Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

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

Nature volume 430, pages 1012–1016 (2004)Cite this article

Abstract

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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: The synthesis of zeotypes by using ionic liquids and eutectic mixtures.
Figure 2: Two views of the SIZ-1 structure.
Figure 3: Two views of the structure of SIZ-2.

Similar content being viewed by others

References

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

    Article  ADS  CAS  Google Scholar 

  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)

    Article  ADS  CAS  Google Scholar 

  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)

    Article  ADS  CAS  Google Scholar 

  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)

    Article  ADS  CAS  Google Scholar 

  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)

    Article  ADS  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

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

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

    Article  CAS  Google Scholar 

  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)

    Article  Google Scholar 

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

  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)

    Article  CAS  Google Scholar 

  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)

    Article  ADS  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

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

    Book  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

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

    CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  ADS  Google Scholar 

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

    Google Scholar 

Download references

Acknowledgements

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

Authors and Affiliations

  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

Authors
  1. Emily R. Cooper
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Christopher D. Andrews
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Paul S. Wheatley
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Paul B. Webb
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Philip Wormald
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Russell E. Morris
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Russell E. Morris.

Ethics declarations

Competing interests

The authors declare that they have no competing financial interests.

Supplementary information

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)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Cooper, E., Andrews, C., Wheatley, P. et al. Ionic liquids and eutectic mixtures as solvent and template in synthesis of zeolite analogues. Nature 430, 1012–1016 (2004). https://doi.org/10.1038/nature02860

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature02860

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing