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https://hdl.handle.net/2440/53151
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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 1095-726X |
Statement of Responsibility: | 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 XANES Oxygen vacancies |
DOI: | 10.1016/j.jssc.2008.07.007 |
Grant ID: | ARC |
Published version: | http://dx.doi.org/10.1016/j.jssc.2008.07.007 |
Appears in Collections: | Aurora harvest 5 Chemistry publications Environment Institute publications |
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