Hydrogen Activation on the Promoted and Unpromoted ReS2 (001) Surfaces under the Sulfidation Conditions: A First-Principles Study

Hydrogen activation, on the promoted and promoter-free ReS2(001) surfaces under the sulfidation conditions is studied by means of periodic density function theory (DFT) calculations within the generalized gradient approximation. First, surface-phase diagrams are investigated by plotting the surface free energy as a function of the chemical potential of S (mu(S)) on the unpromoted and promoted ReS2 (001) surfaces with different loadings of nickel, cobalt, tungsten, and tantalum. The results show that on the unpromoted surface sulfur coverage of 25% and On the promoted surfaces sulfur coverage of 25% as well as 25% promoter modification are the most stable conditions, respectively, under hydrodesulfurization (HDS) reaction conditions. Second, hydrogen adsorption and dissociation are explored on these preferred surfaces. It is found that hydrogen adsorbs weakly on all the surfaces studied. The physical adsorption character makes its diffusion favorable, resulting in various adsorption sites and dissociation pathways, i.e., dissociation at surface Re or promote atom, at the interlayer, as well as at the adsorbed S atom. Calculated results show that hydrogen dissociation at the surface Re site is always kinetically favorable. All of the studied dopants can largely activate the adsorbed S but display distinct roles toward the activity of the nearest Re atom; i.e., Co/Ni dopant passivates the nearest surface Re while W/Ta activates it. The activity difference is found to be closely associated with the difference in the bond strength of metal-S,and the resultant difference in the induced surface geometry. Moreover, promoter effect is localized because it seems nominal when the, reaction occurs at a Re atom with One dopant atom separation. The present results provide a rational understanding of the activity difference between the promoter-free and the promoted surfaces, which would be helpful to further understand the mechanism of HDS and to enhance the development of highly active and selective hydrotreating catalysts.