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Full Record Details
Persistent URL
http://purl.org/net/epubs/work/65389
Record Status
Checked
Record Id
65389
Title
A (3+3)-Dimensional "Hypercubic" Oxide-Ionic Conductor: Type II Bi2O3-Nb2O5
Contributors
CD Ling (Sydney U.)
,
S Schmid (Sydney U.)
,
PER Blanchard (Sydney U.)
,
V Petrícek (Academy of Sciences, Czech Republic)
,
GJ McIntyre (ILL)
,
N Sharma (Sydney U.)
,
A Maljuk (Leibniz Institute for Solid State and Materials Research Dresden)
,
AA Yaremchenko (Aveiro U.)
,
VV Kharton (Aveiro U.)
,
M Gutmann (STFC Rutherford Appleton Lab.)
,
RL Withers (Australian National U.)
Abstract
The high-temperature cubic form of bismuth oxide, ?-Bi2O3, is the best intermediate-temperature oxide-ionic conductor known. The most elegant way of stabilizing ?-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 ?-Bi2O3-like channels, explaining the high oxide-ionic conductivity compared to commensurately modulated phases in the same pseudobinary system.
Organisation
ISIS
,
ISIS-SXD
,
ISIS-ILL
,
STFC
Keywords
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Language
English (EN)
Type
Details
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Year
Journal Article
J Am Chem Soc
135, no. 17 (2013): 6477-6484.
doi:10.1021/ja3109328
2013
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