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Catalysis Letters

, Volume 45, Issue 3–4, pp 155–163 | Cite as

Microcalorimetric studies of interactions of ethene, isobutene, and isobutane with silica-supported Pd, Pt, and PtSn

  • M.A. Natal-Santiago
  • S.G. Podkolzin
  • R.D. Cortright
  • J.A. Dumesic
Article

Abstract

Microcalorimetric measurements were made of the interaction of hydrogen, ethene, isobutene and isobutane at 300 K with silica- supported Pt, Pd, and PtSn catalysts. The initial heats of hydrogen adsorption on silica-supported Pd and Pt are 104 and 95 kJ/mol, respectively. The presence of Sn decreases the saturation uptake of hydrogen on the PtSn sample. The initial heats of ethene interaction with Pd/silica and Pt/silica are 170 and 145 kJ/mol, respectively. The presence of Sn decreases the initial heat to 115 kJ/mol on the PtSn sample. The initial heats of isobutene interaction with silica-supported Pd and Pt are 160 and 190 kJ/mol, respectively. The presence of Sn decreases the initial heat to 125 kJ/mol on the PtSn sample. It appears that ethene and isobutene adsorb dissociatively on silica-supported Pd and Pt to form alkylidyne species at 300 K, with an average strength of carbon-metal bonds for these species near 230 kJ/mol. Ethene and isobutene adsorb on silica-supported PtSn to form di- σ- and π-bonded alkene species at 300 K, with an average strength of carbon-metal bonds for these species near 190 and 130 kJ/mol, respectively. Isobutane appears to adsorb dissociatively on a small number of sites on silica-supported Pd and Pt, and this dissociation is also inhibited by Sn on PtSn samples.

