Mesostructured materials

Higgins D A, Vanden Bout D A, Kerimo J and Barbara P F 1996 Polarization-modulation near-field scanning optical microscopy of mesostructured materials J. Chem. Phys. 100 13 794-803... 

Many studies on template thermal degradation have been reported on zeolites of industrial interest including ZSM5 [1-5], silicalite [1], and beta [6-8], as well as surfactant-templated mesostructured materials [9-13]. The latter are structurally more sensitive than molecular sieves. Their structure usually shrinks upon thermal treatment. The general practice is slow heating at 1 °C min (N2/air) up to 550 °C, followed by a temperature plateau. 

Proceedings of the Fourth Tokyo Conference on Advanced Catalytic Science and Technology, Tokyo, July 14-19, 2002 edited by M. Anpo, M. Onaka and H. Yamashita Volume 146 Nanotechnology in Mesostructured Materials... 

Fig. 11 Pore size distributions and TEM images of ZrOi 4Si02 materials formed from Zr[OSi(O Bu)3]4. The upper portion shows a xerogel and the bottom portion shows a mesostructured material...

Proceedings of the 3rd International Mesostructured Materials Symposium, Jeju, Korea, July 8—11, 2002... 

Most of the supports so far studied are conventional in the field of catalysis. Some new kinds of support have emerged including mesostructured materials,193 dendrimers, organic-inorganic hybrids, and natural polymers such as polysaccharides or polyaminoacids. Nevertheless, at the moment, supported catalysts still suffer from relatively poor stability when compared to classical heterogeneous catalysts, and from limited activity when compared to homogeneous catalysts. The driving force for this research is thus to make up some of these deficits. 

Mesostructured materials with adjustable porous networks have shown a considerable potential in heterogeneous catalysis, separation processes and novel applications in optics and electronics [1], The pore diameter (typically from 2 to 30 nm), the wall thickness and the network topology (2D hexagonal or 3D cubic symmetry) are the major parameters that will dictate the range of possible applications. Therefore, detailed information about the formation mechanism of these mesostructured phases is required to achieve a fine-tuning of the structural characteristics of the final porous samples. 

Other related organizations include the International Committee on Natural Zeolites (ICNC) and the International Mesostructured Materials Association (IMMA (http //www.iza-structure.org). 

Trong, OD Desplantier-Giscard, D Danumah, C Kaliaguine, S. Perspectives in catalytic applications of mesostructured materials, Appl. Catal, A General, 2003, Volume 253, Issue 2, 545-602. 

Figure 20. Chiral diphosphine ligands immobilized in aluminated mesostructured materials with rhodium to form catalytic centers [85, 86, 87].

The second method of catalyst incorporation in mesoporous materials involves, generally, multi-step syntheses where organic moieties (i.e. amines, phosphines, thiols) are immobilized followed by post modification toward the final product. Alternatively, the catalyst may be synthesized as the corresponding alkoxysilane complex followed by immobilization into the mesostructured materials. For instance, Kiihn and co-workers demonstrated covalent... 

The influence of the nature of the aluminum source on the acidic properties of mesostructured materials (MCM41) has also been studied in the literature [244]. Microcalorimetry experiments using ammonia as a probe molecule have shown that Al insertion into the mesoporous silicate framework affected acid site strength and distribution in a manner controlled by the synthesis conditions (materials prepared... 

Through a co-assembling route, mesostructured lamellar molybdenum sulfides are formed hydrothermally at about 85 °C using cationic surfactant molecules as the templates. The reaction temperature and the pH value of the reaction system are important factors that affect the formation of the mesostructured compounds. The amount of the template and that of the S source are less critical in the synthesis of the compounds. For the three as-synthesized mesostructured materials, the interlayer distance increases linearly with the chain length of the surfactant. Infrared and X-ray photoelectron spectroscopy reveals that the individual inorganic layers for the three compounds are essentially the same both in composition and in structure. The formal oxidation state of the molybdenum in the materials is +4 whereas there exist S2 anions and a small amount of (S-S)2 ligands in the mesostructures. The successful synthesis of MoS-L materials indicates that mesostructured compounds can be extended to transition metal sulfides which may exhibit physico-chemical properties more diverse than non-transition metal sulfides because of the ease of the valence variation for a transition metal. 

Since the first synthesis of mesoporous materials MCM-41 at Mobile Coporation,1 most work carried out in this area has focused on the preparation, characterization and applications of silica-based compounds. Recently, the synthesis of metal oxide-based mesostructured materials has attracted research attention due to their catalytic, electric, magnetic and optical properties.2 5 Although metal sulfides have found widespread applications as semiconductors, electro-optical materials and catalysts, to just name a few, only a few attempts have been reported on the synthesis of metal sulfide-based mesostructured materials. Thus far, mesostructured tin sulfides have proven to be most synthetically accessible in aqueous solution at ambient temperatures.6-7 Physical property studies showed that such materials may have potential to be used as semiconducting liquid crystals in electro-optical displays and chemical sensing applications. In addition, mesostructured thiogermanates8-10 and zinc sulfide with textured mesoporosity after surfactant removal11 have been prepared under hydrothermal conditions. 

