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Oxygen Vacancy Ordering in the Double-layered Ruddlesden−Popper Cobaltite Sm2BaCo2O7−δ

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Download Hi-Res ImageDownload to MS-PowerPointCite This:Chem. Mater. 2008, 20, 19, 6231-6237
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    Oxygen Vacancy Ordering in the Double-layered Ruddlesden−Popper Cobaltite Sm2BaCo2O7−δ
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    Department of Chemical & Biological Sciences, School of Applied Sciences, University of Huddersfield, Queensgate, Huddersfield HD1 3HD, United Kingdom, EMAT, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium, and Laboratoire CRISMAT, ISMRA-ENSICAEN, 6 boulevard du Maréchal Juin, 14050 Caen cédex, France
    * Corresponding author. E-mail: [email protected]. Tel: 44 1482 472578. Fax: 44 1484 472182.
    †University of Huddersfield.
    §Laboratoire CRISMAT, ISMRA-ENSICAEN.
    ‡University of Antwerp.
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    Chemistry of Materials

    Cite this: Chem. Mater. 2008, 20, 19, 6231–6237
    Click to copy citationCitation copied!
    https://doi.org/10.1021/cm8010138
    Published September 13, 2008
    Copyright © 2008 American Chemical Society
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    Abstract

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    A new oxygen-deficient Ruddlesden−Popper (RP) cobaltite Sm2BaCo2O7−δ (δ ≈ 1.0) has been synthesized and the crystal structure elucidated by Rietveld analysis of X-ray powder diffraction (XRD) data and transmission electron microscopy (TEM). The phase crystallizes in a primitive orthorhombic unit cell, with lattice parameters a = 5.4371(4) Å; b = 5.4405(4) Å and c = 19.8629(6) Å, and space group Pnnm. Contrary to other oxygen-deficient cobalt RP phases, the oxygen vacancies are located in the equatorial positions of the [CoO] layers to give an intralayer structure similar to Sr2Mn2O5, which is not usually observed for cobalt-containing materials. The Sm3+ and Ba2+ cations show a strong preference for distinct sites, with the majority of the larger Ba2+ cations situated in the perovskite block layers and Sm3+ cations predominantly in the rock salt layers. Magnetic susceptibility data demonstrate the strong antiferromagnetic (AFM) character of Sm2BaCo2O7−δ.

    Copyright © 2008 American Chemical Society

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    Cited By

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    This article is cited by 14 publications.

    1. A. Demont, D. Pelloquin, S. Hébert, M. Hervieu, J. Höwing, and A. Maignan . Sr7Co4(CO3)O13−δ (δ = 1.64), An Original Cobaltite Derivative of the Ruddlesden–Popper Series. Inorganic Chemistry 2013, 52 (9) , 4977-4984. https://doi.org/10.1021/ic3026232
    2. A. Demont, S. Hébert, J. Höwing, Y. Bréard, and D. Pelloquin . Large Oxygen Nonstoichiometry in La0.77Sr3.23Co2.75C0.25O8.40+δ Oxide (δ = 0, 1.3) Related to n = 3 RP Series. Inorganic Chemistry 2013, 52 (3) , 1265-1274. https://doi.org/10.1021/ic3017694
    3. V.A. Dudnikov, Yu S. Orlov, L.A. Solovyov, S.N. Vereshchagin, S. Yu Gavrilkin. The Sr2.4Dy0.6Co2O7-δ Ruddlesden‒Popper Phase: Structural, thermoelectric, and magnetic properties. Ceramics International 2021, 47 (7) , 9068-9074. https://doi.org/10.1016/j.ceramint.2020.12.030
    4. Yong Ding, Yu Chen, Ken C. Pradel, Weilin Zhang, Meilin Liu, Zhong Lin Wang. Domain structures and Prco antisite point defects in double-perovskite PrBaCo2O5+δ and PrBa0.8Ca0.2Co2O5+δ. Ultramicroscopy 2018, 193 , 64-70. https://doi.org/10.1016/j.ultramic.2018.06.008
    5. N. E. Volkova, L. V. Khvostova, A. P. Galaida, L. Ya. Gavrilova, V. A. Cherepanov. Phase equilibria, crystal structure and oxygen nonstoichiometry of the complex oxides in the Sm – (Sr, Ba) – (Co, Fe) – O systems. Chimica Techno Acta 2018, 5 (1) , 55-79. https://doi.org/10.15826/chimtech.2018.5.1.04
    6. V. A. Cherepanov, L. Ya. Gavrilova, N. E. Volkova, A. S. Urusov, T. V. Aksenova, E. Kiselev. Phase equilibria and thermodynamic properties of oxide systems on the basis of rare earth, alkaline earth and 3d-transition (Mn, Fe, Co) metals. A short overview of. Chimica Techno Acta 2015, 2 (4) , 273-305. https://doi.org/10.15826/chimtech.2015.2.4.028
    7. Hanskarl Müller‐Buschbaum. On the Crystal Chemistry of Alkaline Earth‐ and Rare Earth‐Oxocobaltates. Zeitschrift für anorganische und allgemeine Chemie 2013, 639 (15) , 2715-2735. https://doi.org/10.1002/zaac.201300243
    8. B. Raveau. Ruddlesden-Popper Phases and Derivatives: Homologous Series of Transition Metal Oxides. 2013, 63-102. https://doi.org/10.1016/B978-0-08-097774-4.00203-5
    9. . Crystal Chemistry of Cobalt Oxides. 2012, 3-70. https://doi.org/10.1002/9783527645527.ch1
    10. . Electronic and Magnetic Properties of Ruddlesden–Poepper‐Type Cobaltites. 2012, 179-210. https://doi.org/10.1002/9783527645527.ch4
    11. N. Chihaoui, M. Bejar, E. Dharhi, M.A. Valente, M.P.F. Graça. Effect of the oxygen deficiency on the physical properties of Ca2MnO4−δ compounds. Journal of Alloys and Compounds 2011, 509 (36) , 8965-8969. https://doi.org/10.1016/j.jallcom.2011.06.110
    12. L.Ya. Gavrilova, T.V. Aksenova, N.E. Volkova, A.S. Podzorova, V.A. Cherepanov. Phase equilibria and crystal structure of the complex oxides in the Ln–Ba–Co–O (Ln=Nd, Sm) systems. Journal of Solid State Chemistry 2011, 184 (8) , 2083-2087. https://doi.org/10.1016/j.jssc.2011.06.006
    13. T. Riedl, T. Gemming, T. Weissbach, G. Seifert, E. Gutmann, M. Zschornak, D.C. Meyer, S. Gemming. ELNES study of chemical solution deposited SrO ( SrTiO 3 ) n Ruddlesden–Popper films: Experiment and simulation. Ultramicroscopy 2009, 110 (1) , 26-32. https://doi.org/10.1016/j.ultramic.2009.09.001
    14. Lisa J. Gillie, Joke Hadermann, Maryvonne Hervieu, Antoine Maignan, Christine Martin. ChemInform Abstract: Oxygen Vacancy Ordering in the Double‐Layered Ruddlesden—Popper Cobaltite Sm 2 BaCo 2 O 7‐δ .. ChemInform 2009, 40 (1) https://doi.org/10.1002/chin.200901005
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    Chemistry of Materials

    Cite this: Chem. Mater. 2008, 20, 19, 6231–6237
    Click to copy citationCitation copied!
    https://doi.org/10.1021/cm8010138
    Published September 13, 2008
    Copyright © 2008 American Chemical Society
    Request reuse permissions

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