Synthesis of ordered mesoporous materials using surfactant liquid crystals or micellar solutions

Current Opinion in Colloid and Interface Science

Volumn 8, Issue 2, 2003, Pages 145-155

  Palmqvist, Anders E C ^a  

^a CHALMERS UNIVERSITY OF TECHNOLOGY   (Sweden)

Author keywords

Cooperative assembly; Formation mechanism; Mesoporous materials synthesis; Ordered porous solids; Self assembly

Indexed keywords

CONDENSATION; HYDROLYSIS; LIQUID CRYSTALS; MICELLES; OXIDES; SURFACE ACTIVE AGENTS; SYNTHESIS (CHEMICAL); WATER;

INORGANIC PRECURSORS; INORGANIC SPECIES; ORGANIC COMPONENTS; SURFACTANT LIQUID CRYSTALS;

MESOPOROUS MATERIALS;

CHEMICAL INTERACTION; CHEMICAL STRUCTURE; CRYSTAL; HYDROLYSIS; MICELLE; POLYMERIZATION; REVIEW; SURFACE PROPERTY; SYNTHESIS;

EID: 0242452454     PISSN: 13590294     EISSN: None     Source Type: Journal    
DOI: 10.1016/S1359-0294(03)00020-7     Document Type: Review

References (47)

