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Supramolecular self-assembled molecules as organic directing agent for synthesis of zeolites

Nature volume 431, pages 287–290 (2004)Cite this article

Abstract

Solid materials with uniform micropores, such as zeolites, can act as selective catalysts and adsorbents for molecular mixtures by separating those molecules small enough to enter their pores while leaving the larger molecules behind1,2. Zeolite A is a microporous material with a high void volume. Despite its widespread industrial use in, for example, molecular separations and in detergency3,4, its capability as a petroleum-refining material is limited owing to its poor acid-catalytic activity and hydrothermal stability, and its low hydrophobicity. These characteristics are ultimately a consequence of the low framework Si/Al ratio (normally around one) and the resulting high cationic fraction within the pores and cavities1,2. Researchers have modified the properties of type-A zeolites by increasing the Si/Al compositions up to a ratio of three5,6,7,8,9. Here we describe the synthesis of zeolite A structures exhibiting high Si/Al ratios up to infinity (pure silica). We synthesize these materials, named ITQ-29, using a supramolecular organic structure-directing agent obtained by the self-assembly, through π–π type interactions, of two identical organic cationic moieties. The highly hydrophobic pure-silica zeolite A can be used for hydrocarbon separations that avoid oligomerization reactions, whereas materials with high Si/Al ratios give excellent shape-selective cracking additives for increasing propylene yield in fluid catalytic cracking operations. We have also extended the use of our supramolecular structure-directing agents to the synthesis of a range of other zeolites.

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Figure 1: Formation of the LTA structure from the supramolecular self-assembling of the OSDA molecules.
Figure 2: X-ray diffraction patterns of calcined ITQ-29 materials.

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Acknowledgements

We thank M. Benham and K. Gallimore at Hiden Isochema for carrying out the water and hydrocabon adsorption experiments. We also thank P. Atienzar and J. Martínez-Triguero for the photoluminescence and catalytic measurements, respectively. We are grateful to the CICYT for financial support.

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Authors and Affiliations

  1. Instituto de Tecnología Química, UPV-CSIC, Universidad Politécnica de Valencia, Avda de los Naranjos s/n, 46022, Valencia, Spain

    Avelino Corma, Fernando Rey, Maria J. Sabater & Susana Valencia

  2. Institut de Ciència de Materials de Barcelona (CSIC), Campus de la UAB, 08193, Bellaterra, Catalunya, Spain

    Jordi Rius

Authors
  1. Avelino Corma
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  2. Fernando Rey
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  3. Jordi Rius
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  4. Maria J. Sabater
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  5. Susana Valencia
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Correspondence to Avelino Corma.

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The authors declare that they have no competing financial interests.

Supplementary information

Supplementary Information

The crystallographic data of the crystallized template. (DOC 539 kb)

Supplementary Data

Contains: (1) Synthesis and single crystal solution of the Organic Structure Directing Agent (OSDA); (2) Study of the self-assembling of the OSDA by Photoluminiscence spectroscopy; (3) Synthesis of ITQ-29 zeolites. (4) Structure refinement of Si,Ge-LTA and pure silica LTA; (5) Comparison of commercial LTA samples with ITQ-29 zeolites. (DOC 40 kb)

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Corma, A., Rey, F., Rius, J. et al. Supramolecular self-assembled molecules as organic directing agent for synthesis of zeolites. Nature 431, 287–290 (2004). https://doi.org/10.1038/nature02909

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