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Synthesis, characterization and structure-property relations in mullite-type Pb2(Pb1−xSn x )O4 solid solution

  • Christopher S. Reuter ORCID logo , M. Mangir Murshed ORCID logo EMAIL logo , Michael Fischer ORCID logo and Thorsten. M. Gesing ORCID logo
Published/Copyright: July 15, 2024
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 239 Issue 9-10

Abstract

The crystal structures of both Pb2PbO4 (Pb3O4) and Pb2SnO4 at room temperature can be described using mullite-type setting in the space groups P42/mbc and Pbam, respectively. At what chemical extend the crystal structure prefers either of the space groups would be an excellent playground in the Pb2(Pb1−xSn x )O4 solid solution. Members of the solid solutions have been prepared by solid-state reactions carried out in sealed quartz tubes. Each sample has been found to be phase pure confirmed by X-ray powder diffraction data Rietveld refinement. Samples with higher tin content require higher synthesis temperatures, and controlled decomposition of Pb3O4 serves as the source for both Pb2+ and Pb4+ cations. Since the Pb4+ cation is larger than Sn4+, the MO6 polyhedral volume decreases with increasing Sn-content. As such, each metric parameter shows a linear trend following Vegard’s rule. The concomitant contraction of the MO6 octahedra and the high stereo-chemical activity of the 6s2 lone electron pairs of lead in the Pb2+O4 distorted pyramid results in symmetry reduction. DFT suggests dynamical instability of the tetragonal Pb3O4 while Pb2SnO4 keeps orthorhombic symmetry at low temperatures, which agrees well with the experimental findings. The global blue shift of the vibrational mode frequencies is explained by the quasi-harmonic approach. The indirect band-gap linearly increases from 2.1(1) eV (x = 0) to a maximum value of 2.5(1) eV for x = 0.8 followed by a sharp drop towards Pb2SnO4. Thermogravimetric analysis demonstrates higher thermal stability with increasing Sn-content, which is explained in terms of higher bond strength of Sn–O than that of Pb–O in the MO6 octahedra.

Keywords: schafarzikite; crystal structure; vibrational property; DFT; band gap
Corresponding author: M. Mangir Murshed, Institute of Inorganic Chemistry and Crystallography, University of Bremen, Leobener Straße 7, D-28359 Bremen, Germany; and MAPEX Center for Materials and Processes, University of Bremen, Bibliothekstraße 1, D-28359 Bremen, Germany, E-mail:

Acknowledgements

We gratefully acknowledge the German science foundation (Deutsche Forschungsgemeinschaft, DFG) under grant number GE1981/18-1 (project-ID: 514924554) for the financial support of this project and for shared funding of the FTIR-Spectrometer INST144/521-1 FUGG and the computer cluster “lesum” INST144/506-1 FUGG within large instrument application. MF acknowledges funding by the DFG through a Heisenberg fellowship (project-ID: 455871835).

  1. Ethical approval: The local Institutional Review Board deemed the study exempt from review.

  2. Informed consent: Informed consent was obtained from all individuals included in this study.

  3. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  4. Competing interests: The authors hereby state no conflict of interest.

  5. Research funding: German Science Foundation (Deutsche Forschungsgemeinschaft, DFG).

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Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/zkri-2024-0088).

Received: 2024-05-28
Accepted: 2024-06-12
Published Online: 2024-07-15
Published in Print: 2024-10-28

© 2024 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Inorganic Crystal Structures (Original Paper)
  4. Synthesis, characterization and structure-property relations in mullite-type Pb2(Pb1−xSn x )O4 solid solution
  5. Temperature-dependent diffraction studies on the stannides Sr3Rh4Sn4, Sr3Ir4Sn4 and Sr2.43Eu0.57Ir4Sn4
  6. Organic and Metalorganic Crystal Structures (Original Paper)
  7. The crystal and molecular structure of (R)-sirtinol – C26H22N2O2 – a chemo-sensitive enhancer and ligand in metal complexes with important bio-inorganic applications
  8. Synthesis and structural characterization of supramolecular cocrystals of [(4-cyano-1-methylpyridinium)2-(18-crown-6)] diiodide
  9. 1-Nitronaphthalene, a non-OD, non-MDO polytype
  10. Synthesis and crystal structure of a tripeptide comprising a centrally placed non-coded aromatic γ-amino acid
https://doi.org/10.1515/zkri-2024-0088
Keywords for this article
schafarzikite; crystal structure; vibrational property; DFT; band gap

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Inorganic Crystal Structures (Original Paper)
  4. Synthesis, characterization and structure-property relations in mullite-type Pb2(Pb1−xSn x )O4 solid solution
  5. Temperature-dependent diffraction studies on the stannides Sr3Rh4Sn4, Sr3Ir4Sn4 and Sr2.43Eu0.57Ir4Sn4
  6. Organic and Metalorganic Crystal Structures (Original Paper)
  7. The crystal and molecular structure of (R)-sirtinol – C26H22N2O2 – a chemo-sensitive enhancer and ligand in metal complexes with important bio-inorganic applications
  8. Synthesis and structural characterization of supramolecular cocrystals of [(4-cyano-1-methylpyridinium)2-(18-crown-6)] diiodide
  9. 1-Nitronaphthalene, a non-OD, non-MDO polytype
  10. Synthesis and crystal structure of a tripeptide comprising a centrally placed non-coded aromatic γ-amino acid
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