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Ionic liquids and eutectic mixtures as solvent and template in synthesis of zeolite analogues

Naturevolume 430pages10121016 (2004) | Download Citation



The challenges associated with synthesizing porous materials1 mean that new classes of zeolites (zeotypes)—such as aluminosilicate zeolites2,3 and zeolite analogues4—together with new methods of preparing known zeotypes5, continue to be of great importance. Normally these materials are prepared hydrothermally with water as the solvent in a sealed autoclave under autogenous pressure6. The reaction mixture usually includes an organic template or ‘structure-directing agent’ that guides the synthesis pathway towards particular structures. Here we report the preparation of aluminophosphate zeolite analogues by using ionic liquids7 and eutectic mixtures8. An imidazolium-based ionic liquid acts as both solvent and template, leading to four zeotype frameworks under different experimental conditions. The structural characteristics of the materials can be traced back to the solvent chemistry used. Because of the vanishingly low vapour pressure of ionic liquids, synthesis takes place at ambient pressure, eliminating safety concerns associated with high hydrothermal pressures. The ionic liquid can also be recycled for further use. A choline chloride/urea eutectic mixture8 is also used in the preparation of a new zeotype framework.

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  1. 1

    Davis, M. E. Ordered porous materials for emerging applications. Nature 417, 813–821 (2002)

  2. 2

    Corma, A., Díaz-Cabañas, M. J., Joaquín Martínez-Triguero, J., Rey, F. & Rius, J. A large-cavity zeolite with wide pore windows and potential as an oil refining catalyst. Nature 418, 514–517 (2002)

  3. 3

    Freyhardt, C. C., Tsapatsis, M., Lobo, R. F., Balkus, K. J. Jr & Davis, M. E. A high-silica zeolite with a 14-tetrahedral-atom pore opening. Nature 381, 295–298 (1996)

  4. 4

    Feng, P., Bu, X. & Stucky, G. D. Hydrothermal syntheses and structural characterization of zeolite analogue compounds based on cobalt phosphate. Nature 388, 735–741 (1997)

  5. 5

    Lee, H., Zones, S. I. & Davis, M. E. A combustion-free methodology for synthesizing zeolites and zeolite-like materials. Nature 425, 385–388 (2003)

  6. 6

    Cundy, C. S. & Cox, P. A. The hydrothermal synthesis of zeolites: history and development from the earliest days to the present time. Chem. Rev. 103, 663–701 (2003)

  7. 7

    Rogers, R. D. & Seddon, K. R. Ionic liquids–solvents of the future? Science 302, 792–793 (2003)

  8. 8

    Abbott, A. P., Capper, G., Davies, D. L., Rasheed, R. K. & Tambyrajah, V. Novel solvent properties of choline chloride/urea mixtures. Chem. Commun. 70–71 (2003)

  9. 9

    Zones, S. I. Synthesis of pentasil zeolites from sodium-silicate solutions in the presence of quaternary imidazole compounds. Zeolites 9, 458–467 (1989)

  10. 10

    Adams, C. J., Bradley, A. E. & Seddon, K. R. The synthesis of mesoporous materials using novel ionic liquid templates in water. Aust. J. Chem. 54, 679–681 (2001)

  11. 11

    Dai, S. et al. Preparation of silica aerogel using ionic liquids as solvents. Chem. Commun. 243–244 (2000)

  12. 12

    Yu, J. H. & Xu, R. R. Rich structure chemistry in the aluminophosphate family. Acc. Chem. Res. 36, 481–490 (2003)

  13. 13

    Eloísa Medina, M., Iglesias, M., Gutiérrez-Puebla, E. & Angeles Monge, M. Solvothermal synthesis and structural relations among three anionic aluminophosphates; catalytic behaviour. J. Mater. Chem. 14, 845–850 (2004)

  14. 14

    Huo, Q. et al. Synthesis and characterization of a novel extra large ring of aluminophosphate JDF-20. Chem. Commun. 875–876 (1992)

  15. 15

    Yu, J. et al. Al16P20O80H4.4C6H18N2: A new microporous aluminophosphate containing intersecting 12- and 8-membered ring channels. Chem. Mater. 10, 1208–1211 (1998)

  16. 16

    Estermann, M., McCusker, L. B., Baerlocher, C., Merrouche, A. & Kessler, H. A synthetic gallophosphate molecular-sieve with a 20-tetrahedral-atom pore opening. Nature 352, 320–323 (1991)

