The Composition and Structure of Phases, Formed in the Thermolysis of Substitutional Solid Solutions H2Sb2–xVxO6·nH2O
In compounds, crystallized within the pyrochlore-type structure (sp.gr. Fd3m) of the А2В2X6X’ general formula, there could be doubly or triply charged ions in the place of A cations, quadruply or quintuply charged ions in the place of B cations. Most works are devoted to the formation of these structures, depending on the nature and sizes of A and B cations, while little attention has been paid to determining the temperature ranges of their stability. The aim of this work was to study the thermolysis of substitutional solid solutions H2Sb2–xVxO6·nH2O in the range of 25–700 °C and the determination of the
infl uence of the nature of B (Sb, V) cation on the stability of pyrochlore-type structures during heating.
Substitutional solid solutions have been obtained by the co-precipitation method. The samples, containing 0; 5 (x = 0.10); 15 (x = 0.30); 20 (x = 0.40); 24 (x = 0.48) at% of vanadium have been chosen as subjects of the present research. The changes in the proton hydrate sublattice in samples, containing different amounts of V+5 were analysed by IR spectroscopy. The modelling of the thermolysis process and determination of the phase compositions at each stage was possible using X-ray phase and thermogravimetric analysis of the samples.
It was shown that at temperatures of 25–400 °C, proton-containing groups are removed from the hexagonal channels of the pyrochlore-type structure. The increase in number of V+5 ions in solid solutions changed the proton-binding energy with oxygen ions [BO3]–-octahedron, which led to the shift of stage boundaries: oxonium ions and water molecules were removed at higher temperatures, while hydroxide ions were removed at lower temperatures. An increase in temperature to over 500 °C led to the structure destruction due to the oxygen removal from [BO3]–-octahedrons. The model for the atomic fi lling of crystallographic positions in the pyrochlore-type structure for phases, formed during H2Sb2–xVxO6·nH2O
thermolysis at 25–400 °C, has been proposed.
According to the thermogravimetric analysis, the structural formulas of solid solutions under the air-dry condition has been determined. (H3O)Sb2–xVxO5(OH)·nH2O, where 0 < x £ 0.48, 0 <n £ 1.1. It has been shown that the temperature ranges of thermolysis stages were affected by the proton-binding energy with oxygen ions [BO3]–-octahedron temperature ranges, where B = V, Sb, forming the structural frame. It has been found that the studied solid solutions are stable up to 400 °C within the framework of the pyrochlore-type structure.
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