Issue 1, 2016

Effects of crystallite size on the structure and magnetism of ferrihydrite


The structure and magnetic properties of nano-sized (1.6 to 4.4 nm) ferrihydrite samples are systematically investigated through a combination of X-ray diffraction (XRD), X-ray pair distribution function (PDF), X-ray absorption spectroscopy (XAS) and magnetic analyses. The XRD, PDF and Fe K-edge XAS data of the ferrihydrite samples are all fitted well with the Michel ferrihydrite model, indicating similar local-, medium- and long-range ordered structures. PDF and XAS fitting results indicate that, with increasing crystallite size, the average coordination numbers of Fe–Fe and the unit cell parameter c increase, while Fe2 and Fe3 vacancies and the unit cell parameter a decrease. Mössbauer results indicate that the surface layer is relatively disordered, which might have been caused by the random distribution of Fe vacancies. These results support Hiemstra's surface-depletion model in terms of the location of disorder and the variations of Fe2 and Fe3 occupancies with size. Magnetic data indicate that the ferrihydrite samples show antiferromagnetism superimposed with a ferromagnetic-like moment at lower temperatures (100 K and 10 K), but ferrihydrite is paramagnetic at room temperature. In addition, both the magnetization and coercivity decrease with increasing ferrihydrite crystallite size due to strong surface effects in fine-grained ferrihydrites. Smaller ferrihydrite samples show less magnetic hyperfine splitting and a lower unblocking temperature (TB) than larger samples. The dependence of magnetic properties on grain size for nano-sized ferrihydrite provides a practical way to determine the crystallite size of ferrihydrite quantitatively in natural environments or artificial systems.

Graphical abstract: Effects of crystallite size on the structure and magnetism of ferrihydrite

Supplementary files

Article information

Article type
02 Sep 2015
12 Dec 2015
First published
15 Dec 2015
This article is Open Access
Creative Commons BY license

Environ. Sci.: Nano, 2016,3, 190-202

Effects of crystallite size on the structure and magnetism of ferrihydrite

X. Wang, M. Zhu, L. K. Koopal, W. Li, W. Xu, F. Liu, J. Zhang, Q. Liu, X. Feng and D. L. Sparks, Environ. Sci.: Nano, 2016, 3, 190 DOI: 10.1039/C5EN00191A

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