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A quantum-chemical study of adsorbed nonclassical carbonium ions as active intermediates in catalytic transformations of paraffins. I. Protolytic cracking of ethane on high silica zeolites

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Abstract

Ab initio quantum-chemical calculations of protolytic cracking of ethane on Brønsted acid sites of high silica zeolites demonstrated the concerted mechanism of this reaction. The reaction coordinate represents the stretching of the O-H bond in combination with heterolytic splitting of the C-C ethane bond. This results in formation of methane and adsorption of the methyl group on the surface basic oxygen of the active site. The geometry of such activated complex is different from that of adsorbed carbonium ions which also represent highly excited surface complexes

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References

  1. W.O. Haag and R.M. Dessau, in:Proc. 8th Int. Congr. on Catalysis, Vol. 2, Berlin 1984, p. 305.

    Google Scholar 

  2. C. Stefanadis, B.C. Gates and W.O. Haag, J. Molec. Catal. 67 (1991) 363.

    Google Scholar 

  3. H. Krannila, W.O. Haag and B.C. Gates, J. Catal. 135 (1992) 115.

    Google Scholar 

  4. P.V. Shertugde, G. Marcelin, G.A. Still and W.K. Hall, J. Catal. 136 (1992) 446.

    Google Scholar 

  5. V.B. Kazansky and I.N. Senchenya, Catal. Lett. 8 (1991) 317.

    Google Scholar 

  6. G.J. Kramer, R.A. van Santen, C.A. Emeis and A.K. Novak, Nature 363 (1993) 529.

    Google Scholar 

  7. J. Datka and M. Boczar, J. Catal. 114 (1988) 368.

    Google Scholar 

  8. L. Kubelkova, S. Beran and J.A. Lercher, Zeolites 9 (1989) 539.

    Google Scholar 

  9. H.V. Brand, L.A. Kurtiss and L.E. Iton, J. Phys. Chem. 96 (1992) 7725.

    Google Scholar 

  10. K. Hiraoka and P. Kebarle, J. Am. Chem. Soc. 98 (1976) 6119.

    Google Scholar 

  11. D.K. Bohme, in:Interaction between Ions and Molecules, ed. P. Ausloos (Plenum Press, NewYork, 1975).

    Google Scholar 

  12. W.J. Hehre, L. Radom, P. von R. Schleyer and J.A. Pople,Ab Initio Molecular Orbital Theory (Wiley, New York, 1985).

    Google Scholar 

  13. R.A. van Santen, A.J.M. de Man, W.P.I.H. Jacobs, E.H. Teunissen and G.J. Kramer, Catal. Lett. 9 (1991) 273.

    Google Scholar 

  14. E.H. Teunissen, F.B. van Duijneveldt and R.A. van Santen, J. Phys. Chem. 96 (1992) 366; in:Proc. 9th Int. Zeolite Conf., Vol. 1, Montreal 1992, eds. R. von Ballmoos, J.B. Higgins and M.M.J. Treacy (Butterworths-Heinemann, 1993) p. 469.

    Google Scholar 

  15. Dissociation Energies of Chemical Bonds, Ionisation Potentiah, Electron Affinities (Nauka, Moscow, 1974), in Russian.

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Authors and Affiliations

  1. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, B-334, Moscow, Russia

    V. B. Kazansky, I. N. Senchenya & M. Frash

  2. Schuit Institute of Catalysis, Eindhoven University of Technology, PO Box 513, 5600, MB Eindhoven, The Netherlands

    R. A. van Santen

Authors
  1. V. B. Kazansky
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  2. I. N. Senchenya
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  3. M. Frash
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  4. R. A. van Santen
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Kazansky, V.B., Senchenya, I.N., Frash, M. et al. A quantum-chemical study of adsorbed nonclassical carbonium ions as active intermediates in catalytic transformations of paraffins. I. Protolytic cracking of ethane on high silica zeolites. Catal Lett 27, 345–354 (1994). https://doi.org/10.1007/BF00813921

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  • DOI: https://doi.org/10.1007/BF00813921

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