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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References
Zhao, D. et al. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 Ångstrom pores. Science 279, 548–552 (1998).
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).
Alfredsson, V. & Anderson, M. W. Structure of MCM-48 revealed by transmission electron microscopy. Chem. Mater. 8 , 1141–1146 (1996).
Monnier, A. et al. Cooperative formation of inorganic-organic interfaces in the synthesis of silicate mesostructures. Science 261, 1299–1303 (1993).
Schacht, S., Janicke, M. & Schüth, F. Modeling X-ray patterns and TEM images of MCM-41. Microporous Mesoporous Mater. 22, 485– 493 (1998).
Huo, Q. et al. Generalized syntheses of periodic surfactant/inorganic composite materials. Nature 368, 317– 321 (1994).
Huo, Q. et al. Organization of organic molecules with inorganic molecular species into nanocomposite biphase arrays. Chem. Mater. 6, 1176–1191 (1994).
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).
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).
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).
Nakanishi, K. Pore structure control of silica gels based on phase separation. J. Porous Mater. 4, 67–112 (1997).
Geis, H. Studies on clathrasils. III. Crystal structure of melanophlogite, a natural clathrate compound of silica. Z. Kristallogr. 164, 247–257 (1983).
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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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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DOI: https://doi.org/10.1038/35044040
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