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Towards a molecular understanding of shape selectivity

Nature volume 451, pages 671–678 (2008)Cite this article

Abstract

Shape selectivity is a simple concept: the transformation of reactants into products depends on how the processed molecules fit the active site of the catalyst. Nature makes abundant use of this concept, in that enzymes usually process only very few molecules, which fit their active sites. Industry has also exploited shape selectivity in zeolite catalysis for almost 50 years, yet our mechanistic understanding remains rather limited. Here we review shape selectivity in zeolite catalysis, and argue that a simple thermodynamic analysis of the molecules adsorbed inside the zeolite pores can explain which products form and guide the identification of zeolite structures that are particularly suitable for desired catalytic applications.

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Figure 1: Hydroisomerization and hydrocracking of n -decane.
Figure 2: Schematic representation of the free-energy model.
Figure 3: Zeolite screening by computer.

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Acknowledgements

We thank S. Calero, D. Dubbeldam, D. Frenkel, R. Krishna and M. Schenk. This work was supported by the EC through the Marie Curie EXT programme BiMaMoSi.

Author information

Author notes

  1. Berend Smit and Theo L. M. Maesen: These authors contributed equally to this work.

Authors and Affiliations

  1. Centre Européen de Calcul Atomique Moléculaire (CECAM), Ecole Normale Supérieure, 46 Allée d’Italie, 69364 Lyon Cedex 7, France ,

    Berend Smit

  2. Department of Chemical Engineering, University of California, Berkeley, California 94720-1462, USA,

    Berend Smit

  3. Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands ,

    Berend Smit

  4. Chevron, Energy Technology Company, 100 Chevron Way, Richmond, California 94802-0627, USA ,

    Theo L. M. Maesen

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Correspondence to Berend Smit or Theo L. M. Maesen.

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Smit, B., Maesen, T. Towards a molecular understanding of shape selectivity. Nature 451, 671–678 (2008). https://doi.org/10.1038/nature06552

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