Spin effects in oxygen electrocatalysis: a discussion
The reduction of molecular oxygen in triplet and singlet spin states at metal electrodes is analyzed in the framework of quantum mechanical theory of charge transfer. Both outer- and inner-sphere mechanism is considered. Singlet oxygen is argued to be considerably more active in electron transfer pr...
| Autores: | , , |
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| Formato: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2013 |
| País: | Argentina |
| Recursos: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/25372 |
| Acesso em linha: | http://hdl.handle.net/11336/25372 |
| Access Level: | acceso abierto |
| Palavra-chave: | Electron Transfer Quantum Mechanical Theory Electrocatalysis Oxygen Reduction Spin Effects Singlet Molecular Oxygen https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Resumo: | The reduction of molecular oxygen in triplet and singlet spin states at metal electrodes is analyzed in the framework of quantum mechanical theory of charge transfer. Both outer- and inner-sphere mechanism is considered. Singlet oxygen is argued to be considerably more active in electron transfer processes. It is demonstrated that spin polarization may play a catalytic role, parallel with the effect of overlap of reactant orbitals with the d-band of a metal electrode. Our model is based on two main assumptions: (i) some metal surfaces favor the existence of singlet molecular oxygen in adsorbed state; and (ii) short-living singlet O2 molecules may appear as intermediates at some reduction steps. These two reasons are expected to increase the local concentration of active singlet molecular oxygen in reaction layer. |
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