Syngas and HDS catalysts derived from sulphido bimetallic clusters

Abstract

The clusters, CP2'Mo2Fe2S2(CO)8 (MoFeS) and Cp2'Mo2CO2S3(CO)4 (MoCoS) (Cp' = [eta]-C5H4Me) have been supported on the refractory oxides, Al2O3, SiO2, TiO2, and MgO, and subjected to temperature programmed decomposition (TPDE) under flowing H2. Typically, CO evolution commences near 100[deg]C, followed by evolution of 1-2 Cp-ligands from 180 to 400[deg]C along with small amounts of CO2, CH4, and H2S or Me2S. The resulting compositions are shown to be active catalysts for CO hydrogenation and hydrodesulphurization (HDS) of thiophene. Methane is the principal hydrocarbon product from CO hydrogenation except for MoFeS/MgO where high selectivity for C2 products was observed. The activity and selectivity of MoCoS/Al2O3 for thiophene HDS closely resembles those of conventionally prepared "cobalt molybdate" catalysts. The cluster derived catalysts have been characterized by Mossbauer and X-ray absorption (XANES) and EXAFS) spectroscopies. It is concluded that the clusters undergo oxidation by the surface upon loss of organic ligands.AbstractThe results obtained to date show that sulphido bimetallic clusters are excellent precursors for the formation of uniform catalytic surfaces. The uniformity of the surface species facilitates physical characterization of the active site(s). Our results show that the supported clusters are transformed to surface oxo-ensembles which are active for CO hydrogenation and HDS of organic sulphur compounds.