RT Journal Article
T1 Hydroxyapatites as Versatile Inorganic Hosts of Unusual Pentavalent Manganese Cations
A1 Varela Losada, María Áurea
A1 Gómez Recio, Isabel
A1 Serrador, Laura
A1 Hernando González, María
A1 Matesanz, Emilio
A1 Torres Pardo, María De La Almudena
A1 Fernández-Díaz, María Teresa
A1 Martínez, Jose
A1 Gonell, Francisco
A1 Rousse, Gwenaelle
A1 Sanchez, Clément
A1 Laberty-Robert, Christel
A1 Portehault, David
A1 González Calbet, José María
A1 Parras Vázquez, Marina Marta
AB 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 MnVO43– anion: Sr5[(Mn1–xSix)O4]3(OH)1–3x (x = 0 and 0.053), Sr5(MnO4)3(OH)1–yFy (y = 0.90), and Sr5[(Mn1–xSix)O4]3F1–3x (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–L2,3 spectra of manganese with the oxidation state (V). Contrary to other Mn(V) oxides, these solids and the nominal compound Sr5(MnO4)3OH do not comprise Ba2+ cations but rely only on Sr2+ 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.
PB The Royal Society of Chemistry
SN 1359-7345
YR 2020
FD 2020
LK https://hdl.handle.net/20.500.14352/91876
UL https://hdl.handle.net/20.500.14352/91876
LA eng
NO Aurea Varela, Isabel Gómez-Recio, Laura Serrador, María Hernando, Emilio Matesanz, Almudena Torres-Pardo, María Teresa Fernández-Díaz, Jose L. Martínez, Francisco Gonell, Gwenaelle Rousse, Clément Sanchez, Christel Laberty-Robert, David Portehault, José M. González-Calbet, and Marina Parras Chemistry of Materials 2020 32 (24), 10584-10593 DOI: 10.1021/acs.chemmater.0c03673
NO Ministerio de Ciencia e Innovación (España)
NO Ministerio de Economía (España)
DS Docta Complutense
RD 5 abr 2025