Impact of Tb4+ and morphology on the Thermal Evolution of Tb-doped TiO2 Nanostructured Hollow Spheres and Nanoparticles

Tb-doped TiO2 hollow spheres (HSs) in the range 0.0-2.0 at.% have been,synthesized by the first time to the best of our knowledge. The HSs are compared with,nanoparticles (NPs) to evaluate the impact of morphology on their physicochemical and,photoluminescence (PL) behavior upon increasing calcinati...

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Autores: Colomer, M. T., Rodríguez, E., Morán Pedroso, María, Vattier Lagarrigue, María Florencia, Andrés, A. de
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2021
País:España
Institución:Instituto Valenciano de Investigaciones Agrarias (IVIA)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/174367
Acceso en línea:https://hdl.handle.net/11441/174367
https://doi.org/10.1016/j.jallcom.2020.156973
Access Level:acceso abierto
Palabra clave:Tb
Hollow spheres
Anatase
Rutile
Photoluminescence
Raman phonons
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spelling Impact of Tb4+ and morphology on the Thermal Evolution of Tb-doped TiO2 Nanostructured Hollow Spheres and NanoparticlesColomer, M. T.Rodríguez, E.Morán Pedroso, MaríaVattier Lagarrigue, María FlorenciaAndrés, A. deTbHollow spheresAnataseRutilePhotoluminescenceRaman phononsTb-doped TiO2 hollow spheres (HSs) in the range 0.0-2.0 at.% have been,synthesized by the first time to the best of our knowledge. The HSs are compared with,nanoparticles (NPs) to evaluate the impact of morphology on their physicochemical and,photoluminescence (PL) behavior upon increasing calcination temperature. After,calcination at 550ºC, the particles are anatase with a primary average size of 10.0 ± 0.2,nm for the NPs and 12.0 ± 0.2 nm for those that form the micron sized hollow spheres of,1.8 µm diameter and ca. 64 nm shell thickness. The temperature of the anatase–rutile,transition is found to be strongly dependent on the presence of Tb as well as on,morphology. Contrarily to the usual stabilization of anatase when doping with trivalent,rare-earth ions, the transition temperature is reduced when doping with Tb. The rutile,phase is further favored for the HSs compared to the NPs probably related to the low,density of the HSs and/or a more efficient packing of the nanoparticles that form those,spheres with respect to the packing of the NPs. A slight unit-cell volume decrease for the,anatase structure is observed upon Tb doping, in both the NPs and in the HSs, contrary to,the expected increment due to the larger ionic radius of Tb3+ compared to Ti4+,. In addition,,2,the intensity of the characteristic f-f Tb3+ emission bands is extremely weak both in the,anatase and rutile phases. The transition is accompanied with the emergence of an infrared,emission band centered at 810 nm related to the formation of defects during the structural,transformation providing deep levels in the gap that partly quench the f-f emissions in the,rutile phase. The results are consistent with the presence of Tb in both +3 and +4 valence,states. XPS measurements confirmed the presence of Tb3+ as well as of Tb4+ in both HSs,and NPs with a Tb4+ fraction that increases with increasing Tb doping. The large fraction,of Tb4+ present in the samples originates the weak f-f emission intensity, the slight,decrease of the cell parameters and the destabilization of the anatase phaseElsevierFísica de la Materia CondensadaQuímica InorgánicaMinisterio de Ciencia, Innovación y Universidades (MICIU). EspañaEuropean Union (UE)2021info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/174367https://doi.org/10.1016/j.jallcom.2020.156973reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Instituto Valenciano de Investigaciones Agrarias (IVIA)InglésJournal of Alloys and Compounds, 853, 156973.MAT2016-78700-RMAT2015-65356-C3-1-RRTI2018-096918-B-C41https://doi.org/10.1016/j.jallcom.2020.156973info:eu-repo/semantics/openAccessoai:idus.us.es:11441/1743672026-06-17T12:51:07Z
dc.title.none.fl_str_mv Impact of Tb4+ and morphology on the Thermal Evolution of Tb-doped TiO2 Nanostructured Hollow Spheres and Nanoparticles
title Impact of Tb4+ and morphology on the Thermal Evolution of Tb-doped TiO2 Nanostructured Hollow Spheres and Nanoparticles
spellingShingle Impact of Tb4+ and morphology on the Thermal Evolution of Tb-doped TiO2 Nanostructured Hollow Spheres and Nanoparticles
Colomer, M. T.
