Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction

Autores
Calderon, Cecilia Andrea; Ojeda, Claudio; Macagno, Vicente Antonio; Paredes Olivera, Patricia; Patrito, Eduardo Martin
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The interaction of 1-octanethiol, 1,8-octanedithiol, 1-hexadecanethiol, and 16-mercaptohexadecanoic acid with polycrystalline copper surfaces was investigated comparatively using forming solutions with polar (0.05 M NaOH solution) and apolar (n-hexane) solvents. The thiol layers were formed on the freshly chemically polished copper surface as well as on the anodically oxidized surface. The effects of the alkanethiol chain length and terminal group on the blocking properties of the surface were investigated. We show for the first time that compact monolayers and multilayers can be obtained from an alkaline forming solution. Copper oxides are completely reduced in the alkaline forming solution for all of the thiols investigated after an immersion time of 45 min. On the contrary, the presence of a surface oxide was always detected after the formation of the thiol layer in the n-hexane solution. The mechanism of Cu 2O reduction by thiols was investigated by means of density functional theory calculations. The surface reactions involve the protonation of the surface oxygen atoms of the oxide which act as Lewis base sites. In the alkaline electrolyte, the proton transfer involves the water molecules of the solvent, whereas in the n-hexane solution the proton transfer involves the -SH group of the alkanethiol. The surface reactions are not the rate limiting step because they have very low activation energy barriers. The higher reduction rate observed in the alkaline thiol solutions is due to the high concentration of the reacting water molecules, whereas the lower reaction rate in the n-hexane solutions correlates with the lower concentration of the reactant alkanethiol molecules.
Fil: Calderon, Cecilia Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. 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: Ojeda, Claudio. 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: Macagno, Vicente Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad Presidencia; Argentina. 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: 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
Copper
Oxide
Alkanethiol
Dft
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:11336/70466
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/70466
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reductionCalderon, Cecilia AndreaOjeda, ClaudioMacagno, Vicente AntonioParedes Olivera, PatriciaPatrito, Eduardo MartinCopperOxideAlkanethiolDfthttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The interaction of 1-octanethiol, 1,8-octanedithiol, 1-hexadecanethiol, and 16-mercaptohexadecanoic acid with polycrystalline copper surfaces was investigated comparatively using forming solutions with polar (0.05 M NaOH solution) and apolar (n-hexane) solvents. The thiol layers were formed on the freshly chemically polished copper surface as well as on the anodically oxidized surface. The effects of the alkanethiol chain length and terminal group on the blocking properties of the surface were investigated. We show for the first time that compact monolayers and multilayers can be obtained from an alkaline forming solution. Copper oxides are completely reduced in the alkaline forming solution for all of the thiols investigated after an immersion time of 45 min. On the contrary, the presence of a surface oxide was always detected after the formation of the thiol layer in the n-hexane solution. The mechanism of Cu 2O reduction by thiols was investigated by means of density functional theory calculations. The surface reactions involve the protonation of the surface oxygen atoms of the oxide which act as Lewis base sites. In the alkaline electrolyte, the proton transfer involves the water molecules of the solvent, whereas in the n-hexane solution the proton transfer involves the -SH group of the alkanethiol. The surface reactions are not the rate limiting step because they have very low activation energy barriers. The higher reduction rate observed in the alkaline thiol solutions is due to the high concentration of the reacting water molecules, whereas the lower reaction rate in the n-hexane solutions correlates with the lower concentration of the reactant alkanethiol molecules.Fil: Calderon, Cecilia Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. 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: Ojeda, Claudio. 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: Macagno, Vicente Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad Presidencia; Argentina. 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: 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 Society2010-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/70466Calderon, Cecilia Andrea; Ojeda, Claudio; Macagno, Vicente Antonio; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction; American Chemical Society; Journal of Physical Chemistry C; 114; 9; 3-2010; 3945-39571932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp9045148info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp9045148info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:46:52Zoai:ri.conicet.gov.ar:11336/70466instacron: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 10:46:52.524CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction
title Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction
spellingShingle Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction
Calderon, Cecilia Andrea
Copper
Oxide
Alkanethiol
Dft
title_short Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction
