Microscopic Diffusion of Atomic Hydrogen and Water in HER Catalyst MoS₂ Revealed by Neutron Scattering

The design of novel and abundant catalytic materials for electrolysis is crucial for reaching carbon neutrality of the global energy system. A deliberate approach to catalyst design requires both theoretical and experimental knowledge not only of the target reactions but also of the supplementary mechanisms affecting the catalytic activity. In this study, we focus on the interplay of hydrogen mobility and reactivity in the hydrogen evolution reaction catalyst MoS₂. We have studied the diffusion of atomic hydrogen and water by means of neutron and X-ray photoelectron spectroscopies combined with classical molecular dynamics simulations. The observed interaction of water with single-crystal MoS₂ shows the possibility of intercalation within volume defects, where it can access edge sites of the material. Our surface studies also demonstrate that atomic hydrogen can be inserted into MoS₂, where it then occupies various adsorption sites, possibly favoring defect vicinities. The motion of H atoms parallel to the layers of MoS₂ is fast with D ≈ 1 × 10^-9 m²/s at room temperature and exhibits Brownian diffusion behavior with little dependence on temperature, i.e., with a very low diffusion activation barrier.