1. [1a] Beck JS, Vartuli JC, Roth WJ, et al. A new family of mesoporous molecular-sieves prepared with liquid-crystal templates. J Am Chem Soc 1992;114:10834-43.
2. [1b] Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS. Ordered mesoporous molecular sieves synthesized by a liquid crystal template mechanism. Nature 1992;359:710-2.
3. Yanagisawa T, Shimizu T, Kuroda K, Kato C. The preparation of alkyltrimethylammonium-kanemite complexes and their conversion to microporous materials. Bull Chem Soc Jpn 1990;63:988-92.
4. Patarin J, Lebeau B, Zana R. Recent advances in the formation mechanism of organized mesoporous materials. Curr Opin Coll Interface Sci 2002;7:107-15. A recent review on the understanding of the mechanism of formation of organized mesoporous materials. The importance of using in situ techniques for obtaining information of the formation mechanism is emphasised.
5. Huo Q, Margolese DI, Ciesla U, et al. Organization of organic molecules with inorganic molecular species into nanocomposite biphase arrays. Chem Mater 1994;6:1176-91.
6. Ying JY, Mehnert CP, Wong MS. Synthesis and applications of supramolecular-templated mesoporous materials. Angew Chem Int Ed 1999;38:56-77.
7. Coleman NRB, Attard GS. Ordered mesoporous silicas prepared from both micellar solutions and liquid crystal phases. Micropor Mesopor Mater 2001;44-45:73-80. A study of the effects of surfactant concentration on the properties of mesoporous silica prepared from both micellar and liquid crystal phases. An ordered hexagonal phase can be obtained through both routes and the order depends much on the surfactant concentration.
8. Klotz M, Ayral A, Guizard C, Cot L. Synthesis conditions for hexagonal mesoporous silica layers. J Mater Chem 2000;10:663-9. Showed that the two main synthesis parameters of importance in the preparation of hexagonal mesoporous silica from alcoholic acidic solutions of alkyltrimethylammonium bromides and TEOS are an optimal ageing time of the sol before deposition, and the surfactant volume fraction in the medium after removal of the volatile components. The synthesis conditions for ordered silica mesostructures could be predicted from the corresponding water-surfactant phase diagrams.
9. Alberius PCA, Frindell KL, Hayward RC, Kramer EJ, Stucky GD, Chmelka BF. General predictive syntheses of cubic, hexagonal, and lamellar silica and titania mesostructured thin films. Chem Mater 2002;14:3284-94. A general method for predictably controlling mesostructures of silica and titania thin films based on the binary water-surfactant phase diagram is presented. The authors emphasise the necessity to employ inorganic precursors that are hydrophilic but cross-link slowly for the approach to work.
10. Grosso D, Balkenende AR, Albouy PA, Ayral A, Amenitsch H, Babonneau F. Two-dimensional hexagonal mesoporous silica thin films prepared from block copolymers: detailed characterization and formation mechanism. Chem Mater 2001;13:1848-56. In-situ time-resolved SAXS experiments were used to follow the formation of dip-coated two-dimensional hexagonal mesoporous silica films prepared from block copolymers.
11. Klotz M, Albouy P-A, Ayral P-A, et al. The true structure of hexagonal mesophase-templated silica films as revealed by X-ray scattering: effects of thermal treatments and of nanoparticle seeding. Chem Mater 2001;12:1721-8. Structure of mesoporous silica films prepared in alcoholic solutions by CTAB and TEOS studied by TEM and 2D SAXS using two different scattering geometries giving access to both in-plane preferential orientation and out-of-the-plane organisation.
12. 3/mmc) silica thin films using alcoholic solutions of CTAB and TEOS. The c-axis was found normal to substrate throughout the entire film thickness.
13. Besson S, Gacoin T, Jacquiod C, Ricolleau C, Babonneau D, Boilot J-P. Structural study of 3D-hexagonal mesoporous spin-coated sol-gel films. J Mater Chem 2000;10:1331-6. Spin-coated mesostructured silica films deposited on a glass substrate studied by grazing incidence SAXS present a gradient of ordering, with a 3D-hexagonal mesophase near the surface and a disordered micellar structure at the interior. The degree of condensation of the silica in the starting sol and the film thickness affect the overall quality of the films. Optimisation of these two parameters allows extending the 3D-hexagonal ordering and the texturing over all the film thickness.
14. 2 despite their differences in kinetics and coordination aspects.
15. Edler KJ, Goldar A, Hughes AV, Roser SJ, Mann S. Structural studies on surfactant-templated silica films grown at the air/ water interface. Micropor Mesopor Mater 2001;44-45:661-70. In-situ characterisation of the air/water interface of a growing CTAB-templated mesoporous silica film using specular and off-specular X-ray reflectivity techniques, Brewster angle microscopy and surface pressure measurements.
16. Brennan T, Hughes AV, Roser SJ, Mann S, Edler KJ. Concentration-dependent formation mechanisms in mesophase silica-surfactant films. Langmuir 2002;18:9838-44. An in-situ characterisation of the air/water interface of a growing CTAB-templated mesoporous silica film using specular and off-specular X-ray reflectivity. Found that the CTAB/TMOS molar ratio affected the film formation mechanism.
17. Yao N, Ku AY, Nakagawa N, Lee T, Saville DA, Aksay IA. Disorder-order transition in mesoscopic silica thin films. Chem Mater 2000;12:1536-48. An electron microscopy study of the formation of mesoscopic silica thin films showing a disorder-to-order transition occurring in a surface layer and originating at the air/water interface.
18. Yu K, Hurd AJ, Eisenberg A, Brinker CJ. Syntheses of silica/polystyrene- block-poly(ethylene oxide) films with regular and reverse mesostructures of large characteristic length scales by solvent evaporation-induced self-assembly. Langmuir 2001;17:7961-5. Preparation of silica/diblock polymer mesostructures ranging from regular to reverse through vesicular, using the same diblock polymer but different diblock/silica molar ratios.
