Abstract
The presence of ns2 stereo-chemical active lone electron pairs (LEPs) causes asymmetric atomic environments around a given p-block cation, leading to change the crystal chemistry of a respective system. Here we report a series of mullite-type compounds to understand at what extend Sr2+ replaces the stereochemical active Pb2+ cation in (Pb1−xSr x )MnBO4. Each member of the solid solution has been synthesized by conventional solid-state method. The polycrystalline samples are characterized using X-ray powder diffraction followed by Rietveld refinement. Substitution of Pb2+ with Sr2+ leads to contraction of the a lattice parameter with slight elongation in the b and c direction. For a difference of 1 pm of the ionic radius between Sr2+ and Pb2+, the cell volume contracts about 4 % between the end members as the spatial requirement of the LEP activity in the MBO42− channels significantly decreases. Within the solid solution, two distinct Pb/Sr–O2 bond distances significantly differ, which gradually decreases with increasing strontium content leading to a more symmetric coordination around strontium. The calculated BVS of Pb2+/Sr2+ exhibits a linear correlation with the Wang–Liebau eccentricity parameter, indicating to an increased bonding ability cation. The vibrational properties are characterized by both Raman and FTIR spectroscopy, complementing the XPRD results. Electronic band gaps of selected (Pb1−xSr x )MnBO4 samples were obtained from diffuse reflectance spectroscopy data. Additionally, the Sr containing samples show higher thermal stability than the Pb containing counterparts.
Funding source: Deutsche Forschungsgemeinschaft
Award Identifier / Grant number: Unassigned
Acknowledgments
We gratefully acknowledge financial support from the German Science Foundation (Deutsche Forschungsgemeinschaft, DFG) under grant number MU4415/3-1 as well as for supporting the FTIR spectrometer within a large instrumentation grant INST144/521-1-FUGG. We cordially thank the University of Bremen for their technical and administrative support.
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Research ethics: All presented data collected and analyzed are through the voluntary participation of the authors associated with this manuscript. The study was conducted in accordance with the Declaration of Helsinki (as revised in 2013).
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Author contributions: The authors have accepted responsibility for the entire content of this manuscript and approved its submission. Carla M. Uribe-Rincón: Prepared the samples, collected the investigated data and designed the manuscript. M. Mangir Murshed: Contributed to Raman and FTIR data analysis and to writing the manuscript. Thorsten M. Gesing: Contributed to XRD, UV-Vis and TGA/DTG data analysis and to writing the manuscript.
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Competing interests: The authors hereby state no conflict of interest.
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Research funding: Deutsche Forschungsgemeinschaft (DFG) under grant number MU4415/3-1 and INST144/521-1-FUGG.
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Data availability: The raw data can be obtained on request from the corresponding author.
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Supplementary Material
This article contains supplementary material (https://doi.org/10.1515/zkri-2023-0056).
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