Strontium doping in mullite-type bismuth aluminate: a vacancy investigation 
using neutrons, photons and electrons

Gesing, Thorsten M.; Schowalter, Marco; Weidenthaler, Claudia; Murshed, M. Mangir; Nénert, Gwilherm; Mendive, Cecilia B.; Curti, Mariano; Rosenauer, Andreas; Buhl, J.-Christian; Schneider, Hartmut; Fischer, Reinhard

doi:10.1039/c2jm33208f

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Strontium doping in mullite-type bismuth aluminate: a vacancy investigation using neutrons, photons and electrons

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Weidenthaler, Claudia
Research Department Schüth, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Gesing, T. M., Schowalter, M., Weidenthaler, C., Murshed, M. M., Nénert, G., Mendive, C. B., et al. (2012). Strontium doping in mullite-type bismuth aluminate: a vacancy investigation using neutrons, photons and electrons. Journal of Materials Chemistry, 22(36), 18814-18823. doi:10.1039/c2jm33208f.

Cite as: https://hdl.handle.net/11858/00-001M-0000-000E-F34C-9

Abstract

We report on strontium doped dibismuth-nonaoxoaluminate(III) produced at 1023 K. Partial substitution of bismuth by strontium in the structure yields oxygen vacancies for charge balance. Introducing oxygen vacancies rearranged the associated Al₂O₇ double-tetrahedra forming “Al₃O₁₀” tri-clusters which were identified by multi-quantum ²⁷Al MAS NMR. Both STEM-EDX and XPS showed homogeneous distribution of strontium in the bulk and on the surface, respectively. Moreover, XPS confirms the valence state of bismuth after doping. The orientations of bismuth 6s² lone electron pairs were calculated using DFT methods. The amount of strontium in the crystal structure was further confirmed from the decomposition product SrAl₁₂O₁₉ formed during the temperature-dependent X-ray powder diffraction. The structural proof was carried out by refining the structure of (Bi_0.94Sr_0.06)₂Al₄O_8.94 from powder neutron and X-ray diffraction data. Rietveld refinements clearly showed the under occupation of one oxygen site and the shift of two aluminum atoms from the double-tetrahedra to two tri-cluster sites.