Ordered mesoporous solids, syntheses

Besides cooperative pathways, also tme liquid crystal templating (TLCT) and the hard template route (Section 9.3.7) have been developed for the synthesis of ordered mesoporous materials. In the case of the TLCT, a preformed surfactant liquid crystalline mesophase is loaded with the precursor for the inorganic materials (140). The nanocasting route, on the other hand, is a clearly distinct method (141). Here, no soft surfactant template is used but, instead, the pore system of an ordered mesoporous solid is used as the hard template serving as a mold for preparing varieties of new mesostructured materials, for example, metals, carbons, or transition metal oxides. 

Recently Cabrera et al. [47] developed a new synthesis of ordered mesoporous solids involving the use of atrane complexes as precursors. This technique was tested to obtain silica, Al and Ti mesoporous oxides and simply and doubly doped oxides with a large list of metals [see Table 3 in reference 47]. Other dopants or chemical groups were added to MCM type materials. For... 

By contrast, the mechanisms of the synthesis of ordered mesoporous solids are very dilferent from those of silicate and phosphate frameworks. For control over the synthesis of mesoporous solids, the key is to understand the interactions of micellar surfactants with condensable inorganic framework-building units. Synthetic routes are also being developed to prepare mesoporous silicates made up of nanoparticles of zeolites, with the aim of combining advantages of microporous and mesoporous solids. 

The ordered mesoporous materials (or crystalline mesoporous materials) such as MCM-41 (MCM stands for Mobil composite of matter), MCM-48 and SBA-15 (SBA stands for University of California, Santa Barbara) are a new generation of materials that are different from nonordered (amorphous) mesoporous materials. They are amorphous and not ordered at the atomic level from a classical crystallographic view point, but their regular channels or pores are ordered at the nanometer level. Because of this, these materials have certain characteristics of crystalline solids. Their structural information can be obtained by diffraction methods and other structural analysis techniques. The discovery of periodic mesoporous structures is a major advance in composite organic-inorganic materials synthesis. 

In fact, since the mesophase synthesis or reaction is a kinetically control process and the solid formed is not a thermally stable phase, the phase transformation is very common during the synthesis of mesoporous materials. The phase transformations include the transition from one structure or symmetry into another structure or symmetry, or the transition from a disordered phase to an ordered phase, or from an ordered phase to a disordered phase. The intermediate phase can be isolated as a product or be observed by analysis techniques. The phase transformation can occur during the synthesis process or in a post-synthesis treatment. The early famous example is the transition of lamellar mesophase of silicate into hexagonal mesophase in basic or near neutral media.[5]... 

Ordered mesoporous silica seems to be an ideal hard template, which can be used as a mold for other mesostructures with various compositions, such as ordered mesoporous carbon and metal oxides. Mesoporous silicas with various different structures are available, and silica is relatively easily dissolved in HF or NaOH. Alternatively, mesoporous carbons with a solid skeleton structure are also suitable choices as hard templates due to their excellent structural stability on thermal or hydrothermal and chemical treatment. A pronounced advantage of carbon is the fact that it is much easier to remove than silica by simple combustion. The nanocasting synthesis of mesoporous carbon by using mesoporous silica as template will be discussed in detail in the section on mesoporous carbon. In many cases, silica is unsuitable for synthesizing framework compositions other than carbon, since the leaching of the silica typically affects the material which is filled into the silica pore system. 

The early preparations of mesoporous silica film were conducted by growth from solution.[20,276]. The basic principle for the synthesis of ordered mesoporous films by growth from solution is to bring the synthesis solution (including a solvent, surfactant, and inorganic precursor) into contact with a second phase, e.g. solid (ceramic), gas (air), or another liquid (oil). The two-phase system is kept under specific conditions and the ordered film is formed at the interface. When the second phase is solid, it is the support on which the ordered film or membrane is grown. When the second phase is air or oil, the solid films are self-standing. 

The expansion and diversification of the ordered mesoporous materials can be attributed to bringing together two advanced disciplines, i.e. microporous solids and amphiphilic compounds. The latter turned out particularly rich in phenomena that could be exploited for innovation and synthesis of novel and/or designer products. The following developments can be considered as exploiting the principles of surfactant science in the preparation of porous solids. 

