Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations

Autores
Oestreicher, Víctor Santiago Jesús; Hunt, Diego; Torres Cavanillas, Ramon; Abellan, Gonzalo; Scherlis Perel, Damian Ariel; Jobbagy, Matias
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The present study introduces a comprehensive exploration in terms of physicochemical characterization and calculations based on density functional theory with Hubbard's correction (DFT+U) of the whole family of α-Co(II) hydroxyhalide (F, Cl, Br, I). These samples were synthesized at room temperature by employing a one-pot approach based on the epoxide route. A thorough characterization (powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis/mass spectroscopy, and magnetic and conductivity measurements) corroborated by simulation is presented that analyzes the structural, magnetic, and electronic aspects. Beyond the inherent tendency of intercalated anions to modify the interlayer distance, the halide's nature has a marked effect on several aspects. Such as the modulation of the CoOh to CoTd ratio, as well as the inherent tendency towards dehydration and irreversible decomposition. Whereas the magnetic behavior is strongly correlated with the CoTd amount reflected in the presence of glassy behavior with high magnetic disorder, the electrical properties depend mainly on the nature of the halide. The computed electronic structures suggest that the CoTd molar fraction exerts a minor effect on the inherent conductivity of the phases. However, the band gap of the solid turns out to be significantly dependent on the nature of the incorporated halide, governed by ligand to metal charge transfer, which minimizes the gap as the anionic radius becomes larger. Conductivity measurements of pressed pellets confirm this trend. To the best of our knowledge, this is the first report on the magnetic and electrical properties of α-Co(II) hydroxyhalides validated with in silico descriptions, opening the gate for the rational design of layered hydroxylated phases with tunable electrical, optical, and magnetic properties.
Fil: Oestreicher, Víctor Santiago Jesús. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Hunt, Diego. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche; Argentina
Fil: Torres Cavanillas, Ramon. Universidad de Valencia; España
Fil: Abellan, Gonzalo. Universidad de Valencia; España
Fil: Scherlis Perel, Damian Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Jobbagy, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Materia
layered hydroxides
cobalt
magnetism
epoxide route
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/123593
Acceder
id CONICETDig_44684593491a2f7140aab0fe1142777d
oai_identifier_str oai:ri.conicet.gov.ar:11336/123593
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U SimulationsOestreicher, Víctor Santiago JesúsHunt, DiegoTorres Cavanillas, RamonAbellan, GonzaloScherlis Perel, Damian ArielJobbagy, Matiaslayered hydroxidescobaltmagnetismepoxide routehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The present study introduces a comprehensive exploration in terms of physicochemical characterization and calculations based on density functional theory with Hubbard's correction (DFT+U) of the whole family of α-Co(II) hydroxyhalide (F, Cl, Br, I). These samples were synthesized at room temperature by employing a one-pot approach based on the epoxide route. A thorough characterization (powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis/mass spectroscopy, and magnetic and conductivity measurements) corroborated by simulation is presented that analyzes the structural, magnetic, and electronic aspects. Beyond the inherent tendency of intercalated anions to modify the interlayer distance, the halide's nature has a marked effect on several aspects. Such as the modulation of the CoOh to CoTd ratio, as well as the inherent tendency towards dehydration and irreversible decomposition. Whereas the magnetic behavior is strongly correlated with the CoTd amount reflected in the presence of glassy behavior with high magnetic disorder, the electrical properties depend mainly on the nature of the halide. The computed electronic structures suggest that the CoTd molar fraction exerts a minor effect on the inherent conductivity of the phases. However, the band gap of the solid turns out to be significantly dependent on the nature of the incorporated halide, governed by ligand to metal charge transfer, which minimizes the gap as the anionic radius becomes larger. Conductivity measurements of pressed pellets confirm this trend. To the best of our knowledge, this is the first report on the magnetic and electrical properties of α-Co(II) hydroxyhalides validated with in silico descriptions, opening the gate for the rational design of layered hydroxylated phases with tunable electrical, optical, and magnetic properties.Fil: Oestreicher, Víctor Santiago Jesús. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Hunt, Diego. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche; ArgentinaFil: Torres Cavanillas, Ramon. Universidad de Valencia; EspañaFil: Abellan, Gonzalo. Universidad de Valencia; EspañaFil: Scherlis Perel, Damian Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Jobbagy, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaAmerican Chemical Society2019-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/123593Oestreicher, Víctor Santiago Jesús; Hunt, Diego; Torres Cavanillas, Ramon; Abellan, Gonzalo; Scherlis Perel, Damian Ariel; et al.; Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations; American Chemical Society; Inorganic Chemistry; 58; 14; 7-2019; 9414-94240020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b01252info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.9b01252info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:47:57Zoai:ri.conicet.gov.ar:11336/123593instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 09:47:57.796CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations
title Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations
spellingShingle Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations
Oestreicher, Víctor Santiago Jesús