Keywords

Isobutene Dissociative Adsorption Metal Bond Initial Heat Differential Heat 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. [1]
    B.C. Gates, J.R. Katzer and G.C.A. Schuit, Chemistry of CatalyticProcesses (McGraw–;Hill, New York, 1979) ch. 3.Google Scholar
  2. [2]
    G.A. Somorjai, Introduction to Surface Chemistry and Catalysis (Wiley, NewYork, 1994).Google Scholar
  3. [3]
    B.E. Bent and G.A. Somorjai, Adv. Coll. Inter. Sci. 29 (1989) 223.CrossRefGoogle Scholar
  4. [4]
    Z.Karpinski,Adv. Catal. 37 (1990) 45.Google Scholar
  5. [5]
    N. Sheppard and C. de laCruz, Adv. Catal. 41 (1996) 1.CrossRefGoogle Scholar
  6. [6]
    P.S. Cremer, S. Xingcai, Y.R. Shen and G.A. Somorjai, J. Am. Chem. Soc. 118 (1996) 2942.CrossRefGoogle Scholar
  7. [7]
    A.Cassuto, J.Kiss and J.M.White, Surf. Sci. 255 (1991) 289.CrossRefGoogle Scholar
  8. [8]
    P. Cremer, C. Stanners, J.W. Niemantsverdriet, Y.R. Shen and G. Somorjai, Surf. Sci. 328 (1995) 111.CrossRefGoogle Scholar
  9. [9]
    P.D. Szuromi, J.R. Engstrom and W.H. Weinberg, J. Phys. Chem. 89 (1985) 2497.CrossRefGoogle Scholar
  10. [10]
    M. Salmerón and G.A. Somorjai, J. Phys. Chem. 86 (1982) 341.CrossRefGoogle Scholar
  11. [11]
    P. Berlowitz, C. Megiris, J.B. Butt and H.H. Kung, Langmuir 1 (1985) 206.CrossRefGoogle Scholar
  12. [12]
    D. Godbey, F. Zaera, R. Yeates and G.A. Somorjai, Surf. Sci. 167 (1986) 150.CrossRefGoogle Scholar
  13. [13]
    R.G. Windham,M.E. Bartram and B.E. Koel, J. Phys. Chem. 92 (1988) 2862.Google Scholar
  14. [14]
    R.G. Windham and B.E.Koel, J. Phys. Chem. 94 (1990) 1489.CrossRefGoogle Scholar
  15. [15]
    A. Stuck, C.E. Wartnaby, Y.Y. Yeo and D.A. King, Phys. Rev. Lett. 74 (1995) 578.CrossRefGoogle Scholar
  16. [16]
    B.E. Spiewak and J.A.Dumesic, Thermochim.Acta, accepted.Google Scholar
  17. [17]
    B.E. Spiewak, R.D. Cortright and J.A. Dumesic, Handbook of HeterogeneousCatalysis, in press.Google Scholar
  18. [18]
    S. Pálfi, W. Lisowski, M. Smutek and S. Cerny, J. Catal. 88 (1984) 300.CrossRefGoogle Scholar
  19. [19]
    H.A. Benesi, R.M. Curtis and H.P. Studer, J. Catal. 10 (1968) 328.CrossRefGoogle Scholar
  20. [20]
    N. Cardona-Martínez and J.A. Dumesic, J. Catal. 125 (1990) 427.CrossRefGoogle Scholar
  21. [21]
    S.A. Goddard, M.D. Amiridis, J.E. Rekoske, N. Cardona-Martínez and J.A.Dumesic, J. Catal. 117 (1989) 155.CrossRefGoogle Scholar
  22. [22]
    A.D. Becke, J. Chem. Phys. 98 (1993) 5648.CrossRefGoogle Scholar
  23. [23]
    W.J. Hehre, L. Radom and P. von R. Schleyer, Ab Initio MolecularOrbitalTheory (Wiley, NewYork, 1986) ch. 4.Google Scholar
  24. [24]
    T. Ziegler, Chem.Rev. 91 (1991) 651.CrossRefGoogle Scholar
  25. [25]
    W. Kohn, A.D. Becke and R.G. Parr, J. Phys. Chem. 100 (1996) 12974.CrossRefGoogle Scholar
  26. [26]
    M.J. Frisch, G.W. Trucks, H.B. Schlegel, P.M.W. Gill, B.G. Johnson, M.A. Robb, J.R. Cheeseman, T. Keith, G.A. Petersson, J.A. Montgomery, K. Raghavachari, M.A. Al-Laham, V.G. Zakrzewski, J.V. Ortiz, J.B. Foresman, J. Cioslowski, B.B. Stefanov, A. Nanayakkara, M. Challacombe, C.Y. Peng, P.Y. Ayala, W. Chen, M.W. Wong, J.L. Andres, E.S. Replogle, R.Gomperts, R.L. Martin, D.J. Fox, J.S. Binkley, D.J. Defrees, J. Baker, J.P. Stewart, M. Head-Gordon, C. Gonzalez and J.A.J.A. Pople, GAUSSIAN 94 (Revision C.2) (Gaussian Inc., Pittsburgh, 1995).Google Scholar
  27. [27]
    C. Peng, P.Y. Ayala, H.B. Schlegel and M.J. Frisch, J. Comp. Chem. 17 (1996) 49.CrossRefGoogle Scholar
  28. [28]
    W.J. Hehre, L. Radom and P. von R. Schleyer, Ab Initio MolecularOrbitalTheory (Wiley, NewYork, 1986) ch. 7.Google Scholar
  29. [29]
    R.D. Cortright and J.A.Dumesic, J. Catal. 148 (1994) 771.CrossRefGoogle Scholar
  30. [30]
    P. Chou and M.A. Vannice, J. Catal. 104 (1987) 1.CrossRefGoogle Scholar
  31. [31]
    E. Wicke, H. Brodowsky and H. Züchner, in: Hydrogen in Metals II, Vol. 29, eds. G. Alefeld and J. Völkl (Springer, New York, 1978) ch. 3.Google Scholar
  32. [32]
    R.G. Windham, B.E. Koel and M.T. Paffett, Langmuir 4 (1988) 1113.CrossRefGoogle Scholar
  33. [33]
    B.E. Spiewak, R.D. Cortright and J.A. Dumesic, to be published.Google Scholar
  34. [34]
    M.T. Paffett, S.C. Gebhard, R.G. Windham and B.E. Koel, Surf. Sci. 223 (1989) 449.CrossRefGoogle Scholar
  35. [35]
    N.R. Avery and N. Sheppard, Proc. Royal Soc.A405 (1986) 1.Google Scholar
  36. [36]
    A.Cassuto and G. Tourillon, Surf. Sci. 307–;309 (1994) 65.CrossRefGoogle Scholar
  37. [37]
    N.R. Avery, J.Catal. 19 (1970) 15.CrossRefGoogle Scholar
  38. [38]
    G. Shahid and N. Sheppard, Can. J. Chem. 69 (1991) 1812.CrossRefGoogle Scholar
  39. [39]
    L. Hammer, B. Dötsch, F. Brandenstein, A. Fricke and K.Müller, J. Electron. Spectrosc.Rel. Phen. 54/55 (1990) 687.CrossRefGoogle Scholar
  40. [40]
    C. Xu, B.E.Koel and M.T. Paffett, Langmuir 10 (1994) 166.CrossRefGoogle Scholar
  41. [41]
    W.H.Weinberg and Y. Sun, Surf. Sci. Lett. 277 (1992) L39.CrossRefGoogle Scholar
  42. [42]
    J.R.Anderson and N.R. Avery, J. Catal. 5 (1966) 446.CrossRefGoogle Scholar
  43. [43]
    G.C. Bond and M.R. Gelsthorpe, J. Chem. Soc. Faraday Trans. I 85 (1989) 3767.CrossRefGoogle Scholar
  44. [44]
    S.A. Goddard, M.D. Amiridis, J.E. Rekoske, N. Cardona-Martinez and J.A.Dumesic, J. Catal. 117 (1989) 155.CrossRefGoogle Scholar
  45. [45]
    G.C. Bond, R.H. Cunningham and E.L. Short, in: Proc. 10th Int. Congr. on Catalysis (Budapest l992), eds. L. Guczi, F. Solymosi and P. Tétényi (Adadémiai Kiad_o, Budapest, 1993) p.130.Google Scholar
  46. [46]
    R.D. Cortright and J.A.Dumesic, J. Catal. 157 (1995) 576.CrossRefGoogle Scholar

Copyright information

© Kluwer Academic Publishers 1997

Authors and Affiliations

  • M.A. Natal-Santiago
  • S.G. Podkolzin
  • R.D. Cortright
  • J.A. Dumesic

There are no affiliations available

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