Efficient electrocatalytic H2 evolution mediated by 2D Janus MoSSe transition metal dichalcogenide

Recently, 2D JTMDs with asymmetric electronic structures are inviting an intense research interest in modern science and technology. Using the first principles-based periodic hybrid dispersion-corrected Density Functional Theory (DFT-D) method, we have investigated the equilibrium structure, geometry, and electronic properties of the 2D monolayer MoSSe JTMD with the electrocatalytic activities for the H2 evolution reaction (HER). We have performed non-periodic quantum mechanical DFT computations to find out the most favorable HER pathway on the exposed surfaces of the 2D Janus MoSSe material i.e., on the Mo-edges and S- or Se-edges. To explore the electrocatalytic HER mechanism, reaction pathways and barriers, we have considered a cluster model system Mo10S12Se9 to illustrate the Mo-edges and S- or Se-edges of the 2D monolayer MoSSe material. The present study reveals that the Volmer-Heyrovsky reaction mechanism is thermodynamically favorable reaction pathway to evolute H2 at the Se-terminated Mo-edges. It was found that the change of free energy barrier during the Heyrovsky reaction at the Se-terminated Mo-edges is about 3.93-7.10 kcal.mol-1 (in both the gas and the solvent phases), indicating an exceptional electrocatalyst for HER with the lowest activation barriers. This study showed that the Tafel slope (m) is lower in the case of 2D Janus MoSSe material due to the overlap of the s-orbital of the hydrogen and d-orbitals of the Mo atoms appeared in the HOMO and LUMO transition state TS1 of the H-migration reaction step. The better stabilization of the atomic orbitals in the HER rate-limiting step i.e., H-migration TS1 reaction step (in the solvent phase) is a key for reducing the reaction barrier, thus the overall catalysis indicating a better electrocatalytic performance for H2 evolution.