Low-Temperature Synthesis of Tungsten Silicates with Pyrochlore and Tungsten Bronze Structure

Abstract

Polyoxotungstosilicates with the general formulas Cat4[SiW12O40] • mH2O and Cat6[SiW11O39Ni(H2O)] • nH2O were synthesized, where Cat = Rb+, Cs+, (CH3)4N+. By means of IR spectroscopy and x-ray diffraction analysis, it was shown that the compounds have the Keggin anion structure. The thermolysis of the obtained compounds within the temperature range of 600 – 800°C resulted in the formation of previously unknown pyrochlore-structure phases Rb12/13Si2/13W22/13Ni2/13O6 and Cs12/13Si2/13W22/13Ni2/13O6 with the with the unit cell parameters a of 10.284 and 10.309 Å, as well as phases with tungsten bronze structure Rb12/20Si3/20W36/20O6 and Si3/38W36/38O3. The synthesis of tungsten silicates with pyrochlore and tungsten bronze structure through thermolysis of polyoxotungstosilicates reduces the temperature of their preparation to 600 – 650°C and heating time to 1 h, thus extending the ranges of chemical compositions and their morphological diversity.