

Nonmetal doping is an efficient approach to activate inert MoS2 basal plane, which converts MoS2 into an electrocatalyst for the hydrogen evolution reaction (HER). However, the trial-and-error approach through experimental attempt is still a common practice to search for suitable nonmetal dopants. In this work, we employ density functional theory (DFT) and microkinetic model to assess alkaline HER activity of nonmetal-modified MoS2(0 0 1), which show strong variation in the degree of activation by single- or double-dopants across nonmetal element series (B, C, N, P, O, S, Se and Te). To assist the screening of nonmetal dopants to active MoS2 basal plane, a structural descriptor-based prediction model is constructed. It demonstrates that the activation effect of nonmetal dopant is achieved through the adjustment of valence electron occupancy of reaction center, which tunes the adsorption energy of atomic hydrogen and hydroxide radical, and accordingly reaction kinetic for alkaline HER. The structural descriptor-based prediction model reproduce the activity trend among non-metallic doped MoS2 from available experimental references. In addition, we screened out MoS2 modified by BTe and BSe double dopants with lower overpotential than reported nonmetal-modified MoS2 systems. This work gives a deep insight into activation mechanism of nonmetal dopant for MoS2, and provides an efficient screening strategy for future catalyst design of transition metal dichalcogenides.