Decrease of the required dopant concentration for δ-Bi₂O₃ crystal stabilization through thermal quenching during single-step flame spray pyrolysis
J. A. H. Dreyer, S. Pokhrel, J. Birkenstock, M. G. Hevia, M. Schowalter, A. Rosenauer, A. Urakawa, W. Y. Teoh, L. Mädler
CrystEngComm, 2016, 18, 2046-2056

δ-Bi₂O₃ is one of the best oxygen ion conductors known. However, due to its limited thermal stability and complicated synthesis techniques, its applications are limited. Here, the synthesis of stable nano-sized δ-Bi₂O₃ using versatile and rapid flame spray pyrolysis (FSP) combined with in situ Ti and/or Mn doping for an enhanced thermal stability is reported for the first time. Exceptionally low Bi replacing cation concentrations (8 at% Ti) were sufficient to obtain phase-pure δ-Bi₂O₃ which was attributed to the extraordinarily high temperature gradient during FSP. The required cation amount for δ-phase stabilization was even further reduced by introducing mixtures of Mn and Ti (2.5 at% Mn + 2.5 at% Ti). Rietveld analysis revealed that the δ-Bi₂O₃ structure is best represented by the Fmm space group containing two closely neighbored 8c and 32f Wyckoff positions. Depending on the amount of Mn/Ti cations, about 25% of the possible oxygen positions remain vacant, suggesting high bulk oxygen mobility. The enhanced oxygen mobility was confirmed by temperature programmed reduction (H₂-TPR) with bulk reduction for δ-Bi₂O₃ in contrast to exclusive surface reduction for β-Bi₂O₃.

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