Preparation and topotactical oxidation of ScVO3 with bixbyte structure: a low-temperature route to stabilize the new defect fluorite ScVO(3.5) metastable phase

Dalton Transactions : an International Journal of Inorganic Chemistry
J A AlonsoMaría Jesús Martínez-Lope

Abstract

ScVO3 has been prepared by controlled reduction of a ScVO4 precursor under an H2/N2 flow at 1250 degrees C. The crystal structure of this material has been studied at room temperature by Rietveld refinement of high-resolution neutron powder diffraction (NPD) data. Sc3+ and V3+ are distributed at random over the metal sites of a C-M2O3 bixbyite-type structure, space group Ia3, a = 9.6182(1) Angstroms. The thermal analysis of ScVO3 in an air flow shows two subsequent oxidation processes, with a final reversal to ScVO4 above 600 degrees C. An intermediate phase of composition ScVO(3.5), containing V4+ cations, can be isolated by isothermal annealing at 350 degrees C in air. This metastable phase has been identified by X-ray diffraction (XRD) as a fluorite-type oxide (space group Fm3m, a = 4.947(2) Angstroms), also showing a random distribution of Sc and V cations over the metal positions. The Rietveld refinement of the ScVO(3.5) structure from powder XRD data in a fluorite structural model yields abnormally high thermal factors for the oxygen atoms, suggesting oxygen mobility in this metastable material.

References

Apr 29, 2000·Nature·J B Goodenough

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Citations

Apr 3, 2014·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Alexei A Belik, Wei Yi
Apr 18, 2018·Inorganic Chemistry·Joey A LussierMario Bieringer

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