Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films

Autores
Arisnabarreta, Nicolás; Paredes Olivera, Patricia; Cometto, Fernando Pablo; Patrito, Eduardo Martin
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We investigated the conversion of electrochemically grown CuO into copper-alkanethiolate lamellar structures supported on a Cu substrate upon immersion in solutions of n-alkanethiols. After considering different preparation conditions (alkyl chain length, thiol concentration, and type of solvent), we found that the oxide can be rapidly converted into compact and highly passivating lamellar layers in 1-octanethiolate/0.1 M NaOH forming solutions. Alkaline forming solutions play a key role in favoring the conversion of CuO into the lamellar compound vs the competing mechanism in which the oxide is reduced and the thiolates are oxidized to disulfides. The oxide conversion into the layered structure is incomplete for both short and long alkanethiols, and it is almost complete in the case of 1-octanethiol. The use of less polar solvents such as ethanol or n-hexane is much less effective in producing layered Cu-thiolates. Spectroscopic ellipsometry measurements showed that 10-nm-thick CuO is converted into a 100-nm-thick lamellar compound, which corresponds to around 40 lamellae. After the breakage of the layers during O2 evolution at high anodic potentials, a healing behavior was observed: The copper surface became passivated again after exposure of the broken layer in the air for a few minutes. The layered compound was extensively characterized by X-ray photoelectron spectroscopy and Raman spectroscopy. The decrease of O 1s/Cu 3p ratio and the increase of S 2p/Cu 3p and C 1s/Cu 3p ratios clearly showed the conversion of CuO into a copper-thiolate complex. The Raman spectrum of the Cu-octanethiolate compound shows a considerable enhancement of all bands as compared to a self-assembled monolayer. The sharpness of the most prominent peaks indicates the high crystallinity of the alkyl chains in the layered compound. Density functional theory calculations showed that the alkyl chains lie nearly perpendicular to the layer of Cu atoms. The calculation of Raman vibrational frequencies using density functional perturbation theory allowed an unambiguous assignment of experimental Raman peaks.
Fil: Arisnabarreta, Nicolás. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Paredes Olivera, Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Cometto, Fernando Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Patrito, Eduardo Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
ALKANETHIOLS
CU
LAMELLAR STRUCTURES
ELECTROCHEMISTRY
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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CONICET Digital (CONICET)
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Consejo Nacional de Investigaciones Científicas y Técnicas
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oai:ri.conicet.gov.ar:11336/124514
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide FilmsArisnabarreta, NicolásParedes Olivera, PatriciaCometto, Fernando PabloPatrito, Eduardo MartinALKANETHIOLSCULAMELLAR STRUCTURESELECTROCHEMISTRYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We investigated the conversion of electrochemically grown CuO into copper-alkanethiolate lamellar structures supported on a Cu substrate upon immersion in solutions of n-alkanethiols. After considering different preparation conditions (alkyl chain length, thiol concentration, and type of solvent), we found that the oxide can be rapidly converted into compact and highly passivating lamellar layers in 1-octanethiolate/0.1 M NaOH forming solutions. Alkaline forming solutions play a key role in favoring the conversion of CuO into the lamellar compound vs the competing mechanism in which the oxide is reduced and the thiolates are oxidized to disulfides. The oxide conversion into the layered structure is incomplete for both short and long alkanethiols, and it is almost complete in the case of 1-octanethiol. The use of less polar solvents such as ethanol or n-hexane is much less effective in producing layered Cu-thiolates. Spectroscopic ellipsometry measurements showed that 10-nm-thick CuO is converted into a 100-nm-thick lamellar compound, which corresponds to around 40 lamellae. After the breakage of the layers during O2 evolution at high anodic potentials, a healing behavior was observed: The copper surface became passivated again after exposure of the broken layer in the air for a few minutes. The layered compound was extensively characterized by X-ray photoelectron spectroscopy and Raman spectroscopy. The decrease of O 1s/Cu 3p ratio and the increase of S 2p/Cu 3p and C 1s/Cu 3p ratios clearly showed the conversion of CuO into a copper-thiolate complex. The Raman spectrum of the Cu-octanethiolate compound shows a considerable enhancement of all bands as compared to a self-assembled monolayer. The sharpness of the most prominent peaks indicates the high crystallinity of the alkyl chains in the layered compound. Density functional theory calculations showed that the alkyl chains lie nearly perpendicular to the layer of Cu atoms. The calculation of Raman vibrational frequencies using density functional perturbation theory allowed an unambiguous assignment of experimental Raman peaks.Fil: Arisnabarreta, Nicolás. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Paredes Olivera, Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Cometto, Fernando Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Patrito, Eduardo Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaAmerican Chemical Society2019-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/124514Arisnabarreta, Nicolás; Paredes Olivera, Patricia; Cometto, Fernando Pablo; Patrito, Eduardo Martin; Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films; American Chemical Society; Journal of Physical Chemistry C; 123; 28; 6-2019; 17283-172951932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.9b03264info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpcc.9b03264info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:04:50Zoai:ri.conicet.gov.ar:11336/124514instacron: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 10:04:50.484CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films
title Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films
spellingShingle Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films
Arisnabarreta, Nicolás
ALKANETHIOLS
CU
