Metastable structure synthesis

We have developed solvothermal synthesis as an important method in research of metastable structures. In the benzene-thermal synthesis of nanocrystalline GaN at 280°C through the metathesis reaction of GaClj and U3N, the ultrahigh pressure rocksalt type GaN metastable phase, which was previously prepared at 37 GPa, was obtained at ambient condition [5]. Diamond crystallites were prepared from catalytic reduction of CCI4 by metallic sodium in an autoclave at 700°C (Fig.l) [6]. In our recent studies, diamond was also prepared via the solvothermal process. In the solvothermal catalytic metathesis reaction of carbides of transition metals and CX4 (X = F, Cl, Br) at 600-700°C, Raman spectrum of the prepared sample shows a sharp peak at 1330 cm" (Fig. 1), indicating existence of diamond. In another process, multiwalled carbon nanotubes were synthesized at 350°C by the solvothermal catalytic reaction of CgCle with metallic potassium (Fig. 2) [7]. 

These calculations yield, subject to some simplifying assumptions, relative T-site alumimun substitution energies computed (1) for the thermodynamic equilibrium state, (2) at zero K and (3) for models devoid of non-firamework species. Framework zeolites, metastable structures, are produced under luetic control and if, as indicated by the most recent calculations, the relative T-site substitution energies for the (Cerent sites are not grossly disparate, the actual distributions in reed materitds will be determined by the particular conditions of synthesis. As the molecular-level mechanisms of zeolite sjmthesis remain obscure, we especially need some experimental indicator of which sites are actually adopted by aluminum in real MFI-framework materials. 

H. Hirano, A. Miyashita, and H. Nohira, Synthesis and metastable structure of new photochromic... 

Something commonly seen in the synthesis of nanomaterials is that many metastable structures appear stable in the nanometric range. A typical case is the synthesis of Ti02 polymorphs. Ti02 has three crystalline polymorphs, anatase, brookite, and rutile [84]. Although several papers report on the synthesis of nanocrystalline anatase [12, 85-89], few report on nanocrystalline rutile [90,91] as an example. However, several papers state that the rutile formation passes through the three metastable phases, and it has been established that rutile is the most stable Ti02 polymorph (observations of micrometric anatase are scarce) [92-96]. 

Tsuji, H., Oshima, K. and Koyasu, Y. (2003). Synthesis of Molybdenum And Vanadium-Based Mixed Oxide Catalysts with Metastable Structure Easy Access to the MoVNbTe(Sb) 0-x Catalytically Active Structure Using Reductant And Oxoacid, Chem. Mater., 15, pp. 2112-2114. 

The importance of framework density and molar volume is evident also for large pore, mesoporous silica [33] and for AIPO4 polymorphs [34], Data for the latter are included in Figure 7.19. For mesoporous silica a transition from a regime where cages and pores affects the energetics to one in which the large pores act as inert diluent is reported. A further increase in pore diameter does not appear to increase the enthalpy of the compound [33], The similarity in enthalpy of many different structures shows that the synthesis of metastable microporous framework... 

Under similar reaction conditions used for the synthesis of the above-mentioned A177R2o2 cluster 63, the Ga cluster Gag4R2o4 [R = N(SiMe3)2] 83 [4], is obtained from a metastable GaBr solution and LiN(SiMe3)2. The molecular structure of 83 is illustrated in a similar fashion to that of 63 in Figure 2.3-28(a). 

The synthesis of chalcogenides such as those of the rare earth elements has traditionally been performed through the reaction of rare earth metals or oxides with a molten or vaporous chalcogen source in a high-temperature environment. Soft synthetic methods utilizing lower temperature conditions, such as hydrothermal or flux syntheses, can allow access also to thermodynamically metastable phases. Flux syntheses of R chalcogenides via an alkali poly-chalcogenide flux have been shown to be extremely versatile for the preparation of many new structures, some of which cannot be obtained by direct synthesis from the elements. 

Cubic Phase of Boron Nitride c-BN. The cubic phase of boron nitride (c-BN) is one of the hardest materials, second only to diamond and with similar crystal structure. It is the first example of a new material theoretically predicted and then synthesized in laboratory. From automated synthesis a microcrystalline phase of cubic boron nitride is recovered at ambient conditions in a metastable state, providing the basic material for a wide range of cutting and grinding applications. Synthetic polycrystalline diamonds and nitrides are principally used as abrasives but in spite of the greater hardness of diamond, its employment as a superabrasive is limited by a relatively low chemical and thermal stability. Cubic boron nitride, on the contrary, has only half the hardness of diamond but an extremely high thermal stability and inertness. 

Zeolite formation depends on reaction conditions 2-4). It is generally believed that most zeolites are formed as metastable phases. According to Barrer (3), the course of the synthesis, beginning with the type of starting material, determines the structure of the zeolite formed. The studies of Zhdanov 2, 5) on the composition of liquid and solid phases of hydrogels indicate that the kind and composition of the zeolite formed depend on the hydrogel composition and that the results of crystallization of aluminosilicate gels obtained in the same way are reproducible. 

This paper consists of three parts. The first part describes the high pressure synthesis of bimetallic compounds of NbN and MN where M is a Group 13 metal such as Al, Ga, or In. The second part discusses crystal structure investigations of a series of alkaline earth and transition metal nitrides, carried out to understand the bonding surrounding the transition metals. The third part describes the preparation of new metastable transition metal nitride and their solid solutions by rf-sputter deposition. 

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