Skip to main content
    • Aa
    • Aa

Tuning cooperative vesicle templating and liquid crystal templating simply by varying silica source

  • Jun Zhang, Meihua Yu, Pei Yuan, Hongning Wang, Kun Qian, Lei Tan, Yunhua Wang (a1) and Chengzhong Yu (a2)...

The cooperative self-assembly of organic–inorganic siliceous composite structures has been studied from the aspect of inorganic precursors. We reveal that the vesicular or mesostructured materials can be obtained selectively by just changing the silica sources in one templating system. For poly(ethylene oxide)-type block copolymers with either poly(propylene oxide) or poly(butylene oxide) as the hydrophobic moieties, when the other synthesis parameters are exactly the same, the use of tetramethyl orthosilicate (TMOS) as a silica source gives rise to highly ordered mesostructures, while the use of tetraethyl orthosilicate (TEOS) leads to vesicles or foams. The attenuated total reflection Fourier transform infrared (ATR-FTIR) technique is used to monitor the silicate species derived from the hydrolysis and condensation of TMOS and TEOS as a function of the reaction time. On the basis of the ATR-FTIR results, we propose a “differentiating effect” at relatively high pH (4.7) to interpret the influence of different silica sources on the self-organized composite structures. For comparison, a “leveling effect” at relatively low pH (strong acidic conditions) is revealed to explain that both TMOS and TEOS lead to the same mesostructures. Our contribution provides a feasible and designable method to synthesize from conventional ordered mesostructures to novel vesicular structures, which are significant for their future practical applications.

Corresponding author
a)Address all correspondence to this author. e-mail:
Linked references
Hide All

This list contains references from the content that can be linked to their source. For a full set of references and notes please see the PDF or HTML where available.

1. L.F. Zhang , A. Eisenberg Multiple morphologies of crew-cut aggregates of polystyrene-B-poly(acrylic acid) block-copolymers. Science 268, 1728(1995)

2. M. Antonietti , S. Forster Vesicles and liposomes: A self-assembly principle beyond lipids. Adv. Mater. 15, 1323(2003)

3. K. Kita-Tokarczyk , J. Grumelard , T. Haefele , W. Meier Block copolymer vesicles—Using concepts from polymer chemistry to mimic biomembranes. Polymer (Guildf.) 46, 3540(2005)

4. B.M. Discher , Y.Y. Won , D.S. Ege , J.C.M. Lee , F.S. Bates , D.E. Discher , D.A. Hammer Polymersomes: Tough vesicles made from diblock copolymers. Science 284, 1143(1999)

5. P. Alexandridis , U. Olsson , B. Lindman A record nine different phases (four cubic, two hexagonal, and one lamellar lyotropic liquid crystalline and two micellar solutions) in a ternary isothermal system of an amphiphilic block copolymer and selective solvents (water and oil). Langmuir 14, 2627(1998)

6. F.S. Bates , G.H. Fredrickson Block copolymer thermodynamics: Theory and experiment. Annu. Rev. Phys. Chem. 41, 525(1990)

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

8. G.S. Attard , J.C. Glyde , C.G. Goltner Liquid-crystalline phases as templates for the synthesis of mesoporous silica. Nature 378, 366(1995)

9. A. Monnier , F. Schuth , Q. Huo , D. Kumar , D. Margolese , R.S. Maxwell , G.D. Stucky , M. Krishnamurty , P. Petroff , A. Firouzi , M. Janicke , B.F. Chmelka Cooperative formation of inorganic–organic interfaces in the synthesis of silicate mesostructures. Science 261, 1299(1993)

10. Q.S. Huo , D.I. Margolese , U. Ciesla , D.G. Demuth , P.Y. Feng , T.E. Gier , P. Sieger , A. Firouzi , B.F. Chmelka , F. Schuth , G.D. Stucky Organization of organic-molecules with inorganic molecular species into nanocomposite biphase arrays. Chem. Mater. 6, 1176(1994)

11. D.Y. Zhao , J.L. Feng , Q.S. Huo , N. Melosh , G.H. Fredrickson , B.F. Chmelka , G.D. Stucky Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279, 548(1998)

