Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability

Autores
Xu, Tao; Waehler, Tobias; Vecchietti, María Julia; Bonivardi, Adrian Lionel; Bauer, Tanja; Schwegler, Johannes; Schulz, Peter S.; Wasserscheid, Peter; Libuda, Joerg
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Hybrid materials consisting of ionic liquid (ILs) films on supported oxides hold a great potential for applications in electronic and energy materials. In this work, we have performed surface science model studies scrutinizing the interaction of ester-functionalized ILs with atomically defined Co3O4(111) and CoO(100) surfaces. Both supports are prepared under ultra-high vacuum (UHV) conditions in form of thin films on Ir(100) single crystals. Subsequently, thin films of three ILs, 3-butyl-1-methyl imidazolium bis(trifluoromethyl-sulfonyl) imide ([BMIM][NTf2]), 3-(4-methoxyl-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([MBMIM][NTf2]), and 3-(4-isopropoxy-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([IPBMIM][NTf2]), were deposited on these surfaces by physical vapor deposition (PVD). Time-resolved and temperature-programmed infrared reflection absorption spectroscopy (TR-IRAS, TP-IRAS) were applied to monitor in situ the adsorption, film growth, and thermally induced desorption. By TP-IRAS, we determined the multilayer desorption temperature of [BMIM][NTf2] (360±5 K), [MBMIM][NTf2] (380 K) and [IPBMIM][NTf2] (380 K). Upon deposition below the multilayer desorption temperature, all three ILs physisorb on both cobalt oxide surfaces. However, strong orientation effects are observed in the first monolayer, where the [NTf2]− ion interacts with the surface through the SO2 groups and the CF3 groups point towards the vacuum. For the two functionalized ILs, the [MBMIM]+ and [IPBMIM]+ interact with the surface Co2+ ions of both surfaces via the CO group of their ester function. A very different behavior is found, if the ILs are deposited above the multilayer desorption temperature (400 K). While for [BMIM][NTf2] and [MBMIM][NTf2] a molecularly adsorbed monolayer film is formed, [IPBMIM][NTf2] undergoes a chemical transformation on the CoO(100) surface. Here, the ester group is cleaved and the cation is chemically linked to the surface by formation of a surface carboxylate. The IL-derived species in the monolayer desorb at temperatures around 500 to 550 K.
Fil: Xu, Tao. Universitat Erlangen-Nuremberg; Alemania
Fil: Waehler, Tobias. Universitat Erlangen-Nuremberg; Alemania
Fil: Vecchietti, María Julia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Bauer, Tanja. Universitat Erlangen-Nuremberg; Alemania
Fil: Schwegler, Johannes. Universitat Erlangen-Nuremberg; Alemania
Fil: Schulz, Peter S.. Universitat Erlangen-Nuremberg; Alemania
Fil: Wasserscheid, Peter. Universitat Erlangen-Nuremberg; Alemania
Fil: Libuda, Joerg. Universitat Erlangen-Nuremberg; Alemania
Materia
Chemical Anchoring
Cobalt Oxide
Ionic Liquids
Iras
Thermal Stability
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:11336/40365
Acceder
id CONICETDig_d15ba1789c0d671ea142ea08059dd6a8
oai_identifier_str oai:ri.conicet.gov.ar:11336/40365
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal StabilityXu, TaoWaehler, TobiasVecchietti, María JuliaBonivardi, Adrian LionelBauer, TanjaSchwegler, JohannesSchulz, Peter S.Wasserscheid, PeterLibuda, JoergChemical AnchoringCobalt OxideIonic LiquidsIrasThermal Stabilityhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Hybrid materials consisting of ionic liquid (ILs) films on supported oxides hold a great potential for applications in electronic and energy materials. In this work, we have performed surface science model studies scrutinizing the interaction of ester-functionalized ILs with atomically defined Co3O4(111) and CoO(100) surfaces. Both supports are prepared under ultra-high vacuum (UHV) conditions in form of thin films on Ir(100) single crystals. Subsequently, thin films of three ILs, 3-butyl-1-methyl imidazolium bis(trifluoromethyl-sulfonyl) imide ([BMIM][NTf2]), 3-(4-methoxyl-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([MBMIM][NTf2]), and 3-(4-isopropoxy-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([IPBMIM][NTf2]), were deposited on these surfaces by physical vapor deposition (PVD). Time-resolved and temperature-programmed infrared reflection absorption spectroscopy (TR-IRAS, TP-IRAS) were applied to monitor in situ the adsorption, film growth, and thermally induced desorption. By TP-IRAS, we determined the multilayer desorption temperature of [BMIM][NTf2] (360±5 K), [MBMIM][NTf2] (380 K) and [IPBMIM][NTf2] (380 K). Upon deposition below the multilayer desorption temperature, all three ILs physisorb on both cobalt oxide surfaces. However, strong orientation effects are observed in the first monolayer, where the [NTf2]− ion interacts with the surface through the SO2 groups and the CF3 groups point towards the vacuum. For the two functionalized ILs, the [MBMIM]+ and [IPBMIM]+ interact with the surface Co2+ ions of both surfaces via the CO group of their ester