Abstract
In the present work, the oxidation and spin state of Fe and the local structure around Fe in the supercapacitor birnessite with different contents of the Fe dopant were investigated using Mössbauer spectroscopy. It was found that Fe ions were exclusively present as high spin Fe3+ in octahedral coordination with about 70% iron occupying the Mn3+ positions and about 30% iron occupying the Mn4+ positions in the [MnO6] octahedra for all Fe-doped birnessite samples. Based on these new findings, the trend of typical cell parameters, selected bond lengths of the Fe-doped birnessites and their corresponding quadrupole splittings in the Mössbauer spectra were well explained by considering both the weakened Jahn–Teller effect during the replacement of Mn3+ by Fe3+ and the expansion of octahedra during the replacement of Mn4+ by Fe3+. The present work offers some new insights into the understanding of the mechanism of the heterogeneous atomic doping on the crystal structure of birnessite, with importance for both mineralogy and material science.
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Dr. Hao Liu thanks for support from the National Natural Science Foundation of China (no. 21875223).
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Prof. LL and Prof. GA contributed to the study conception and design. Material preparation, data collection and analysis were performed by Dr. HL, Dr. GT and Dr. WL. The first draft of the manuscript was written by Dr. HL and Prof. GA and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
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Liu, H., Liao, L., Tippelt, G. et al. 57Fe Mössbauer spectroscopic study on the Fe doped supercapacitor birnessite, \( ({\text{Na}},{\text{K}})_{x} {\text{Mn}}^{4 + }_{2 - x} {\text{Mn}}^{3 + }_{x} {\text{O}}_{4} \cdot 1.5{\text{H}}_{2} {\text{O}} \). Phys Chem Minerals 47, 42 (2020). https://doi.org/10.1007/s00269-020-01112-8
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DOI: https://doi.org/10.1007/s00269-020-01112-8