Journal
INORGANIC CHEMISTRY
Volume 57, Issue 21, Pages 13702-13712Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.8b02275
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Funding
- CAMPUS FRANCE (PHC STEFANIK project) [31799NM]
- Slovak bilateral project [SK-FR-2013-0039]
- Slovak Grant Agencies [APVV-15-0738, APVV-15-0479, VEGA-2/0060/18]
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Precise research on the RbF-Al2O3 system was carried out by means of combining X-ray powder diffraction, high-field solid-state NMR spectroscopy, and thermal analysis methods. alpha-Rb3AlF6, RbAO(2), Rb2Al22O34, and new phase, Rb2Al2O3F2, were identified in the system. The structure of this new rubidium oxofluoroaluminate was determined. It is built up from single layers of oxygen-connected AlO3F tetrahedra, those layers beeing separated by fluorine atoms. This type of structure exhibits a decent ionic conductivity at ambient temperature, 1.74 X 10(-6) S cm(-1). The similar structural arrangement of O3Al-O-AlO3 and FO2Al-O-AlO2F tetrahedra of the conduction planes in Rb2Al22O34 and Rb2Al2O3F2 were confirmed by Al-27 NMR measurements. A thermal analysis of the RbF-Al2O3 system revealed that it can be defined as a pseudobinary subsystem of the more general quaternary RbF-AlF3-Al2O3-Rb2O phase diagram. From a phase analysis of individual phase fields, the mutual metastable behavior of all founded phases can be considered. It was observed that fluoro- and oxoaluminates exist together. Rb2Al2O3F2 is more stable under high temperature. Rubidium fluoro- and oxoaluminates are metastable precursors of the thermodynamically more stable structure of rubidium oxofluoroaluminate.
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