Composition and structure of tungsten antimony acid
Abstract
Tungsten antimony acids (TAA) with the composition H(2)Sb(2)WXO6·nH2O (0 < x ≤ 1.45; 0 < n ≤ 2.0) have been synthesized by hydrolysis of antimony trichloride pre-oxidized with nitric acid in the presence of varying amounts of Na2WO4. To obtain TAA protonated forms, the samples were kept in a 96% solution of sulphuric acid, the precipitate was washed until reaction became neutral and dried in air. The amount of tungsten, antimony, and silver ions in TAA was determined using energy dispersive analysis. Changes in structural parameters upon doping of AA with tungsten ions were studied using a Bruker D8 ADVANCE X-ray diffractometer (CuKa1-radiation). The number of oxonium ions in TAA was determined by the substitution
of these ions by silver ions in equivalent amounts (Ag+-TAA forms).
All obtained TAA samples and Ag+ TAA forms had a pyrochlore-type structure, space group symmetry Fd3m. Refinement of the arrangement of atoms in the structure using the Rietveld method showed that tungsten ions replace antimony ions and are statistically located in 16c, oxygen anions in 48f, and oxonium ions and water molecules in 16d and 8b positions, respectively.
When tungsten ions were introduced into samples, the structural parameters of the resulting phases changed. There was a decrease in the unit cell parameter and the distance between antimony ions and oxygen anions, while an increase in the distance between oxonium ions and oxygen anions located in 48f positions was observed. This allowed the removal of a proton from oxonium molecules and its transport via a system of hydrogen bonds formed by water molecules
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