  17. 17

    Camblor, M. A., Villaescusa, L. A. & Diaz-Cabanas, M. J. Synthesis of all-silica and high-silica molecular sieves in fluoride media. Top. Catal. 9, 59–76 (1999)

  18. 18

    Richardson, J. W. Jr, Pluth, J. J. & Smith, J. V. Rietveld profile analysis of calcined AlPO4-11 using pulsed neutron powder diffraction. Acta Crystallogr. B 44, 367–373 (1988)

  19. 19

    Oliver, S., Kuperman, A., Lough, A. & Ozin, G. A. Synthesis and characterization of a fluorinated anionic aluminophosphate framework UT-6, and its high-temperature dehydrofluorination to AlPO4-CHA. J. Mater. Chem. 7, 807–812 (1997)

  20. 20

    Feng, P., Bu, X., Gier, T. E. & Stucky, G. D. Amine-directed syntheses and crystal structures of phosphate-based zeolite analogs. Microporous Mesoporous Mater. 23, 221–229 (1998)

  21. 21

    Taulelle, F. et al. Isomerization of the prenucleation building unit during crystallization of ALPO4-CJ2: An MQMAS, CP-MQMAS, and HETCOR NMR study. J. Am. Chem. Soc. 121, 12148–12153 (1999)

  22. 22

    Robson, H. in Verified Synthesis of Zeolitic Materials (ed. Robson, H.) 45–46 (Elsevier, Amsterdam, 2001)

  23. 23

    Cammarata, L., Kazarian, S. G., Salter, P. A. & Welton, T. Molecular states of water in room temperature ionic liquids. Phys. Chem. Chem. Phys. 3, 5192–5200 (2001)

  24. 24

    Hanke, C. G. & Lynden-Bell, R. M. A simulation study of water-dialkylimidazolium ionic liquid mixtures. J. Phys. Chem. B 107, 10873–10878 (2003)

  25. 25

    Lobo, R. F., Zones, S. I. & Davis, M. E. Structure-direction in zeolite synthesis. J. Inclus. Phenom. Mol. 21, 47–78 (1995)

  26. 26

    Del Popolo, M. G. & Voth, G. A. On the structure and dynamics of ionic liquids. J. Phys. Chem. B 108, 1744–1752 (2004)

  27. 27

    Kirchner, R. M. & Bennett, J. M. The structure of calcined AlPO4-41: A new framework topology containing one-dimensional 10-ring pores. Zeolites 14, 523–528 (1994)

  28. 28

    Delgado Friedrichs, O., Dress, A. W. M., Huson, D. H., Klinowski, J. & Mackay, A. L. Systematic enumeration of crystalline networks. Nature 400, 644–657 (1999)

  29. 29

    Wasserscheid, P. & Welton, T. Ionic Liquids in Synthesis Ch. 2.1.2, 9–12 (Wiley-VCH, Weinheim, Germany, 2003)

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We thank C. Hardacre (Queen's University, Belfast) and D. Cole-Hamilton (University of St Andrews) for discussions. We thank the CCLRC and S. Teat for access to the Synchrotron Radiation Source (Daresbury) and the EPSRC and D. Apperley for access to solid-state NMR. R.E.M. was supported by a Royal Society University Research Fellowship.

Author information


  1. School of Chemistry, University of St Andrews, Purdie Building, St Andrews, KY16 9ST, UK

    • Emily R. Cooper
    • , Christopher D. Andrews
    • , Paul S. Wheatley
    • , Paul B. Webb
    • , Philip Wormald
    •  & Russell E. Morris


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The authors declare that they have no competing financial interests.

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Correspondence to Russell E. Morris.

Supplementary information

  1. Supplementary Methods

    An extended explanation of the characterisation of all materials, including single crystal X-ray diffraction, magic angle spinning NMR and thermal analysis. The file contains 9 figures showing the structures of materials SIZ-3 and SIZ-4, powder X-ray diffraction of SIZ-5 and AlPO-CJ2, MAS NMR spectra and thermal analysis traces of all SIZ-n materials and 8 tables of crystallography details and atomic coordinates for SIZ-1, SIZ-2, SIZ-3 and SIZ-4. It also includes a description of the chemistry of ionic liquids and ionic liquid/water mixtures. (DOC 1116 kb)

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