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Type: Journal article
Title: Phase and valence transitions in Ba₂LnSnₓSb₁−xO₆−δ (Ln=Pr and Tb)
Other Titles: Phase and valence transitions in Ba(2)LnSn(x)Sb(1-x)O(6-delta) (Ln = Pr and Tb)
Author: Saines, P.
Kennedy, B.
Elcombe, M.
Harris, H.
Jang, L.
Zhang, Z.
Citation: Journal of Solid State Chemistry, 2008; 181(11):2941-2952
Publisher: Academic Press Inc
Issue Date: 2008
ISSN: 0022-4596
Statement of
Paul J. Saines, Brendan J. Kennedy, Margaret M. Elcombe, Hugh H. Harris, Ling-Yun Jang and Zhaoming Zhang
Abstract: Compounds in the double perovskites series Ba2LnSnxSb1-xO6-δ (Ln=Pr and Tb) have been synthesised and structurally characterised using synchrotron X-ray and neutron powder diffraction. It was found that the two end-members of the Ba2PrSnxSb1-xO6-δ series both adopt rhombohedral symmetry but the antimonate is a fully ordered double perovskite while the stannate has no B-site cation ordering. X-ray absorption near-edge structure (XANES) and near-infrared spectroscopy indicate that the Pr cations gradually change oxidation state from Pr3+ to Pr4+ with increasing x and that this is likely to be the cause of the loss of B-site ordering. Similarly, both Ba2TbSbO6 and Ba2TbSnO6-δ are cubic with B-site ordering present in the former but absent in the latter due to the oxidation state change of the Tb from Tb3+ to Tb4+. Multiple linear regression analysis of the Pr and Tb LIII-edge XANES indicates that the rate of Ln3+ transforming to Ln4+ is such that there are no oxygen vacancies in Ba2PrSnxSb1-xO6-δ but in Ba2TbSnxSb1-xO6-δ there is a small amount of oxygen vacancies, with a maximum of δ≈0.05 present. Crown Copyright © 2008.
Keywords: Perovskite
Structural phase transition
Lanthanide valence state
Oxygen vacancies
DOI: 10.1016/j.jssc.2008.07.007
Grant ID: ARC
Appears in Collections:Aurora harvest 5
Chemistry publications
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