Abstract
Surfactants have been shown to organize silica into a variety of mesoporous forms, through the mediation of electrostatic, hydrogen-bonding, covalent and van der Waals interactions1,2,3,4,5,6,7,8. This approach to mesostructured materials has been extended, with sporadic success, to non-silica oxides5,6,7,8,9,10,11,12,13,14,15,16,17, which might promise applications involving electron transfer or magnetic interactions. Here we report a simple and versatile procedure for the synthesis of thermally stable, ordered, large-pore (up to 140 Å) mesoporous metal oxides, including TiO2, ZrO2, Al2O3, Nb2O5, Ta2O5, WO3, HfO2, SnO2, and mixed oxides SiAlO3.5, SiTiO4, ZrTiO4, Al2TiO5 and ZrW2O8. We used amphiphilic poly(alkylene oxide) block copolymers as structure-directing agents in non-aqueous solutions for organizing the network-forming metal-oxide species, for which inorganic salts serve as precursors. Whereas the pore walls of surfactant-templated mesoporous silica1 are amorphous, our mesoporous oxides contain nanocrystalline domains within relatively thick amorphous walls. We believe that these materials are formed through a mechanism that combines block copolymer self-assembly with complexation of the inorganic species.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Kresge, C. T., Leonowicz, M. E., Roth, W. J., Vartuli, J. C. & Beck, J. S. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359, 710–712 (1992).
Huo, Q. et al. Generalized synthesis 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).
Tanev, P. T. & Pinnavaia, T. J. Aneutral templating route to mesoporous molecular sieves. Science 267, 865–868 (1995).
Antonelli, D. M. & Ying, J. Y. Synthesis and characterization of hexagonal packed mesoporous tantalum oxide molecular sieves. Chem. Mater. 8, 874–881 (1996).
Förster, S. & Antonietti, M. Amphiphilic block copolymers in structure-controlled nanomaterial hybrids. Adv. Mater. 10, 195–217 (1998).
Templin, M. et al. Organically modified aluminosilicate mesostructures from block copolymer phases. Science 278, 1795–1798 (1997).
Zhao, D. et al. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279, 548–552 (1998).
Tian, Z. et al. Manganese oxide mesoporous structures: mixed-valent semiconducting catalysts. Science 276, 926–930 (1997).
Bagshaw, S. A. & Pinnavaia, T. J. Mesoporous alumina molecular sieves. Angew. Chem. Int. Edn Engl. 35, 1102–1105 (1996).
Antonelli, D. M. & Ying, J. Y. Synthesis of hexagonal packed mesoporous TiO2by a modified sol-gel method. Angew. Chem. Int. Edn Engl. 34, 2014–2017 (1995).
Ciesla, U., Schacht, S., Stucky, G. D., Unger, K. K. & Schüth, F. Formation of a porous zirconium oxo phosphate with a high surface area by a surfactant-assisted synthesis. Angew. Chem. Int. Edn Engl. 35, 541–543 (1996).
Liu, P., Liu, J. & Sayari, A. Preparation of porous hafnium oxide in the presence of a cationic surfactant. Chem. Commun. 557–578 (1997).
Attard, G. S. et al. Mesoporous platinum films from lyotropic liquid crystalline phases. Science 278, 838–840 (1997).
Ulagappan, N. & Rao, C. N. R. Mesoporous phases based on SnO2and TiO2. Chem. Commun. 1685–1686 (1996).
Braun, P. V., Osenar, P. & Stupp, S. I. Semiconducting superlattices templated by molecular assemblies. Nature 380, 325–328 (1996).
Sayari, A. & Liu, P. Non-silica mesostructured materials: recent progress. Microporous Mater. 12, 149–177 (1997).
Stucky, G. D. et al. in The Robert A. Welch Foundation 40th Conference on Chemical Research: Chemistry on the Nanometer Scale 101–112 (Houston, Texas), (1996).
Monnier, A. et al. Cooperative formation of inorganic-organic interfaces in the synthesis of silicate mesostructures. Science 261, 1299–1302 (1993).
Beck, J. S. et al. Anew family of mesoporous molecular sieves prepared with liquid crystal templates. J.Am. Chem. Soc. 114, 10834–10843 (1992).
Huang, Y., McCarthy, T. J. & Sachtler, W. M. Preparation and catalytic testing of mesoporous sulfated zirconium dioxide with partially tetragonal wall structure. Appl. Catal. A 148, 135–154 (1996).
Gregg, S. J. & Sing, K. S. W. Adsorption, Surface Area and Porosity (Academic, London, (1982).
Bailey, F. E. J & Koleske, J. V. Alkylene Oxides and their Polymers (Marcel Dekker, New York, (1990).
Zhao, D. et al. 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).
Yang, P. et al. Triblock-copolymer-directed syntheses of large-pore mesoporous silica fibers. Chem. Mater. 10, 2033–2036 (1998).
Vioux, A. Nonhydrolytic sol-gel routes to oxides. Chem. Mater. 9, 2292–2299 (1997).
Acknowledgements
This work was supported by the NSF and the US Army Research Office. This work made use of MRL Central Facilities supported by the NSF. B.F.C. is a Camille and Henry Dreyfus teacher-scholar and an Alfred P. Sloan research fellow. We thank BASF (Mt Olive, New Jersey) and Dow Chemicals for providing block copolymer surfactants.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Yang, P., Zhao, D., Margolese, D. et al. Generalized syntheses of large-pore mesoporous metal oxides with semicrystalline frameworks. Nature 396, 152–155 (1998). https://doi.org/10.1038/24132
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/24132
This article is cited by
-
Zirconium oxide-porous carbon derived from metal-organic frameworks as a new sensing platform: application to simultaneous voltammetric determination of ascorbic acid, dopamine and uric acid
Journal of the Iranian Chemical Society (2024)
-
Solvent-pair surfactants enabled assembly of clusters and copolymers towards programmed mesoporous metal oxides
Nature Communications (2023)
-
Monomicellar assembly to synthesize structured and functional mesoporous carbonaceous nanomaterials
Nature Protocols (2023)
-
N-doped nanocarbon embedded in hierarchically porous metal-organic frameworks for highly efficient CO2 fixation
Science China Chemistry (2022)
-
The interaction of molybdenum and titanium in mesoporous materials for olefin epoxidation
Reaction Kinetics, Mechanisms and Catalysis (2022)
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.