Site-dependent reactivity of MoS2 nanoparticles in hydrodesulfurization of thiophene Salazar Moreira, Norberto José Rangarajan, Srinivas Rodríguez Fernández, Jonathan Mavrikakis, Manos Lauritsen, Jeppe V. N.S. and J.R.F. performed the experiments. N.S. analyzed the experimental data. S.R. performed the theory. J.V.L. and M.M. planned and organized the studies. N.S. wrote the first draft. J.V.L. wrote the final version. All authors contributed to the final version of the manuscript. 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 MoS2 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 MoS2 nanoparticles and the subsequent adsorption of thiophene (C4H4S) depends strongly on the location on the edge of MoS2. Thiophene adsorbs directly at open corner vacancy sites, however, we find that its adsorption at S-vacancy sites away from the MoS2 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. 2020-11-19T11:14:52Z 2020-11-19T11:14:52Z 2020-08-31 journal article Salazar, N., Rangarajan, S., Rodríguez-Fernández, J. et al. Site-dependent reactivity of MoS2 nanoparticles in hydrodesulfurization of thiophene. Nat Commun 11, 4369 (2020). [https://doi.org/10.1038/s41467-020-18183-4] http://hdl.handle.net/10481/64346 10.1038/s41467-020-18183-4 eng http://creativecommons.org/licenses/by/3.0/es/ open access Atribución 3.0 España Nature Communications