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The structure of compositionally constrained zinc-ferrite spinel nanoparticles

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Abstract

ZnFe2O4 bulk material shows a normal-spinel structure and a closely defined composition at Zn2+/Fe3+ ≅ 0.5. However, the composition of zinc ferrite, prepared as nanoparticles, can be varied in a broad range without losing the single-phase spinel structure. In this article, structural mechanisms enabling this non-stoichiometry were studied using the X-ray absorption fine structure (EXAFS) in combination with X-ray diffractometry (XRD), transmission electron microscopy (TEM), and magnetic measurements. Nanoparticles with a narrow size distribution were synthesized using co-precipitation in water-in-oil microemulsions. First, the structure of the stoichiometric zinc-ferrite nanoparticles was studied in dependence of their size and the annealing temperature. EXAFS analysis showed that the degree of inversion x (as defined in the compound formula (Zn1 − x Fe x )[Fe2 − x Zn x ]O4, with round and square brackets representing the tetrahedral and octahedral sites, respectively) increased with decreasing nanoparticles size. The structure of the stoichiometric nanoparticles and the nanoparticles of comparable size displaying Zn/Fe ratio of 0.2 (Fe-rich) and 0.7 (Zn-rich) were then compared. Analysis showed that the non-stoichiometry is structurally compensated predominantly in the core of the nanoparticle by the adjusted distribution of Zn and Fe ions over the two sublattices of the spinel structure.

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Acknowledgments

This study was supported by the Slovenian Research Agency, the Ministry of Higher Education, Science and Technology of the Republic of Slovenia within the National Research Program, and by DESY and the European Community under Contract RII3-CT-2004-506008 (IA-SFS). Provision of synchrotron radiation facilities by HASYLAB (project II-04-065 EC) is acknowledged. The authors would also like to thank Sašo Gyergyek for help with the magnetic measurements and E. Welter of HASYLAB for expert advice on beamline operation.

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Authors and Affiliations

  1. Jožef Stefan Institute, Ljubljana, Slovenia

    Darko Makovec, Alojz Kodre, Iztok Arčon & Miha Drofenik

  2. Faculty of Mathematics and Physics, University of Ljubljana, Ljubljana, Slovenia

    Alojz Kodre

  3. University of Nova Gorica, Nova Gorica, Slovenia

    Iztok Arčon

  4. Faculty for Chemistry and Chemical Engineering, University of Maribor, Maribor, Slovenia

    Miha Drofenik

Authors
  1. Darko Makovec
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  2. Alojz Kodre
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  4. Miha Drofenik
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Correspondence to Darko Makovec.

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Makovec, D., Kodre, A., Arčon, I. et al. The structure of compositionally constrained zinc-ferrite spinel nanoparticles. J Nanopart Res 13, 1781–1790 (2011). https://doi.org/10.1007/s11051-010-9929-y

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  • DOI: https://doi.org/10.1007/s11051-010-9929-y

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