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The sulfidation of disk-shaped MOO, particles with a thickness of 5-10 nm supported on a 5-nm-thick layer of Si02 on Si(100) in a mixture of 10% H2S in H2 at atmospheric pressure has been studied as a function of temperature. XPS and SIMS indicate the formation of Mo4+OS, at the surface and Mo(1V) oxides (probably H1.6Mo03 or MOO?) in the interior of the particles at temperatures between 20 and 100 OC, whereas MoS2 forms at temperatures of 125 OC and higher. Sulfur is present in two forms, as S2- and in a second form which is most probably Sz2- or SH-, but not elemental sulfur. The additional sulfur species disappear at temperatures between 150 and 200 OC. Rutherford backscattering analysis indicates S:Moatomicratios of 1-1.5 at sulfidation temperatures below 100 OC and of 2-2.5 above 100 OC. It is concluded that the sulfidation of Moo3 to MoS2 proceeds through a Mo(1V) oxysulfide, formed initially at the outside of the particle, and Mo(1V) oxide in the interior of the particle. Sulfidic species are believed to facilitate the reduction of Moo3 to Mo(1V) species at low temperatures.

Sulfidation mechanism by molybdenum catalysts supported on silica/silicon(100) model support studied by surface spectroscopy