A density functional theory study of the hydrodesulfurization reaction of dibenzothiophene to biphenyl on a single-layer NiMoS cluster

Abstract The hydrodesulfurization of dibenzothiophene on a NiMoS cluster consisting of 1 Ni and 18 Mo atoms was investigated by means of density functional theory. The calculations focus on the direct desulfurization pathway where dibenzothiophene reacts with H 2 to biphenyl and H 2 S. Critical steps with high activation energies are breaking of the two C–S bonds of the DBT molecule (ca. 32 kcal/mol), the activation of H 2 by heterolytic dissociation and the removal of the formed biphenyl molecule from the catalyst surface (17 kcal/mol, respectively). All other reaction steps have activation energies of ≤10 kcal/mol.

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