RT Journal Article
T1 Crystallization of manganese(V) oxides by hydroflux synthesis:control of anisotropic growth and electrochemical stability
A1 Inocêncio, Carlos
A1 Torres Pardo, María De La Almudena
A1 Montero, David
A1 Roach, Lucien
A1 Autran, Pierre Olivier
A1 Sassoye, Capucine
A1 Aymonier, Cyril
A1 Varela Losada, María Áurea
A1 Parras Vázquez, Marina Marta
A1 Laberty Robert, Christel
A1 Portehault, David
AB Despite intriguing optical, magnetic, and redox properties, inorganic materials containing pentavalent manganese (MnV) are rare and could never be designed as shape-controlled crystals, which limits the ability to tune properties. Herein, we explore alkali hydroxide mixtures with controlled water content, namely, hydrofluxes, to demonstrate phase, shape, and nanostructure control of Mn(V) oxides. We demonstrate speciation amongKSrMnVO4, Sr5(MnVO4)3OH, and SrMnIVO3 with the water and strontium content and the nature of the alkali cation of the hydroxide salt. We then provide evidence of the key role of water in enabling shape and nanostructure control, which we relate to thepreferential interaction of water with specific crystal facets of the hydroxyapatite Sr5(MnVO4)3OH, and to the impact of water on precursor solubility in water-poor hydrofluxes. We then show that nanostructured Mn(V) hydroxyapatite possesses an acid−base redox stability window, enabling electrochemical operation in strongly oxidative conditions. By correlating the fundamental knowledge of hydrofluxes with crystallization mechanisms, this work sheds light on the possibilities offered by hydrofluxes for crystalshape, size, and property control.
PB ACS
SN 0020-1669
YR 2025
FD 2025-02-28
LK https://hdl.handle.net/20.500.14352/118990
UL https://hdl.handle.net/20.500.14352/118990
LA eng
NO Inocêncio, C. V. M.; Torres-Pardo, A.; Montero, D.; Roach, L.; Autran, P.-O.; Sassoye, C.; Aymonier, C.; Varela, A.; Parras, M.; Laberty-Robert, C.; Portehault, D. Crystallization of Manganese(V) Oxides by Hydroflux Synthesis: Control of Anisotropic Growth and Electrochemical Stability. Inorg. Chem. 2025, 64 (10), 5122–5131. https://doi.org/10.1021/acs.inorgchem.4c05439.
NO This work was funded by the Agence Nationale de la Recherche (ANR, Grant No. ANR-21-CE50-0021). M.P, A.V and A.T.P acknowledge the support from “(MAD2D-CM)-UCM” and PR65/19-22438 Research Projects funded by Comunidad de Madrid and from the Ministerio de Ciencia, Innovación y Universidades through Research Project PID2020-113753RB-I00. The Federation of Chemistry and Materials of Paris-Center (FCMat) is gratefully acknowledged for SEM experiments. SEM was funded by Sorbonne Université, CNRS, and Région Ile de France. We acknowledge the European Synchrotron Radiation Facility (ESRF) for providing synchrotron radiation facilities under proposal number MA-5619.
NO Agence Nationale de la Recherche (France)
NO Universidad Complutense de Madrid
NO Comunidad de Madrid
NO Ministerio de Ciencia, Innovación y Universidades (España)
NO Federation of Chemistry and Materials of Paris-Center (France)
NO European Synchrotron Radiation Facility
DS Docta Complutense
RD 1 abr 2025