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Magnetic properties and cation ordering of nanopowders of the synthetic analogue of kuramite, Cu3SnS4

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Abstract

An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu3SnS4, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu3SnS4 crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)2Cu(II)SnS4 and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.

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Acknowledgments

The authors want to express their warmest thanks to S. Bellandi, F. Capolupo and A. De Luca (Univ. Florence) for their assistance during the syntheses, to M. Paolieri and M. Ulivi (Univ. Florence) for their help in centrifugation and SEM investigations, and to L. Sorace (Univ. Florence) for the EPR measurements. Authors are also indebted to G.P. Bernardini for the stimulating discussion and enthusiastic support to this research.

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Authors and Affiliations

  1. Dipartimento di Chimica, Università di Firenze, Florence, Italy

    Francesco Di Benedetto, Andrea Caneschi, Gabriele Fornaciai, Massimo Innocenti & Maurizio Romanelli

  2. Dipartimento di Scienze della Terra, Università di Firenze, Florence, Italy

    Daniele Borrini

  3. Istituto di Chimica dei Composti OrganoMetallici, Consiglio Nazionale delle Ricerche, Florence, Italy

    Alessandro Lavacchi & Werner Oberhauser

  4. Istituto Processi Chimico-Fisici, Consiglio Nazionale delle Ricerche, Pisa, Italy

    Carlo Andrea Massa & Luca A. Pardi

  5. Istituto Geoscienze e Georisorse, Consiglio Nazionale delle Ricerche, Florence, Italy

    Giordano Montegrossi

Authors
  1. Francesco Di Benedetto
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  2. Daniele Borrini
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  3. Andrea Caneschi
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  4. Gabriele Fornaciai
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  6. Alessandro Lavacchi
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  7. Carlo Andrea Massa
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  8. Giordano Montegrossi
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  9. Werner Oberhauser
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  10. Luca A. Pardi
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  11. Maurizio Romanelli
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Correspondence to Francesco Di Benedetto.

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This manuscript is dedicated to Gian Piero Bernardini in occasion of his 80th birthday.

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Benedetto, F.D., Borrini, D., Caneschi, A. et al. Magnetic properties and cation ordering of nanopowders of the synthetic analogue of kuramite, Cu3SnS4 . Phys Chem Minerals 38, 483–490 (2011). https://doi.org/10.1007/s00269-011-0421-8

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  • DOI: https://doi.org/10.1007/s00269-011-0421-8

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