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:

The ITQ-37 mesoporous chiral zeolite

Nature volume 458, pages 1154–1157 (2009)Cite this article

Abstract

The synthesis of crystalline molecular sieves with pore dimensions that fill the gap between microporous and mesoporous materials is a matter of fundamental and industrial interest1,2,3. The preparation of zeolitic materials with extralarge pores and chiral frameworks would permit many new applications. Two important steps in this direction include the synthesis4 of ITQ-33, a stable zeolite with 18 × 10 × 10 ring windows, and the synthesis5 of SU-32, which has an intrinsically chiral zeolite structure and where each crystal exhibits only one handedness. Here we present a germanosilicate zeolite (ITQ-37) with extralarge 30-ring windows. Its structure was determined by combining selected area electron diffraction (SAED) and powder X-ray diffraction (PXRD) in a charge-flipping algorithm6. The framework follows the SrSi2 (srs) minimal net7 and forms two unique cavities, each of which is connected to three other cavities to form a gyroidal channel system. These cavities comprise the enantiomorphous srs net of the framework. ITQ-37 is the first chiral zeolite with one single gyroidal channel. It has the lowest framework density (10.3 T atoms per 1,000 Å3) of all existing 4-coordinated crystalline oxide frameworks, and the pore volume of the corresponding silica polymorph would be 0.38 cm3 g-1.

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: Structure of SDA2 used for synthesizing the ITQ–37 zeolite.
Figure 2: Observed (blue), calculated (red) and difference (black) PXRD profiles for the Rietveld refinement of the as-synthesized ITQ-37 ( λ = 1.5406 Å).
Figure 3: Electron density map derived by the charge-flipping algorithm and the obtained structure model, both are viewed along the c axis.
Figure 4: The framework and corresponding nets of ITQ-37.
Figure 5: Tiling of ITQ-37.

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. State of the art and future challenges of zeolites as catalysis. J. Catal. 216, 298–312 (2003)

    Article  CAS  Google Scholar 

  3. Férey, G. Materials science: the simplicity of complexity—rational design of giant pores. Science 291, 994–995 (2001)

    Article  Google Scholar 

  4. Corma, A., Díaz-Cabañas, M. J., Jorda, J. L., Martínez, C. & Moliner, M. High-throughput synthesis and catalytic properties of a molecular sieve with 18- and 10-member rings. Nature 443, 842–845 (2006)

    Article  ADS  CAS  Google Scholar 

  5. Tang, L. Q. et al. A zeolite family with chiral and achiral structures built from the same building layer. Nature Mater. 7, 381–385 (2008)

    Article  ADS  CAS  Google Scholar 

  6. Baerlocher, McCusker, L. B. & Palatinus, L. Charge flipping combined with histogram matching to solve complex crystal structures from powder diffraction data. Z. Kristallogr. 222, 47–53 (2007)

    Article  CAS  Google Scholar 

  7. Delgado-Friedrichs, O., O’Keeffe, M. & Yaghi, O. M. Three-periodic nets and tilings: regular and quasiregular nets. Acta Crystallogr. A 59, 22–27 (2003)

    Article  Google Scholar 

  8. Schröder, G. E., Fogden, A. & Hyde, S. T. Bicontinuous geometries and molecular self-assembly: comparison of local curvature and global packing variation in genus-three cubic, tetragonal and rhombohedral surfaces. Eur. Phys. J. B 54, 509–524 (2006)

    Article  ADS  Google Scholar 

  9. Taylor, W. H. The structure of analcite (NaAlSi2O6.H2O). Z. Kristallogr. 74, 1–19 (1930)

    Article  CAS  Google Scholar 

  10. Gier, T. E., Bu, X., Feng, P. & Stucky, G. D. Synthesis and organization of zeolite-like materials with three-dimensional helical pores. Nature 395, 154–157 (1998)

    Article  ADS  CAS  Google Scholar 

  11. Zou, X., Conradsson, T., Klingstedt, M., Dadachov, M. S. & O’Keeffe, M. A mesoporous germanium oxide with crystalline pore walls and its chiral derivative. Nature 437, 716–719 (2005)

    Article  ADS  CAS  Google Scholar 

  12. Cantín, Á., Corma, A., Díaz-Cabañas, M. J., Jorda, J. L. & Moliner, M. Rational design and HT techniques allow the synthesis of new IWR zeolite polymorphs. J. Am. Chem. Soc. 128, 4216–4217 (2006)

    Article  Google Scholar 

  13. Gramm, F. et al. Complex zeolite structure solved by combining powder diffraction and electron microscopy. Nature 444, 79–81 (2006)

    Article  ADS  CAS  Google Scholar 

  14. Baerlocher, Ch et al. Structure of the polycrystalline zeolite catalyst IM-5 solved by enhanced charge flipping. Science 315, 1113–1116 (2007)

    Article  ADS  CAS  Google Scholar 

  15. Baerlocher, Ch et al. Ordered silicon vacancies in the framework structure of the zeolite catalyst SSZ-74. Nature Mater. 7, 631–635 (2008)

    Article  ADS  CAS  Google Scholar 

  16. Grosse-Kunstleve, R. W., McCusker, L. B. & Baerlocher, Ch Powder diffraction data and crystal chemical information combined in an automated structure determination procedure for zeolites. J. Appl. Cryst. 30, 985–995 (1997)

