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Al/Fe isomorphic substitution versus Fe2O3 clusters formation in Fe-doped aluminosilicate nanotubes (imogolite)

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Abstract

Textural, magnetic and spectroscopic properties are reported of Fe-doped aluminosilicate nanotubes (NTs) of the imogolite type, IMO, with nominal composition (OH)3Al2−x Fe x O3SiOH (x = 0, 0.025, 0.050). Samples were obtained by either direct synthesis (Fe-0.025-IMO, Fe-0.050-IMO) or post-synthesis loading (Fe-L-IMO). The Fe content was either 1.4 wt% (both Fe-0.050-IMO and Fe-L-IMO) or 0.7 wt% (Fe-0.025-IMO). Textural properties were characterized by High-Resolution Transmission Electron Microscopy, X-ray diffraction and N2 adsorption/desorption isotherms at 77 K. The presence of different iron species was studied by magnetic moment measurements and three spectroscopies: Mössbauer, UV–Vis and electron paramagnetic resonance, respectively. Fe3+/Al3+ isomorphic substitution (IS) at octahedral sites at the external surface of NTs is the main process occurring by direct synthesis at low Fe loadings, giving rise to the formation of isolated high-spin Fe3+ sites. Higher loadings give rise, besides IS, to the formation of Fe2O3 clusters. IS occurs up to a limit of Al/Fe atomic ratio of ca. 60 (corresponding to x = 0.032). A fraction of the magnetism related to NCs is pinned by the surface anisotropy; also, clusters are magnetically interacting with each other. Post-synthesis loading leads to a system rather close to that obtained by direct synthesis, involving both IS and cluster formations. Slightly larger clusters than with direct synthesis samples, however, are formed. The occurrence of IS indicates a facile cleavage/sealing of Al–O–Al bonds: this opens the possibility to exchange Al3+ ions in pre-formed IMO NTs, a much simpler procedure compared with direct synthesis.

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Authors and Affiliations

  1. Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Turin, Italy

    Ehsan Shafia, Paolo Allia, Edoardo Garrone & Barbara Bonelli

  2. Department of Civil and Mechanical Engineering, Università degli Studi di Cassino e del Lazio Meridionale, Via G. Di Biasio 43, 03043, Cassino, FR, Italy

    Serena Esposito

  3. Dipartimento di Chimica and Centro Interdipartimentale NIS, Università di Torino, Via Giuria 7, 10125, Turin, Italy

    Maela Manzoli, Mario Chiesa & Gabriele Barrera

  4. Electromagnetism, I.N.Ri.M., Strada delle Cacce 91, 10135, Turin, Italy

    Paola Tiberto & Gabriele Barrera

  5. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St., Cambridge, MA, 02138, USA

    Gabriel Menard

  6. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave, Cambridge, MA, 02139, USA

    Francesca S. Freyria

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  1. Ehsan Shafia
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Correspondence to Paolo Allia or Barbara Bonelli.

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Shafia, E., Esposito, S., Manzoli, M. et al. Al/Fe isomorphic substitution versus Fe2O3 clusters formation in Fe-doped aluminosilicate nanotubes (imogolite). J Nanopart Res 17, 336 (2015). https://doi.org/10.1007/s11051-015-3130-2

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