Mesoporous silica silicate framework

Figure 1. Scheme for the liquid crystalline templating mechanism proposed by Kresge et al 1 for synthesis of mesoporous silica MCM-41. Formation of a hexagonal array of cylindrical micelles possibly mediated by silicate anions followed by condensation of the silicate anions from the silicate source (tetraethylorthosilicate) leads to templated framework structure. Calcination or extraction of the template produces hexagonally ordered mesoporous silica. 

The contents of the current volume presents a sampling of more than 150 oral and poster papers delivered at the Symposium on Access in Nanoporous Materials II held in Banff, Alberta on May 25-28, 2000. The selected papers cover the three main themes of the symposium (i) synthesis of mesoporous silicas, framework-modified mesoporous silicas, and surface-modified mesoporous silicas, (ii) synthesis of other nanoporous and nanostructured materials, and (iii) characterization and applications of nanoporous materials. About 70% of the papers are devoted to the synthesis of siliceous mesoporous molecular sieves, their modification, characterization and applications, which represent the current research trend in nanoporous materials. The remaining contributions provide some indications on the future developments in the area of non-siliceous molecular sieves and related materials. Although the present book does not cover all topics in the area of nanoporous materials, it reflects the current trends and advances in this area, which will certainly attract the attention of materials chemists in the 21st Century. 

One of the first examples of mesoscopic-macroscopic two-dimensional ordering within a structure involved a bacterial superstructure formed from the co-aligned multicellular filaments of Bacillus subtilis that was used to template macroporous fibers of either amorphous or ordered mesoporous silica [82], The interfilament space was mineralized with mesoporous silica and, following removal of the organic, a macroporous framework with 0.5 pm wide channels remained. Mesoporous silica channel walls in this hierarchical structure were curved and approximately 100 nm in thickness. Dense, amorphous walls were obtained by replacing the surfactant-silicate synthesis mixture with a silica sol solution. The difference in the mode of formation between porous and non-porous wall structures was explained in terms of assembly from close-packed mesoporous silica coated bacterial filaments in the former compared to consolidation of silica nanoparticles within interfilament voids in the latter. 

The regenerated HUM-1 (T41/a),11941 a silica replica of mesoporous carbon, is a cubic mesoporous silica that is distinctly different from the original MCM-48 silica and represents a previously unreported new mesoporous silica material. HUM-1 does not possess the two noninterconnecting channel systems found in the starting MCM-48 framework. This new mesoporous silicate was prepared by a cyclic serial replication process and it may not be possible to make this material using the current conventional surfactant assembly methods employed for the synthesis of mesoporous silicas. 

Several framework titanium-substituted mesoporous silicates, including Ti-MCM-41 (42,43), Ti-HMS (198), Ti-MCM-36 (180), Ti-MCM-48 (199), and Ti-SBA-15 (200), have shown promising activity for the epoxidation of bulky olefins with alkyl hydroperoxides as oxidants. Unfortunately, compared with the microporous MFI-type titanium silicates, the mesoporous materials exhibit low activity for epoxidation reactions. The hydrophilic nature of mesoporous silica catalysts with isomorphous titanium substitution is considered to be one of the major reasons for the low activity (179). Various attempts have been made to improve the activity. Using a different synthetic procedure, titanium species have been grafted onto... 

There are two main techniques for the incorporation of atomically dispersed titanium into a mesoporous silica framework. In the cocondensation method a titanium source is added during the preparation of the silica material framework and formation proceeds via simultaneous condensation of both titanium and silicon precursors, resulting in titanium incorporation throughout the material. Conversely, postmodification involves the grafting of a titanium-alkoxide precursor to the pore surface by condensation with surface hydroxyls of a preformed silica material. This forms a surface-modified titanium silicate. 

He, Q. and Shi, J. 2011. Mesoporous silica nanoparticle based nano drug delivery systems Synthesis, controlled drug release and delivery, pharmacokinetics and biocompatibility. J. Mater. Chem. 21 5845-5855. Hedin, N., Graf, R., Christiansen, S.C. et al. 2004. Structure of a surfactant-templated silicate framework in the absence of 3D crystallinity. J.Am. Chem. Soc. 126 9425-9432. 

The key property required of the inorganic species is ability to build up (polymerize) around the template molecules into a stable framework. As is already evident in this article, the most commonly used inorganic species are silicate ions, which yield a silica framework. The silica can be doped with a wide variety of other elements (heteroatoms), which are able to occupy positions within the framework. For example, addition of an aluminium source to the synthesis gel provides aluminosilicate ions and ultimately an aluminosilicate mesoporous molecular sieve. Other nonsilica metal oxides can also be used to construct stable mesoporous materials. These include alumina, zirconia, and titania. Metal oxide mesophases, of varying stability, have also been obtained from metals such as antimony (Sb), iron (Fe), zinc (Zn), lead (Pb), tungsten (W), molybdenum (M), niobium (Nb), tantalum (Ta), and manganese (Mn). The thermal stability, after template removal, and structural ordering of these mesostructured metal oxides, is far lower, however, than that of mesoporous silica. Other compositions that are possible include mesostructured metal sulfides (though these are unstable to template removal) and mesoporous metals (e.g., platinum, Pt). 

The isomorphous substitution of Si with Ti and Zr in mesoporous sih-cates with MCM-41 structure has also been studied by means of NH3 mi-crocalorimetry experiments [284]. These materials are weakly acidic solids, and the introduction of Ti or Zr into the mesoporous silicate framework has been found to increase the acidity in the order silica-gel [Pg.137]

Various synthesis methods of mesoporous carbon based on different mesoporous silicate or aluminosilicate templates have been developed [5,7]. The first report on the synthesis of OMC used mesoporous silica MCM-48 with the bicontinuous cubic Ia3d symmetry as the template the as-prepared OMC was denoted as CMK-1. Thereafter, various OMCs with different pore topologies have been actively investigated. For these OMCs, the imiform mesopores are interconnected, resulting in the appearance of distinct X-ray diffraction lines below 2 theta of 5. Meanwhile, they have a large siu ace area and high pore volume. The other structural parameters such as pore diameters, particle morphologies and sizes, and microstructures of carbon frameworks could be tuned by... 

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