12. C. Sanchez , C. Boissiere , D. Grosso , C. Laberty , L. Nicole Design, synthesis, and properties of inorganic and hybrid thin films having periodically organized nanoporosity. Chem. Mater. 20, 682(2008)

13. F. Hoffmann , M. Cornelius , J. Morell , M. Froba Silica-based mesoporous organic–inorganic hybrid materials. Angew. Chem. Int. Ed. 45, 3216(2006)

14. D.H.W. Hubert , M. Jung , P.M. Frederik , P.H.H. Bomans , J. Meuldijk , A.L. German Vesicle-directed growth of silica. Adv. Mater. 12, 1286(2000)

15. P. Yuan , X.F. Zhou , H.N. Wang , N.A. Liu , Y.F. Hu , G.J. Auchterlonie , J. Drennan , X.D. Yao , G.Q. Lu , J. Zou , C.Z. Yu Electron-tomography determination of the packing structure of macroporous ordered siliceous foams assembled from vesicles. Small 5, 377(2009)

16. H.N. Wang , X.F. Zhou , M.H. Yu , Y.H. Wang , L. Han , J. Zhang , P. Yuan , G. Auchterlonie , J. Zou , C.Z. Yu Supra-assembly of siliceous vesicles. J. Am. Chem. Soc. 128, 15992(2006)

17. H.N. Wang , Y.H. Wang , X.F. Zhou , L. Zhou , J.W. Tang , J. Lei , C.Z. Yu Siliceous unilamellar vesicles and foams by using block-copolymer cooperative vesicle templating. Adv. Funct. Mater. 17, 613(2007)

18. B. Tan , S.M. Vyas , H.J. Lehmer , B.L. Knutson , S.E. Rankin Synthesis of inorganic and organic–inorganic hybrid hollow particles using a cationic surfactant with a partially fluorinated tail. Adv. Funct. Mater. 17, 2500(2007)

19. J. Fan , S.W. Boettcher , C.K. Tsung , Q. Shi , M. Schierhorn , G.D. Stucky Field-directed and confined molecular assembly of mesostructured materials: Basic principles and new opportunities. Chem. Mater. 20, 909(2008)

20. S. Forster , M. Zisenis , E. Wenz , M. Antonietti Micellization of strongly segregated block copolymers. J. Chem. Phys. 104, 9956(1996)

21. P. Bhargava , Y.F. Tu , J.X. Zheng , H.M. Xiong , R.P. Quirk , S.Z.D. Cheng Temperature-induced reversible morphological changes of polystyrene-block-poly(ethylene oxide) micelles in solution. J. Am. Chem. Soc. 129, 1113(2007)

22. J.M. Sun , D. Ma , H. Zhang , C.L. Wang , X.H. Bao , D.S. Su , A. Klein-Hoffmann , G. Weinberg , S. Mann Phase evolution in the alkane-P123-water-TEOS quadru-component system: A feasible route to different complex mesostructured materials. J. Mater. Chem. 16, 1507(2006)

23. T.S. Davies , A.M. Ketner , S.R. Raghavan Self-assembly of surfactant vesicles that transform into viscoelastic wormlike micelles upon heating. J. Am. Chem. Soc. 128, 6669(2006)

24. G.W. Zhou , Y.J. Chen , J.H. Yang , S.H. Yang From cylindrical-channel mesoporous silica to vesicle-like silica with well defined multilamella shells and large inter-shell mesopores. J. Mater. Chem. 17, 2839(2007)

25. J. Liu , Q.H. Yang , L. Zhang , D.M. Jiang , X. Shi , J. Yang , H. Zhong , C. Li Thioether-bridged mesoporous organosilicas: Mesophase transformations induced by the bridged organosilane precursor. Adv. Funct. Mater. 17, 569(2007)

26. J. Liu , C.M. Li , Q.H. Yang , J. Yang , C. Li Morphological and structural evolution of mesoporous silicas in a mild buffer solution and lysozyme adsorption. Langmuir 23, 7255(2007)

27. S.C. Warren , F.J. Disalvo , U. Wiesner Nanoparticle-tuned assembly and disassembly of mesostructured silica hybrids. Nat. Mater. 6, 156(2007)

28. C.J. Brinker , Y.F. Lu , A. Sellinger , H.Y. Fan Evaporation-induced self-assembly: Nanostructures made easy. Adv. Mater. 11, 579(1999)

