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:

Ordered macroporous materials by emulsion templating

Nature volume 389, pages 948–951 (1997)Cite this article

Abstract

Ordered macroporous materials with pore diameters comparable to optical wavelengths are predicted to have unique and highly useful optical properties such as photonic bandgaps1,2,3 and optical stop-bands4. Tight control over the pore size distribution might also lead to improved macroporous materials (those with pores greater than approximately 50 nm) for application as catalytic surfaces and supports5, adsorbents, chromatographic materials, filters6, light-weight structural materials7, and thermal, acoustic8 and electrical insulators9. Although methods exist for producing ordered porous materials with pore diameters less than 10 nm (refs 10, 11), there is no general method for producing such materials with uniform pore sizes at larger length scales. Here we report a new method for producing highly monodisperse macroporous materials with pore sizes ranging from 50 nm to several micrometres. Starting with an emulsion of equally sized droplets (produced through a repeated fractionation procedure12), we form macroporous materials of titania, silica and zirconia by using the emulsion droplets as templates around which material is deposited through a sol–gel process13. Subsequent drying and heat treatment yields solid materials with spherical pores left behind by the emulsion droplets. These pores are highly ordered, reflecting the self-assembly of the original monodisperse emulsion droplets into a nearly crystalline array14. We show that the pore size can be accurately controlled, and that the technique should be applicable to a wide variety of metal oxides and even organic polymer gels.

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: Scanning electron micrographs of porous titania produced in a nearly monodisperse emulsion showing honeycomb structures.
Figure 2: Control over pore size.
Figure 3: Effect of calcination temperature on physical properties of porous titania.
Figure 4: Scanning electron micrographs of emulsion templated materials, showing the applicability of the technique to different materials.

Similar content being viewed by others

References

  1. Yablonovitch, E. Photonic band-gap structures. J. Opt. Soc. Am. B 10, 283–295 (1993).

    Article  ADS  CAS  Google Scholar 

  2. Joannopoulos, J. D., Meade, R. D. & Winn, J. N. Photonic Crystals: Molding the Flow of Light (Princeton Univ. Press, (1995)).

    MATH  Google Scholar 

  3. Soukoulis, C. Photonic Band Gap Materials (Kluwer, Dordrecht, (1996)).

    Book  Google Scholar 

  4. Flaugh, P. L., O'Donnel, S. E. & Asher, S. A. Development of a new optical wavelength rejection filter: Demonstration of its utility in Raman spectroscopy. Appl. Spectrosc. 38, 847–850 (1984).

    Article  ADS  CAS  Google Scholar 

  5. Harold, M. P. et al. Catalysis with inorganic membranes. MRS Bull. 19, 34–39 (1994).

    Article  CAS  Google Scholar 

  6. Bhave, R. R. Inorganic membranes synthesis, characteristics, and applications (Van Nostrand Reinhold, New York, (1991)).

    Book  Google Scholar 

  7. Wu, M. X., Fujiu, T. & Messing, G. L. Synthesis of cellular inorganic materials by foaming sol gels. J. Non-Cryst. Solids 121, 407–412 (1990).

    Article  ADS  CAS  Google Scholar 

  8. Litovsky, E., Shapiro, M. & Shavit, A. Gas pressure and temperature dependences of thermal conductivity of porous ceramic materials. 2. Refractories and ceramics with porosity exceeding 30%. J. Am. Ceram. Soc. 79, 1366–1376 (1996).

    Article  CAS  Google Scholar 

  9. Singer, P. Low k dielectrics: the search continues. Semicond. Int. 19, 88–96 (1996).

    CAS  Google Scholar 

  10. Beck, J. S. et al. Anew family of mesoporous molecular sieves prepared with liquid crystal templates. J. Am. Chem. Soc. 114, 10834–10843 (1992).

    Article  CAS  Google Scholar 

  11. Krauss, T., Song, Y. P., Thoms, S., Wilkinson, C. D. W. & DelaRue, R. M. Fabrication of 2-D photonic bandgap stuctures in GaAs/AlGaAs. Electron. Lett. 30, 1444–1446 (1994).

    Article  CAS  Google Scholar 

  12. Bibette, J. Depletion interactions and fractionated crystallization for polydisperse emulsion purification. J. Colloid. Interface Sci. 147, 474–478 (1991).

    Article  ADS  CAS  Google Scholar 

  13. Brinker, C. J. & Scherer, G. W. Sol-Gel Science (Academic, San Diego, (1990)).

    Google Scholar 

  14. Pusey, P. N. & van Megen, W. Phase behaviour of concentrated suspensions of hard colloidal spheres. Nature 320, 340–342 (1986).

    Article  ADS  CAS  Google Scholar 

  15. Walsh, D. & Mann, S. Fabrication of hollow porous shells of calcium carbonate from self-organizing media. Nature 377, 320–323 (1995).

    Article  ADS  CAS  Google Scholar 

  16. Imhof, A. & Pine, D. J. Stability of nonaqueous emulsions. J. Colloid Interface Sci.(in the press).

  17. Dinsmore, A. D., Yodh, A. G. & Pine, D. J. Entropic control of particle motion using passive surface microstructures. Nature 383, 239–242 (1996).

    Article  ADS  CAS  Google Scholar 

  18. van Blaaderen, A., Ruel, R. & Wiltzius, P. Template-directed colloidal crystallization. Nature 385, 321–324 (1997).

    Article  ADS  CAS  Google Scholar 

  19. Hachisu, S. & Yoshimura, S. Optical demonstration of crystalline superstructures in binary mixtures of latex globules. Nature 283, 188–189 (1980).

    Article  ADS  CAS  Google Scholar 

  20. Bartlett, P., Ottewill, R. H. & Pusey, P. N. Superlattice formation in binary mixtures of hard-sphere colloids. Phys. Rev. Lett. 68, 3801–3804 (1992).

    Article  ADS  CAS  Google Scholar 

  21. Sanchez, C., Babonneau, F., Doeuff, S. & Leaustic, A. in Ultrastructure Processing of Advanced Ceramics (eds Mackenzie, J. D. & Ulrich, D. R.) 77–87 (Wiley, New York, (1988)).

    Google Scholar 

Download references

Acknowledgements

We thank F. Lange and G. Stucky for discussions, and Q. Huo for help with the adsorption measurements.

Author information

Authors and Affiliations

  1. Departments of Chemical Engineering and Materials, University of California, Santa Barbara, 93106-5080, California, USA

    A. Imhof & D. J. Pine

Authors
  1. A. Imhof
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. D. J. Pine
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to D. J. Pine.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Imhof, A., Pine, D. Ordered macroporous materials by emulsion templating. Nature 389, 948–951 (1997). https://doi.org/10.1038/40105

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/40105

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