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Hexagonal and pyrochlore-type cesium tungstate synthesized from cesium peroxo-polytungstate and their redox chemistry

Journal Article · · Journal of Solid State Chemistry; (United States)

Thermal decomposition of cesium peroxo-polytungstate, an amorphous precursor, yielded not only pyrochlore-type but also hexagonal WO[sub 3]-type cesium tungstate, depending on the Cs/W ratio (x) in the precursors; the former is in the range 0.48 [le] x [le] 0.54 and the latter 0.30 [le] x 0.34. Mixtures of these two phases were formed in the intermediate region of x. On reduction at 700[degrees]C, the pyrochlore phase gave a compound with the same framework, with its cubic cell parameter being elongated from 10.25 to 10.32 [Angstrom], but reoxidation resulted in a mixture of pyrochlore and hexagonal phases. In contrast, reduction and oxidation of the hexagonal phase at 600[degrees]C was reversible. Power XRD profile refinements were performed with reduced and oxidized hexagonal cesium tungstates (x = 0.30) in the space group P6[sub 3]/mcm. The former compounds (a = 7.4049(1) and c = 7.6098(1)) are based on an almost idealized h-WO[sub 3] framework with Cs sitting on its large 2b interstices (R[sub f] = 0.0240). The oxidized compounds (7.4012(18) and 7.6728(17) [Angstrom], R[sub f] = 0.007) possessed a lacunar tungsten sublattice. 12 refs., 11 refs., 2 tabs.

OSTI ID:
6206570
Journal Information:
Journal of Solid State Chemistry; (United States), Journal Name: Journal of Solid State Chemistry; (United States) Vol. 103:1; ISSN 0022-4596; ISSN JSSCBI
Country of Publication:
United States
Language:
English