First Mixed-Metal Fluoride Pyrochlores Obtained By Topotactic Oxidation Of Ammonium Fluorides Under F-2 Gas
CRYSTAL GROWTH & DESIGN(2021)
Abstract
Metal fluorides with 3D open structures, pyrochlore (pyr) or hexagonal tungsten bronze (HTB), are promising materials as positive electrodes for rechargeable batteries or catalysts. Herein, we have developed a two-step synthesis procedure to obtain new anhydrous mixed-metal-cation fluorides crystallizing in the pyrochlore structure. The first step consists of preparing mixed-metal ammonium fluorides (NH4)M2+Fe3+F6 (M = Mn, Fe, Co Ni) using different synthesis strategies. For M = Mn, three allotropic varieties of (NH4)Mn2+Fe3+F6 are obtained; two phases adopt the expected pyrochlore network with either the cubic Fm(3)m or the orthorhombic Pnma space group, and the third phase exhibits a 3D network with narrow pseudotriangular cavities. Fe-57 Mossbauer spectrometry indicates that the crystal structures are governed by the Fe3+/Mn2+ cationic order or disorder. The second step is a topotactic oxidation of pyr-(NH4)(M2+Fe3+F6) under a molecular F-2 flow. To better understand the reaction mechanism, the topotactic oxidation was followed by thermogravimetry, XRD, FTIR, and Mossbauer spectrometry. The successful synthesis of the first anhydrous pyr-M0.53+Fe0.5F3 provides a new route to prepare anhydrous mixed-metal fluorides pyrochlore with empty cavities of the open framework.
MoreTranslated text
Key words
ammonium fluorides,topotactic oxidation,mixed-metal
AI Read Science
Must-Reading Tree
Example
Generate MRT to find the research sequence of this paper
Chat Paper
Summary is being generated by the instructions you defined