Hydroxyapatites as Versatile Inorganic Hosts of Unusual Pentavalent Manganese Cations
Résumé
Contrary to molecular species, only very few solids are reported to host manganese (V) species. Herein, we report three new compounds with a hydroxyapatite structural backbone built on the Mn V O 4 3− anion: Sr 5 [(Mn 1−x Si x)O 4 ] 3 (OH) 1−3x (x =0 and 0.053), Sr 5 (MnO 4) 3 (OH) 1−y F y (y = 0.90), and Sr 5 [(Mn 1−x Si x)-O 4 ] 3 F 1−3x (x = 0.058). These solids are fully characterized using powder X-ray and neutron powder diffraction, scanning transmission electron microscopy, electron energy loss spectroscopy (EELS), thermogravimetric analysis, and magnetic measurements. Especially, we report for the first time EELS Mn−L 2,3 spectra of manganese with the oxidation state (V). Contrary to other Mn(V) oxides, these solids and the nominal compound Sr 5 (MnO 4) 3 OH do not comprise Ba 2+ cations but rely only on Sr 2+ cations, showing that barium is not a required element to stabilize Mn(V) species in inorganic solids. We show that by tuning soft chemistry conditions on the one hand and post-treatment topological transformation conditions on the other hand, Mn(V) and hydroxyl groups can be substituted by Si(IV) and fluoride ions, respectively. Hence, we deliver solids with a potentially wide composition range. These compounds show significant oxygen anionic conduction, thus suggesting the emergence of new functional materials built from high-oxidation state manganese cations.
Domaines
Matériaux| Origine | Fichiers produits par l'(les) auteur(s) |
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