function. A very different behavior is found, if the ILs are deposited above the multilayer desorption temperature (400 K). While for [BMIM][NTf2] and [MBMIM][NTf2] a molecularly adsorbed monolayer film is formed, [IPBMIM][NTf2] undergoes a chemical transformation on the CoO(100) surface. Here, the ester group is cleaved and the cation is chemically linked to the surface by formation of a surface carboxylate. The IL-derived species in the monolayer desorb at temperatures around 500 to 550 K.Fil: Xu, Tao. Universitat Erlangen-Nuremberg; AlemaniaFil: Waehler, Tobias. Universitat Erlangen-Nuremberg; AlemaniaFil: Vecchietti, María Julia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Bauer, Tanja. Universitat Erlangen-Nuremberg; AlemaniaFil: Schwegler, Johannes. Universitat Erlangen-Nuremberg; AlemaniaFil: Schulz, Peter S.. Universitat Erlangen-Nuremberg; AlemaniaFil: Wasserscheid, Peter. Universitat Erlangen-Nuremberg; AlemaniaFil: Libuda, Joerg. Universitat Erlangen-Nuremberg; AlemaniaWiley VCH Verlag2017-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/40365Xu, Tao; Waehler, Tobias; Vecchietti, María Julia; Bonivardi, Adrian Lionel; Bauer, Tanja; et al.; Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability; Wiley VCH Verlag; Chemphyschem; 18; 23; 12-2017; 3443-34531439-4235CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.201700843info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:48:17Zoai:ri.conicet.gov.ar:11336/40365instacron: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 09:48:17.407CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability
title Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability
spellingShingle Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability
Xu, Tao
Chemical Anchoring
Cobalt Oxide
Ionic Liquids
Iras
Thermal Stability
title_short Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability
title_full Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability
title_fullStr Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability
title_full_unstemmed Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability
title_sort Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability
dc.creator.none.fl_str_mv Xu, Tao
Waehler, Tobias
Vecchietti, María Julia
Bonivardi, Adrian Lionel
Bauer, Tanja
Schwegler, Johannes
Schulz, Peter S.
Wasserscheid, Peter
Libuda, Joerg
author Xu, Tao
author_facet Xu, Tao
Waehler, Tobias
Vecchietti, María Julia
Bonivardi, Adrian Lionel
Bauer, Tanja
Schwegler, Johannes
Schulz, Peter S.
Wasserscheid, Peter
Libuda, Joerg
author_role author
author2 Waehler, Tobias
Vecchietti, María Julia
Bonivardi, Adrian Lionel
Bauer, Tanja
Schwegler, Johannes
Schulz, Peter S.
Wasserscheid, Peter
Libuda, Joerg
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Chemical Anchoring
Cobalt Oxide
Ionic Liquids
Iras
Thermal Stability
topic Chemical Anchoring
Cobalt Oxide
Ionic Liquids
Iras
Thermal Stability
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Hybrid materials consisting of ionic liquid (ILs) films on supported oxides hold a great potential for applications in electronic and energy materials. In this work, we have performed surface science model studies scrutinizing the interaction of ester-functionalized ILs with atomically defined Co3O4(111) and CoO(100) surfaces. Both supports are prepared under ultra-high vacuum (UHV) conditions in form of thin films on Ir(100) single crystals. Subsequently, thin films of three ILs, 3-butyl-1-methyl imidazolium bis(trifluoromethyl-sulfonyl) imide ([BMIM][NTf2]), 3-(4-methoxyl-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([MBMIM][NTf2]), and 3-(4-isopropoxy-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([IPBMIM][NTf2]), were deposited on these surfaces by physical vapor deposition (PVD). Time-resolved and temperature-programmed infrared reflection absorption spectroscopy (TR-IRAS, TP-IRAS) were applied to monitor in situ the adsorption, film growth, and thermally induced desorption. By TP-IRAS, we determined the multilayer desorption temperature of [BMIM][NTf2] (360±5 K), [MBMIM][NTf2] (380 K) and [IPBMIM][NTf2] (380 K). Upon deposition below the multilayer desorption temperature, all three ILs physisorb on both cobalt oxide surfaces. However, strong orientation effects are observed in the first monolayer, where the [NTf2]− ion interacts with the surface through the SO2 groups and the CF3 groups point towards the vacuum. For the two functionalized ILs, the [MBMIM]+ and [IPBMIM]+ interact with the surface Co2+ ions of both surfaces via the CO group of their ester function. A very different behavior is found, if the ILs are deposited above the multilayer desorption temperature (400 K). While for [BMIM][NTf2] and [MBMIM][NTf2] a molecularly adsorbed monolayer film is formed, [IPBMIM][NTf2] undergoes a chemical transformation on the CoO(100) surface. Here, the ester group is cleaved and the cation is chemically linked to the surface by formation of a surface carboxylate. The IL-derived species in the monolayer desorb at temperatures around 500 to 550 K.