LAMELLAR STRUCTURES
ELECTROCHEMISTRY
title_short Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films
title_full Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films
title_fullStr Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films
title_full_unstemmed Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films
title_sort Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films
dc.creator.none.fl_str_mv Arisnabarreta, Nicolás
Paredes Olivera, Patricia
Cometto, Fernando Pablo
Patrito, Eduardo Martin
author Arisnabarreta, Nicolás
author_facet Arisnabarreta, Nicolás
Paredes Olivera, Patricia
Cometto, Fernando Pablo
Patrito, Eduardo Martin
author_role author
author2 Paredes Olivera, Patricia
Cometto, Fernando Pablo
Patrito, Eduardo Martin
author2_role author
author
author
dc.subject.none.fl_str_mv ALKANETHIOLS
CU
LAMELLAR STRUCTURES
ELECTROCHEMISTRY
topic ALKANETHIOLS
CU
LAMELLAR STRUCTURES
ELECTROCHEMISTRY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We investigated the conversion of electrochemically grown CuO into copper-alkanethiolate lamellar structures supported on a Cu substrate upon immersion in solutions of n-alkanethiols. After considering different preparation conditions (alkyl chain length, thiol concentration, and type of solvent), we found that the oxide can be rapidly converted into compact and highly passivating lamellar layers in 1-octanethiolate/0.1 M NaOH forming solutions. Alkaline forming solutions play a key role in favoring the conversion of CuO into the lamellar compound vs the competing mechanism in which the oxide is reduced and the thiolates are oxidized to disulfides. The oxide conversion into the layered structure is incomplete for both short and long alkanethiols, and it is almost complete in the case of 1-octanethiol. The use of less polar solvents such as ethanol or n-hexane is much less effective in producing layered Cu-thiolates. Spectroscopic ellipsometry measurements showed that 10-nm-thick CuO is converted into a 100-nm-thick lamellar compound, which corresponds to around 40 lamellae. After the breakage of the layers during O2 evolution at high anodic potentials, a healing behavior was observed: The copper surface became passivated again after exposure of the broken layer in the air for a few minutes. The layered compound was extensively characterized by X-ray photoelectron spectroscopy and Raman spectroscopy. The decrease of O 1s/Cu 3p ratio and the increase of S 2p/Cu 3p and C 1s/Cu 3p ratios clearly showed the conversion of CuO into a copper-thiolate complex. The Raman spectrum of the Cu-octanethiolate compound shows a considerable enhancement of all bands as compared to a self-assembled monolayer. The sharpness of the most prominent peaks indicates the high crystallinity of the alkyl chains in the layered compound. Density functional theory calculations showed that the alkyl chains lie nearly perpendicular to the layer of Cu atoms. The calculation of Raman vibrational frequencies using density functional perturbation theory allowed an unambiguous assignment of experimental Raman peaks.
Fil: Arisnabarreta, Nicolás. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Paredes Olivera, Patricia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Cometto, Fernando Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Patrito, Eduardo Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description We investigated the conversion of electrochemically grown CuO into copper-alkanethiolate lamellar structures supported on a Cu substrate upon immersion in solutions of n-alkanethiols. After considering different preparation conditions (alkyl chain length, thiol concentration, and type of solvent), we found that the oxide can be rapidly converted into compact and highly passivating lamellar layers in 1-octanethiolate/0.1 M NaOH forming solutions. Alkaline forming solutions play a key role in favoring the conversion of CuO into the lamellar compound vs the competing mechanism in which the oxide is reduced and the thiolates are oxidized to disulfides. The oxide conversion into the layered structure is incomplete for both short and long alkanethiols, and it is almost complete in the case of 1-octanethiol. The use of less polar solvents such as ethanol or n-hexane is much less effective in producing layered Cu-thiolates. Spectroscopic ellipsometry measurements showed that 10-nm-thick CuO is converted into a 100-nm-thick lamellar compound, which corresponds to around 40 lamellae. After the breakage of the layers during O2 evolution at high anodic potentials, a healing behavior was observed: The copper surface became passivated again after exposure of the broken layer in the air for a few minutes. The layered compound was extensively characterized by X-ray photoelectron spectroscopy and Raman spectroscopy. The decrease of O 1s/Cu 3p ratio and the increase of S 2p/Cu 3p and C 1s/Cu 3p ratios clearly showed the conversion of CuO into a copper-thiolate complex. The Raman spectrum of the Cu-octanethiolate compound shows a considerable enhancement of all bands as compared to a self-assembled monolayer. The sharpness of the most prominent peaks indicates the high crystallinity of the alkyl chains in the layered compound. Density functional theory calculations showed that the alkyl chains lie nearly perpendicular to the layer of Cu atoms. The calculation of Raman vibrational frequencies using density functional perturbation theory allowed an unambiguous assignment of experimental Raman peaks.
publishDate 2019
dc.date.none.fl_str_mv 2019-06
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/11336/124514
Arisnabarreta, Nicolás; Paredes Olivera, Patricia; Cometto, Fernando Pablo; Patrito, Eduardo Martin; Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films; American Chemical Society; Journal of Physical Chemistry C; 123; 28; 6-2019; 17283-17295
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/124514
identifier_str_mv Arisnabarreta, Nicolás; Paredes Olivera, Patricia; Cometto, Fernando Pablo; Patrito, Eduardo Martin; Growth of Layered Copper-Alkanethiolate Frameworks from Thin Anodic Copper Oxide Films; American Chemical Society; Journal of Physical Chemistry C; 123; 28; 6-2019; 17283-17295
1932-7447
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.9b03264
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpcc.9b03264
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
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score 13.070432

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