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Towards a molecular understanding of shape selectivity

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.

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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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