layered hydroxides
cobalt
magnetism
epoxide route
title_short Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations
title_full Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations
title_fullStr Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations
title_full_unstemmed Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations
title_sort Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations
dc.creator.none.fl_str_mv Oestreicher, Víctor Santiago Jesús
Hunt, Diego
Torres Cavanillas, Ramon
Abellan, Gonzalo
Scherlis Perel, Damian Ariel
Jobbagy, Matias
author Oestreicher, Víctor Santiago Jesús
author_facet Oestreicher, Víctor Santiago Jesús
Hunt, Diego
Torres Cavanillas, Ramon
Abellan, Gonzalo
Scherlis Perel, Damian Ariel
Jobbagy, Matias
author_role author
author2 Hunt, Diego
Torres Cavanillas, Ramon
Abellan, Gonzalo
Scherlis Perel, Damian Ariel
Jobbagy, Matias
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv layered hydroxides
cobalt
magnetism
epoxide route
topic layered hydroxides
cobalt
magnetism
epoxide route
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The present study introduces a comprehensive exploration in terms of physicochemical characterization and calculations based on density functional theory with Hubbard's correction (DFT+U) of the whole family of α-Co(II) hydroxyhalide (F, Cl, Br, I). These samples were synthesized at room temperature by employing a one-pot approach based on the epoxide route. A thorough characterization (powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis/mass spectroscopy, and magnetic and conductivity measurements) corroborated by simulation is presented that analyzes the structural, magnetic, and electronic aspects. Beyond the inherent tendency of intercalated anions to modify the interlayer distance, the halide's nature has a marked effect on several aspects. Such as the modulation of the CoOh to CoTd ratio, as well as the inherent tendency towards dehydration and irreversible decomposition. Whereas the magnetic behavior is strongly correlated with the CoTd amount reflected in the presence of glassy behavior with high magnetic disorder, the electrical properties depend mainly on the nature of the halide. The computed electronic structures suggest that the CoTd molar fraction exerts a minor effect on the inherent conductivity of the phases. However, the band gap of the solid turns out to be significantly dependent on the nature of the incorporated halide, governed by ligand to metal charge transfer, which minimizes the gap as the anionic radius becomes larger. Conductivity measurements of pressed pellets confirm this trend. To the best of our knowledge, this is the first report on the magnetic and electrical properties of α-Co(II) hydroxyhalides validated with in silico descriptions, opening the gate for the rational design of layered hydroxylated phases with tunable electrical, optical, and magnetic properties.
Fil: Oestreicher, Víctor Santiago Jesús. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Hunt, Diego. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche; Argentina
Fil: Torres Cavanillas, Ramon. Universidad de Valencia; España
Fil: Abellan, Gonzalo. Universidad de Valencia; España
Fil: Scherlis Perel, Damian Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Jobbagy, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
description The present study introduces a comprehensive exploration in terms of physicochemical characterization and calculations based on density functional theory with Hubbard's correction (DFT+U) of the whole family of α-Co(II) hydroxyhalide (F, Cl, Br, I). These samples were synthesized at room temperature by employing a one-pot approach based on the epoxide route. A thorough characterization (powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis/mass spectroscopy, and magnetic and conductivity measurements) corroborated by simulation is presented that analyzes the structural, magnetic, and electronic aspects. Beyond the inherent tendency of intercalated anions to modify the interlayer distance, the halide's nature has a marked effect on several aspects. Such as the modulation of the CoOh to CoTd ratio, as well as the inherent tendency towards dehydration and irreversible decomposition. Whereas the magnetic behavior is strongly correlated with the CoTd amount reflected in the presence of glassy behavior with high magnetic disorder, the electrical properties depend mainly on the nature of the halide. The computed electronic structures suggest that the CoTd molar fraction exerts a minor effect on the inherent conductivity of the phases. However, the band gap of the solid turns out to be significantly dependent on the nature of the incorporated halide, governed by ligand to metal charge transfer, which minimizes the gap as the anionic radius becomes larger. Conductivity measurements of pressed pellets confirm this trend. To the best of our knowledge, this is the first report on the magnetic and electrical properties of α-Co(II) hydroxyhalides validated with in silico descriptions, opening the gate for the rational design of layered hydroxylated phases with tunable electrical, optical, and magnetic properties.
publishDate 2019
dc.date.none.fl_str_mv 2019-07
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/123593
Oestreicher, Víctor Santiago Jesús; Hunt, Diego; Torres Cavanillas, Ramon; Abellan, Gonzalo; Scherlis Perel, Damian Ariel; et al.; Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations; American Chemical Society; Inorganic Chemistry; 58; 14; 7-2019; 9414-9424
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/123593
identifier_str_mv Oestreicher, Víctor Santiago Jesús; Hunt, Diego; Torres Cavanillas, Ramon; Abellan, Gonzalo; Scherlis Perel, Damian Ariel; et al.; Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations; American Chemical Society; Inorganic Chemistry; 58; 14; 7-2019; 9414-9424
0020-1669
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b01252
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.9b01252
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1842268893022781440
score 13.13397

Publicaciones similares