Therefore, the mesostructured tungsten sulfides MTS-W, MTS-M and MTS-C must consist of organic templates intercalated between condensed inorganic walls made up of layered WS2 and chain-like WS3. On the other hand. The product prepared at room temperature in aqueous solution (i.e. MTS-RT) mainly contains organic templates and discrete WS42 clusters. It should be noted that WS3is X-ray amorphous. Its presence in the mesostructured materials was further confirmed by the elemental analysis results of the products (Table 1). 

Over the last years the utilisation of supramolecular arrays of surfactant molecules as structure-directing templates [1] has been applied to the synthesis of numerous mesostructured aluminophosphates [2-11]. In most cases the preparations were carried out in aqueous systems under hydrothermal conditions, but tetraethylene glycol and/or unbranched primary alcohols were also used [2,4]. Several discussions have been made on the reaction mechanisms that are involved in the syntheses of mesostructured materials [1,12-15] and recently a number of in-situ investigations on the formation processes of mesostructured silica phases in aqueous media have been reported these studies employed small angle X-ray diffraction [16-19] as well as 2H, 13C, 29Si, and 8lBr NMR spectroscopy and polarised light optical microscopy [17]. 

Diffusion of high molecular weight hydrocarbons in mesostructured materials of the MCM-41 type... 

Mesostructured materials are granules containing individual platelets (crystals) associated in a fairly random manner. This type of configuration is always associated with a bi-porous structure, in which small particles (platelets) have pores, usually mesopores, different from the composite particle (secondary mesopores and macropores). The secondary pore structure controls access to the individual crystal mesoporosity. As a result, different mass transfer resistances to diffusion through bi-porous structures could be present. In order to evaluate the relative significance of both primary and secondary pore diffusion, usually two different particle sizes are employed in diffusion measurements. 

The immobilization of photoactive species into the silica-surfactant mesostructured materials is worth investigating toward future photofunctional materials. Photochemistry on solid surfaces is a growing new field which yields a wide variety of useful application such as sensitive optical media, reaction paths for controlled photochemical reactions, molecular devices for optics, etc. [17] Along this line, the incorporation of organic dyes into silica-surfactant mesostructured materials [17-20] as well as nanoporous silica films[3] have been reported so far. 

The thin film of silica-surfactant mesostructured material was prepared by the reactions of TMOS and C18TAC, as reported previously[3]. The film was calcined in air to prepare nanoporous silica films. The adsorption of the dye onto the nanoporous silica film was conducted either by immersing the calcined film into an ethanol solution of the dye or casting the solution onto the film. 

By spin coating the mixture containing the prehydrolyzed TMOS and a 0.2 M aqueous solution of C18TAC (pH=2, at the molar ratio of TMOS C18TAC=9.2.T), a transparent thin film formed on the substrate. The X-ray diffraction pattern of the film (Figure 1a) showed a sharp diffraction peak with the d value of 4.6 nm, which accompanied the 2nd order reflection. In order to remove the surfactants from the substrate to obtain porous silica films, the as coated film of the silica-surfactant mesostructured material was calcined in air at 450 °C. Sharp diffraction peak was observed in the XRD pattern of the calcined film... 

Figure 1b), showing that the ordered microstructure was retained even after the removal of surfactants. The d value of the calcined film was 4.1 nm. The SEM image of the film surface (data not shown) also indicates that the film is continuous and crack free. These observations are well consistent with those reported in the previous paper[2], showing the formation of silica-surfactant mesostructured material and the successful transformation of the as coated film into a nanoporous silica film. 

Diffusion of High Molecular Weight Hydrocarbons in MesoStructured Materials of 639 the MCM-41 Type... 

Figure 18.6 Fabrication of polymer-silica mesostructured materials through a self-assembly process by (a) addition of reactive monomers to the precursor solution, followed by postdeposition polymerization (b) addition of a polymerizable surfactant and (c) direct addition of a soluble polymer to the synthesis solution.

The range of organosilane precursor structures potentially available for the synthesis of hybrid mesoporous (and mesostructured) materials is extremely large development of new material compositions will continue to be a fertile area of research. 

Fan J Boettcher SW Tsung CK Shi Q Schierhorn M Stocky GD, Field-directed and confined molecular assembly of mesostructured materials Basic principles and new opportunities, Chem. Mater., 2008, 20, 909-921. 

The characteristic line of attack for the development of mesostructured materials is the use of the following standard synthesis conditions low temperatures, coexistence of inorganic and organic moieties, and extensive choice of precursors [61],... 

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