Order/Disorder and in Situ Oxide Defect Control in the Bixbyite Phase YPrO3+δ (0 ≤ δ < 0.5)

Inorganic Chemistry
Joey A LussierMario Bieringer

Abstract

The YPrO3+δ system is a nearly ideal model system for the investigation of oxide defect creation and annihilation in oxide ion conductor related phases with potential applications as solid state electrolytes in solid oxide fuel cells. The formation, structure, high temperature reactivity, and magnetic susceptibility of phase pure YPrO3+δ (0 ≤ δ ≤ 0.46) are reported. The topotactic reduction and oxidation of the YPrO3+δ system was investigated by powder X-ray in situ diffraction experiments and revealed bixbyite structures (space group: Ia3̅) throughout the series. Combined neutron and X-ray data clearly show oxygen uptake and removal. The research provides a detailed picture of the Y(3+)/Pr(3+)/Pr(4+) sublattice evolution in response to the redox chemistry. Upon oxidation, cation site splitting is observed where the cation in the ((1)/4, (1)/4, (1)/4) position migrates along the body diagonal to the (x, x, x) position. Any oxygen in excess of YPrO3.0 is located in the additional 16c site without depopulating the original 48e site. The in situ X-ray diffraction data and thermal gravimetric analysis have revealed the reversible topotactic redox reactivity at low temperatures (below 425 °C) for all compositions from YPrO3 to YPrO3...Continue Reading

References

Apr 29, 2000·Nature·J B Goodenough
Jul 1, 1960·Journal of Research of the National Bureau of Standards. Section A, Physics and Chemistry·R S Roth, S J Schneider
Jul 1, 1961·Journal of Research of the National Bureau of Standards. Section A, Physics and Chemistry·S J SchneiderJ L Waring

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