Mesoporous Silica Sieves

The mesoporous molecular sieve SBA-15 has been functionalized with aminopropyl moieties via grafting. Further treatment of the 3-aminopropyl-modified material with glutardialdehyde (GA) results in GA-ATS-SBA-15. The modified silica materials were characterized by NMR and IR spectroscopy as well elemental analysis confirming the successful modification. Furthermore, the elemental analysis suggests that two of three amino moieties of the 3-aminopropyl modified material react further with... 

Dispersion of POMs onto inert solid supports with high surface areas is very important for catalytic application because the surface areas of unsupported POMs are usually very low (—10 m2g). Another advantage of dispersion of POMs onto inert supports is improvement of the stability. Therefore, immobilization of POMs on a number of supports has been extensively studied. Silica and active carbon are the representative supports [25], Basic supports such as MgO tend to decompose POMs [101-104], Certain kinds of active carbons firmly entrap POMs [105,106], The maximum loading level of POMs on active carbons is 14 wt% [107], Dispersion of POMs onto other supports such as zeolites, mesoporous molecular sieves, and apatites, is of considerable interest because of their high surface areas, unique pore systems, and possibility to modify their compositions, morphologies, and sorption properties. However, a simple impregnation of POM compounds on inert supports often results in leaching of POMs. 

The past nearly six decades have seen a chronological progression in molecular sieve materials from the aluminosilicate zeolites to microporous silica polymorphs, microporous aluminophosphate-based polymorphs, metallosilicate and metaHo-phosphate compositions, octahedral-tetrahedral frameworks, mesoporous molecular sieves and most recently hybrid metal organic frameworks (MOFs). A brief discussion of the historical progression is reviewed here. For a more detailed description prior to 2001 the reader is referred to [1]. The robustness of the field is evident from the fact that publications and patents are steadily increasing each year. 

Since this initial work there has been a plethora of literature on mesoporous molecular sieves. In addition to the silica and aluminosilicate frameworks similar mesoporous structures of metal oxides now include the oxides of Fe, Ti, V, Sb, Zr, Mn, W and others. Templates have been expanded to include nonionic, neutral surfactants and block copolymers. Pore sizes have broadened to the macroscopic size, in excess of 40 nm in diameter. A recent detailed review of the mesoporous molecular sieves is given in ref [73]. Vartuli and Degnan have reported a Mobil M41S mesoporous-based catalyst in commercial use, but to date the application has not been publicly identified.[74]. 

Up to now, a variety of non-zeolite/polymer mixed-matrix membranes have been developed comprising either nonporous or porous non-zeolitic materials as the dispersed phase in the continuous polymer phase. For example, non-porous and porous silica nanoparticles, alumina, activated carbon, poly(ethylene glycol) impregnated activated carbon, carbon molecular sieves, Ti02 nanoparticles, layered materials, metal-organic frameworks and mesoporous molecular sieves have been studied as the dispersed non-zeolitic materials in the mixed-matrix membranes in the literature [23-35]. This chapter does not focus on these non-zeoUte/polymer mixed-matrix membranes. Instead we describe recent progress in molecular sieve/ polymer mixed-matrix membranes, as much of the research conducted to date on mixed-matrix membranes has focused on the combination of a dispersed zeolite phase with an easily processed continuous polymer matrix. The molecular sieve/ polymer mixed-matrix membranes covered in this chapter include zeolite/polymer and non-zeolitic molecular sieve/polymer mixed-matrix membranes, such as alu-minophosphate molecular sieve (AlPO)/polymer and silicoaluminophosphate molecular sieve (SAPO)/polymer mixed-matrix membranes. 

In principle the bicontinuous 3-dimensional network structure of MCM-48 would act as a good catalytic support.[7] However, its lower hydrothermal and thermal stability has led to much less application of MCM-48 in catalysis. Recently, a family of mesoporous molecular sieves (denoted as MSU-G) with vesicle-like hierarchical structure, worm-like mesoporous structure and bicontinuous nano-porous silica had been synthesized.[8-10] It was proposed that highly accessible mesoporous materials could be obtained through different synthetic procedure and composition. 

Synthesis of mesoporous silica molecular sieves via a novel templating scheme... 

XRD patterns of the sample prepared mesoporous silica molecular sieves. 

Figure 2. XRD patterns of as-synthesized LZC mesoporous silica molecular sieves with different pH. (A) 2, (B) 7. (C) 10...

Properties of LZC mesoporous silica molecular sieves with different aging time... 

The structures of mesoporous molecular sieves were closely related to the surfactants to silica ratios.4 Because of the absence of high order reflections on the XRD patterns of all LZC... 

Figure 5. Nj adsorption/desorption isotherms of calcined LZC mesoporous silica molecular sieves with different surfactant/SiOj (A) 0.1, (B) 0.2. (C) 0.5, (D) 1.0, and (E) 1.5...

In 1995, Tanev and Pinnavaia [1] have reported the synthesis of a new type of mesoporous molecular sieve designated as the hexagonal mesoporous silica (HMS). Instead of using the ionic inorganic precursor and surfactant as in the case of MCM-41 [2], HMS is manufactured by hydrolysis reaction between a neutral inorganic precursor, tetraethyl-orthosilicate (TEOS) and a neutral primary amine surfactant (8-18 carbons). HMS possesses numerous favourable characteristics, but, like MCM-41, its synthesis process can only be concluded by the removal of the surfactant. This was reportedly done either by calcination at 630°C or by warm ethanol extraction [1]. 

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