Phosphates and Aluminophosphates

The tetrahedral phosphate ion P04 , like the silicate ion with which it is isoelectronic, can form chains and networks, and indeed its parent oxide, a white, extremely hygroscopic solid commonly called phosphorus pentoxide (P2O5), consists of discrete P4O10 molecular units in which four PO4 units each share three corner oxygens such that the four P centers themselves form a tetrahedron. We customarily distinguish the following classes of phosphates  

In DNA and the related single-stranded RNA (ribonucleic acid), the phosphate units are monomeric and play a strictly structural role. Phosphates, however, are also essential to the metabolism of living cells, in which formation and subsequent hydrolysis of phosphate-phosphate bonds 

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Figure 7.20. Schematic diagram of the range of P chemical shifts in crystalline phosphate and aluminophosphate phases. The Q° range refers to the alkali and alkaline earth orthophosphates, Q denotes the end groups, the middle and ring groups and the branching groups in these compounds. The upper three bands refer to aluminophosphates, including those of the alkali and alkaline earth metals. From data of Turner et al. (1986a).

The application of P NMR to structural studies of alkali and alkaline earth phosphate and aluminophosphate glasses, fluorophosphate glasses and phosphorus oxynitride glasses has been reviewed by Kirkpatrick and Brow (1995). 

It is interesting that this cement has been known for over 100 years and yet certain features of its chemistry remain obscure. The exact nature of the matrix is still a matter for conjecture. It is known that the principal phase is amorphous, as a result of the presence of aluminium in the liquid. It is also known that after a lapse of time, crystallites sometimes form on the surface of the cement. A cement gel may be likened to a glass and this process of crystallization could be likened to the devitrification of a glass. Therefore, it is reasonable to suppose that the gel matrix is a zinc aluminophosphate and that entry of aluminium into the zinc phosphate matrix causes disorder and prevents crystallization. It is not so easy to accept the alternative explanation that there are two amorphous phases, one of aluminium phosphate and the other of zinc phosphate. This is because it is difficult to see how aluminium could act in this case to prevent zinc phosphate from crystallizing. 

The aluminum in the zinc phosphate cements was considered very important, van Dalen [21] recognized its importance first. The reaction of zinc oxide and phosphoric acid was greatly moderated by aluminum. This effect was attributed to formation of an aluminum phosphate gelatinous coating on zinc oxide particles. In fact, Wilson and Nicholson believe that the gelatinous substance may even be zinc aluminophosphate phase [3], which subsequently crystallizes into hopeite and aluminophosphate amorphous gel (AlP04-nH20). 

The products of such reactions depend upon the pressure, temperature, pH, phosphate, and cation concentrations, and may be difficult to predict or rationalize. For example, the equation (3) produces an acid phosphate and a phosphate hydroxide. Microporous aluminophosphates and related phases (see Section 5.1.2) are prepared in hydrothermal bombs using hydrated cations or molecular templates such as organic amines or ammonium cations to direct the porous framework. Many new structures with metal phosphate chains, layers, or three-dimensional networks have been prepared hydrothermally in recent years, for example, templated vanadium phosphates and iron phosphates. ... 

The synthesis of aluminophosphate molecular sieves in 1980s represents a breakthrough in the development of microporous materials. Since then, much of the worldwide synthetic efforts have been directed toward nonsilicate microporous materials. Many novel framework topologies could be found with phosphates, and many other elements could be incorporated into phosphates to produce additional new framework topologies or new compositions. 

In 1995, Morgan et al. synthesized a layered aluminophosphate compound by using a chiral cobaltammine complex as the template for the first time.[61] Recently, the Jilin group has synthesized a number of 2-D layered and 3-D open-framework metal phosphates by using a racemic mixture or an optically pure chiral metal complex as the template, and has systematically studied the chirality transfer from the guest chiral complex templates to the host inorganic open frameworks.1901 Table 7.15 lists some metal phosphates and oxides with open-framework structures templated by optically pure or racemic cobalt ammine complexes. 

Takahashi, K., Binary Phosphate, Silicophosphate, Borophosphate, and Aluminophosphate Glasses, their Properties and Structure, a report presented at the 6th International Congress on Glass, Washington, July, 1962. 

In particular, Alberti et al. (1991) proposed zeolite-based sensors for detection of hydrocarbons such as butane and Balkus et al. (1997) used thin film aluminophosphate (AlPO)-5 molecular sieve as the dielectric phase in a capacitance-type chemical sensor for CO and CO. AlPO-n is a family of phosphorus molecular sieves which, similar to zeolites, have ordered molecular-sized pores. The AlPO-5 structure used for the dielectric layer consists of four- and six-membered rings of alternating phosphate and aluminum ions bridged by oxygen. These rings are arranged to produce one-dimensional channels 0.73 nm in diameter. The properties of AlPO-n are reviewed in detail by Ishihara and Takita (1996), and one of the attractive properties of these materials is their heat stability. The properties of zeolites as they relate to zeolite-based gas sensors are discussed in a special section in Vol. 2. 

A novel basic support and catalyst have been prepared by activation of aluminium phosphate with ammonia. Fine control of time and temperature allows to adjust the 0/N ratio of these oxynitride solids and thus to tune the acid-base properties. The aluminophosphate oxynitrides are active in Knoevenagel condensation, but a basicity range can not yet determined. Supporting Pt or Pt/Sn on AlPONs allows to prepare catalysts that are highly active and selective in dehydrogenation reactions. 

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