Synthesis of new Ln4(Al2O6F2)O2 (Ln = Sm, Eu, Gd) phases with a cuspidine-related structure

The first fluorination of the cuspidine-related phases of Ln4(Al2O7¿)O2 (where Ln = Sm, Eu, Gd) is reported. A low-temperature reaction with poly(vinyl­idene difluoride) lead to the fluorine being substituted in place of oxygen and inserted into the vacant position between the dialuminate groups. X-...

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Detalles Bibliográficos
Autores: Morán-Ruiz, A., Wain-Martin, A., Orer, A., Sanjuán, M.L., Larrañaga, A., Slater, P.R., Arriortua, M.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2019
País:España
Institución:Universidad de Zaragoza
Repositorio:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:77190
Acceso en línea:http://zaguan.unizar.es/record/77190
Access Level:acceso abierto
Descripción
Sumario:The first fluorination of the cuspidine-related phases of Ln4(Al2O7¿)O2 (where Ln = Sm, Eu, Gd) is reported. A low-temperature reaction with poly(vinyl­idene difluoride) lead to the fluorine being substituted in place of oxygen and inserted into the vacant position between the dialuminate groups. X-ray photoelectron spectroscopy shows the presence of the F 1s photoelectron together with an increase in Al 2p and rare-earth 4d binding energies supporting F incorporation. Energy-dispersive X-ray spectroscopy analyses are consistent with the formula Ln4(Al2O6F2)O2, confirming that substitution of one oxygen by two fluoride atoms has been achieved. Rietveld refinements show an expansion in the cell upon fluorination and confirm that the incorporation of fluoride in the Ln4(Al2O7¿)O2 structure results in changes in Al coordination from four to five. Thus, the isolated tetrahedral dialuminate Al2O7 groups are converted to chains of distorted square-based pyramids. These structural results are also discussed based on Raman spectra.