title_full Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction
title_fullStr Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction
title_full_unstemmed Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction
title_sort Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction
dc.creator.none.fl_str_mv Calderon, Cecilia Andrea
Ojeda, Claudio
Macagno, Vicente Antonio
Paredes Olivera, Patricia
Patrito, Eduardo Martin
author Calderon, Cecilia Andrea
author_facet Calderon, Cecilia Andrea
Ojeda, Claudio
Macagno, Vicente Antonio
Paredes Olivera, Patricia
Patrito, Eduardo Martin
author_role author
author2 Ojeda, Claudio
Macagno, Vicente Antonio
Paredes Olivera, Patricia
Patrito, Eduardo Martin
author2_role author
author
author
author
dc.subject.none.fl_str_mv Copper
Oxide
Alkanethiol
Dft
topic Copper
Oxide
Alkanethiol
Dft
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 interaction of 1-octanethiol, 1,8-octanedithiol, 1-hexadecanethiol, and 16-mercaptohexadecanoic acid with polycrystalline copper surfaces was investigated comparatively using forming solutions with polar (0.05 M NaOH solution) and apolar (n-hexane) solvents. The thiol layers were formed on the freshly chemically polished copper surface as well as on the anodically oxidized surface. The effects of the alkanethiol chain length and terminal group on the blocking properties of the surface were investigated. We show for the first time that compact monolayers and multilayers can be obtained from an alkaline forming solution. Copper oxides are completely reduced in the alkaline forming solution for all of the thiols investigated after an immersion time of 45 min. On the contrary, the presence of a surface oxide was always detected after the formation of the thiol layer in the n-hexane solution. The mechanism of Cu 2O reduction by thiols was investigated by means of density functional theory calculations. The surface reactions involve the protonation of the surface oxygen atoms of the oxide which act as Lewis base sites. In the alkaline electrolyte, the proton transfer involves the water molecules of the solvent, whereas in the n-hexane solution the proton transfer involves the -SH group of the alkanethiol. The surface reactions are not the rate limiting step because they have very low activation energy barriers. The higher reduction rate observed in the alkaline thiol solutions is due to the high concentration of the reacting water molecules, whereas the lower reaction rate in the n-hexane solutions correlates with the lower concentration of the reactant alkanethiol molecules.
Fil: Calderon, Cecilia Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. 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: Ojeda, Claudio. 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: Macagno, Vicente Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Unidad Presidencia; Argentina. 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: 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 The interaction of 1-octanethiol, 1,8-octanedithiol, 1-hexadecanethiol, and 16-mercaptohexadecanoic acid with polycrystalline copper surfaces was investigated comparatively using forming solutions with polar (0.05 M NaOH solution) and apolar (n-hexane) solvents. The thiol layers were formed on the freshly chemically polished copper surface as well as on the anodically oxidized surface. The effects of the alkanethiol chain length and terminal group on the blocking properties of the surface were investigated. We show for the first time that compact monolayers and multilayers can be obtained from an alkaline forming solution. Copper oxides are completely reduced in the alkaline forming solution for all of the thiols investigated after an immersion time of 45 min. On the contrary, the presence of a surface oxide was always detected after the formation of the thiol layer in the n-hexane solution. The mechanism of Cu 2O reduction by thiols was investigated by means of density functional theory calculations. The surface reactions involve the protonation of the surface oxygen atoms of the oxide which act as Lewis base sites. In the alkaline electrolyte, the proton transfer involves the water molecules of the solvent, whereas in the n-hexane solution the proton transfer involves the -SH group of the alkanethiol. The surface reactions are not the rate limiting step because they have very low activation energy barriers. The higher reduction rate observed in the alkaline thiol solutions is due to the high concentration of the reacting water molecules, whereas the lower reaction rate in the n-hexane solutions correlates with the lower concentration of the reactant alkanethiol molecules.
publishDate 2010
dc.date.none.fl_str_mv 2010-03
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/11336/70466
Calderon, Cecilia Andrea; Ojeda, Claudio; Macagno, Vicente Antonio; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction; American Chemical Society; Journal of Physical Chemistry C; 114; 9; 3-2010; 3945-3957
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/70466
identifier_str_mv Calderon, Cecilia Andrea; Ojeda, Claudio; Macagno, Vicente Antonio; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Interaction of oxidized copper surfaces with alkanethiols in organic and aqueous solvents. the mechanism of Cu2O reduction; American Chemical Society; Journal of Physical Chemistry C; 114; 9; 3-2010; 3945-3957
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/jp9045148
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp9045148
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
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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