Advertisement

Catalysis Letters

, Volume 6, Issue 1, pp 111–119 | Cite as

Propylene conversion reactions; metathesis, cyclization and hydrogenolysis catalyzed by Mo(100) and oxygen-covered Mo(100)

  • L. P. Wang
  • W. T. Tysoe
Article

Abstract

Analysis of the products formed in the Mo(100) single crystal-catalyzed decomposition of propylene using an isolatable high-pressure reactor shows that this surface simultaneously catalyzes metathesis, hydrogenolysis and also methylcyclopropane formation. The activation energy for olefin metathesis on Mo(100) is measured to be 65±1 kcal/mole, and the reaction is first order in propylene pressure. These results are consistent with the reaction proceeding via a carbene mechanism on Mo(100) since hydrogenolysis indicates that carbon-carbon bonds can cleave selectively, and methylcyclopropane formation suggests that a metallacycle has formed. The observed first-order reaction kinetics are also in accord with this view. Pre-dosing the Mo(100) surface with a monolayer of oxygen reduces the catalytic activity by a factor of ∼ 17. This implies that the four-fold hollow site is active for propylene metathesis on Mo(100) since atomic oxygen adsorbs at this site.

Propylene conversion metathesis hydrogenolysis methylcyclopropane formation cyclization Mo(100) catalyst 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. [1]
    R.L. Banks and G.C. Bailey, Ind. Eng. Chem., Prod. Res. Develop. 3 (1964) 170.Google Scholar
  2. [2]
    C.P.C. Bradshaw, E.J. Howman and L. Turner, J. Catal. 7 (1967) 269.Google Scholar
  3. [3]
    R.H. Grubbs and T.K. Brunk, J. Am. Chem. Soc. 94 (1972) 2538.Google Scholar
  4. [4]
    J.L. Hérrison and Y. Chauvin, Makromol. Chem. 141 (1970) 161.Google Scholar
  5. [5]
    D.J. Cardin, M.J. Doyle and M.F. Lappert, J. Chem. Soc., Chem. Commun. (1972) 927.Google Scholar
  6. [6]
    M. Ephritikhine, M.L.H. Green and R.E. MacKenzie, J. Chem. Soc., Chem. Comm. (1976) 619.Google Scholar
  7. [7]
    R.G. Bowman and R.L. Burwell, Jr., J. Catal. 88 (1984) 388.Google Scholar
  8. [8]
    R. Makamura, D. Pioch, R.G. Bowman and R.L. Burwell, Jr., J. Catal. 93 (1985) 338.Google Scholar
  9. [9]
    R. Nakamura, R.G. Bowman and R.L. Burwell, Jr., J. Am. Chem. Soc. 103 (1981) 673.Google Scholar
  10. [10]
    J.-S. Chung, J.P. Zhang and R.L. Burwell, Jr., J. Catal. 116 (1989) 506.Google Scholar
  11. [11]
    R.L. Burwell, Jr., J. Catal. 113 (1988) 567.Google Scholar
  12. [12]
    J.-S. Chung and R.L. Burwell, Jr., J. Catal. 116 (1989) 519.Google Scholar
  13. [13]
    R. Nakamura and R.L. Burwell, Jr., J. Catal. 93 (1985) 399.Google Scholar
  14. [14]
    R.L. Burwell, Jr. and J.S. Chung, React. Kinet. Catal. Lett. 35 (1987) 381.Google Scholar
  15. [15]
    R.L. Burwell, Jr., J. Catal. 86 (1984) 301.Google Scholar
  16. [16]
    A. Brenner and R.L. Burwell, Jr., J. Catal. 52 (1978) 364.Google Scholar
  17. [17]
    K.A. Vikulov, I.V. Elev, B.N. Shelimove and V.B. Kazansky, Catal. Lett. 2 (1989) 121.Google Scholar
  18. [18]
    M. Kazuta and K. Tanaka, Catal. Lett. 1 (1988) 7.Google Scholar
  19. [19]
    L.P. Wang and W.T. Tysoe, Catal. Lett. 1 (1988) 159.Google Scholar
  20. [20]
    L.P. Wang and W.T. Tysoe, Surf. Sci. in press.Google Scholar
  21. [21]
    J.P. Fulmer, F. Zaera and W.T. Tysoe, J. Chem. Phys. 87 (1987) 4147.Google Scholar
  22. [22]
    L.P. Wang and W.T. Tysoe, J. Catal. submitted.Google Scholar
  23. [23]
    C. Zhang, M.A. Van Hove and G.A. Somorjai, Surf. Sci. 149 (1985) 326.Google Scholar
  24. [24]
    L.P. Wang, Ph.D. Thesis, University of Wisconsin-Milwaukee, 1990.Google Scholar
  25. [25]
    C.P. Casey and T.J. Burkhardt, J. Am. Chem. Soc. 95 (1973) 5833.Google Scholar
  26. [26]
    C.P. Casey and T.J. Burkhardt, J. Am. Chem. Soc. 96 (1973) 7808.Google Scholar
  27. [27]
    L.P. Wang and W.T. Tysoe, Surf. Sci., submitted.Google Scholar
  28. [28]
    S.H. Overbury and P.C. Stair, J. Vac. Sci. Technol. A1 (1983) 1055.Google Scholar

Copyright information

© J.C. Baltzer A.G. Scientific Publishing Company 1990

Authors and Affiliations

  • L. P. Wang
    • 1
  • W. T. Tysoe
    • 1
  1. 1.Department of Chemistry and Laboratory for Surface StudiesUniversity of Wisconsin-MilwaukeeUSA

Personalised recommendations