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:

Synthesis and organization of zeolite-like materials with three-dimensional helical pores

Nature volume 395, pages 154–157 (1998)Cite this article

Abstract

The increasing demand for enantiomerically pure chemicals has stimulated extensive research into the preparation of heterogeneous chiral catalysts or separation media that combine both shape selectivity and enantioselectivity1. Helical pores in inorganic materials might be able to perform such functions, but their occurrence is rare1. Attempts have been reported to synthesize a specific enantiomorph of the chiral zeolite beta2, and chiral metal complexes have been used to assemble inorganic precursors into chiral frameworks3,4. Materials with a fully three-dimensional array of helical structural units are particularly rare, because helical structures (such as quartz) are commonly generated by a uni-dimensional symmetry element acting on an achiral structural subunit5,6. Here we report on a family of zeolite-type materials (which we call UCSB-7) that possess two independent sets of three-dimensional crosslinked helical pores, separated by a gyroid periodic minimal surface13. We have synthesized the UCSB-7 framework for various compositions (zinc and beryllium arsenates, gallium germanate) using either inorganic cations or amines as structure-directing agents. The helical-ribbon motif that we identify might be exploited more widely for developing useful chiral solid-state structures.

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 helical ribbons are crosslinked in three dimensions to give 12-ring pores.
Figure 2: Helices viewed parallel to cubic unit cell edges and body diagonal directions.
Figure 3: The crystalline gyroid minimal surface of UCSB-7 separates the space into two disconnected volumes.

Similar content being viewed by others

References

  1. Baiker, A. Chiral catalysis on solids. Curr. Opin. Solid State Mater. Sci. 3, 86–93 (1998).

    Article  ADS  CAS  Google Scholar 

  2. Davis, M. E. New vistas in zeolite and molecular sieve catalysis. Acc. Chem. Res. 26, 111–115 (1993).

    Article  CAS  Google Scholar 

  3. Bruce, D. A., Wilkinson, A. P., White, M. G. & Bertrand, J. A. The synthesis and characterization of an aluminophosphate with chiral layers: trans-Co(dien)2·Al3P4O16·3H2O. J. Solid State Chem. 125, 228–233 (1996).

    Article  ADS  CAS  Google Scholar 

  4. Morgan, K., Gainsofrd, G. & Milestone, N. Anovel layered aluminum phosphate [Co(en) Al3P4O16·3H2O] assembled about a chiral metal complex. J. Chem. Soc. Chem. Commun. 425–426 (1995).

  5. Harrison, W. T. A., Gier, T. E., Stucky, G. D., Broach, R. W. & Bedard, R. A. NaZnPO4·H2O, an open-framework sodium zincophosphate with a new chiral tetrahedral framework topology. Chem. Mater. 8, 145–151 (1996).

    Article  CAS  Google Scholar 

  6. Soghomonian, V., Chen, Q., Haushalter, R. C., Zubieta, J. & O'Connor, C. J. An inorganic double helix:hydrothermal synthesis, structure, and magnetism of chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]·4H2O. Science 259, 1596–1599 (1993).

    Article  ADS  CAS  Google Scholar 

  7. Bu, X., Feng, P., Gier, T. E. & Stucky, G. D. Two ethylenediamine templated zeolite type structure sin zinc arsenate and cobalt phosphate systems. J. Solid State Chem. 136, 210–215 (1998).

    Article  ADS  CAS  Google Scholar 

  8. Smith, J. V. Topochemistry of zeolites and related materials. 1. Topology and geometry. Chem. Rev. 88, 148–182 (1988).

    Article  Google Scholar 

  9. Meier, W. M., Olson, D. H. & Baerlocher, C. Atlas of Zeolite Structure Types (Elsevier, Boston, (1996)).

    Google Scholar 

  10. Bu, X., Feng, P. & Stucky, G. D. Large-cage zeolite structures with multidimensional 12-ring channels. Science 278, 2080–2085 (1997).

    Article  ADS  CAS  Google Scholar 

  11. Monnier, A.et al. Cooperative formation of inorganic–organic interfaces in the synthesis of silicate mesostructures. Science 261, 1299–1303 (1994).

    Article  ADS  Google Scholar 

  12. Andersson, S. & Jacob, M. The Mathematics of Structures (R. Oldenbourg, München, (1997)).

    MATH  Google Scholar 

  13. Andersson, S., Hyde, S. T., Larsson, K. & Lidin, S. Minimal surfaces and structures: from inorganic and metal crystals to cell membranes and biopolymers. Chem. Rev. 88, 221–242 (1988).

    Article  CAS  Google Scholar 

  14. Nenoff, T. M.et al. Structural and chemical investigations of Na3(ABO4)3·4H2O-type sodalite phases. Inorg. Chem. 33, 2472–2480 (1994).

    Article  CAS  Google Scholar 

  15. Harrison, W. T. A., Gier, T. E. & Stucky, G. D. Two lithium chloroberyllo(phosphate/arsenate) sodalites: Li4Cl(BePO4)3and Li4Cl(BeAsO4)3. Acta Crystallogr. C 50, 471–473 (1994).

    Article  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

This research was supported in part by the National Science Foundation and the Office of Naval Research. P.F. thanks the Materials Research Laboratory for a Corning Foundation Fellowship. All figures were generated using software programs from Molecular Simulations.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of California, Santa Barbara, 93106, California, USA

    Thurman E. Gier, Xianhui Bu, Pingyun Feng & Galen D. Stucky

Authors
  1. Thurman E. Gier
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xianhui Bu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Pingyun Feng
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Galen D. Stucky
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Galen D. Stucky.

Supplementary Information

Rights and permissions

Reprints and permissions

About this article

Cite this article

Gier, T., Bu, X., Feng, P. et al. Synthesis and organization of zeolite-like materials with three-dimensional helical pores. Nature 395, 154–157 (1998). https://doi.org/10.1038/25960

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/25960

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