Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase

Autores
Cometto, Fernando Pablo; Macagno, Vicente Antonio; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Ascolani, Hugo del Lujan; Zampieri, Guillermo Enrique
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We investigated the formation and stability of layers of methylthiolate prepared on the Au(111) surface by the method of immersion in an ethanolic solution of dimethyl disulfide (DMDS). The surface species were characterized by electrochemical reductive desorption and high-resolution photoelectron spectroscopy. Both techniques confirmed the formation of a methylthiolate monolayer at short immersion times (around 1 min). As the immersion time increased, the electrochemical experiments showed the disappearance of the methylthiolate reductive desorption current peak and the appearance of a current peak at ca. −0.9 V which was attributed to sulfur species. At long immersion times, the XPS measurements showed two main components for the S 2p signal: a component at ca. 161 eV which corresponds to atomic sulfur and a component at ca. 162 eV which we attributed to polysulfide species. We propose that the breakage of the S−C bond of methylthiolate is responsible for the appearance of sulfur species on the surface. Density functional theory (DFT) calculations were performed to identify the elementary steps that may lead to the decomposition of methylthiolate. We found that the cleavage of the S−C bond is only activated by the oxidative dehydrogenation of the methyl group of methylthiolate. Thio-oxymethylene, SCH2O, is the key intermediate leading to the breakage of the S−C bond because it decomposes into atomic sulfur and formaldehyde with an activation energy barrier of only 1.1 kcal/mol.
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: Macagno, Vicente Antonio. 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
Fil: Ascolani, Hugo del Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comision Nacional de Energia Atomica. Gerencia D/area Invest y Aplicaciones No Nucleares. Gerencia Física (cac). Grupo Superficies; Argentina
Fil: Zampieri, Guillermo Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comision Nacional de Energia Atomica. Gerencia D/area Invest y Aplicaciones No Nucleares. Gerencia Física (cac). Grupo Superficies; Argentina
Materia
SAMs
Alkanethiols
Gold
Cyclic voltammetry
XPS
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
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oai:ri.conicet.gov.ar:11336/279481
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution PhaseCometto, Fernando PabloMacagno, Vicente AntonioParedes Olivera, PatriciaPatrito, Eduardo MartinAscolani, Hugo del LujanZampieri, Guillermo EnriqueSAMsAlkanethiolsGoldCyclic voltammetryXPShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We investigated the formation and stability of layers of methylthiolate prepared on the Au(111) surface by the method of immersion in an ethanolic solution of dimethyl disulfide (DMDS). The surface species were characterized by electrochemical reductive desorption and high-resolution photoelectron spectroscopy. Both techniques confirmed the formation of a methylthiolate monolayer at short immersion times (around 1 min). As the immersion time increased, the electrochemical experiments showed the disappearance of the methylthiolate reductive desorption current peak and the appearance of a current peak at ca. −0.9 V which was attributed to sulfur species. At long immersion times, the XPS measurements showed two main components for the S 2p signal: a component at ca. 161 eV which corresponds to atomic sulfur and a component at ca. 162 eV which we attributed to polysulfide species. We propose that the breakage of the S−C bond of methylthiolate is responsible for the appearance of sulfur species on the surface. Density functional theory (DFT) calculations were performed to identify the elementary steps that may lead to the decomposition of methylthiolate. We found that the cleavage of the S−C bond is only activated by the oxidative dehydrogenation of the methyl group of methylthiolate. Thio-oxymethylene, SCH2O, is the key intermediate leading to the breakage of the S−C bond because it decomposes into atomic sulfur and formaldehyde with an activation energy barrier of only 1.1 kcal/mol.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; ArgentinaFil: Macagno, Vicente Antonio. 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; ArgentinaFil: Ascolani, Hugo del Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comision Nacional de Energia Atomica. Gerencia D/area Invest y Aplicaciones No Nucleares. Gerencia Física (cac). Grupo Superficies; ArgentinaFil: Zampieri, Guillermo Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comision Nacional de Energia Atomica. Gerencia D/area Invest y Aplicaciones No Nucleares. Gerencia Física (cac). Grupo Superficies; ArgentinaAmerican Chemical Society2010-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/279481Cometto, Fernando Pablo; Macagno, Vicente Antonio; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Ascolani, Hugo del Lujan; et al.; Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase; American Chemical Society; Journal of Physical Chemistry C; 114; 22; 5-2010; 10183-101941932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp912060einfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp912060einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-02-06T13:13:54Zoai:ri.conicet.gov.ar:11336/279481instacron: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:34982026-02-06 13:13:54.644CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase
title Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase
spellingShingle Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase
Cometto, Fernando Pablo
