Aluminosilicates, tetrahedral

Zeolites have the following characteristics (ref. 1) they are crystalline aluminosilicates (tetrahedral connection) with accessibility ranging from. 3-.8 ran. All atoms are exposed to the pore system which can consist of parallel channels (1-D) or of a threedimensional system (3-D). Some common zeolites with their accessibility and minimum Si/Al ratios are given in Table 1. 

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... 

Many varieties of clay are aluminosilicates with a layered structure which consists of silica (SiOa" ) tetrahedral sheets bonded to alumina (AlOg ) octahedral ones. These sheets can be arranged in a variety of ways in smectite clays, a 2 1 ratio of the tetrahedral to the octahedral is observed. MMT and hectorite are the most common of smectite clays. 

Figure 2 (Left) shows the 27Al NMR spectra for the aluminosilicates. All of them displayed a tetrahedral incorporation of aluminum inside the silica network. That is corroborated by the signal at 55 ppm [9, 10] which also become more intense with the decreasing of Si/Al ratio. Octahedral aluminum was observed just for the samples with the lowest Si/Al ratio. Tetrahedral aluminum gives place to strong Bronsted acid sites, which were identified by the interaction of these groups with pyridine that generates a...

Figure 10a, Scheme of the aluminosilicate framework of a typical faujasitic zeolite Si/Al ratio of LI8 (arbitrarily chosen to illustrate the ordering among tetrahedral sites) before (left half) and after (right half) exposure to SiCls, which dealuminates the zeolite (see Figure 10b),... 

Zeolite structures typically consist of silicon and aluminum finked by tetrahedrally coordinating oxygen atoms. However, similar structures as found for these aluminosilicates can be formed by substitution of the aluminum by other elements (e.g., Ga in gallosilicates or Ti in titanosilicates). Even the substitution of both Si and A1 is possible, as for example in aluminophosphates or... 

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. 

Figure 4.33 Si MAS NMR chemical shift ranges for aluminosilicates. This figure is redrawn based on references [152-155], Here Q" is the tetrahedral silicon connected to n aluminum atoms n = 0 ) via oxygen bridges.

Fig. 2.1 Configurations of the tetrahedral units and chain, double chain, and sheet structures in the silicate and aluminosilicate minerals. (A) Two-dimensional representation of a single silicate tetrahedron. (A ) Two-dimensional representation of an extended silicate chain. (B) Three-dimensional representations of single tetra-hedra in two orientations. The apexes of the tetrahedra point above or below the plane of the paper. (B ) Three-dimensional representations of extended silicate chains showing different orientations of the tetrahedra in two of the many possible configurations. Single chain pyroxenes (C), wollastonite (D), rhodonite (E). Double chains amphiboles (F). Sheets as found in the serpentines, micas, and clays (G).

Some of the diversity that characterizes the properties and compositions of the silicate minerals stems from the ability of the aluminum ion (Al ) to substitute for silicon in the tetrahedral unit. When silicate tetrahedra in a mineral are replaced by aluminum-containing tetrahedra, concomitant changes occur in the size of the tetrahedron (usual Si—O bond length = 0.160 nm. A1—O bond length = 0.178 nm) and in the cations or protons that balance the tetrahedral unit charge. Regular substitutions with distinct chemistries and structures lead to the formation of groups of discrete minerals called aluminosilicates. 

Fig. 2.12 Structural components and variations in the micas. (A) Plan view of the continuous aluminosilicate sheet (T), [Si,Al205] , a portion of the mica structure. (B) Stereographic representation of an idealized mica. The structure is composed of continuous layers containing two tetrahedral aluminosilicate sheets (T) that enclose octahedrally coordinated cations, or Mg (O). This layer or sandwich," the T-O-T or 2 1 aggregate, is held together by or Na ions. (C) The two possible positions (I and II) of octahedral cations in the micas. Sets of three locations for each are superimposed on the tetrahedral hexagonal aluminosilicate sheet. (D) The three possible directions of intralayer shift when octahedral set I (upper) or II (lower) are occupied. The dashed lines and circles represent ions below the plane of the paper. (E) Distorted hexagonal rings of apical oxygens in the tetrahedral sheet of dioctahedral micas compared with the undistorted positions of the apical oxygens in the tetrahedral sheet of trioctahedral micas.

In order to interpret the results of the following correctly, we must consider that they obey Loewenstein s rule [16] which forbids the occurrence of Al-O-Al linkages in tetrahedrally bonded aluminosilicates. As a result ... 

Tsomaia, N., Brantley, S. L., Hamilton, J. P., Patano, C. G. Mueller, K. T. 2003. NMR evidence for formation of octahedral and tetrahedral Al and repolymerization of the Si network during dissolution of aluminosilicate glass and crystal. American Mineralogist, 88, 54-67. 

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... 

Clays are layer silicates (phyllosilicates) of particle size less than about 4 pm, produced by the weathering of aluminosilicate rocks. Clay minerals fall roughly into two structural classes the kaolinite type, based on paired sheets of tetrahedral (SiC>44-) and octahedral [A10n(0H) g " or... 

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