Abstract
ZEOLITES are microporous aluminosilicates which, in their protonated form, act as solid catalysts1, and are widely used in the oil and petrochemical industries for processes such as cracking, isomerization and alkylation if hydrocarbons2. The proposed mechanisms3–5 of these processes mostly involve proton transfer and formation of carbenium or carbonium ions as reactive intermediates, but the detailed function of the zeolite and in particular the relation between acidity and catalytic activity is not well understood. Here we report experimental and theoretical studies of denterium–hydrogen exchange between deuterated methane and protonated zeolites — a prototypical hetero-geneous catalytic reaction between a hydrocarbon and an acid zeolite. We monitored this slow exchange reaction in two different zeolites using infrared spectroscopy, and used ab initio quantum chemistry calculations to determine both the reaction mechanism and the acidity–activity relationship. Combining our theoretical results with recent estimates8–11 of the acidity differences within zeolites enables us to reproduce the experimentally observed reaction rates and thus to obtain a detailed microscopic picture of this heterogeneous catalytic process.
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References
Thomas, J. M. Scient. Am., 266 (IV), 82–88 (1992).
Maxwell, I. E. & Stork, W. H. J. in Introduction to Zeolite Science and Practice, (eds van Bekkum, H. et al.) 571–630 (Elsevier, Amsterdam, 1991).
Jacobs, P. A. & Martens, J. A. in Introduction to Zeolite Science and Practice. (eds van Bekkum, H. et al.) 445–496 (Elsevier, Amsterdam, 1991).
Abbot, J. & Wojciechowski, B. W. J. Catal. 115, 1–15 (1989).
Stefanidis, C., Gates, B. C. & Haag, W. O. J. Molec. Catal. 67, 363–367 (1991).
Sauer, J., Kölmel, C. M., Hill, J. R. & Ahlrichs, R. Chem. Phys. Lett. 164, 193–198 (1989).
Sauer, J., Horn, H., Häser, M. & Ahlrichs, R. Chem. Phys. Lett. 173, 26–32 (1990).
Dubsky, J. Beran, S. & Bosác̆ek, V. J. Molec. Catal. 6, 321–326 (1979).
Schröder, K.-P., Sauer, J., Leslie, M., Catlow, R. C. A. & Thomas, J. M. Chem. Phys. Lett. 188, 320–325 (1992).
Schröder, K.-P., Sauer, J., Leslie, M. & Catlow, R. C. A. Zeolites 12, 20–23 (1992).
Kramer, G. J. & van Santen, R. A. J. Am. chem. Soc. 115, 2887–2897 (1993).
Kramer, G. J., de Man, A. J. M. & van Santen, R. A. J. Am. chem. Soc. 113, 6435–6441 (1991).
Sauer, J. chem. Rev. 89, 199–255 (1989).
Dupuis, M., Sprangler, D. & Wendolowski, D. NRCC Software Catalog 1, Program No. QG01, GAMESS (1980).
Szabo, A. & Ostlund, N. S. Modern Quantum Chemistry: Introduction to Advanced Electronic Structure Theory (Macmillan, New York, 1982).
Rice, O. K. Statistical Mechanics, Thermodynamics and Kinetics (Freeman, San Francisco, 1966).
Thruhlar, D. G. & Gordon, M. S. Science 249, 491–497 (1990).
Gilbert, R. G. & Smith, S. C. Theory of Unimolecular and Recombination Reactions (Blackwell, Oxford, 1990).
Barrer, R. M., & Sutherland, J. W. Proc. R. Soc. A237, 439–450 (1956).
Papp, H., Hinsen, W., Do, N. T. & Baerns, M., Thermochim. Acta 82, 137–148 (1984).
Yashonath, S., Thomas, J. M., Nowak, A. K. & Cheetham, A. K. Nature 331, 601–604 (1988).
Johnston, H. S. Gas Phase Reaction Rate Theory (Ronald, New York, 1966).
Meier, W. M. & Olson, D. H. Atlas of Zeolite Structure Types, 2nd edn (Butterworth, Cambridge, 1987).
Lombardo, E. A., Sill, G. A. & Hall, W. K. J. Catal. 119, 426–440 (1989).
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Kramer, G., van Santen, R., Emeis, C. et al. Understanding the acid behaviour of zeolites from theory and experiment. Nature 363, 529–531 (1993). https://doi.org/10.1038/363529a0
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DOI: https://doi.org/10.1038/363529a0
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