Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments

Autores
Hunt, Diego; Oestreicher, Víctor Santiago Jesús; Mizrahi, Martin Daniel; Requejo, Felix Gregorio; Jobbagy, Matias
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Co- and Ni-based layered hydroxides constitute a unique class of two-dimensional inorganic materials with exceptional chemical diversity, physicochemical properties and outstanding performance as supercapacitors and overall water splitting catalysts. Recently, the occurrence of Co(III) in these phases has been proposed as a key factor that enhance their electrochemical performance. However, the origin of this centers and control over its contents remains as an open question. We employed the Epoxide Route to synthesize a whole set of α-NiCo layered hydroxides. The PXRD and XAS characterization alert about the occurrence of Co(III) as a consequence of the increment in the Ni content. DFT+U simulation suggest that the shortening of the Co−O distance promotes a structural distortion in the Co environments, resulting in a double degeneration in the octahedral Co 3d orbitals. Hence, a strong modification of the electronic properties leaves the system prone to oxidation, by the appearance of Co localized electronic states on the Fermi level. This work combines a microscopic interpretation supported by a multiscale crystallochemical analysis, regarding the so-called synergistic redox behavior of Co and Ni, offering fundamental tools for the controllable design of highly efficient electroactive materials. To the best of our knowledge, this is the first computational–experimental investigation of the electronic and structural details of α-NiCo hydroxides, laying the foundation for the fine tuning of electronic properties in layered hydroxides.
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 Constituyentes | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Constituyentes; Argentina
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: Mizrahi, Martin Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Requejo, Felix Gregorio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; 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
2D MATERIALS
ENERGY STORAGE
LAYERED HYDROXIDES
SUPERCAPACITANCE
WATER SPLITTING
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:11336/146771
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted EnvironmentsHunt, DiegoOestreicher, Víctor Santiago JesúsMizrahi, Martin DanielRequejo, Felix GregorioJobbagy, Matias2D MATERIALSENERGY STORAGELAYERED HYDROXIDESSUPERCAPACITANCEWATER SPLITTINGhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Co- and Ni-based layered hydroxides constitute a unique class of two-dimensional inorganic materials with exceptional chemical diversity, physicochemical properties and outstanding performance as supercapacitors and overall water splitting catalysts. Recently, the occurrence of Co(III) in these phases has been proposed as a key factor that enhance their electrochemical performance. However, the origin of this centers and control over its contents remains as an open question. We employed the Epoxide Route to synthesize a whole set of α-NiCo layered hydroxides. The PXRD and XAS characterization alert about the occurrence of Co(III) as a consequence of the increment in the Ni content. DFT+U simulation suggest that the shortening of the Co−O distance promotes a structural distortion in the Co environments, resulting in a double degeneration in the octahedral Co 3d orbitals. Hence, a strong modification of the electronic properties leaves the system prone to oxidation, by the appearance of Co localized electronic states on the Fermi level. This work combines a microscopic interpretation supported by a multiscale crystallochemical analysis, regarding the so-called synergistic redox behavior of Co and Ni, offering fundamental tools for the controllable design of highly efficient electroactive materials. To the best of our knowledge, this is the first computational–experimental investigation of the electronic and structural details of α-NiCo hydroxides, laying the foundation for the fine tuning of electronic properties in layered hydroxides.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 Constituyentes | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Constituyentes; ArgentinaFil: 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: Mizrahi, Martin Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Requejo, Felix Gregorio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; 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; ArgentinaWiley VCH Verlag2020-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/146771Hunt, Diego; Oestreicher, Víctor Santiago Jesús; Mizrahi, Martin Daniel; Requejo, Felix Gregorio; Jobbagy, Matias; Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments; Wiley VCH Verlag; Chemistry- A European Journal; 26; 71; 7-2020; 17081-170900947-6539CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.202001944info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.202001944info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:45:17Zoai:ri.conicet.gov.ar:11336/146771instacron: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:34982025-09-29 10:45:17.365CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments
title Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments
spellingShingle Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments
Hunt, Diego
2D MATERIALS
ENERGY STORAGE
LAYERED HYDROXIDES
SUPERCAPACITANCE
WATER SPLITTING
title_short Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments
