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Evaluation of the structural model for ferrihydrite derived from real-space modelling of high-energy X-ray diffraction data

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A new structural model for ferrihydrite that challenges the standard ferrihydrite model established by X-ray diffraction and confirmed by neutron diffraction and single-crystal electron nanodiffraction was recently proposed by Michel et al. (2007a) from the simulation of the pair distribution function obtained by Fourier transformation of diffraction data measured at  = 0.137 Å. The new ferrihydrite model is isostructural to akdalaite (Al10O14(OH)2), a mineral having the Baker-Figgis -isomer of the Al13-Keggin structure as its structural motif. The new model is unrealistic because: (1) it is completely periodic (i.e. defect-free); (2), it has 20% tetravalent octahedral iron (VIFe4+), 20% divalent tetrahedral iron (IVFe2+), and some IVFe–O distances equal to or larger than the VIFe3+–O distances, thus violating Pauling's 2nd rule; (3) it does not describe X-ray diffraction and EXAFS spectroscopic data; and, (4) it is inconsistent with electron microscopy results and contradicts previous X-ray scattering studies.
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Keywords: BOND VALENCE; EXAFS SPECTROSCOPY; FEROXYHITE; FERRIHYDRITE; PDF; STRUCTURE; XRD

Document Type: Research Article

Publication date: 01 March 2009

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