Microporous silica, types

The sorption of n-butyl alcohol and (err-butyl alcohol on phenyl modified MCM-41 type sorbent having pores of approximately 20 A diameter (i.e. in the microporous range), has been studied. Comparison of butanol sorption with nitrogen, water, and benzene sorption data indicates that steric hindrance significantly affects the sorption of n-butyl alcohol by the microporous silica, far more so than for tert-butyl alcohol. The different shapes of the isotherms obtained on the microporous material (Type I for fert-butyl alcohol, Type IV for 71-butyl alcohol) suggest that the preferred mechanism for adsorption of leiY-butyl alcohol is via organic interactions with surface phenyls, whereas for n-butyl alcohol, a mechanism of polar interaction is more likely. 

Pure silica is used as a stationary phase in various types of liquid chromatography.28 In size exclusion chromatography29 the separation of polymer compounds is effectuated on basis of diffusion rate of variably-sized molecules through a microporous silica packing with uniform pore size. 

In addition to the Pd-based membranes, microporous silica membranes for hydrogen permeation [8] can be produced by a special type of chemical vapor deposition [140] named chemical vapor infiltration (CVI) [141], A large amount of studies have been carried out on silica membranes made by CVI for hydrogen separation purposes [8,121], CVI [141] is another form of chemical vapor deposition (CVD) [140] (see Section 3.7.3). CVD involves deposition onto a surface, while CVI implies deposition within a porous material [141], Both methods use almost similar equipment [140] and precursors (see Figure 3.19) however, each one functions using different operation parameters, that is, flow rates, pressures, furnace temperatures, and other parameters. 

A novel type of membrane reactor, emerging presently, is the pervaporation reactor. Conventional pervaporation processes only involve separation and most pervaporation set-ups are used in combination with distillation to break azeotropes or to remove trace impurities from product streams, but using membranes also products can be removed selectively from the reaction zone. Next to the polymer membranes, microporous silica membranes are currently under investigation, because they are more resistant to chemicals like Methyl Tertair Butyl Ether (MTBE) [23-24], Another application is the use of pervaporation with microporous silica membranes to remove water from polycondensation reactions [25], A general representation of such a reaction is ... 

A third type of membrane is the sol-gel microporous silica membrane. This type of membrane is of major importance in this thesis. Below, a short overview will be provided of state-of-the-art silica membranes at the start of the project (1995). This has been the starting point from which the new membranes described in this thesis were developed. 

Somewhat surprisingly, however, only a very limited amount of literature is available on hydrothermal stability of even the most commonly applied mesoporous membrane type, namely y-alumina membranes on OC-AI2O3 supports. These mesoporous y-alumina membranes are the common supports for the microporous silica membranes to be used in membrane steam reformers. In the investigations that finally led to the present study, delamination of the y-alumina membrane from the OC-AI2O3 supports in hot steam was found to be a major compli-... 

The first iron-containing silsesquioxanes which appeared in the literature were compounds containing ferrocenyl units as side-groups.102 104 However, these are not within the scope of this review as iron is not part of the metallasilsesquioxane skeleton. Meanwhile, several ferrasilsesquioxane complexes have been synthesized. The first iron(III) compound of this type was prepared in our laboratory according to Scheme 56.105 In 161, the coordination sphere of iron is completed by TMEDA (NjNjN N -tetramethylethylenediamine) as a chelating amine ligand. Pale yellow, crystalline 161 was isolated in 80% yield and structurally characterized by X-ray diffraction. This compound was later used by Maxim et al.106 107 to prepare iron particles dispersed on microporous silica via controlled calcination of the ferrasilsesquioxane precursor as depicted in Scheme 56. 

A high degree of hydrophobic character is an almost unique characteristic of silicon-rich or pure-silica-type microporous crystals. In contrast to the surface of crystalline or amorphous oxides decorated with coordinatively unsaturated atoms (in activated form), the silicon-rich zeolites offer a well-defined, coordinatively saturated sur ce. Such surfrces, based on the strong covalent character of the silicon-oxygen bond and the absence of hydrophilic centers, display a strong hydrophobic character unmatched by the coordinativeiy unsaturated, imperfect surfaces. Also, hydrophobic zeolite crystals have been reported to suppress the water affinity of transition metal cations contained in the zeolite pores. This property permits the adsorption of reactants such as carbon monoxide or hydrocarbons in the presence of water. 

Research on other types of materials for H2 separation has been motivated by relatively high cost of Pd and possible membrane degradation by acidic gases and carbon as summarized in Tsuru et al.76 These authors examined microporous silica membranes together with an Ni catalyst layer for SMR reaction. However, this type of membrane allows the permeation of hydrogen as well as other gases in reactants and products, which markedly reduces hydrogen selectivity and limits methane... 

Linde type X and Y zeolites are two typical microporous materials with the FAU framework. So far, both low-silica type X and high-silica type Y molecular sieves are... 

