Hydrogen Chemical Configuration and Thermal Stability in Tungsten Disulfide Nanoparticles Exposed to Hydrogen Plasma

The chemical configuration and interaction mechanism of hydrogen adsorbed in inorganic nanoparticles of WS₂ are investigated. Our recent approaches of using hydrogen activated by either microwave or radiofrequency plasma dramatically increased the efficiency of its adsorption on the nanoparticles surface. In the current work we make an emphasis on elucidation of the chemical configuration of the adsorbed hydrogen. This configuration is of primary importance as it affects its adsorption stability and possibility of release. To get insight on the chemical configuration, we combined the experimental analysis methods with theoretical modeling based on the density functional theory (DFT). Micro-Raman spectroscopy was used as a primary tool to elucidate chemical bonding of hydrogen and to distinguish between chemi- and physisorption. Hydrogen adsorbed in molecular form (H₂) was clearly identified in all the plasma-hydrogenated WS₂ nanoparticles samples. It was shown that the adsorbed hydrogen is generally stable under high vacuum conditions at room temperature, which implies its stability at the ambient atmosphere. A DFT model was developed to simulate the adsorption of hydrogen in the WS₂ nanoparticles. This model considers various adsorption sites and identifies the preferential locations of the adsorbed hydrogen in several WS₂ structures, demonstrating good concordance between theory and experiment and providing tools for optimizing of hydrogen exposure conditions and the type of substrate materials.