Dataset for 'Controlling Mixed Mo/MoS₂ Domains on Si by Molecular Beam Epitaxy for the Hydrogen Evolution Reaction'

Molybdenum disulfide (MoS₂) is a prototypical layered transition-metal dichalcogenide whose electrocatalytic performance is governed by a delicate balance between crystallinity, defect density, and electronic conductivity. Here we report a systematic molecular beam epitaxy (MBE) study in which annealing temperature, deposition cycle number, and Mo/S thickness ratio were independently varied to control the structural and electronic properties of MoS₂ thin films. The successful epitaxial growth of atomically uniform MoS₂ directly on Si substrates enables strong interfacial coupling and efficient charge transfer, offering a viable route toward semiconductor-integrated catalytic architectures. X-ray diffraction, Raman spectroscopy, and X-ray absorption analyses reveal that higher annealing temperatures and excessive deposition cycles enhance crystallinity but reduce edge-site density and electrical conductivity, leading to diminished hydrogen evolution reaction (HER) activity. In contrast, intermediate cycle numbers and sulfur-deficient growth conditions yield heterostructures composed of MoS₂ with residual metallic Mo and sulfur vacancies, which activate otherwise inert basal planes while providing conductive pathways. These defect-engineered films deliver the best catalytic performance, achieving overpotentials as low as −0.33 V at −10 mA cm⁻², enlarged electrochemical surface area (ECSA) up to 8.0 cm², and mass-based turnover frequencies exceeding 23 mmol H₂ g⁻¹ s⁻¹, more than double those of stoichiometric counterparts. Our findings establish sulfur stoichiometry and growth kinetics as powerful levers to tune the interplay between structural order and catalytic activity in MBE-grown MoS₂ and point toward a broader strategy for engineering layered catalysts at the atomic scale.