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Infrared Spectroscopic Characterization of Sulfide Cluster-Derived Ensembles

Published online by Cambridge University Press:  15 February 2011

James R. Brenner  and
Levi T. Thompson
James R. Brenner
Affiliation:
Argonne National Laboratory, Department of Chemistry, 9700 S. Cass Ave., Bldg. 200, Room C-113, Argonne, IL 60439
Levi T. Thompson
Affiliation:
The University of Michigan, Department of Chemical Engineering, 2300 Hayward Ave., 3230 H.H. Dow Bldg., Ann Arbor, MI 48109–2136
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Abstract

The transition metal sulfide clusters (MeCp)2Mo2(μ-SH)2(μ-S)2, (MeCp)2Mo2Co2(μ3-S)2(μ4-S)(CO)4 [MoCoS], and (MeCp)2Mo2 Fe2 (μ3-S)2(CO)8, (MeCp = methylcyclopentadienyl) were used to prepare γ-Al2O3-supported catalysts. For comparison, a series of supported materials was also prepared using conventional incipient wetness impregnation. Infrared spectroscopy of adsorbed species was used to characterize the sites in the clusterderived and conventionally prepared catalysts. Nitric oxide chemisorbed onto the MoCoS/A catalyst was associated initially only with Co sites and then upon gentle heating shifted to the Mo sites, indicating that Co and Mo were in close proximity. In contrast, NO adsorbed onto both Co and Mo sites in the conventionally prepared materials and desorbed independently from these two types of sites. Infrared spectra of adsorbed thiophene and pyridine were similar for the clusterderived and conventionally prepared catalysts. Thiophene reacted at 100 °C to produce both olefinic species. The most abundant products from thiophene HDS were 1-butene, cis-2-butene, and trans-2-butene. Displacement studies showed that thiophene, pyridine, and NO adsorbed to the same site. The most active sites for HDS and HDN contained both Mo and a late transition metal. The HDN product distributions suggested that Mo was selective for C=N bond cleavage while the late transition metals were more active for C=C hydrogenolysis.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 368: Symposium T – Synthesis and Properties of Advanced Catalytic Materials , 1994 , 203
Copyright
Copyright © Materials Research Society 1995

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References

REFERENCES

1. RakowskiDuBois, M., VanDerveer, M.C., Dubois, D.L., Haltiwanger, R.C., and Miller, W.K., J. Am. Chem. Soc. 102, 7456 (1980).Google Scholar
2. Williams, P.D.,Curtis, M.D., Duffy, D.N., and Butler, W.M., Organometallics 2, 165 (1983).Google Scholar
3. Curtis, M.D., and Williams, P.D., Inorg. Chem. 22, 2261 (1983).Google Scholar
4. Uchtman, V.A., and Dahl, L.F., J. Am. Chem. Soc. 91, 3756 (1969).Google Scholar
5. Bogan, L.E., Lesch, D.A., and Rauchfuss, T.B., J. Organomet. Chem. 250, 429 (1983).Google Scholar
6. Brenner, J.R., Ph.D.Dissertation, The University of Michigan, 1994.Google Scholar
7. Carvill, B.T. and Thompson, L.T., Appl. Catal. 75, 249 (1991).Google Scholar
8. Brenner, J.R., Carvill, B.T., and Thompson, L.T., Appl. Organomet. Chem. 6, 463 (1992).Google Scholar
9. Brenner, J.R., and Thompson, L.T., Catal. Today 21, 101 (1994).Google Scholar
10. Rosen, R.P.,Segawa, K., Millman, W.S., and Hall, W.K., J. Catal. 90, 10 (1984).Google Scholar
11. Waddington, G./, Knowlton, J.W., Scott, D.W., Oliver, G.D., Todd, S.S., Hubbard, W.N., Smith, J.C., and Huffman, H.M., J. Am. Chem. Soc. 71, 797 (1949).Google Scholar
12. TopsΦe, H., Clausen, B.S., TopsΦe, N.Y., and Pedersen, E., Ind. Eng. Chem. Fundam. 25, 25 (1986).Google Scholar