Site-dependent reactivity of MoS(2) nanoparticles in hydrodesulfurization of thiophene

The catalytically active site for the removal of S from organosulfur compounds in catalytic hydrodesulfurization has been attributed to a generic site at an S-vacancy on the edge of MoS(2) particles. However, steric constraints in adsorption and variations in S-coordination means that not all S-vacancy sites should be considered equally active. Here, we use a combination of atom-resolved scanning probe microscopy and density functional theory to reveal how the generation of S-vacancies within MoS(2) nanoparticles and the subsequent adsorption of thiophene (C(4)H(4)S) depends strongly on the location on the edge of MoS(2). Thiophene adsorbs directly at open corner vacancy sites, however, we find that its adsorption at S-vacancy sites away from the MoS(2) particle corners leads to an activated and concerted displacement of neighboring edge S. This mechanism allows the reactant to self-generate a double CUS site that reduces steric effects in more constrained sites along the edge.