Nanocomposite structure of two-line ferrihydrite powder from total scattering

Ferrihydrite is one of the most important iron-containing minerals on Earth. Yet determination of its atomic-scale structure has been frustrated by its intrinsically poor crystallinity. The key difficulty is that physically-different models can appear consistent with the same experimental data. Using X-ray total scattering and a nancomposite reverse Monte Carlo approach, we evaluate the two principal contending models—one a multi-phase system without tetrahedral iron(III), and the other a single phase with tetrahedral iron(III). Our methodology is unique in considering explicitly the complex nanocomposite structure the material adopts: namely, crystalline domains embedded in a poorly-ordered matrix. The multi-phase model requires unphysical structural rearrangements to fit the data, whereas the single-phase model accounts for the data straightforwardly. Hence the latter provides the more accurate description of the short- and intermediate-range order of ferrihydrite. We discuss how this approach might allow experiment-driven (in)validation of complex models for important nanostructured phases beyond ferrihydrite. Although a geologically important mineral, the atomic-scale structure of ferrihydrite remains unresolved. Here the authors combine X-ray total scattering and reverse Monto Carlo to evaluate the two principal contending models, explicitly considering the material’s complex nanocomposite structure.