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Correlation of Local Structure and Diffusion Pathways in the Modulated Anisotropic Oxide Ion Conductor CeNbO4.25

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Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ, United Kingdom
§ Energy Research Institute at NTU, Research Technoplaza and §Division of Materials Science and Engineering, Nanyang Technological University, Nanyang Drive, Singapore, Singapore
ISIS Facility, Rutherford Appleton Laboratory, Didcot OX11 0QX, United Kingdom
Diamond Light Source, Chilton, Oxfordshire, OX11 0DE, United Kingdom
# Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore
Institute of Materials Research and Engineering, 3 Research Link, Singapore, Singapore
Cite this: J. Am. Chem. Soc. 2016, 138, 4, 1273–1279
Publication Date (Web):January 15, 2016
Copyright © 2016 American Chemical Society

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    CeNbO4.25 is reported to exhibit fast oxygen ion diffusion at moderate temperatures, making this the prototype of a new class of ion conductor with applications in a range of energy generation and storage devices. To date, the mechanism by which this ion transport is achieved has remained obscure, in part due to the long-range commensurately modulated structural motif. Here we show that CeNbO4.25 forms with a unit cell ∼12 times larger than the stoichiometric tetragonal parent phase of CeNbO4 as a result of the helical ordering of Ce3+ and Ce4+ ions along z. Interstitial oxygen ion incorporation leads to a cooperative displacement of the surrounding oxygen species, creating interlayer “NbO6” connectivity by extending the oxygen coordination number to 7 and 8. Molecular dynamic simulations suggest that fast ion migration occurs predominantly within the xz plane. It is concluded that the oxide ion diffuses anisotropically, with the major migration mechanism being intralayer; however, when obstructed, oxygen can readily move to an adjacent layer along y via alternate lower energy barrier pathways.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.5b11373.

    • Table of refined single-crystal X-ray diffraction data; table of refined atomic positions; table of selected bond lengths; table of Buckingham potentials; table of experimental and calculated lattice parameters; micrograph of the single crystal; model crystal structures; refined diffraction data; refined total scattering data; pair distributions correlations from MD; and associated references (PDF)

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