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Self-adjusted synthesis of ordered stable mesoporous minerals by acid–base pairs

Abstract

Although the chemical diversity of ordered composite mesoporous materials has been expanding during the past decade1,2,3,4,5,6,7,8,9,10,11,12,13, progress has been limited by the need for a general synthetic approach that is predictive and makes use of well developed fundamental chemical principles. Researchers have previously used the interaction of organic–inorganic (OI) species that are present during the nucleation of the composite phase, and several synthesis pathways, such as direct surfactant–inorganic interaction (S+I, SI+, S0I0) and mediated interaction (S+XI+, SX+I), have been proposed2,3. Here we describe a new perspective in which the self-adjusted inorganic–inorganic (II) interplay between two or more inorganic precursors is guided by acid–base chemistry considerations, and in this simple way we produce an overall 'framework' for the sophisticated combination of synergic inorganic acid–base precursor pairs. We propose several new routes and demonstrate their versatility and validity through the successful syntheses of a wide variety of highly ordered, large-pore, homogeneous, stable and multicomponent mesostructured minerals, including metal phosphates and metal borates, as well as various metal oxides and mixed metal oxides. We show that the highly ordered mesostructured metal phosphates can be moulded into morphologies of choice, and that they show interesting physicochemical properties.

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Figure 1: General scheme of the 'acid–base pair' concept and guided synthetic routes for mesoporous minerals.
Figure 2: XRD patterns of representative calcined (except for the lamellar mesophase) mesoporous metal phosphates.
Figure 3: TEM images.
Figure 4: Designer morphologies.

References

  1. Kresge, C.T., Leonowicz, M.E., Roth, W.J., Varuli, J.C. & Beck, J.S. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359, 710–712 (1992).

    CAS  Article  Google Scholar 

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

    CAS  Article  Google Scholar 

  3. Tanev, P.T. & Pinnavaia, T.J. A neutral templating route to mesoporous molecular-sieves. Science 267, 865–867 (1995).

    CAS  Article  Google Scholar 

  4. Antonelli, D.M. & Ying, J.Y. Synthesis of a stable hexagonally packed mesoporous niobium oxide molecular sieve through a novel ligand-assisted templating mechanism. Angew. Chem. Int. Edn 35, 426–430 (1996).

    CAS  Article  Google Scholar 

  5. Attard, G.S. et al. Mesoporous platinum films from lyotropic liquid crystalline phases. Science 278, 838–840 (1997).

    CAS  Article  Google Scholar 

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

    CAS  Article  Google Scholar 

  7. Yang, P., Zhao, D., Margolese, D.I., Chmelka, B.F. & Stucky, G.D. Generalized syntheses of large-pore mesoporous metal oxides with semicrystalline frameworks. Nature 396, 152–155 (1998).

    CAS  Article  Google Scholar 

  8. Asefa, T., MacLachlan, M.J., Coombs. N. & Ozin, G.A. Periodic mesoporous organosilicas with organic groups inside the channel walls. Nature 402, 867–871 (1999).

    CAS  Article  Google Scholar 

  9. Ryoo, R., Joo, S.H. & Jun, S. Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation. J. Phys. Chem. B 103, 7743–7746 (1999).

    CAS  Article  Google Scholar 

  10. Inagaki, S., Guan, S., Ohsuna, T. & Terasaki, O. Mesoporous organic–silica hybrid with crystal-like pore walls. Nature 416, 304–307 (2002).

    CAS  Article  Google Scholar 

  11. Schüth, F. Non-siliceous mesostructured and mesoporous materials. Chem. Mater. 13, 3184–3195 (2001).

    Article  Google Scholar 

  12. Sakamoto, Y. et al. Direct imaging of the pores and cages of three-dimensional mesoporous materials. Nature 408, 449–453 (2000).

    CAS  Article  Google Scholar 

  13. Stucky, G.D. et al. Directed synthesis of organic/inorganic composite structures. Stud. Surf. Sci. Catal. 105, 3–28 (1997).

    Article  Google Scholar 

  14. Corriu, R.J.P. & Leclercq, D. Recent developments of molecular chemistry for sol–gel process. Angew. Chem. Int. Edn 35, 1420–1436 (1996).