SAMs
Alkanethiols
Gold
Cyclic voltammetry
XPS
title_short Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase
title_full Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase
title_fullStr Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase
title_full_unstemmed Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase
title_sort Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase
dc.creator.none.fl_str_mv Cometto, Fernando Pablo
Macagno, Vicente Antonio
Paredes Olivera, Patricia
Patrito, Eduardo Martin
Ascolani, Hugo del Lujan
Zampieri, Guillermo Enrique
author Cometto, Fernando Pablo
author_facet Cometto, Fernando Pablo
Macagno, Vicente Antonio
Paredes Olivera, Patricia
Patrito, Eduardo Martin
Ascolani, Hugo del Lujan
Zampieri, Guillermo Enrique
author_role author
author2 Macagno, Vicente Antonio
Paredes Olivera, Patricia
Patrito, Eduardo Martin
Ascolani, Hugo del Lujan
Zampieri, Guillermo Enrique
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv SAMs
Alkanethiols
Gold
Cyclic voltammetry
XPS
topic SAMs
Alkanethiols
Gold
Cyclic voltammetry
XPS
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 formation and stability of layers of methylthiolate prepared on the Au(111) surface by the method of immersion in an ethanolic solution of dimethyl disulfide (DMDS). The surface species were characterized by electrochemical reductive desorption and high-resolution photoelectron spectroscopy. Both techniques confirmed the formation of a methylthiolate monolayer at short immersion times (around 1 min). As the immersion time increased, the electrochemical experiments showed the disappearance of the methylthiolate reductive desorption current peak and the appearance of a current peak at ca. −0.9 V which was attributed to sulfur species. At long immersion times, the XPS measurements showed two main components for the S 2p signal: a component at ca. 161 eV which corresponds to atomic sulfur and a component at ca. 162 eV which we attributed to polysulfide species. We propose that the breakage of the S−C bond of methylthiolate is responsible for the appearance of sulfur species on the surface. Density functional theory (DFT) calculations were performed to identify the elementary steps that may lead to the decomposition of methylthiolate. We found that the cleavage of the S−C bond is only activated by the oxidative dehydrogenation of the methyl group of methylthiolate. Thio-oxymethylene, SCH2O, is the key intermediate leading to the breakage of the S−C bond because it decomposes into atomic sulfur and formaldehyde with an activation energy barrier of only 1.1 kcal/mol.
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: Macagno, Vicente Antonio. 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
Fil: Ascolani, Hugo del Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comision Nacional de Energia Atomica. Gerencia D/area Invest y Aplicaciones No Nucleares. Gerencia Física (cac). Grupo Superficies; Argentina
Fil: Zampieri, Guillermo Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comision Nacional de Energia Atomica. Gerencia D/area Invest y Aplicaciones No Nucleares. Gerencia Física (cac). Grupo Superficies; Argentina
description We investigated the formation and stability of layers of methylthiolate prepared on the Au(111) surface by the method of immersion in an ethanolic solution of dimethyl disulfide (DMDS). The surface species were characterized by electrochemical reductive desorption and high-resolution photoelectron spectroscopy. Both techniques confirmed the formation of a methylthiolate monolayer at short immersion times (around 1 min). As the immersion time increased, the electrochemical experiments showed the disappearance of the methylthiolate reductive desorption current peak and the appearance of a current peak at ca. −0.9 V which was attributed to sulfur species. At long immersion times, the XPS measurements showed two main components for the S 2p signal: a component at ca. 161 eV which corresponds to atomic sulfur and a component at ca. 162 eV which we attributed to polysulfide species. We propose that the breakage of the S−C bond of methylthiolate is responsible for the appearance of sulfur species on the surface. Density functional theory (DFT) calculations were performed to identify the elementary steps that may lead to the decomposition of methylthiolate. We found that the cleavage of the S−C bond is only activated by the oxidative dehydrogenation of the methyl group of methylthiolate. Thio-oxymethylene, SCH2O, is the key intermediate leading to the breakage of the S−C bond because it decomposes into atomic sulfur and formaldehyde with an activation energy barrier of only 1.1 kcal/mol.
publishDate 2010
dc.date.none.fl_str_mv 2010-05
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/11336/279481
Cometto, Fernando Pablo; Macagno, Vicente Antonio; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Ascolani, Hugo del Lujan; et al.; Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase; American Chemical Society; Journal of Physical Chemistry C; 114; 22; 5-2010; 10183-10194
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/279481
identifier_str_mv Cometto, Fernando Pablo; Macagno, Vicente Antonio; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Ascolani, Hugo del Lujan; et al.; Decomposition of Methylthiolate Monolayers on Au(111) Prepared from Dimethyl Disulfide in Solution Phase; American Chemical Society; Journal of Physical Chemistry C; 114; 22; 5-2010; 10183-10194
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/url/https://pubs.acs.org/doi/10.1021/jp912060e
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp912060e
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
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 13.106097

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