4 years ago

Rational Design of a Commensurate (3 + 3)-D Modulated Structure within the Fast-Ion Conducting Stabilized δ-Bi2O3 Series

Rational Design of a Commensurate (3 + 3)-D Modulated Structure within the Fast-Ion Conducting Stabilized δ-Bi2O3 Series
Thomas Vogt, Zhaoming Zhang, Douglas A. Blom, Ray L. Withers, Chris D. Ling, Julia Polt, Julia Wind
We report the systematic design, preparation, and characterization of the first commensurate member of the oxide-ionic conducting, (3 + 3)-D modulated, Type II phases of doped δ-Bi2O3. The incommensurate Type II modulation vector ε was previously described as continuously variable, but high-resolution synchrotron X-ray powder diffraction data show that close to the composition Bi23CrNb3O45, it “locks in” to ε = 1/3. The space group of the resulting 3 × 3 × 3 fluorite-type supercell was found to be F4̅3m by selected-area electron diffraction, and the structure was solved and Rietveld-refined against neutron powder diffraction data in conjunction with local structural information from X-ray absorption spectroscopy, high-resolution transmission electron microscopy, and ab initio geometry optimization calculations. The result unambiguously validates the crystal-chemical model of the Type II phases as being based on the local ordering of oxygen around transition metals M into tetrahedral clusters of MO6 octahedra and isolated MO4 tetrahedra, separating relatively disordered fluorite-type regions that facilitate the highest oxide-ionic conduction among transition metal-doped δ-Bi2O3 phases.

Publisher URL: http://dx.doi.org/10.1021/acs.chemmater.7b03012

DOI: 10.1021/acs.chemmater.7b03012

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