Natural Nanomaterials: Reappraising the Elusive Structure of the Nano-Sized Mineral Ferrihydrite through X-Ray Absorption Spectroscopy at the Iron K-Edge

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Abstract

Ferrihydrite is natural ferric oxyhydroxide occurring exclusively nanocrystalline. With ideal formula 5 Fe2 O3 . 9 H2 O, ferrihydrite is quite abundant in sediments, weathering crusts and mine wastes, being characteristic of red pre-soils formed by loose weathered rock plus mineral debris (regoliths) and commonly designated as "2-line" or "6-line" on the basis of the broadened maxima observed in the X-ray diffraction pattern. Synthetic nanocrystalline "6-line" ferrihydrite was recently studied through methods based on atomic-pair distribution functions disclosing the possible occurrence of icosahedral clusters formed by twelve octahedra centred by an inner tetrahedron, all filled by Fe 3+ ions. However, Mössbauer studies were inconclusive about the existence of 4-coordinated iron, thus suggesting that the tetrahedral cation may well be Si4+. In view of such structural uncertainty, a XANES study at the Fe K-edge was undertaken on ferrihydrite from a regolith to ascertain the occurrence of tetrahedral iron. Comparison with data collected from well crystallized iron oxide and hydroxide minerals where Fe 3+/2+ ions occur in octahedral and tetrahedral coordination is described and the results so far obtained are discussed, showing that supplementary study is needed on the elusive structure of ferrihydrite.
Original languageUnknown
Pages (from-to)931-935
JournalAdvanced Materials Forum
Volume730-732
Issue numberNA
Publication statusPublished - 1 Jan 2013

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