Abstract

The effects of the sulfidation atmosphere on the local structure and intrinsic activity of the active sites, Co–Mo–S, are studied with SiO 2-supported Co–Mo sulfide catalysts prepared by a chemical vapor deposition method using Co(CO) 3NO. The Co–Mo sulfide catalysts were sulfided in a stream of 10% H 2S/H 2 or 10% H 2S/He or their combinations. The intrinsic activity of Co–Mo/SiO 2 presulfided in H 2S/He is 1.6 times as high as that of Co–Mo–S Type II presulfided in H 2S/H 2 for the hydrodesulfurization (HDS) of thiophene, demonstrating that the location and/or local structure of Co–Mo–S are varied by the sulfidation atmosphere as well as by the MoS 2-support interaction. The catalysts were characterized by X-ray absorption fine structure and transmission electron microscope. It is suggested that the intrinsic activities of Co–Mo–S on the S-edge and Mo-edge of MoS 2 particles are distinctly different for HDS. Extended X-ray absorption fine structure analysis shows a good correlation between the coordination number of Co–S and the intrinsic activity of “active Co–Mo–S”.

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