    Article  CAS  Google Scholar 

  17. Palatinus, L. & Chapuis, G. Superflip—a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions. J. Appl. Cryst. 40, 786–790 (2007)

    Article  CAS  Google Scholar 

  18. Zou, X. D., Sukharev, Y. & Hovmöller, S. Quantitative measurement of intensities from electron diffraction patterns for structure determination—new features in the program system ELD. Ultramicroscopy 52, 436–444 (1993)

    Article  CAS  Google Scholar 

  19. O'Keeffe, M., Peskov, M. A., Ramsden, S. J. & Yaghi, O. M. The Reticular Chemistry Structure Resource (RCSR) database of, and symbols for, crystal nets. Acc. Chem. Res. 41, 1782–1798 (2008)

    Article  CAS  Google Scholar 

  20. Climent, M. J., Corma, A. & Velty, A. Zeolites for the production of fine chemicals. Synthesis of the fructone fragance. J. Catal. 196, 345–351 (2000)

    Article  CAS  Google Scholar 

  21. Climent, M. J., Corma, A. & Velty, A. Design of a solid catalyst for the synthesis of a molecule with a orange blossom scent. Green Chem. 4, 565–569 (2002)

    Article  CAS  Google Scholar 

  22. Climent, M. J., Corma, A. & Velty, A. Synthesis of hyacinth, vanilla and orange blossom fragrances. The benefit of using zeikutes and delaminated zeolites as catalysts. Appl. Catal. Gen. 263, 155–161 (2004)

    Article  CAS  Google Scholar 

  23. Hovmöller, S. CRISP: Crystallographic image processing on a personal computer. Ultramicroscopy 41, 121–135 (1992)

    Article  Google Scholar 

  24. Young, R. A. The Rietveld Method 1–39 (IUCr Book Serials, Oxford Univ. Press, 1993)

    Google Scholar 

  25. Delgado-Friedrichs, O. & O'Keeffe, M. Identification and symmetry computation for crystal nets. Acta Crystallogr. A 59, 351–360 (2003)

    Article  Google Scholar 

  26. Delgado-Friedrichs, O. Data structures and algorithms for tilings. I. Theor. Comput. Sci. 303, 431–445 (2003)

    Article  MathSciNet  Google Scholar 

  27. Blatov, V. A. Multipurpose crystallochemical analysis with the program package TOPOS. IUCr Comp. Commun. Newsl. 7, 4–38 (2006)

    Google Scholar 

Download references

Acknowledgements

This project is supported by the CICYT (Project MAT 2006-14274-C02-01 and Prometeo 2008 GV), the Swedish Research Council (VR) and the Swedish Governmental Agency for Innovation Systems (VINNOVA). J.S. and C.B. are supported by post-doctoral grants from the Carl-Trygger and Wenner-Gren foundations respectively. M.M. thanks ITQ for a scholarship.

Author Contributions D.Z. and M.L. carried out the TEM work. J.S. solved and refined the structures. C.B. did the topological analysis. M.M., M.J.D.-C. and A.C. carried out the zeolite synthesis work. Á.C. synthesized the organic structure directing agents. J.S., C.B., A.C. and X.Z. wrote and corrected the manuscript.

Author information

Authors and Affiliations

  1. Structural Chemistry and Berzelii Centre, EXSELENT on Porous Materials, Stockholm University, SE-106 91, Stockholm, Sweden ,

    Junliang Sun, Charlotte Bonneau, Daliang Zhang, Mingrun Li & Xiaodong Zou

  2. Instituto de Tecnología Química (UPV-CSIC), Av. Naranjos s/n, E-46022 Valencia, Spain ,

    Ángel Cantín, Avelino Corma, María J. Díaz-Cabañas & Manuel Moliner

Authors
  1. Junliang Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Charlotte Bonneau
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ángel Cantín
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Avelino Corma
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. María J. Díaz-Cabañas
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Manuel Moliner
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Daliang Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Mingrun Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Xiaodong Zou
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Avelino Corma or Xiaodong Zou.

Supplementary information

Supplementary Information

This file contains Supplementary Figures S1-S12 with Legends and Supplementary Tables S1-S4. (PDF 929 kb)

Supplementary Information

This file contains Crystallographic Information of ITQ-37. (TXT 4 kb)

Supplementary Framework Structure Movie

This movie shows the framework structure of ITQ-37. Only the Si-Si connections are shown. (MOV 20518 kb)

Supplementary Channel Structure Movie

This movie shows the structure of extra-large pores in ITQ-37 in tiling representation. Only framework tiles are represented (green and gold). The green tiles correspond to the D4Rs. (MOV 4528 kb)

Supplementary Cage Structure Movie

This movie shows the structure of an extra-large cage with three pore-openings in ITQ-37 in tiling representation. Only framework tiles are represented (green and gold). The green tiles correspond to the D4Rs. (MOV 5113 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Cite this article

Sun, J., Bonneau, C., Cantín, Á. et al. The ITQ-37 mesoporous chiral zeolite. Nature 458, 1154–1157 (2009). https://doi.org/10.1038/nature07957

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature07957

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