    Article  Google Scholar 

  15. Vioux, A. Nonhydrolytic sol–gel routes to oxides. Chem. Mater. 9, 2292–2299 (1997).

    CAS  Article  Google Scholar 

  16. Tiemann, M. & Fröba, M. Mesostructured aluminophosphates synthesized with supramolecular structure directors. Chem. Mater. 13, 3211–3217 (2001).

    CAS  Article  Google Scholar 

  17. Braun, P.V., Osenar, P., Tohver, V., Kennedy, S.B. & Stupp. S.I. Nanostructure templating in inorganic solids with organic lyotropic liquid crystals. J. Am. Chem. Soc. 121, 7302–7309 (1999).

    CAS  Article  Google Scholar 

  18. Zhao, D., Luan, Z. & Kevan, L. Synthesis of thermally stable mesoporous hexagonal aluminophosphate molecular sieves. Chem. Commun. 1009–1010 (1997).

  19. Bhaumik, A. & Inagaki, S. Mesoporous titanium phosphate molecular sieves with ion-exchange capacity. J. Am. Chem. Soc. 123, 691–696 (2001).

    CAS  Article  Google Scholar 

  20. Serre, C., Magnier, C., Hervieu, M., Taulelle, F. & Férey, G. Synthesis and characterization of mesostructured titanium(IV) fluorophosphates with a semicrystalline inorganic framework. Chem. Mater. 14, 180–188 (2002).

    CAS  Article  Google Scholar 

  21. 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 35, 541–543 (1996).

    CAS  Article  Google Scholar 

  22. Jiménez-Jiménez, J. et al. Surfactant-assisted synthesis of a mesoporous form of zirconium phosphate with acidic properties. Adv. Mater. 10, 812–815 (1998).

    Article  Google Scholar 

  23. Doi, T. & Miyake, T. Synthesis of a novel mesoporous VPO compound. Chem. Commun. 1635–1636 (1996).

  24. Mizuno, N., Hatayama, H., Uchida, S. & Taguchi, A. Tunable one-pot syntheses of hexagonal-, cubic-, and lamellar-mesostructured vanadium-phosphorus oxides. Chem. Mater. 13, 179–184 (2001).

    CAS  Article  Google Scholar 

  25. Guo, X.F., Ding, W.P., Wang, X.G. & Yan, Q.J. Synthesis of a novel mesoporous iron phosphate. Chem. Commun. 709–710 (2001).

  26. Nenoff, T.M., Thoma, S.G., Provencio, P. & Maxwell, R.S. Novel zinc phosphate phases formed with chiral d-glucosamine molecules. Chem. Mater. 10, 3077–3080 (1998).

    CAS  Article  Google Scholar 

  27. Mal, N.K., Ichikawa, S. & Fujiwara, M. Synthesis of a novel mesoporous tin phosphate, SnPO4 . Chem. Commun. 112–113 (2002).

  28. Serre, C., Auroux, A., Gervasini, A., Hervieu, M. & Férey, G. Hexagonal and cubic thermally stable mesoporous tin(IV) phosphates with acidic and catalytic properties. Angew. Chem. Int. Edn 41, 1594–1597 (2002).

    CAS  Article  Google Scholar 

  29. Tian, B. et. al. Fast preparation of highly ordered nonsiliceous mesoporous materials via mixed inorganic precursors. Chem. Commun. 1824–1825 (2002).

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant nos 29925309, 20233030 and 20173012), Shanghai Nanotechnology Center (0152nm029, 0212nm043), State Key Basic Research Program of PR China (2002AA321010, G2000048001 and 2001CB610505) and Graduate Funds of Fudan University. G.D.S. thanks the US National Science Foundation for support under the MRL Program, award no. DMR-0080034. B.Z.T. and D.Y.Z. thank H. H. He, Z. Y. Jiang, Q. Z. Li, M. J. Yuan, H. F. Yang, H. W. Jiang, H. Y. Chen, Y. Huang, Q. Wu, F. Q. Zhang and J. X. Chen for experimental and characterization assistance.

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Correspondence to Dongyuan Zhao.

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Tian, B., Liu, X., Tu, B. et al. Self-adjusted synthesis of ordered stable mesoporous minerals by acid–base pairs. Nature Mater 2, 159–163 (2003). https://doi.org/10.1038/nmat838

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