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Cation Distribution and Anion Transport in the La3Ga5-xGe1+xO14+0.5x Langasite Structure.
Corti, Lucia; Hung, Ivan; Venkatesh, Amrit; Gan, Zhehong; Claridge, John B; Rosseinsky, Matthew J; Blanc, Frédéric.
Afiliación
  • Corti L; Department of Chemistry, University of Liverpool, Liverpool L69 7ZD, U.K.
  • Hung I; Leverhulme Research Centre for Functional Materials Design, Materials Innovation Factory, University of Liverpool, Liverpool L69 7ZD, U.K.
  • Venkatesh A; National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States.
  • Gan Z; National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States.
  • Claridge JB; National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States.
  • Rosseinsky MJ; Department of Chemistry, University of Liverpool, Liverpool L69 7ZD, U.K.
  • Blanc F; Leverhulme Research Centre for Functional Materials Design, Materials Innovation Factory, University of Liverpool, Liverpool L69 7ZD, U.K.
J Am Chem Soc ; 146(20): 14022-14035, 2024 May 22.
Article en En | MEDLINE | ID: mdl-38717031
ABSTRACT
Exploration of compositional disorder using conventional diffraction-based techniques is challenging for systems containing isoelectronic ions possessing similar coherent neutron scattering lengths. Here, we show that a multinuclear solid-state Nuclear Magnetic Resonance (NMR) approach provides compelling insight into the Ga3+/Ge4+ cation distribution and oxygen anion transport in a family of solid electrolytes with langasite structure and La3Ga5-xGe1+xO14+0.5x composition. Ultrahigh field 71Ga Magic Angle Spinning (MAS) NMR experiments acquired at 35.2 T offer striking resolution enhancement, thereby enabling clear detection of Ga sites in different coordination environments. Three-connected GaO4, four-connected GaO4 and GaO6 polyhedra are probed for the parent La3Ga5GeO14 structure, while one additional spectral feature corresponding to the key (Ga,Ge)2O8 structural unit which forms to accommodate the interstitial oxide ions is detected for the Ge4+-doped La3Ga3.5Ge2.5O14.75 phase. The complex spectral line shapes observed in the MAS NMR spectra are reproduced very accurately by the NMR parameters computed for a symmetry-adapted configurational ensemble that comprehensively models site disorder. This approach further reveals a Ga3+/Ge4+ distribution across all Ga/Ge sites that is controlled by a kinetically governed cation diffusion process. Variable temperature 17O MAS NMR experiments up to 700 °C importantly indicate that the presence of interstitial oxide ions triggers chemical exchange between all oxygen sites, thereby enabling atomic-scale understanding of the anion diffusion mechanism underpinning the transport properties of these materials.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Am Chem Soc Año: 2024 Tipo del documento: Article País de afiliación: Reino Unido Pais de publicación: Estados Unidos
Texto completo
Añadir a Mi BVS
Imprimir
XML
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Am Chem Soc Año: 2024 Tipo del documento: Article País de afiliación: Reino Unido Pais de publicación: Estados Unidos