Oxygen Reduction in Alkaline Media—a Discussion

We propose a complete reaction sequence for oxygen reduction in alkaline solutions, in which the first two steps occur in the outer sphere mode. The oxygen-oxygen bond is broken in the third step, which involves adsorption of OH, which is desorbed in the last step. We have investigated the sequence...

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Detalles Bibliográficos
Autores: Ignaczak, Anna, Nazmutdinov, Renat, Goduljan, Aleksej, de Campos Pinto, Leandro Moreira, Juarez, Fernanda, Quaino, Paola Monica, Belletti, Gustavo Daniel, Santos, Elizabeth del Carmen, Schmickler, Wolfgang
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2017
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/66108
Acceso en línea:http://hdl.handle.net/11336/66108
Access Level:acceso abierto
Palabra clave:Alkaline Fuel Cells
Dft
Electron Transfer
Oxygen Reduction
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/1.4
Descripción
Sumario:We propose a complete reaction sequence for oxygen reduction in alkaline solutions, in which the first two steps occur in the outer sphere mode. The oxygen-oxygen bond is broken in the third step, which involves adsorption of OH, which is desorbed in the last step. We have investigated the sequence by quantum-chemical methods and determined the energies of activation. Whether the reaction follows a four- or a two-electron mechanism, depends critically on the energy of adsorption of OH. We surmise that our mechanism holds on all electrodes which interact weakly with oxygen, in particular on gold, silver, and graphite. We explain, why Au(100) is a better catalyst than Au(111), why at high overpotentials the reaction on Au(100) reverts to a two-electron mechanism, and why this does not happen on silver. [Figure not available: see fulltext.]