Unusual cation coordination in nanostructured mullites
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Vladimir Šepelák
,
Klebson Lucenildo Da Silva
Abstract
Nanocrystalline mullite-type bismuth-bearing complex oxides Bi2(M0.5Al0.5)4O9 (M=Fe3+, Ga3+) are prepared by high-energy ball milling of the corresponding microcrystalline counterparts. An unusual five-fold coordination of metal cations is revealed in nanostructured Bi2(M0.5Al0.5)4O9 by means of 27Al magic angle spinning nuclear magnetic resonance and 57Fe Mössbauer spectroscopies. The concentration of five-fold coordinated cations increases with decreasing crystallite size of a material at the expense of octahedrally coordinated ones. In addition to the nuclear spectroscopic methods, Rietveld analyses of the X-ray diffraction data of the as-prepared nanooxides show that the constituent tetrahedra, octahedra, and the newly formed structural units with five-fold cation coordination are strongly distorted. With decreasing crystallite size of mullites, the average volume of their octahedra increases whereas this parameter decreases for tetrahedra. The macroscopic behaviour of the non-equilibrium nanomullites is characterised by SQUID magnetometry. The Fe-containing mullites exhibit a superposition of a dominant antiferromagnetism and a weak ferromagnetism. The increase in both the remanent magnetization and the coercive field with decreasing crystallite size is attributed to the effect of spin canting. The latter is confined to the interfacial and surface regions of the nanomaterials, and arises due to both the mechanically induced deformation of constituent structural units and the formation of cation sites with the unusual five-fold coordination.
Funding source: DFG
Award Identifier / Grant number: SE 1407/4-2
Acknowledgements
The present work is supported by the DFG (project SE 1407/4-2) and the CAPES. One of the authors (K.L.S.) thanks the Karlsruhe Institute of Technology (KIT) and the APVV (project 19-0526) for supporting his research work at KIT and the Slovak Academy of Sciences, respectively. This work benefited from networking activities carried out within the EU funded COST Action CA18112 “Mechanochemistry for Sustainable Industry” and represents a contribution to it.
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Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
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Research funding: This work was funded by the DFG (project SE 1407/4-2).
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Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
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© 2021 Walter de Gruyter GmbH, Berlin/Boston
Artikel in diesem Heft
- Frontmatter
- Preface
- Special issue on the occasion of the 75th birthday of Paul Heitjans
- Contribution to Special Issue dedicated to Paul Heitjans
- Unusual cation coordination in nanostructured mullites
- A novel high entropy spinel-type aluminate MAl2O4 (M = Zn, Mg, Cu, Co) and its lithiated oxyfluoride and oxychloride derivatives prepared by one-step mechanosynthesis
- Two new quaternary copper bismuth sulfide halides: CuBi2S3Cl and CuBi2S3Br as candidates for copper ion conductivity
- Sintering behavior and ionic conductivity of Li1.5Al0.5Ti1.5(PO4)3 synthesized with different precursors
- Status and progress of ion-implanted βNMR at TRIUMF
- How Li diffusion in spinel Li[Ni1/2Mn3/2]O4 is seen with μ ±SR
- Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li1.5Al0.5Ti1.5(PO4)3
- Anion reorientations and cation diffusion in a carbon-substituted sodium nido-borate Na-7,9-C2B9H12: 1H and 23Na NMR studies
- Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: I. A multinuclear solid state NMR study of the system Li6PS5-xSexI and of Li6AsS5I
- Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: II. Multinuclear solid state NMR of the systems Li6PS5−x Se x Cl and Li6PS5−x Se x Br
- Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T 1 3D 7Li NMR of superionic Li10GeP2S12
- How the cation size impacts on the relaxational and diffusional dynamics of supercooled butylammonium-based ionic liquids: DPEBA–TFSI versus BTMA–TFSI
- Solid-state NMR studies of non-ionic surfactants confined in mesoporous silica
- Inorganic-organic hybrid materials based on the intercalation of radical cations: 2-(4-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide in fluoromica clay
- Lithium tracer diffusion in near stoichiometric LiNi0.5Mn1.5O4 cathode material for lithium-ion batteries
- On the CaF2-BaF2 interface
- The ionic conductivity of alkali aluminum germanium phosphate glasses – comparison of Plasma CAIT with two electrode DC measurements
- Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study
- Predicting conductivities of alkali borophosphate glasses based on site energy distributions derived from network former unit concentrations
- Ionic transport in K2Ti6O13
- F anion transport in nanocrystalline SmF3 and in mechanosynthesized, vacancy-rich Sm1—x BaxF3—x
- An overview of thermotransport in fluorite-related ionic oxides
Artikel in diesem Heft
- Frontmatter
- Preface
- Special issue on the occasion of the 75th birthday of Paul Heitjans
- Contribution to Special Issue dedicated to Paul Heitjans
- Unusual cation coordination in nanostructured mullites
- A novel high entropy spinel-type aluminate MAl2O4 (M = Zn, Mg, Cu, Co) and its lithiated oxyfluoride and oxychloride derivatives prepared by one-step mechanosynthesis
- Two new quaternary copper bismuth sulfide halides: CuBi2S3Cl and CuBi2S3Br as candidates for copper ion conductivity
- Sintering behavior and ionic conductivity of Li1.5Al0.5Ti1.5(PO4)3 synthesized with different precursors
- Status and progress of ion-implanted βNMR at TRIUMF
- How Li diffusion in spinel Li[Ni1/2Mn3/2]O4 is seen with μ ±SR
- Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li1.5Al0.5Ti1.5(PO4)3
- Anion reorientations and cation diffusion in a carbon-substituted sodium nido-borate Na-7,9-C2B9H12: 1H and 23Na NMR studies
- Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: I. A multinuclear solid state NMR study of the system Li6PS5-xSexI and of Li6AsS5I
- Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: II. Multinuclear solid state NMR of the systems Li6PS5−x Se x Cl and Li6PS5−x Se x Br
- Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T 1 3D 7Li NMR of superionic Li10GeP2S12
- How the cation size impacts on the relaxational and diffusional dynamics of supercooled butylammonium-based ionic liquids: DPEBA–TFSI versus BTMA–TFSI
- Solid-state NMR studies of non-ionic surfactants confined in mesoporous silica
- Inorganic-organic hybrid materials based on the intercalation of radical cations: 2-(4-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide in fluoromica clay
- Lithium tracer diffusion in near stoichiometric LiNi0.5Mn1.5O4 cathode material for lithium-ion batteries
- On the CaF2-BaF2 interface
- The ionic conductivity of alkali aluminum germanium phosphate glasses – comparison of Plasma CAIT with two electrode DC measurements
- Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study
- Predicting conductivities of alkali borophosphate glasses based on site energy distributions derived from network former unit concentrations
- Ionic transport in K2Ti6O13
- F anion transport in nanocrystalline SmF3 and in mechanosynthesized, vacancy-rich Sm1—x BaxF3—x
- An overview of thermotransport in fluorite-related ionic oxides
