On the Electrochemical Deposition and Dissolution of Divalent Metal Ions
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 t...
| Authors: | ; ; ; |
|---|---|
| Format: | Article |
| Status: | Published version |
| Publication date: | 2014 |
| Country: | Argentina |
| Institution: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repository: | CONICET Digital (CONICET) |
| Language: | English |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/31437 |
| Online Access: | http://hdl.handle.net/11336/31437 |
| Access Level: | Open access |
| Keyword: | Electrochemical Deposition Dissolution Divalent Metal Ions https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| _version_ | 1878403528287846401 |
|---|---|
| author | Pinto, Leandro M. C. |
| author2 | Quaino, Paola Monica Santos, Elizabeth del Carmen Schmickler, Wolfgang |
| author2_role | author author author |
| author_browse | Pinto, Leandro M. C. Quaino, Paola Monica Santos, Elizabeth del Carmen Schmickler, Wolfgang |
| author_facet | Pinto, Leandro M. C. Quaino, Paola Monica Santos, Elizabeth del Carmen Schmickler, Wolfgang |
| author_role | author |
| collection | CONICET Digital (CONICET) |
| 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. |
| eu_rights_str_mv | openAccess |
| format | article |
| id | AR_8f2d3bc4425dd0aa862addefa934400a |
| 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 |
| institution | Consejo Nacional de Investigaciones Científicas y Técnicas |
| instname_str | Consejo Nacional de Investigaciones Científicas y Técnicas |
| language | eng |
| network_acronym_str | AR |
| network_name_str | Argentina |
| oai_identifier_str | oai:ri.conicet.gov.ar:11336/31437 |
| publishDate | 2014 |
| publishDateSort | 2014 |
| publisher | Wiley VCH Verlag |
| publisherStr | Wiley VCH Verlag |
| reponame_str | CONICET Digital (CONICET) |
| spelling | On the Electrochemical Deposition and Dissolution of Divalent Metal Ions Pinto, Leandro M. C. Quaino, Paola Monica Santos, Elizabeth del Carmen Schmickler, Wolfgang Electrochemical Deposition Dissolution Divalent Metal Ions https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 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 Wiley VCH Verlag 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 |
| spellingShingle | On the Electrochemical Deposition and Dissolution of Divalent Metal Ions Pinto, Leandro M. C. Electrochemical Deposition Dissolution Divalent Metal Ions https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| status_str | publishedVersion |
| title | 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_short | On the Electrochemical Deposition and Dissolution of Divalent Metal Ions |
| title_sort | On the Electrochemical Deposition and Dissolution of Divalent Metal Ions |
| topic | Electrochemical Deposition Dissolution Divalent Metal Ions https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| topic_facet | Electrochemical Deposition Dissolution Divalent Metal Ions https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| url | http://hdl.handle.net/11336/31437 |