Four main types of porous silica adsorbents have been identified compacts of pyrogenic powders, precipitated silicas, silica gels, and zeolitic silicas. The importance of porosity relative to the adsorptive properties of each group is reviewed, with particular reference to the adsorption of nitrogen, argon, and water vapor. The differences in size and specificity of these adsorptive molecules may be exploited to explore the surface properties of each grade of silica. A notable feature cf Silicalite I, which is the best known of the zeolitic silicas, is its remarkable hydrophobic character. Furthermore, the uniform tubular pore structure of this microporous silica is responsible for other highly distinctive properties. 

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... 

Concepts in Crystal Engineering, p. 319 Crystal Engineering with Hydrogen Bonds, p. 357 Crystal Structure Prediction, p. 371 Cfystalline Microporous Silicas, p. 380 Dye Inclusion Crystals, p. 497 Hofmann-Type Clathrates, p. 645 Mineralomimetic Structures, p. 868 Molecular Squares, Boxes, and Cubes, p. 909 Organic Zeolites, p. 996 Soft/Smart Materials, p. 1302... 

Chemical Topology, p. 229 Concepts in Crystal Engineering, p. 2 9 Crystalline Microporous Silicas, p. 380 Hofmann-Type Clathrates, p. 645 Interpenetration, p. 135... 

In other respects, we can consider zeolite membranes as pertaining to the ceramic material category. Indeed, zeolites are classified for the most part as microporous, crystalline silicoaluminate structures with different aluminum/silicon ratios. Thus, the chemical compositions are close to those of ceramic oxide membranes, in particular of microporous silica and alumina membranes. On the other hand, zeolites are crystalline materials and they have a structural porosity very different from microporous amorphous silica [167]. Zeolite films can be grown as intergrown layers on porous metallic and ceramic membrane supports. These zeolite films constitute a special type of nanostructured interface capable of very specific interactions with individual molecules so that it can be used as membrane for the selective separation of molecular... 

The synthesis of molecular sieves containing transition metals in the framework represents a reliable route for preparing materials with novel catalytic properties. In spite of the large number of papers and patents claiming the incorporation of several transition metal ions in different microporous silica frameworks, unambiguous evidence in favor of the isomorphous substitution of silicon has been achieved only for Ti and Fe, for the former limited to few framework types. Some evidence exists also for V and Cr, but the data available do not allow definite conclusions to be drawn in this regard. 

Although the immobilization of Rh2POM in microporous silica yielded a stable electrode, the disparity in molecular size relative to pore width is insufficient to extend this approach to use of mesoporous sol-gel materials as supports for these catalysts. Mesoporous structures have an intrinsic advantage over microporous materials in that effective diffusion coefficients are greater in the former materials [36]. Macromolecular dendrimers have several attractive features for use in sol-gel materials other than projected stable encapsulation. They may provide a template around which mesoporous silica can form [37]. Metal centers that are potential catalysts can be incorporated readily into dendrimeric compounds. Further, the structure of dendrimers assures spatial distribution of metal centers, which is optimum geometry for most types of catalysis. 

Adsorbents such as some silica gels and types of carbons and zeolites have pores of the order of molecular dimensions, that is, from several up to 10-15 A in diameter. Adsorption in such pores is not readily treated as a capillary condensation phenomenon—in fact, there is typically no hysteresis loop. What happens physically is that as multilayer adsorption develops, the pore becomes filled by a meeting of the adsorbed films from opposing walls. Pores showing this type of adsorption behavior have come to be called micropores—a conventional definition is that micropore diameters are of width not exceeding 20 A (larger pores are called mesopores), see Ref. 221a. 

Presently, the most successful adsorbents arc microporous carbons, but there is considerable interest in other possible adsorbents, mainly porous polymers, silica based xerogels or zeolite type materials. Regardless of the type of material, the above principles still apply to achieving a satisfactory storage capacity. The limiting storage uptake will be directly proportional to the accessible micropore volume per volume of storage capacity. 

It is a common procedure to assume certain conditions for the chromatographic system and operating conditions and, as a result, simplify equations (20) and (21). However, in many cases the assumptions can easily be over-optimistic, to say the least. It is necessary, therefore, to carefully consider the conditions that may allow such simplifying procedures and take steps to ensure that such conditions are carefully met when such expressions are used in practice. Now, the relative magnitudes of the resistance to mass transfer terms will vary with the type of columns (packed or capillary), the type of chromatography (GC or LC) and the type of particle, i.e., porous or microporous (diatomaceous support or silica gel). 

Adsorption of hard sphere fluid mixtures in disordered hard sphere matrices has not been studied profoundly and the accuracy of the ROZ-type theory in the description of the structure and thermodynamics of simple mixtures is difficult to discuss. Adsorption of mixtures consisting of argon with ethane and methane in a matrix mimicking silica xerogel has been simulated by Kaminsky and Monson [42,43] in the framework of the Lennard-Jones model. A comparison with experimentally measured properties has also been performed. However, we are not aware of similar studies for simpler hard sphere mixtures, but the work from our laboratory has focused on a two-dimensional partly quenched model of hard discs [44]. That makes it impossible to judge the accuracy of theoretical approaches even for simple binary mixtures in disordered microporous media. 

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