CHARACTERIZATION OF HDS/HDN ACTIVE-SITES IN CLUSTER-DERIVED AND CONVENTIONALLY-PREPARED SULFIDE CATALYSTS

The catalytic and sorptive properties of a series of sulfide cluster-derived catalysts were compared to those of an analogous series of conventionally-prepared sulfides. The cluster-derived and conventionally-prepared catalysts had similar hydrotreatment activities and chemisorbed similar amounts of O-2 and NO. From infrared spectroscopy, it was observed that the clusters retained much of their character upon adsorption, and that the CO ligands were lost upon heating up to 350 K. Nitric oxide chemisorbed onto the bimetallic cluster-derived catalysts was initially associated with the Co sites then shifted to the Mo sites upon heating, indicating that the promoter and Mo were in close proximity. For the conventionally-prepared materials, NO adsorption suggested that the promoted and unpromoted sites behaved independently. Nitric oxide was more strongly held to the unpromoted sites in both the cluster-derived and conventionally-prepared materials. Thiophene adsorbed onto the cluster-derived and conventionally-prepared catalysts gave rise to nearly identical infrared spectra. Upon heating, the thiophene peaks disappeared and were replaced by peaks that we have attributed to a linear olefin, which is noteworthy since 1-butene was the primary product from thiophene HDS. Nitric oxide easily displaced adsorbed thiophene from the cluster-derived materials, indicating that NO and thiophene adsorbed onto the same sites.