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, Aroa, Wain Martin, Aritza, Orera Utrilla, Alodia, Sanjuán, María Luisa, Larrañaga Varga, Aitor, Slater, Peter R., Arriortua Marcaida, María Isabel
Tipo de recurso: artículo
Fecha de publicación:2019
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/60619
Acceso en línea:http://hdl.handle.net/10810/60619
Access Level:acceso abierto
Palabra clave:cuspidine-type rare-earth aluminates
fluorination
X-ray diffraction
poly(vinyl­idene difluoride)
Raman spectroscopy
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.