29. S. Pevzner , O. Regev , A. Lind , M. Linden Evidence for vesicle formation during the synthesis of catanionic templated mesoscopically ordered silica as studied by Cryo-TEM. J. Am. Chem. Soc. 125, 652(2003)

30. M.J. Yuan , J.W. Tang , C.Z. Yu , Y.H. Chen , B. Tu , D.Y. Zhao The upper temperature limit in cooperative assembly of ordered mesoporous materials. Chem. Lett. 32, 660(2003)

31. N.L. Allinger , M. Rahman , J.H. Lii A molecular mechanics force-field (Mm3) for alcohols and ethers. J. Am. Chem. Soc. 112, 8293(1990)

32. M.I. Tejedor-Tejedor , L. Paredes , M.A. Anderson Evaluation of ATR-FTIR spectroscopy as an “in situ” tool for following the hydrolysis and condensation of alkoxysilanes under rich H2O conditions. Chem. Mater. 10, 3410(1998)

33. B. Tan , S.E. Rankin Study of the effects of progressive changes in alkoxysilane structure on sol-gel reactivity. J. Phys. Chem. B 110, 22353(2006)

34. D.Y. Zhao , J.Y. Sun , Q.Z. Li , G.D. Stucky Morphological control of highly ordered mesoporous silica SBA-15. Chem. Mater. 12, 275(2000)

35. C.Z. Yu , Y.H. Yu , D.Y. Zhao Highly ordered large caged cubic mesoporous silica structures templated by triblock PEO–PBO–PEO copolymer. Chem. Commun. (Camb.) 575(2000)

36. J.R. Matos , M. Kruk , L.P. Mercuri , M. Jaroniec , L. Zhao , T. Kamiyama , O. Terasaki , T.J. Pinnavaia , Y. Liu Ordered mesoporous silica with large cage-like pores: Structural identification and pore connectivity design by controlling the synthesis temperature and time. J. Am. Chem. Soc. 125, 821(2003)

37. L.C.C. da Silva , L.B.O. dos Santos , G. Abate , I.C. Cosentino , M.C.A. Fantini , J.C. Masini , J.R. Matos Adsorption of Pb2+, Cu2+ and Cd2+ in FDU-1 silica and FDU-1 silica modified with humic acid. Microporous Mesoporous Mater. 110, 250(2008)

38. T. Azzam , A. Eisenberg Control of vesicular morphologies through hydrophobic block length. Angew. Chem. Int. Ed. 45, 7443(2006)

39. J.C.M. Vanhest , D.A.P. Delnoye , M. Baars , M.H.P. Vangenderen , E.W. Meijer Polystyrene-dendrimer amphiphilic block-copolymers with a generation-dependent aggregation. Science 268, 1592(1995)

41. C.J. Brinker , G.W. Scherer Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing (Academic Press, New York1990)

42. C.E.A. Kirschhock , S.P.B. Kremer , P.J. Grobet , P.A. Jacobs , J.A. Martens New evidence for precursor species in the formation of MFI zeolite in the tetrapropylammonium hydroxide-tetraethyl orthosilicate-water system. J. Phys. Chem. B 106, 4897(2002)

43. S.A. Pelster , W. Schrader , F. Schuth Monitoring temporal evolution of silicate species during hydrolysis and condensation of silicates using mass spectrometry. J. Am. Chem. Soc. 128, 4310(2006)

44. S. Ruthstein , J. Schmidt , E. Kesselman , Y. Talmon , D. Goldfarb Resolving intermediate solution structures during the formation of mesoporous SBA-15. J. Am. Chem. Soc. 128, 3366(2006)

Recommend this journal

Email your librarian or administrator to recommend adding this journal to your organisation's collection.

Journal of Materials Research
  • ISSN: 0884-2914
  • EISSN: 2044-5326
  • URL: /core/journals/journal-of-materials-research
Please enter your name
Please enter a valid email address
Who would you like to send this to? *



Full text views

Total number of HTML views: 0
Total number of PDF views: 15 *
Loading metrics...

Abstract views

Total abstract views: 66 *
Loading metrics...

* Views captured on Cambridge Core between September 2016 - 21st September 2017. This data will be updated every 24 hours.