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The stoichiometry of synthetic alunite as a function of hydrothermal aging investigated by solid-state NMR spectroscopy, powder X-ray diffraction and infrared spectroscopy

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Abstract

The stoichiometry of a series of synthetic alunite [nominally KAl3(SO4)2(OH)6] samples prepared by hydrothermal methods as a function of reaction time (1–31 days) has been investigated by powder X-ray diffraction, Fourier transform infrared spectroscopy as well as solid-state 1H and 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The 1H MAS NMR spectra recorded at high magnetic field (21.1 T, 900 MHz) allowed for a clear separation of the different proton environments and for quantitative determination of the aluminum vacancy concentration as a function of time. The concentration of structural defects determined from, i.e., aluminum vacancies was reduced from 4 to 1 %, as the reaction time was extended from one to 31 days based on 1H MAS NMR. This was further supported by an increase of the unit cell parameter c, which is indicative of the relative concentration of potassium defects present, from 17.261(1) to 17.324(5) Å. Solid-state 27Al MAS NMR revealed a decrease in the defect concentration as a function of time and showed the presence of 7–10 % impurities in the samples.

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Acknowledgments

U.G.N. acknowledges funding from the Danish Research Council (Steno stipend and NMR equipment), the L’Oréal-UNESCO for Women in Science Fellowship and Villumfonden for a Young Investigator Fellowship. E.G. is grateful for financial support from Oticon Fonden. A portion of this research (1H MAS NMR) was performed using EMSL, a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Drs Andrew S. Lipton and Sarah Burton are thanked for assistance with the experimental equipment.

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  1. Elisabeth Grube

    Present address: Interdisciplinary Nanoscience Center and Department of Chemistry, Aarhus University, Langelandsgade 140, 8000, Århus C, Denmark

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  1. Department of Physics, Chemistry, and Pharmacy, University of Southern Denmark, Campusvej 55, 5230, Odense M, Denmark

    Elisabeth Grube & Ulla Gro Nielsen

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Correspondence to Ulla Gro Nielsen.

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Grube, E., Nielsen, U.G. The stoichiometry of synthetic alunite as a function of hydrothermal aging investigated by solid-state NMR spectroscopy, powder X-ray diffraction and infrared spectroscopy. Phys Chem Minerals 42, 337–345 (2015). https://doi.org/10.1007/s00269-014-0724-7

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