19. Pevzner S, Regev O. The in-situ phase transitions occurring during bicontinuous cubic phase formation. Micropor Mesopor Mater 2000;38:413-21. In-situ XRD is used to study the phase transformations in the formation of cubic MCM-48 under alkaline pH conditions.
20. Landry CC, Tolbert SH, Gallis KW, et al. Phase transformations in mesostructured silica/surfactant composites. Mechanisms for change and applications to materials synthesis. Chem Mater 2001;13:1600-8. In-situ XRD is used to study the phase transformation from hexagonal MCM-41 to cubic MCM-48 under high pH conditions when the system responds to changes in surfactant packing. The effects of temperature and alcohols partitioning from different silicon alkoxides on the phase transformation were illuminated.
21. Tolbert SH, Landry CC, Stucky GD, et al. Phase transitions in mesostructured silica/surfactant composites. Surfactant packing and the role of charge density matching. Chem Mater 2001;13:2247-56. In-situ XRD was used to study the phase transformation from hexagonal MCM-41 to cubic MCM-48 under high pH conditions when the system responds to changes in surfactant packing. Effects of charge density matching on the kinetics of the phase transitions and the observed phases were found.
22. 29Si MAS-NMR were used to study the effect of pH on kinetics of annealing and phase transformation of silica/ surfactant composites prepared under alkaline conditions.
23. Che S, Kamiya S, Terasaki O, Tatsumi T. The formation of cubic Pm-3n mesostructure by an epitaxial phase transformation from hexagonal p6mm mesophase. J Am Chem Soc 2002;123:12089-90. An electron crystallography and SAXS study of the synthesis of cubic SBA-1 from an acidic solution of CTEABr and TEOS. Showed that the formation involves epitaxial phase transformation from a hexagonal phase.
24. Soler-Illia GJDAA, Sanchez C. Interactions between poly(ethylene oxide)-based surfactants and transition metal alkoxides: their role in the templated construction of mesostructured hybrid organic-inorganic composites. New J Chem 2000;24:493-9. Solid state NMR and UV-Vis spectroscopy were used to study the interactions between PEO-based amphiphiles and transition metal alkoxides that occur in the first steps of mesostructured oxide formation.
25. Soler-Illia GJDAA, Scolan E, Louis A, Albouy P-A, Sanchez C. Design of meso-structured titanium oxo based hybrid organic-inorganic networks. New J Chem 2001;25:156-65. The synthesis of titanium oxo clusters and their use in the preparation of mesostructured hybrid materials were studied. Self-assembly of clusters is an interesting approach to achieve structural control at the mesoscale.
26. Soler-Illia GJDAA, Louis A, Sanchez C. Synthesis and characterization of mesostructured titania-based materials through evaporation-induced self-assembly. Chem Mater 2002;14:750-9. Hydrophilic titanium oxo clusters are first formed and then self-assemble together with CTAB upon solvent evaporation to produce organized hybrid mesostructures. The role of surfactant and acid concentrations and temperature were discussed to further understand their influence on the formation.
27. Boissière C, Larbot A, van der Lee A, Kooyman PJ, Prouzet E. A New synthesis of mesoporous MSU-X silica controlled by a two-step pathway. Chem Mater 2000;12:2902-13. A two-step method was used to prepare mesoporous MSU-X silica materials. The first step resulted in stable micellar hybrid particles that were condensed in the second step either by increasing the pH or preferably by addition of fluoride.
28. Boissière C, Larbot A, Bourgaux C, Prouzet E, Bunton CA. A study of the assembly mechanism of the mesoporous MSU-X silica two-step synthesis. Chem Mater 2001;13:3580-6. The stable micellar hybrid particles formed in the two-step method were analysed using NMR, SAXS and DLS. They were found to be adjustable in size between 7 and 12 nm and have a three-layered structure consisting of an alkyl core, a first shell of PEO, and a second shell of silica.
29. Sakamoto Y, Kaneda M, Terasaki O, et al. Direct imaging of the pores and cages of three-dimensional mesoporous materials. Nature 2000;408:449-53. Modified the original synthesis of SBA-1 and SBA-16 to obtain faceted single crystals and used these to solve the structure of the materials using electron microscopy.
30. Che S, Sakamoto Y, Terasaki O, Tatsumi T. Control of crystal morphology of SBA-1 mesoporous silica. Chem Mater 2001;13:2237-9. By varying the synthesis temperature of mesoporous SBA-1 the morphology of single crystals could be controlled. This was explained by a transition between kinetically and thermodynamically controlled crystallisation.
31. Kipkemboi P, Fogden A, Alfredsson V, Flodström K. Triblock copolymers as templates in mesoporous silica formation: structural dependence on polymer chain length and synthesis temperature. Langmuir 2001;17:5398-402. A study of the effect of EO block length in Pluronic block copolymers on the mesostructure of silica. It was shown that the same tendency to adopt different structures depending on temperature and EO/PO ratio found in the binary water/polymer systems also appears when including silica.
32. El Haskouri J, Cabrera S, Caldés M, et al. Surfactant-assisted synthesis of the SBA-8 mesoporous silica by using nonrigid commercial alkyltrimethyl ammonium surfactants. Chem Mater 2002;14:2637-43. By replacing TEOS with silatrane derivatives of TEAH3 it was shown possible to use CTAB as template instead of the bolaform surfactant used in the original SBA-8 synthesis. This was explained by that TEAH3 distorts the micelles and affects the temperature dependence of the phase diagram.
