Aluminosilicates, microporous

Huddersman, K. Patruno, V. Blake, G. J. Dahm, R. H. Azo dyes encapsulated within aluminosilicate microporous materials. J. Soc. Dyers Colourists 1998,114, 155-159. 

The traditional definition of a zeolite refers to microporous, crystalline, hydrated aluminosilicates with a tliree-dimensional framework consisting of comer-linked SiO or AlO tetrahedra, although today the definition is used in a much broader sense, comprising microporous crystalline solids containing a variety of elements as tetrahedral building units. The aluminosilicate-based zeolites are represented by the empirical fonmila... 

Additional to tire aluminosilicate-based zeolites, a number of otlier crystalline microporous tliree-dimensional oxides have been syntliesized [25]. Most prominent among tliese are tire aluminophosphates (ALPO series) [26,... 

Microporous catalysts are heterogeneous catalysts used in catalytic converters and for many other specialized applications, because of their very large surface areas and reaction specificity. Zeolites, for example, are microporous aluminosilicates (see Section 14.19) with three-dimensional structures riddled with hexagonal channels connected by tunnels (Fig. 13.38). The enclosed nature of the active sites in zeolites gives them a special advantage over other heterogeneous catalysts, because an intermediate can be held in place inside the channels until the products form. Moreover, the channels allow products to grow only to a particular size. 

Solvent extraction is the most important technique for recovering surfactants from mesoporous materials. However, it is not very effective when applied to microporous compounds. Davis et al. [186] successfully extracted borosilicate and silicate BEA stractures with acetic acid while a small template fraction could be removed for the aluminosilicate. 

Zeolites form a unique class of oxides, consisting of microporous, crystalline aluminosilicates that can either be found in nature or synthesized artificially [J.M. Thomas, R.G. Bell and C.R.A. Catlow in Handbook of Heterogeneous Catalysis (Ed. G. Ertl, H. Knbzinger and J. Weitkamp) (1997), Vol. 1, p. 206, VCH, Weinheim.]. The zeolite framework is very open and contains channels and cages where cations, water and adsorbed molecules may reside and react. The specific absorption properties of zeolites are used in detergents, toothpaste, and desiccants, whereas their acidity makes them attractive catalysts. 

Molecular sieves (zeolites) are artificially prepared aluminosilicates of alXali metals. The most common types for gas chromatography are molecular sieve 5A, a calcium aluminosilicate with an effective pore diameter of 0.5 nm, and molecular sieve 13X, a sodium aluminosilicate with an effective pore diameter of 1 nm. The molecular sieves have a tunnel-liXe pore structure with the pore size being dependent on the geometrical structure of the zeolite and the size of the cation. The pores are essentially microporous as the cross-sectional diameter of the channels is of similar dimensions to those of small molecules. This also contrilsutes to the enormous surface area of these materials. Two features primarily govern retention on molecular sieves. The size of the analyte idiich determines whether it can enter the porous... 

This application of sensitivity enhanced RAPT-CP-CPMG HETCOR, to microporous aluminosilicates illustrates the potential of... 

The formation of the microporous phase dispersed in porous, amorphous matrices was followed by XRD and TEM. The XRD patterns of the BEA-composite prepared using the Al-poor aluminosilicate (6A187Si) are shown in Figure 1. BEA was the sole... 

In general, zeolites are crystalline aluminosilicates with microporous channels and/or cages in their structures. The first zeolitic minerals were discovered in 1756 by the Swedish mineralogist Cronstedt [3], Upon heating of the minerals, he observed the release of steam from the crystals and called this new class of minerals zeolites (Greek zeos = to boil, lithos = stone). Currently, about 160 different zeolite structure topologies are known [4] and many of them are found in natural zeolites. However, for catalytic applications only a small number of synthetic zeolites are used. Natural zeolites typically have many impurities and are therefore of limited use for catalytic applications. Synthetic zeolites can be obtained with exactly defined compositions, and desired particle sizes and shapes can be obtained by controlling the crystallization process. 

Considering all we know up to now, the specific properties of zeolites can be summarized as follows. Zeolites are aluminosilicates with defined microporous channels or cages. They have excellent ion-exchange properties and can thus be used as water softeners and to remove heavy metal cations from solutions. Furthermore, zeolites have molecular sieve properties, making them very useful for gas separation and adsorption processes, e.g., they can be used as desiccants or for separation of product gas streams in chemical processes. Protonated zeolites are efficient solid-state acids, which are used in catalysis and metal-impregnated zeolites are useful catalysts as well. 

A recent investigation has demonstrated the usefulness of ultrasonic irradiation in the preparation of delaminated zeolites, which are a particular type of modified oxides - microporous crystalline aluminosilicates with three-dimensional structures - having a greater catalytic activity than the layered structures (clays) and mesoporous catalysts. In an attempt to increase the pore size of zeolites, a layered zeolite precursor was... 

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. 

The concept zeolites conventionally served as the synonym for aluminosilicates with microporous host lattice structures. Upon removal of the guest water, zeolites demonstrate adsorptive property at the molecular level as a result they are also referred to as molecular sieves. Crystalline zeosils, AlPO s, SAPO s, MAPO s (M=metal), expanded clay minerals and Werner compounds are also able to adsorb molecules vitally on reproval of any of the guest species they occlude and play an Important role in fields such as separation and catalysis (ref. 1). Inclusion compounds are another kind of crystalline materials with open framework structures. The guest molecules in an inclusion compound are believed to be indispensable to sustaining the framework structure their removal from the host lattice usually results in collapse of the host into a more compact crystal structure or even into an amorphous structure. 

In zeolite synthesis, large cations such as tetramethylammonium (NMe4" ) and tetrapropylammonium (N(C3H7)4" ) can be used as a template around which the aluminosilicate framework crystallizes with large cavities to accommodate the ion. On subsequent heating the cation is pyrolysed, but the structure retains the cavities. Such structures formed around a single molecule template, with pore sizes between 200 and 2000 pm, are known as microporous. 

Zeolites are intrinsically microporous aluminosilicates of the general formula [(A102) t(Si02) ] mH20 and may be considered as open structures of silica in which aluminium has been substituted in a fraction x/(x + y) of the tetrahedral sites. The net negative charge of the aluminosilicate framework is neutralized by exchangeable... 

Oxides of transition metals can act as acid-base or redox catalysts. Oxides of non-transition metals (AI2O3, SiOj) are, however, good acid-base catalysts. There is a large family of aluminosilicate zeolitic acids (e.g. H -ZSM-5, H-mordenite). Micropor-ous aluminium phosphates (ALPOs) can be modified to yield acidic SAPOs (Si replaces... 

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