Spinel ferrites method

Han, M., Vestal, C.R. and Zhang, Z.J. (2004) Quantum couplings and magnetic properties of CoCrxFe2-x04 (0 < x < 1) spinel ferrite nanoparticles synthesized with reverse micelle method. /. Phys. Chem. B, 108, 583-597. 

Takada, T. (1982). Development and application of synthesising technique of spinel ferrites by the wet method. In Ferrites Proceedings of the Third International Conference on Ferrites, 1980, Japan, Eds H. Watanabe, S. lida and M. Sugimoto. Center for Academic Publications, Tokyo, pp. 3-8.. 

In the present study, spinel ferrites nanocrystals with different structures were prepared from an aqueous solution containing metal nitrates, poly (vinyl pyrrolidon), and deionized water using a relatively low temperature thermal treatment method, followed by grinding and calcinations. No other chemicals were added to the solution. This method is environmentally friendly in that it neither uses nor produces toxic substances, and it offers the advantages of simplicity, low cost, and low reaction temperatures. The textural and morphological characteristics of the spinel ferrites nanocrystals we prepared were studied with various techniques to determine the influence of calcination temperature on the crystallization, morphology, and particle size distribution of the nanocrystals and to explore other parameters of interest. 

Furthermore, this method can be extended to the synthesis of other spinel ferrite nanoparticles of interest. 

Spinel ferrite nanoparticles have been intensively studied in the recent years, because of their typical ferromagnetic properties, low conductivity, high electrochemical stability and catalytic behavior. These materials are widely used in large-scale applications (i) in electric and electronic devices, (ii) in H2O, CO2 and alcohols decomposition and in CO and CH4 oxidation [1, 2]. Several routes are used for the preparation of NiFe204 catalysts such as co-precipitation, hydrothermal, sol gel, combustion [3-6] etc. However, the structural and textural properties of ferrite spinel are strongly influenced by the preparation methodology used in their synthesis and may influence the catalytic activity of these materials when used as catalysts. Hence, the effect of the preparation method on the surface acid-basic properties and therefore on the catalytic activity is a very interesting subject. 

In addition to the above reported synthesis of ferrites our search has revealed that aluminates [119], nickelates [120], and manganates [121], have also been prepared by the sonochemical method. Nanosized nickel aluminate spinel particles have been synthesized [119] with the aid of ultrasound radiation by a precursor approach. Sonicating an aqueous solution of nickel nitrate, aluminum nitrate, and urea yields a precursor which, on heating at 950 °C for 14 h yields nanosized N1A1204 particles with a size of ca. 13 nm and with a surface area of about 108 m g-i. 

Chemical vapour deposition (CVD), or more specifically, organo-metallic CVD can also be used to prepare ferrite thin films (Itoh, Takeda Naka, 1986). A mixture of acetylacetonate complexes of the desired metal is evaporated in a quartz boat (number 1 in Fig. 3.27) and is reacted with O2, which is introduced directly in the deposition zone. By adding a second furnace (B), an additional component evaporating at a different temperature can be transported to the substrate. Glass or MgO single crystals can be used as the substrates an annealing up to 1(X)0°C is performed on the film to improve its crystallisation. Spinel thin films (Ni, Ni-Zn) have been prepared by this method. 

Solid-state reactions are also used to produce new materials. For example, although equimolar Mg-Al spinel (i.e., MgAl204 or Mg0 Al203) powder is available commercially, nonequimolar Mg-Al spinel powders may be less easy to obtain. (A similar processing method is used to produce many of the spinel-structured ferrites.) These spinel powders may have useful properties since they can be used to produce polycrystalline compacts that deform more readily than the equimolar material. Such materials can be prepared by bring an intimate mixture of the equimolar spinel with high-purity alumina powder. A closely related process (structurally the opposite) occurs when y-alumina is transformed to a-alumina, for example, when alumina is prepared from boehmite. 

Fe is the active metal for high-temperature WGS reaction. Hence, we introduced a variety of metal dopants (M = Cr, Mn, Co, Ni, Cu, Zn and Ce) for iron oxide (spinel lattice) and screened their effectiveness for high-temperature WGS reaction [1]. The idea was to examine if ferrite formation can occur with dopants and promote the Fe Fe redox couple. The substitution of Fe sites in the ferrite strucmre with other transition/non-transition/inner transition metal atoms leads to the crystallization of an inverse (or mixed) spinel. The stoichiometry of an inverse spinel can be represented as A(i a)Ba[AaB(2 a)]04, where 8 is the degree of inversion, while A and B represent typical divalent and trivalent cations, respectively. The catalysts were synthesized by coprecipitation method using nitrates as precursors. The synthesized catalysts were evaluated for ultra high temperature WGS reaction in the temperature region 400-550 °C and GHSV 60,000 h- ... 

Of all solid state reactions, the formation of oxide spinels is at present the most thoroughly investigated [4, 5, 33]. The first reason for this is the relatively simple crystallographic structure of the spinel lattice. Essentially, this consists of a nearly close-packed face-centred-cubic sublattice of oxygen ions. The tetrahedral and octrahedral interstices of this sublattice are filled in a certain way by the cations. The second reason is that spinels are technically very interesting substances, and one would like to be able to find optimal methods for their preparation. For instance, ferrites are used as control or circuit elements in the electronics industry, and chromite brick is used as cladding in ovens which are used for the production of steel. Therefore, the formation of spinels will now be discussed in detail as a model of a classical solid state reaction. 

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