Metal vapor synthesis clusters

Other approaches use metal-atom synthesis (metal-vapor synthesis, MVS [91, 92]) to produce labile complexes that are absorbed in porous supports and form catalytically active metal cluster compounds. 

Metal-containing polymers may be produced by various methods, such as chemical reactions of precursors— in particular, reactions of metal salts in polymer solutions, the treatment of polymers with metal vapors, or the polymerization of various metal-monomer systems [1-4], Depending on the metal nature and the polymer structure, these processes lead to organometallic units incorporated into polymer chains, metal-polymer complexes, or metal clusters and nanoparticles physically connected with polymer matrix. Of special interest are syntheses with the use of metal vapors. In this case, metal atoms or clusters are not protected by complexones or solvate envelopes and consequently have specific high reactivity. It should be noted that the apparatus and principles of metal vapor synthesis techniques are closely related to many industrial processes with participation of atomic and molecular species [5]—for example, manufacturing devices for microelectronic from different metals and metal containing precursors [6]. Vapor synthesis methods employ varying metals and... 

Metal vapor techniques provide unique means for cryochemical solid-phase synthesis of metal-containing systems. In this way, metastable compounds, whose existence earlier was only supposed, have been obtained [7]. Besides, cryochemical processes produce stabilized small metal clusters of quantum type, which are the intermediate form of matter between isolated atoms and bulk metal [8, 9]. However, known methods of cryochemical solid-phase synthesis used low-molecular-weight matrices, in which the initial products of such a synthesis can be conserved only at low temperatures, when the matrix is enough rigid to hinder transformation or loss of these products. 

Metal-polymer systems obtained as a result of vapor deposition cryochemical synthesis contain stabilized small nonmetallic clusters of metal atoms and metal nanocrystals, but only metal nanocrystals participate in conductivity processes. The data on Ag-containing PPX composites [44] testify to the fact that the relative part of metal stabilized in cluster form at ambient temperature sharply decreases with increasing total metal content even in the range 0-2 vol. %. Therefore, at measurements of conductivity, which were carried out at considerably higher metal concentrations, it was accepted that as a first approximation, all metal is as nanocrystals. 

Techniques for the preparation of metal cluster/nanoparticles can be classified into three primary categories condensed phase, gas phase, and vacuum methods. In condensed phase synthesis, metal and semiconductor nanoparticles are prepared by means of chemical synthesis, which is also known as wet chemical preparation. In gas phase synthesis, metal is vaporized, and the vaporized atoms are condensed in the presence or absence of an inert gas. In vacuum methods, the metal of interest is vaporized with high-energy Ar, Kr ions, or laser beams in a vacuum, and thus generated metal vapor is deposited on a support. 

Non-aqueous synthetic methods have recently been used to assemble mesoporous transition metal oxides and sulfides. This approach may afford greater control over the condensation-polymerization chemistry of precursor species and lead to enhanced surface area materials and well ordered structures [38, 39], For the first time, a rational synthesis of mesostructured metal germanium sulfides from the co-assembly of adamantanoid [Ge4S ()]4 cluster precursors was reported [38], Formamide was used as a solvent to co-assemble surfactant and adamantanoid clusters, while M2+/1+ transition metal ions were used to link the clusters (see Fig. 2.2). This produced exceptionally well-ordered mesostructured metal germanium sulfide materials, which could find application in detoxification of heavy metals, sensing of sulfurous vapors and the formation of semiconductor quantum anti-dot devices. 

The synthesis of large clusters such as [A Ris]3- (Chapters 2 and 3) proceeds by A1 atom cluster-core build up. Cluster-core growth is terminated at some point by external ligands. The method of Schnockel is a variation of metal-atom vapor-deposition techniques and relies on (a) the reversibility of the equilibrium between the liquid metal, e.g., Al, and gaseous metal halide, e.g., AICI3, with gaseous subhalide, e.g., A1C1 (b) the shift in equilibrium position with temperature and (c) competitive rates at similar temperatures of subhalide disproportionation to metal... 

As more sophisticated metal hydrides are developed (nanocrystalline, multicomponent systems, composites and nanocomposites, graphite/metals or similar hybrid systems, clusters, etc.), it is important to be a vare that, for practical applications, a large volume of material should be processed in a fast, inexpensive and reliable vay, for example casting. Techniques such as cold vapor deposition may be impossible to scale up but this does not mean they should be discarded as a means of studying new metal hydrides. On the contrary, laboratory techniques allow much better control of the end product and permit the elaboration of new compounds. Once an attractive compound is found then another challenge w ill have to be faced scaling up the synthesis. In this respect, it is important for the community of metal hydrides researchers to also study large-scale production techniques in order to make the transition from laboratory to industrial scale easier. 

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