The relation between morphology and hydrotreating activity for supported MoS2 particles

Supported Mo-sulfide catalysts were structurally characterized by means of transmission electron microscopy (TEM), dynamic oxygen chemisorption (DOC), and EXAFS, The catalysts show the well-known MoS2 slab structures with a m ultilayered morphology in the case of Mo/SiO2 and Mo/ASA. The MoS2 edge dis persion was evaluated from the TEM micrographs. While sulfidation of Mo/Al2 O3 results in a highly dispersed, mostly single-layered MoS2 phase, a decre ased metal-support interaction (NTA addition) or use of supports with a low er metal-support interaction leads to a higher stacking degree concomitant with a loss in edge dispersion. Combined TEM and DOC results reveal that Mo /C has the highest MoS2 dispersion. Reaction rate constants corrected for M oS2 dispersion for hydrodesulfurization (HDS) and hydrogenation (HYD) of th iophene and dibenzothiophene and HYD of toluene were measured. In general, HYD rates increase with an increasing stacking degree attributed to a less hampered planar adsorption geometry of reactants on multilayered MoS2. In c ontrast to the HDS rate constant of the small thiophene molecule, the DBT H DS rate constant is also strongly dependent on the stacking degree. It is c oncluded that perpendicular adsorption via sulfur is favored for HDS of thi ophene, while in the DBT case a planar adsorption geometry is preferred. Ca rbon is the preferred support for the HYD of thiophene and toluene, most li kely due to the large fraction of corner sites. A real support effect is al so found for Mo/ASA, which exhibits low intrinsic HDS activities compensate d by very high HYD activity. The present results indicate that the selectiv ities for hydrodesulfurization and hydrogenation can be fine-tuned by the m orphology of the MoS2 phase and the choice of support. (C) 2001 Academic Pr ess.