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Probing the local environment of substitutional Al\(^{3+}\) in goethite using X-ray absorption spectroscopy and first-principles calculations

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Abstract

We present experimental and calculated Al K-edge X-ray absorption near-edge structure (XANES) spectra of aluminous goethite with 10–33 mol% of AlOOH and diaspore. Significant changes are observed experimentally in the near- and pre-edge regions with increasing Al concentration in goethite. First-principles calculations based on density functional theory (DFT) reproduce successfully the experimental trends. This permits to identify the electronic and structural parameters controlling the spectral features and to improve our knowledge of the local environment of \(\hbox {Al}^{3+}\) in the goethite–diaspore partial solid solution. In the near-edge region, the larger peak spacing in diaspore compared to Al-bearing goethite is related to the nature (Fe or Al) of the first cation neighbours around the absorbing Al atom (Al*). The intensity ratio of the two near-edge peaks, which decreases with Al concentration, is correlated with the average distance of the first cations around Al* and the distortion of the \(\hbox {AlO}_6\) octahedron. Finally, the decrease in intensity of the pre-edge features with increasing Al concentration is due to the smaller number of Fe atoms in the local environment of Al since Al atoms tend to cluster. In addition, it is found that the pre-edge features of the Al K-edge XANES spectra enable to probe indirectly empty 3d states of Fe. Energetic, structural and spectroscopic results suggest that for Al concentrations around 10 mol%, Al atoms can be considered as isolated, whereas above 25 mol%, Al clusters are more likely to occur.

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Acknowledgments

We acknowledge SOLEIL for provision of synchrotron radiation facilities on the LUCIA beamline (project no: 99140120). This work was performed using HPC resources from GENCI-IDRIS (Grant 2014 - 100172). This work has been supported by the French National Research Agency (ANR, project 11-JS56-001 “CrIMin”). The authors thank Blair Lebert for proofreading the manuscript. Etienne Balan and Amélie Juhin are acknowledged for fruitful discussions. DC dedicates this paper to the memory of her late colleague, Philippe Ildefonse.

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  1. Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC), Sorbonne Universités, UPMC Univ Paris 06, CNRS UMR 7590, Muséum National d’Histoire Naturelle, IRD UMR 206, 4 Place Jussieu, 75005, Paris, France

    Manoj Ducher, Marc Blanchard, Ruidy Nemausat & Delphine Cabaret

  2. Synchrotron SOLEIL, L’Orme des Merisiers, 91192, Gif-sur-Yvette Cedex, France

    Delphine Vantelon

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  1. Manoj Ducher
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Correspondence to Manoj Ducher.

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Ducher, M., Blanchard, M., Vantelon, D. et al. Probing the local environment of substitutional Al\(^{3+}\) in goethite using X-ray absorption spectroscopy and first-principles calculations. Phys Chem Minerals 43, 217–227 (2016). https://doi.org/10.1007/s00269-015-0788-z

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