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Direct imaging of the pores and cages of three-dimensional mesoporous materials

Nature volume 408, pages 449–453 (2000)Cite this article

Abstract

Mesostructured composite materials, with features ranging from 20 to 500 Å in size, are obtained by the kinetically controlled competitive assembly of organic and inorganic species into nanostructured domains. Short-range order is limited, and long-range order is determined by weak forces such as van der Waals or hydrogen-bonding. Three-dimensional mesoporous materials obtained by removing the organic phase are of particular interest for applications such as catalysis and chemical sensing or separation, for which structural features such as cavity shape, connectivity and ordered bimodal porosity are critical. But atomic-scale structural characterization by the usual diffraction techniques is challenging for these partially ordered materials because of the difficulty in obtaining large (> 10 µm) single crystals, and because large repeat spacings cause diffraction intensities to fall off rapidly with scattering angle so that only limited small-angle data are available. Here we present a general approach for the direct determination of three-dimensional mesoporous structures by electron microscopy. The structure solutions are obtained uniquely without pre-assumed models or parametrization. We report high-resolution details of cage and pore structures of periodically ordered mesoporous materials1,2, which reveal a highly ordered dual micro- and mesoscale pore structure.

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Figure 1: SEM images and X-ray powder diffraction patterns of as-synthesized SBA-1 (a) and SBA-6 (b) .
Figure 2: HREM images of SBA-6 (calcined) and their Fourier diffractograms.
Figure 3: Direct image of 3D cages and bimodal pore structure in SBA-6 and SBA-1.
Figure 4: HREM images of SBA-16 (calcined) and their Fourier diffractograms.
Figure 5: Direct image of 3D pore structure of SBA-16.

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References

  1. Zhao, D. et al. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 Ångstrom pores. Science 279, 548–552 (1998).

    Article  ADS  CAS  Google Scholar 

  2. Zhao, D., Huo, Q., Feng, J., Chmelka, B. F. & Stucky, G. D. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures. J. Am. Chem. Soc. 120 , 6024–6036 (1998).

    Article  CAS  Google Scholar 

  3. Alfredsson, V. & Anderson, M. W. Structure of MCM-48 revealed by transmission electron microscopy. Chem. Mater. 8 , 1141–1146 (1996).

    Article  CAS  Google Scholar 

  4. Monnier, A. et al. Cooperative formation of inorganic-organic interfaces in the synthesis of silicate mesostructures. Science 261, 1299–1303 (1993).

    Article  ADS  CAS  Google Scholar 

  5. Schacht, S., Janicke, M. & Schüth, F. Modeling X-ray patterns and TEM images of MCM-41. Microporous Mesoporous Mater. 22, 485– 493 (1998).

    Article  CAS  Google Scholar 

  6. Huo, Q. et al. Generalized syntheses of periodic surfactant/inorganic composite materials. Nature 368, 317– 321 (1994).

    Article  ADS  CAS  Google Scholar 

  7. Huo, Q. et al. Organization of organic molecules with inorganic molecular species into nanocomposite biphase arrays. Chem. Mater. 6, 1176–1191 (1994).

    Article  MathSciNet  CAS  Google Scholar 

  8. Auvray, X. et al. X-ray diffraction and freeze-fracture electron microscopy study of the cubic phase in the cetylpyridinium chloride formamide and cetyltrimethylammonium chloride formamide systems. Langmuir 9, 444–448 (1993).

    Article  CAS  Google Scholar 

  9. Charvolin, J. & Sadoc, J. F. Periodic systems of frustrated fluid films and “micellar” cubic structures in liquid crystals. J. Phys. France 49, 521– 526 (1988).

    Article  Google Scholar 

  10. Ryoo, R., Kim, J. M. & Ko, C. H. in Studies in Surface Science and Catalysis Vol. 117 (eds Bonneviot, L., Béland, F., Danumah, C., Giasson, S. & Kaliaguine, S.) 151–158 (Elsevier, Amsterdam, 1998).

    Google Scholar 

  11. Nakanishi, K. Pore structure control of silica gels based on phase separation. J. Porous Mater. 4, 67–112 (1997).

    Article  CAS  Google Scholar 

  12. Geis, H. Studies on clathrasils. III. Crystal structure of melanophlogite, a natural clathrate compound of silica. Z. Kristallogr. 164, 247–257 (1983).

    Google Scholar 

Download references

Acknowledgements

This work was supported in part by CREST, Japan Science and Technology Corporation (O.T.), by the National Research Laboratory Program of Korea (R.R.), and by the National Science Foundation (G.D.S.) and the Army Research Office (G.D.S.). O.T. thanks S. Andersson for encouragement and support. Y.S. thanks the Japan Society for the Promotion of Science.

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Author notes

  1. Osamu Terasaki, Galen Stucky and Ryong Ryoo: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Physics and CIR, Tohoku University, Sendai, 980-8578, Japan

    Yasuhiro Sakamoto, Mizue Kaneda & Osamu Terasaki

  2. CREST, Japan Science and Technology Corporation, Tohoku University, Sendai, 980-8578, Japan

    Osamu Terasaki

  3. Department of Chemistry, Fudan University, Shanghai, 200433, China

    Dong Yuan Zhao

  4. Department of Chemistry and Biochemistry University of California, Santa Barbara, 93106, California, USA

    Ji Man Kim

  5. Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical Technology, Yusong, Taejon , 305-600, Korea

    Ji Man Kim

  6. Department of Chemistry and Biochemistry and Materials Department, University of California, Santa Barbara , 93106, California, USA

    Galen Stucky

  7. Department of Chemistry (School of Molecular Science-BK21), Materials Chemistry Laboratory, Korea Advanced Institute of Science and Technology, Taejon, 305-701, Korea

    Hyun June Shin & Ryong Ryoo

Authors
  1. Yasuhiro Sakamoto
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  2. Mizue Kaneda
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  4. Dong Yuan Zhao
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  6. Galen Stucky
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  8. Ryong Ryoo
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Sakamoto, Y., Kaneda, M., Terasaki, O. et al. Direct imaging of the pores and cages of three-dimensional mesoporous materials. Nature 408, 449–453 (2000). https://doi.org/10.1038/35044040

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