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Origin of Magnetism in Hydrothermally Aged 2‑Line Ferrihydrite Suspensions

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journal contribution
posted on 26.01.2017, 00:00 authored by Liang Cao, Zhao-Xia Jiang, Yong-Hua Du, Xin-Mao Yin, Shi-Bo Xi, Wen Wen, Andrew P. Roberts, Andrew T. S. Wee, Yi-Min Xiong, Qing-Song Liu, Xing-Yu Gao
As an iron oxyhydroxide, nanosized ferrihydrite (Fh) is important in Earth science, biology, and industrial applications. However, its basic structure and origin of its magnetism have long been debated. We integrate synchrotron-based techniques to explore the chemical structures of 2-line ferrihydrite and to determine the origin of its magnetism during hydrothermal aging in air. Our results demonstrate that both the magnetism and X-ray magnetic circular dichroism (XMCD) signal of 2-line ferrihydrite are enhanced with aging time, and that XMCD spectral patterns resemble that of maghemite (γ-Fe2O3) rather than magnetite (Fe3O4). Fe L-edge and K-edge X-ray absorption spectroscopy (XAS) further indicate formation of both maghemite and hematite (α-Fe2O3) with increasing concentrations with longer hydrothermal aging time. Thus, magnetic enhancement with longer hydrothermal aging time is attributed to increasing maghemite concentration instead of a magnetically ordered ferrihydrite as previously reported. Moreover, L-edge and K-edge XAS spectra with different probing depths yield different ratios of these Fe oxides, which suggest the formation of a core (ferrihydrite-rich)-shell (with a mixture of both allotropes; α-Fe2O3 and γ-Fe2O3) structure during hydrothermal aging. Our results provide insights into the chemical evolution of 2-line ferrihydrite that reveal unambiguously the origin of its magnetism.

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