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Title: A (3 + 3)-Dimensional “Hypercubic” Oxide-Ionic Conductor: Type II Bi2O3–Nb2O5
Authors: Ling, CD
Schmid, S
Blanchard, PER
Petříček, V
McIntyre, GJ
Sharma, N
Maljuk, A
Yaremchenko, AA
Kharton, VV
Gutmann, M
Withers, RL
Keywords: Bismuth oxides
Thermal conductivity
Transition elements
Zone melting
Issue Date: 9-Apr-2013
Publisher: ACS Publications
Citation: Ling, C.D., Schmid, S., Blanchard, P.E.R., Petříček, V., McIntyre, G.J., Sharma, N., Maljuk, A., Yaremchenko, A.A., Kharton, V.V., Gutmann, M., & Withers, R.L. (2013). A (3 + 3)-dimensional “hypercubic” oxide-ionic conductor: Type ii bi2o3–nb2o5. Journal of the American Chemical Society, 135(17), 6477-6484. doi:10.1021/ja3109328
Abstract: The high-temperature cubic form of bismuth oxide, δ-Bi2O3, is the best intermediate-temperature oxide-ionic conductor known. The most elegant way of stabilizing δ-Bi2O3 to room temperature, while preserving a large part of its conductivity, is by doping with higher valent transition metals to create wide solid-solutions fields with exceedingly rare and complex (3 + 3)-dimensional incommensurately modulated ?hypercubic? structures. These materials remain poorly understood because no such structure has ever been quantitatively solved and refined, due to both the complexity of the problem and a lack of adequate experimental data. We have addressed this by growing a large (centimeter scale) crystal using a novel refluxing floating-zone method, collecting high-quality single-crystal neutron diffraction data, and treating its structure together with X-ray diffraction data within the superspace symmetry formalism. The structure can be understood as an ?inflated? pyrochlore, in which corner-connected NbO6 octahedral chains move smoothly apart to accommodate the solid solution. While some oxide vacancies are ordered into these chains, the rest are distributed throughout a continuous three-dimensional network of wide δ-Bi2O3-like channels, explaining the high oxide-ionic conductivity compared to commensurately modulated phases in the same pseudobinary system. © 2013, American Chemical Society.
ISSN: 0002-7863
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