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Nucleation and growth of magnetite from solution

Nature Materials volume 12, pages 310314 (2013) | Download Citation

Abstract

The formation of crystalline materials from solution is usually described by the nucleation and growth theory, where atoms or molecules are assumed to assemble directly from solution1. For numerous systems, the formation of the thermodynamically stable crystalline phase is additionally preceded by metastable intermediates 2. More complex pathways have recently been proposed, such as aggregational processes of nanoparticle precursors or pre-nucleation clusters, which seem to contradict the classical theory3,4,5,6. Here we show by cryogenic transmission electron microscopy that the nucleation and growth of magnetite—a magnetic iron oxide with numerous bio- and nanotechnological applications7—proceed through rapid agglomeration of nanometric primary particles and that in contrast to the nucleation of other minerals5, no intermediate amorphous bulk precursor phase is involved. We also demonstrate that these observations can be described within the framework of classical nucleation theory.

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References

  1. 1.

    Nucleation: Theory and Basic Applications (Butterworth-Heinemann, 2000).

  2. 2.

    Studien uber die Bildung und Umwandlung fester Korper. Z. Phys. Chem. 22, 289–330 (1897).

  3. 3.

    , , , & Aggregation-based crystal growth and microstructure development in natural iron oxyhydroxide biomineralization products. Science 289, 751–754 (2000).

  4. 4.

    Energetic clues to pathways to biomineralization: Precursors, clusters, and nanoparticles. Proc. Natl Acad. Sci. USA 101, 12096–12101 (2004).

  5. 5.

    , & Stable prenucleation calcium carbonate clusters. Science 322, 1819–1822 (2008).

  6. 6.

    et al. The initial stages of template-controlled CaCO3 formation revealed by cryo-TEM. Science 323, 1455–1458 (2009).

  7. 7.

    et al. Magnetic iron oxide nanoparticles: Synthesis, stabilization, vectorization, physicochemical characterizations, and biological applications. Chem. Rev. 108, 2064–2110 (2008).

  8. 8.

    & Half-metallic ferromagnetic oxides. Mater. Res. Bull. 28, 720–724 (2003).

  9. 9.

    & Mesocrystals: Inorganic superstructures made by highly parallel crystallization and controlled alignment. Angew. Chem. Int. Ed. 44, 5576–5591 (2005).

  10. 10.

    et al. The thermodynamics of calcite nucleation at organic interfaces: Classical vs. non-classical pathways. Faraday Discuss. 159, 509–523 (2012).

  11. 11.

    , , & Oriented aggregation: Formation and transformation of mesocrystal intermediates revealed. J. Am. Chem. Soc. 132, 2163–2165 (2010).

  12. 12.

    et al. The role and implications of bassanite as a stable precursor phase to gypsum precipitation. Science 336, 69–72 (2012).

  13. 13.

    , , , & Superparamagnetic magnetite colloidal nanocrystal clusters. Angew. Chem. Int. Ed. 46, 4342–4345 (2007).

  14. 14.

    & The Iron Oxides (Structure, Properties, Reactions, Occurrences and Uses) (Wiley-VCH, 2003).

  15. 15.

    & Magnetotactic bacteria and magnetosomes. Chem. Rev. 108, 4875–4898 (2008).

  16. 16.

    Lepidocrocite an apatite mineral and magnetite in teeth of chitons (Polyplacophora). Science 156, 1373–1375 (1967).

  17. 17.

    , , , & Magnetite defines a vertebrate magnetoreceptor. Nature 406, 299–302 (2000).

  18. 18.

    , , & Crystallochemical characterization of magnetic spinels prepared from aqueous solution. J. Chem. Soc. 85, 3033–3044 (1989).

  19. 19.

    & Phase-transformations of iron-oxides, oxohydroxides, and hydrous oxides in aqueous-media. Adv. Colloid Interface Sci. 29, 173–221 (1989).

  20. 20.

    , , & Influence of Fe(II) on the formation of the spinel iron-oxide in alkaline-medium. Clay Clay Min. 40, 531–539 (1992).

  21. 21.

    et al. Mineralogical and isotopic properties of inorganic nanocrystalline magnetites. Geochim. Cosmochim. Acta 68, 4395–4403 (2004).

  22. 22.

    et al. The role of prenucleation clusters in surface-induced calcium phosphate crystallization. Nature Mater. 9, 1010–1014 (2010).

  23. 23.

    Hydrolysis of inorganic Iron(III) salts. Chem. Rev. 84, 31–41 (1984).

  24. 24.

    et al. Identification of hydrolysis products of FeCl3.6H2O by ESI-MS. J. Mass Spectrom. 41, 1421–1429 (2006).

  25. 25.

    , , & Transformation of ferric hydroxide into spinel by Fe(II) adsorption. Langmuir 8, 313–319 (1992).

  26. 26.

    , , & Scaling functions, self-similarity, and the morphology of phase-separating systems. Phys. Rev. B 44, 4794–4811 (1991).

  27. 27.

    Crystallization 3rd edn (Butterworth-Heinemann, 1992).

  28. 28.

    , & Magnetite solubility and phase stability in alkaline media at elevated temperatures. J. Solut. Chem. 24, 837–877 (1995).

  29. 29.

    , , & Nanophase transition metal oxides show large thermodynamically driven shifts in oxidation-reduction equilibria. Science 330, 199–201 (2010).

  30. 30.

    Nanoscale effects on thermodynamics and phase equilibria in oxide systems. ChemPhysChem 12, 2207–2215 (2011).

  31. 31.

    , , , & Density functional theory study of ferrihydrite and related Fe-oxyhydroxides. Chem. Mater. 21, 5727–5742 (2009).

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Acknowledgements

H. Runge, R. Pitschke, S. Siegel and C. Li are acknowledged for technical assistance with electron microscopy and at the synchrotron. F. Nudelman helped prepare cryo-TEM samples. We thank E. Zolotoyabko, J. De Yoreo and M. Antonietti for discussions. This research was supported in D.F’s laboratory by the Max Planck Society, and a starting grant from the ERC (Project MB2, no. 256915).

Author information

Affiliations

  1. Department of Biomaterials, Max Planck Institute of Colloids and Interfaces, Science Park Golm, 14424 Potsdam, Germany

    • Jens Baumgartner
    • , Cécile Le Coadou
    • , Peter Fratzl
    •  & Damien Faivre
  2. Laboratory of Materials and Interface Chemistry and Soft Matter CryoTEM research Unit, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands

    • Archan Dey
    • , Paul H. H. Bomans
    •  & Nico A. J. M. Sommerdijk

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Contributions

J.B. and C.L.C. carried out precipitation experiments. J.B. performed X-ray diffraction, TEM, analysed data and wrote the manuscript. P.H.H.B. performed cryo-TEM. A.D. carried out ferrihydrite experiments, performed cryo-TEM and analysed data. P.F. and J.B. developed the model. P.F., N.A.J.M.S. and D.F. supervised the project, analysed data and wrote the manuscript. All authors discussed the results and revised the manuscript.

Competing interests

Max Planck Innovation has applied for the following patent: J. Baumgartner & D. Faivre, Process for preparing magnetite or maghemite nanoparticles with controlled size using mild conditions, international patent’s application number WO2010EP03983 priority date July 1st, 2010.

Corresponding author

Correspondence to Damien Faivre.

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DOI

https://doi.org/10.1038/nmat3558

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