33. Hüsing N, Launay B, Doshi D, Kickelbick G. Mesostructured silica-titania mixed oxide thin films. Chem Mater 2002;14:2429-32. A method for formation of mixed silica-titania mesoporous films utilizing the self-assembly behaviour of new metal-coordinated surfactant molecules and simultaneous sol-gel processing. Coordinating the titanium alkoxide with the polar head-group of the non-ionic surfactant solved the problem with unequal hydrolysis rates of the two alkoxides.
34. Kim JM, Sakamoto Y, Hwang YK, et al. Structural design of mesoporous silica by micelle-packing control using blends of amphiphilic block copolymers. J Phys Chem B 2002;106:2552-8. Blends of non-ionic amphiphilic block copolymers were used to obtain lamellar, hexagonal and cubic mesostructures. A relationship between the hydrophilic-hydrophobic ratios in the polymer blends and the resulting silica/amphiphile mesostructures was found.
35. Zhao D, Sun J, Li Q, Stucky GD. Morphological control of highly ordered mesoporous silica SBA-15. Chem Mater 2000;12:275-9. A wide range of morphologies was obtained for the highly ordered mesoporous silica SBA-15 through additions of cosolvents, cosurfactants and inorganic electrolytes to acidic solutions of Pluronic block copolymers.
36. Liu X, Tian B, Yu C, et al. Room-temperature synthesis in acidic media of large-pore three-dimensional bicontinuous mesoporous silica with Ia3d symmetry. Angew Chem Int Ed 2002;41:3876-8. A synthesis of three-dimensional bicontinuous mesoporous silica with Ia3d symmetry prepared under acidic conditions and low temperature in ethanol solution by a solvent-evaporation method using Pluronic amphiphiles and additives of organosiloxane and small organic molecules. The additives affect the curvature of the cooperatively assembled inorganic-organic mesostructure, which results in a transition from high-curvature hexagonal p6mm to low-curvature Ia3d.
37. 3 as acid.
38. Leontidis E. Hofmeister anion effects on surfactant self-assembly and the formation of mesoporous solids. Curr Opin Coll Interface Sci 2002;7:81-91. A recent review over the reported Hofmeister anion effects on surfactant self-assembly and the formation of mesoporous solids.
39. 2-adsorption and electron microscopy. Discusses the effects on both the aggregation characteristics of the amphiphile and on the rate and extent of silicon alkoxide hydrolysis and condensation.
40. Kim JM, Han Y-J, Chmelka BF, Stucky GD. One-step synthesis of ordered mesocomposites with non-ionic amphiphilic block copolymers: implications of isoelectric point, hydrolysis rate and fluoride. Chem Commun 2000;2437-8. Shows the preparation of highly ordered block copolymer/silica mesostructures over the wide pH range 0-9 by controlling the relative rates of hydrolysis and condensation of silica species through the use of fluoride and TMOS.
41. Yu C, Tian B, Fan J, Stucky GD, Zhao D. Salt effect in the synthesis of mesoporous silica templated by non-ionic block copolymers. Chem Commun 2001;2726-7. Salt additions lower the temperature required to achieve high mesostructured order in silica as a result of decreased CMC. The effect provides an interesting alternative for syntheses of highly ordered mesoporous materials using surfactants with high CMC values or when a high temperature is undesired.
42. 4 to increase the usually weaker interaction between the silicate species and the non-ionic block copolymer.
43. Frasch J, Lebeau B, Soulard M, Patarin J, Zana R. In situ investigations on cetyltrimethylammonium surfactant/silicate systems, precursors of organized mesoporous MCM-41-type siliceous materials. Langmuir 2000;16:9049-57. Fluoresence probing techniques were used to study the properties of CTAC and CTAB micelles upon additions of base and silicate to generate systems used in the preparation of mesoporous silica under alkaline conditions. A mechanism was proposed in which siliceous prepolymers form and grow via binding of surfactant ions, and at some point precipitate as a mesomorphous surfactant ion/polymerised silica complex.
44. Zhang J, Luz Z, Zimmermann H, Goldfarb D. The formation of the mesoporous material MCM-41 as studied by EPR line shape analysis of spin probes. J Phys Chem B 2000;104:279-85. Electron spin echo envelope modulation (ESEEM) experiments of the spin probe 5DSA were used to study formation mechanism of mesoporous MCM-41 silica. The results showed that 5DSA is incorporated into the organic part of the CTAB micelles and that its nitroxide radical is located near the organic-inorganic interface of the surfactant molecules during the formation of MCM-41. In situ EPR spectra of 5DSA were measured during the formation of mesoporous silica and showed two clear stages in the coarse of reaction.
45. Zhang J, Goldfarb D. In situ investigations of the formation mechanism of mesoporous materials via the dynamics and ordering of spin-probes - pH and Si/surfactant effect. Micropor Mesopor Mater 2001;48:143-9. In situ EPR of 5DSA was used to study the effects of pH and silica/surfactant ratio on the formation mechanism of mesoporous silica. The results suggest that the rate-determining step of the reaction is the silicate condensation, which strongly depends on the hydrolysis rate of TEOS.
46. Zhang J, Carl PJ, Zimmermann H, Goldfarb D. Investigation of the formation of MCM-41 by electron spin-echo envelope modulation spectroscopy. J Phys Chem B 2002;106:5382-9. The spin probe CAT16 was added to the in-situ EPR experiments of MCM-41 formation. It was found that the formed silica layer has high water content, which was easily removed by filtering and drying at room temperature.
47. Ottaviani MF, Galameau A, Desplantier-Giscard D, Di Renzo F, Fajula F. EPR investigations on the formation of micelle-templated silica. Micropor Mesopor Mater 2001;44-45:1-8. In situ EPR investigation using CATm spin probes of the formation of micelle-templated silica in combination with XRD. The surfactant mobility decrease corresponded to a transformation of an amorphous solid into an ordered hexagonal mesostructure according to XRD.