The use of microporous solid catalysts such as zeolites and related molecular sieves has an additional benefit in organic synthesis. The highly precise organization and discrimination between molecules by molecular sieves endows them with shape-selective properties [12] reminiscent of enzyme catalysis. The scope of molecular sieve catalysis has been considerably extended by the discovery of ordered mesoporous materials of the M41S type by Mobil scientists [13,14]. Furthermore, the incorporation of transition metal ions and complexes into molecular sieves extends their catalytic scope to redox reactions and a variety of other transition metal-catalyzed processes [15,16]. 

The synthesis of mesoporous silicas was performed from an isotropic reaction mixture using cationic surfactant as a structure directing agent. The decrease in pH, which causes the formation of solid particles, was achieved by hydrolysis of methyl acetate. The procedure enabled to obtain not only siliceous MCM-41 but also a less well-ordered hexagonal silica with extraordinary large surface area and silica with bimodal mesoporous structure containing the MCM-41 mesopore system and a system of mesopores with a mean diameter of 14 nm. 

The so-called template-based technique has been found to be particularly suitable for the synthesis of carbons whose porosity is not only uniform in size and shape, but also periodically ordered in some cases. In this approach, the porous carbon is prepared through infiltration of an organic precursor into the nanochannels of an appropriate inorganic material (the template), followed by carbonization and then liberation of the resultant carbon from the template. Different nanospaces in templates have been used to confine the carbon precursors. The first templates used included, e.g., silica gel or porous glass [84,85], layered clays such as montmorillonite ortaeniolite [86,87], or pillared clays [88-90]. Several detailed reviews on this topic have been published [75,91-95] that cover the areas of microporous and, especially, mesoporous solids. Here, some illustrative examples will he presented in some detail rather than reviewing systematically the literature. 

Oxides Compared to silica-based networks, nonsiliceous ordered meso-poious materials have attracted less attention, due to the relative difficulty of applying the same synthesis principles to non-sihcate species and their lower stability (227). Nonsiliceous framework compositions are more susceptible to redox reactions, hydrolysis, or phase transformations to the thermodynamically preferred denser crystalline phases. Template removal has been a major issue and calcination often resulted in the collapse of the mesostracture. This was the case for mesostractured surfactant composites of mngsten oxide, molybdenum oxide, and antimony oxide, and meso-structured materials based on vanadia that were obtained at early stages. Because of their poor thermal stability, none of these mesostructures were obtained as template-free mesoporous solids (85, 228, 229). 

Titanium has also been incorporated into ordered mesoporous silicas of the SBA-15 type (126). The influence of synthesis parameters on the properties of titanium-substituted SB A-15 silicas prepared by a direct one-step synthesis (cocondensation) was systematically investigated (127) through characterizing the products by N2 physisorption, XRD, diffuse reflectance UV-vis spectroscopy, and elemental analysis. The results showed that when a low titanium precursor concentration (i.e., less than 0.05 mol/1) was used in the initial synthesis gel, incorporation of titanium into the solid was not completed. Under these conditions, titanium ions were well dispersed in the silica framework and present mainly in tetrahedral coordination in the product. When the isolated titanium species present in the gel reached a critical concentration, an increase in titanium incorporation into the sofid was observed as a consequence of the formation of anatase clusters on the material s surface. The titanium loading at which anatase formation was observed was found to he strongly influenced by the synthesis conditions. Moreover, when the formation of anatase takes place, the amorphous titanium species... 

The diversity of ordered porous solids increases at an astonishing rate, particularly among the readily crystallised MOFs, and continues to olfer novel materials properties. There is no obvious barrier to the synthesis of a myriad of new zeolite, zeotype or hybrid structures. Challenges remain, however. For zeolitic aluminosilicates, the 10 A pore size restriction remains an important barrier, and an enantiomerically pure zeolite is still out of reach. For nonsilicate crystalline microporous solids, thermal and hydrothermal stability, rather than framework geometry, limit their applicability, since fully crystalline germanates and carboxylates with pores in the mesoporous range now exist, and these solids have enormous specific surface areas. In these hybrid solids the ability to choose chirality in the building units indicates that it will be possible to prepare these in chiral form the first examples have already been prepared. 

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