Inorganic solid preparation methods

Hagenmuller, P., Ed., 1985, Inorganic Solid Fluorides, Academic, New York. Chapter 2 of this book, Preparative Methods, gives an extensively referenced account of synthetic methods used in inorganic fluoride research. Several apparatus are pictured and described in detail. 

The reader is referred to the second chapter Preparative Methods by J. Grannec and L. Lozano in Inorganic Solid Fluorides , edited by P. Hagenmuller [3], for information on chemical syntheses and crystal growth techniques anterior to 1985, and for general instructions in major preparative techniques in the field of inorganic fluorine chemistry. Some excellent reviews of different topics in the field have been published past 1985 [4-9]. The wide synthetic possibilities of super-acidic media are described in T.A. O Donnell s book [10]. Synthetic and characterization methods with emphasis on solid compounds have been summarized in a book edited by A.K. Cheetham and P. Day [11],... 

The use of organic molecules in the synthesis of zeotype solids is an especially interesting preparative method for extended inorganic solid materials. Organic molecules cannot survive the harsh conditions of the classical high-temperature route involving reaction of the components in the solid state. Structure-directed synthesis thus belongs to the "soft chemistry" routes for the preparation of solid-state compounds [12, 13]. 

An alternative approach to the use of high-temperature solvents, which can be both toxic and expensive, is to use more usual solvents conventionally limited by their rather low boiling points. However, solvents can be used well-above their boiling point at atmospheric pressure if heated in a sealed vessel (an autoclave or bomb ) the autogenous pressure then far exceeds the ambient pressure raising the boiling point of the solvent. Such solvothermal reaction conditions are extensively used in the preparation of inorganic solids, especially zeolites [64]. Eor a comprehensive review of this method for nanopartides see [65]. 

Moreover, this method appears suitable for the synthesis of phosphine-substituted molecular clusters of different nuclearity, depending on which phosphine is used. The availability of these clusters offers the opportunity to exert a stoichiometric control in those processes that lead from molecular metal chalcogenides such as [MxEy(PR3) ,J to extended inorganic solids like MxEy. The stoichiometric control, combined with the kinetic control, which derives from low activation energies of these processes, often allows the preparation of otherwise inaccessible solid phases or microinhomogeneous materials such as nanocomposites. ... 

Different ways to immobilize ILs are described, particularly for chloroaluminate-based ILs (see Section 5.2.1.3). Two preparation procedures can be envisioned. The simplest one is just an impregnation of the chloroaluminate IL to fiU the pores of the dehydrated inorganic solid. The chloroaluminate anion is grafted on the surface by reaction with the surface hydroxyl group. This method may present some disadvantages, such as destruction of the structure of the support and the modification of the acidity of the Lewis acid. 

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