On the Electrochemical Deposition and Dissolution of Divalent Metal Ions

Autores
Pinto, Leandro M. C.; Quaino, Paola Monica; Santos, Elizabeth del Carmen; Schmickler, Wolfgang
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The deposition of Cu²+ and Zn²+ from aqueous solution has been investigated by a combination of classical molecular dynamics, density functional theory, and a theory developed by the authors. For both cases, the reaction proceeds through two one-electron steps. The monovalent ions can get close to the electrode surface without losing hydration energy, while the divalent ions, which have a stronger solvation sheath, cannot. The 4s orbital of Cu interacts strongly with the sp band and more weakly with the d band of the copper surface, while the Zn 4s orbital couples only to the sp band of Zn. At the equilibrium potential for the overall reaction, the energy of the intermediate Cu+ ion is only a little higher than that of the divalent ion, so that the first electron transfer can occur in an outer-sphere mode. In contrast, the energy of the Zn+ ion lies too high for a simple outer-sphere reaction to be favorable; in accord with experimental data this suggests that this step is affected by anions.
Fil: Pinto, Leandro M. C.. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Quaino, Paola Monica. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
Fil: Santos, Elizabeth del Carmen. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina. 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. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina
Fil: Schmickler, Wolfgang. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania
Materia
Electrochemical Deposition
Dissolution
Divalent Metal Ions
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:11336/31437
Acceder
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spelling On the Electrochemical Deposition and Dissolution of Divalent Metal IonsPinto, Leandro M. C.Quaino, Paola MonicaSantos, Elizabeth del CarmenSchmickler, WolfgangElectrochemical DepositionDissolutionDivalent Metal Ionshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The deposition of Cu²+ and Zn²+ from aqueous solution has been investigated by a combination of classical molecular dynamics, density functional theory, and a theory developed by the authors. For both cases, the reaction proceeds through two one-electron steps. The monovalent ions can get close to the electrode surface without losing hydration energy, while the divalent ions, which have a stronger solvation sheath, cannot. The 4s orbital of Cu interacts strongly with the sp band and more weakly with the d band of the copper surface, while the Zn 4s orbital couples only to the sp band of Zn. At the equilibrium potential for the overall reaction, the energy of the intermediate Cu+ ion is only a little higher than that of the divalent ion, so that the first electron transfer can occur in an outer-sphere mode. In contrast, the energy of the Zn+ ion lies too high for a simple outer-sphere reaction to be favorable; in accord with experimental data this suggests that this step is affected by anions.Fil: Pinto, Leandro M. C.. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: Quaino, Paola Monica. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Santos, Elizabeth del Carmen. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina. 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. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; ArgentinaFil: Schmickler, Wolfgang. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; AlemaniaWiley VCH Verlag2014-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/31437Santos, Elizabeth del Carmen; Quaino, Paola Monica; Pinto, Leandro M. C.; Schmickler, Wolfgang; On the Electrochemical Deposition and Dissolution of Divalent Metal Ions; Wiley VCH Verlag; Chemphyschem; 15; 1; 1-2014; 132-1381439-4235CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.201300856info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/cphc.201300856/abstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:01:32Zoai:ri.conicet.gov.ar:11336/31437instacron: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 10:01:33.241CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv On the Electrochemical Deposition and Dissolution of Divalent Metal Ions
title On the Electrochemical Deposition and Dissolution of Divalent Metal Ions
spellingShingle On the Electrochemical Deposition and Dissolution of Divalent Metal Ions
Pinto, Leandro M. C.
Electrochemical Deposition
Dissolution
Divalent Metal Ions
title_short On the Electrochemical Deposition and Dissolution of Divalent Metal Ions
title_full On the Electrochemical Deposition and Dissolution of Divalent Metal Ions
title_fullStr On the Electrochemical Deposition and Dissolution of Divalent Metal Ions
title_full_unstemmed On the Electrochemical Deposition and Dissolution of Divalent Metal Ions
title_sort On the Electrochemical Deposition and Dissolution of Divalent Metal Ions
dc.creator.none.fl_str_mv Pinto, Leandro M. C.
Quaino, Paola Monica
Santos, Elizabeth del Carmen
Schmickler, Wolfgang
author Pinto, Leandro M. C.
author_facet Pinto, Leandro M. C.
Quaino, Paola Monica
Santos, Elizabeth del Carmen
Schmickler, Wolfgang
author_role author
author2 Quaino, Paola Monica
Santos, Elizabeth del Carmen
Schmickler, Wolfgang
author2_role author
author
author
dc.subject.none.fl_str_mv Electrochemical Deposition
Dissolution
Divalent Metal Ions
topic Electrochemical Deposition
Dissolution
Divalent Metal Ions
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 deposition of Cu²+ and Zn²+ from aqueous solution has been investigated by a combination of classical molecular dynamics, density functional theory, and a theory developed by the authors. For both cases, the reaction proceeds through two one-electron steps. The monovalent ions can get close to the electrode surface without losing hydration energy, while the divalent ions, which have a stronger solvation sheath, cannot. The 4s orbital of Cu interacts strongly with the sp band and more weakly with the d band of the copper surface, while the Zn 4s orbital couples only to the sp band of Zn. At the equilibrium potential for the overall reaction, the energy of the intermediate Cu+ ion is only a little higher than that of the divalent ion, so that the first electron transfer can occur in an outer-sphere mode. In contrast, the energy of the Zn+ ion lies too high for a simple outer-sphere reaction to be favorable; in accord with experimental data this suggests that this step is affected by anions.
Fil: Pinto, Leandro M. C.. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Quaino, Paola Monica. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
Fil: Santos, Elizabeth del Carmen. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina. 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. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina
Fil: Schmickler, Wolfgang. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania
description The deposition of Cu²+ and Zn²+ from aqueous solution has been investigated by a combination of classical molecular dynamics, density functional theory, and a theory developed by the authors. For both cases, the reaction proceeds through two one-electron steps. The monovalent ions can get close to the electrode surface without losing hydration energy, while the divalent ions, which have a stronger solvation sheath, cannot. The 4s orbital of Cu interacts strongly with the sp band and more weakly with the d band of the copper surface, while the Zn 4s orbital couples only to the sp band of Zn. At the equilibrium potential for the overall reaction, the energy of the intermediate Cu+ ion is only a little higher than that of the divalent ion, so that the first electron transfer can occur in an outer-sphere mode. In contrast, the energy of the Zn+ ion lies too high for a simple outer-sphere reaction to be favorable; in accord with experimental data this suggests that this step is affected by anions.
publishDate 2014
dc.date.none.fl_str_mv 2014-01
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/11336/31437
Santos, Elizabeth del Carmen; Quaino, Paola Monica; Pinto, Leandro M. C.; Schmickler, Wolfgang; On the Electrochemical Deposition and Dissolution of Divalent Metal Ions; Wiley VCH Verlag; Chemphyschem; 15; 1; 1-2014; 132-138
1439-4235
CONICET Digital
CONICET
url http://hdl.handle.net/11336/31437
identifier_str_mv Santos, Elizabeth del Carmen; Quaino, Paola Monica; Pinto, Leandro M. C.; Schmickler, Wolfgang; On the Electrochemical Deposition and Dissolution of Divalent Metal Ions; Wiley VCH Verlag; Chemphyschem; 15; 1; 1-2014; 132-138
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.201300856
info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/cphc.201300856/abstract
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
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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