Fil: Xu, Tao. Universitat Erlangen-Nuremberg; Alemania
Fil: Waehler, Tobias. Universitat Erlangen-Nuremberg; Alemania
Fil: Vecchietti, María Julia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Bonivardi, Adrian Lionel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Bauer, Tanja. Universitat Erlangen-Nuremberg; Alemania
Fil: Schwegler, Johannes. Universitat Erlangen-Nuremberg; Alemania
Fil: Schulz, Peter S.. Universitat Erlangen-Nuremberg; Alemania
Fil: Wasserscheid, Peter. Universitat Erlangen-Nuremberg; Alemania
Fil: Libuda, Joerg. Universitat Erlangen-Nuremberg; Alemania
description Hybrid materials consisting of ionic liquid (ILs) films on supported oxides hold a great potential for applications in electronic and energy materials. In this work, we have performed surface science model studies scrutinizing the interaction of ester-functionalized ILs with atomically defined Co3O4(111) and CoO(100) surfaces. Both supports are prepared under ultra-high vacuum (UHV) conditions in form of thin films on Ir(100) single crystals. Subsequently, thin films of three ILs, 3-butyl-1-methyl imidazolium bis(trifluoromethyl-sulfonyl) imide ([BMIM][NTf2]), 3-(4-methoxyl-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([MBMIM][NTf2]), and 3-(4-isopropoxy-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([IPBMIM][NTf2]), were deposited on these surfaces by physical vapor deposition (PVD). Time-resolved and temperature-programmed infrared reflection absorption spectroscopy (TR-IRAS, TP-IRAS) were applied to monitor in situ the adsorption, film growth, and thermally induced desorption. By TP-IRAS, we determined the multilayer desorption temperature of [BMIM][NTf2] (360±5 K), [MBMIM][NTf2] (380 K) and [IPBMIM][NTf2] (380 K). Upon deposition below the multilayer desorption temperature, all three ILs physisorb on both cobalt oxide surfaces. However, strong orientation effects are observed in the first monolayer, where the [NTf2]− ion interacts with the surface through the SO2 groups and the CF3 groups point towards the vacuum. For the two functionalized ILs, the [MBMIM]+ and [IPBMIM]+ interact with the surface Co2+ ions of both surfaces via the CO group of their ester function. A very different behavior is found, if the ILs are deposited above the multilayer desorption temperature (400 K). While for [BMIM][NTf2] and [MBMIM][NTf2] a molecularly adsorbed monolayer film is formed, [IPBMIM][NTf2] undergoes a chemical transformation on the CoO(100) surface. Here, the ester group is cleaved and the cation is chemically linked to the surface by formation of a surface carboxylate. The IL-derived species in the monolayer desorb at temperatures around 500 to 550 K.
publishDate 2017
dc.date.none.fl_str_mv 2017-12
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/11336/40365
Xu, Tao; Waehler, Tobias; Vecchietti, María Julia; Bonivardi, Adrian Lionel; Bauer, Tanja; et al.; Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability; Wiley VCH Verlag; Chemphyschem; 18; 23; 12-2017; 3443-3453
1439-4235
CONICET Digital
CONICET
url http://hdl.handle.net/11336/40365
identifier_str_mv Xu, Tao; Waehler, Tobias; Vecchietti, María Julia; Bonivardi, Adrian Lionel; Bauer, Tanja; et al.; Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability; Wiley VCH Verlag; Chemphyschem; 18; 23; 12-2017; 3443-3453
1439-4235
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.201700843
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
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 13.13397

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