Tb
Hollow spheres
Anatase
Rutile
Photoluminescence
Raman phonons
title_short Impact of Tb4+ and morphology on the Thermal Evolution of Tb-doped TiO2 Nanostructured Hollow Spheres and Nanoparticles
title_full Impact of Tb4+ and morphology on the Thermal Evolution of Tb-doped TiO2 Nanostructured Hollow Spheres and Nanoparticles
title_fullStr Impact of Tb4+ and morphology on the Thermal Evolution of Tb-doped TiO2 Nanostructured Hollow Spheres and Nanoparticles
title_full_unstemmed Impact of Tb4+ and morphology on the Thermal Evolution of Tb-doped TiO2 Nanostructured Hollow Spheres and Nanoparticles
title_sort Impact of Tb4+ and morphology on the Thermal Evolution of Tb-doped TiO2 Nanostructured Hollow Spheres and Nanoparticles
dc.creator.none.fl_str_mv Colomer, M. T.
Rodríguez, E.
Morán Pedroso, María
Vattier Lagarrigue, María Florencia
Andrés, A. de
author Colomer, M. T.
author_facet Colomer, M. T.
Rodríguez, E.
Morán Pedroso, María
Vattier Lagarrigue, María Florencia
Andrés, A. de
author_role author
author2 Rodríguez, E.
Morán Pedroso, María
Vattier Lagarrigue, María Florencia
Andrés, A. de
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Física de la Materia Condensada
Química Inorgánica
Ministerio de Ciencia, Innovación y Universidades (MICIU). España
European Union (UE)
dc.subject.none.fl_str_mv Tb
Hollow spheres
Anatase
Rutile
Photoluminescence
Raman phonons
topic Tb
Hollow spheres
Anatase
Rutile
Photoluminescence
Raman phonons
description Tb-doped TiO2 hollow spheres (HSs) in the range 0.0-2.0 at.% have been,synthesized by the first time to the best of our knowledge. The HSs are compared with,nanoparticles (NPs) to evaluate the impact of morphology on their physicochemical and,photoluminescence (PL) behavior upon increasing calcination temperature. After,calcination at 550ºC, the particles are anatase with a primary average size of 10.0 ± 0.2,nm for the NPs and 12.0 ± 0.2 nm for those that form the micron sized hollow spheres of,1.8 µm diameter and ca. 64 nm shell thickness. The temperature of the anatase–rutile,transition is found to be strongly dependent on the presence of Tb as well as on,morphology. Contrarily to the usual stabilization of anatase when doping with trivalent,rare-earth ions, the transition temperature is reduced when doping with Tb. The rutile,phase is further favored for the HSs compared to the NPs probably related to the low,density of the HSs and/or a more efficient packing of the nanoparticles that form those,spheres with respect to the packing of the NPs. A slight unit-cell volume decrease for the,anatase structure is observed upon Tb doping, in both the NPs and in the HSs, contrary to,the expected increment due to the larger ionic radius of Tb3+ compared to Ti4+,. In addition,,2,the intensity of the characteristic f-f Tb3+ emission bands is extremely weak both in the,anatase and rutile phases. The transition is accompanied with the emergence of an infrared,emission band centered at 810 nm related to the formation of defects during the structural,transformation providing deep levels in the gap that partly quench the f-f emissions in the,rutile phase. The results are consistent with the presence of Tb in both +3 and +4 valence,states. XPS measurements confirmed the presence of Tb3+ as well as of Tb4+ in both HSs,and NPs with a Tb4+ fraction that increases with increasing Tb doping. The large fraction,of Tb4+ present in the samples originates the weak f-f emission intensity, the slight,decrease of the cell parameters and the destabilization of the anatase phase
publishDate 2021
dc.date.none.fl_str_mv 2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/11441/174367
https://doi.org/10.1016/j.jallcom.2020.156973
url https://hdl.handle.net/11441/174367
https://doi.org/10.1016/j.jallcom.2020.156973
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Journal of Alloys and Compounds, 853, 156973.
MAT2016-78700-R
MAT2015-65356-C3-1-R
RTI2018-096918-B-C41
https://doi.org/10.1016/j.jallcom.2020.156973
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Instituto Valenciano de Investigaciones Agrarias (IVIA)
instname_str Instituto Valenciano de Investigaciones Agrarias (IVIA)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
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