title_full Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments
title_fullStr Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments
title_full_unstemmed Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments
title_sort Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments
dc.creator.none.fl_str_mv Hunt, Diego
Oestreicher, Víctor Santiago Jesús
Mizrahi, Martin Daniel
Requejo, Felix Gregorio
Jobbagy, Matias
author Hunt, Diego
author_facet Hunt, Diego
Oestreicher, Víctor Santiago Jesús
Mizrahi, Martin Daniel
Requejo, Felix Gregorio
Jobbagy, Matias
author_role author
author2 Oestreicher, Víctor Santiago Jesús
Mizrahi, Martin Daniel
Requejo, Felix Gregorio
Jobbagy, Matias
author2_role author
author
author
author
dc.subject.none.fl_str_mv 2D MATERIALS
ENERGY STORAGE
LAYERED HYDROXIDES
SUPERCAPACITANCE
WATER SPLITTING
topic 2D MATERIALS
ENERGY STORAGE
LAYERED HYDROXIDES
SUPERCAPACITANCE
WATER SPLITTING
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Co- and Ni-based layered hydroxides constitute a unique class of two-dimensional inorganic materials with exceptional chemical diversity, physicochemical properties and outstanding performance as supercapacitors and overall water splitting catalysts. Recently, the occurrence of Co(III) in these phases has been proposed as a key factor that enhance their electrochemical performance. However, the origin of this centers and control over its contents remains as an open question. We employed the Epoxide Route to synthesize a whole set of α-NiCo layered hydroxides. The PXRD and XAS characterization alert about the occurrence of Co(III) as a consequence of the increment in the Ni content. DFT+U simulation suggest that the shortening of the Co−O distance promotes a structural distortion in the Co environments, resulting in a double degeneration in the octahedral Co 3d orbitals. Hence, a strong modification of the electronic properties leaves the system prone to oxidation, by the appearance of Co localized electronic states on the Fermi level. This work combines a microscopic interpretation supported by a multiscale crystallochemical analysis, regarding the so-called synergistic redox behavior of Co and Ni, offering fundamental tools for the controllable design of highly efficient electroactive materials. To the best of our knowledge, this is the first computational–experimental investigation of the electronic and structural details of α-NiCo hydroxides, laying the foundation for the fine tuning of electronic properties in layered hydroxides.
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 Constituyentes | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Constituyentes; Argentina
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: Mizrahi, Martin Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Requejo, Felix Gregorio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; 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 Co- and Ni-based layered hydroxides constitute a unique class of two-dimensional inorganic materials with exceptional chemical diversity, physicochemical properties and outstanding performance as supercapacitors and overall water splitting catalysts. Recently, the occurrence of Co(III) in these phases has been proposed as a key factor that enhance their electrochemical performance. However, the origin of this centers and control over its contents remains as an open question. We employed the Epoxide Route to synthesize a whole set of α-NiCo layered hydroxides. The PXRD and XAS characterization alert about the occurrence of Co(III) as a consequence of the increment in the Ni content. DFT+U simulation suggest that the shortening of the Co−O distance promotes a structural distortion in the Co environments, resulting in a double degeneration in the octahedral Co 3d orbitals. Hence, a strong modification of the electronic properties leaves the system prone to oxidation, by the appearance of Co localized electronic states on the Fermi level. This work combines a microscopic interpretation supported by a multiscale crystallochemical analysis, regarding the so-called synergistic redox behavior of Co and Ni, offering fundamental tools for the controllable design of highly efficient electroactive materials. To the best of our knowledge, this is the first computational–experimental investigation of the electronic and structural details of α-NiCo hydroxides, laying the foundation for the fine tuning of electronic properties in layered hydroxides.
publishDate 2020
dc.date.none.fl_str_mv 2020-07
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/11336/146771
Hunt, Diego; Oestreicher, Víctor Santiago Jesús; Mizrahi, Martin Daniel; Requejo, Felix Gregorio; Jobbagy, Matias; Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments; Wiley VCH Verlag; Chemistry- A European Journal; 26; 71; 7-2020; 17081-17090
0947-6539
CONICET Digital
CONICET
url http://hdl.handle.net/11336/146771
identifier_str_mv Hunt, Diego; Oestreicher, Víctor Santiago Jesús; Mizrahi, Martin Daniel; Requejo, Felix Gregorio; Jobbagy, Matias; Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments; Wiley VCH Verlag; Chemistry- A European Journal; 26; 71; 7-2020; 17081-17090
0947-6539
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.202001944
info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.202001944
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 Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
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
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score 13.070432

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