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Contribution of Mössbauer spectrometry to structural characterizations of iron-based fluorinated materials: Application to pyrochlore (NH4)CuFeF6 and a new derived hydrate

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  • FOCUS ISSUE: Mössbauer Spectroscopy from Artificial Nano Architectures to Environmental Applications
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Abstract

This paper brings together the latest studies on iron-based fluorides, anhydrous, hydrates, or hybrids, particularly composed of HTB sheets, with the help of 57Fe Mössbauer spectrometry to accurately describe the chemical compositions and to highlight the anionic and/or cationic orders or disorders. As an illustration, a new ammonium hexafluoride with the formulation (NH4)Cu2+Fe3+F6 is synthesized by mechanical milling. Structural analysis by powder XRD made it possible to establish the disordered cubic pyrochlore structure. Because of its local probe behavior, the hyperfine structure observed by Mössbauer spectrometry not only specifies the oxidation state of Fe species but also confirms the cationic disorder and thus the magnetic frustration with a paramagnetic doublet at 77 K for Fe3+. The hydration of (NH4)CuFeF6 leads to a new structure corresponding to the hydrate (NH4)CuFeF6(H2O)4.H2O through self-crystallization under ambient air atmosphere. Such a process, giving millimeter size single crystals, is rarely encountered.

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The Supplementary Information is available free of charge: synthesis conditions of fluorinated materials, XRD patterns, and FT-IR spectra of (NH4)CuFeF6 under ambient air. Refinements, crystallographic data, isothermal hydration, and thermal analysis of (NH4)CuFeF6 and (NH4)CuFeF6(H2O)4·H2O. FT-IR and XRD patterns of (NH4)CuFeF6 before and after fluorination.

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Acknowledgments

The authors gratefully acknowledge the “X-ray Diffusion and Diffraction” and the “Electron Microscopy” technical platforms of IMMM (Le Mans University). The authors thank Cyrille Galven for the hydration and fluorination experiments.

Funding

One of the authors (K.L.) thanks the French Research Ministry for a doctoral grant.

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  1. Kévin Lemoine

    Present address: Université Clermont Auvergne, CNRS, ICCF, 63000, Clermont-Ferrand, France

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  1. Institut des Molécules et Matériaux du Mans (IMMM) - UMR 6283 CNRS, Le Mans Université, Avenue Olivier Messiaen, 72085, Cedex 9, Le Mans, France

    Kévin Lemoine, Alexandre Terry, Annie Hémon-Ribaud, Jean-Marc Grenèche, Marc Leblanc, Jérôme Lhoste & Vincent Maisonneuve

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Lemoine, K., Terry, A., Hémon-Ribaud, A. et al. Contribution of Mössbauer spectrometry to structural characterizations of iron-based fluorinated materials: Application to pyrochlore (NH4)CuFeF6 and a new derived hydrate. Journal of Materials Research 38, 1138–1148 (2023). https://doi.org/10.1557/s43578-022-00836-3

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