Single Electron Transfer Steps in Water Oxidation Catalysis. Redefining the Mechanistic Scenario
<p> The systematic computational study of the mechanism for water oxidation in four different complexes confirms the existence of an alternative mechanism for the O–O bond formation step to those previously reported: the single electron transfer–water nucleophilic attack (S...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2017 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2072/305775 |
| Acceso en línea: | http://hdl.handle.net/2072/305775 https://doi.org/10.1021/acscatal.6b03253 |
| Access Level: | acceso abierto |
| Palabra clave: | DFT first row transition metal complexes mechanism water oxidation water splitting |
| Sumario: | <p> The systematic computational study of the mechanism for water oxidation in four different complexes confirms the existence of an alternative mechanism for the O–O bond formation step to those previously reported: the single electron transfer–water nucleophilic attack (SET-WNA). The calculated mechanism relies on two SET steps and features the existence of an intermediate with a (HO···OH)− moiety in the vicinity of the metal center. It is operative in at least three representative copper based complexes and is the only option that explains the experimentally observed efficiency in two of them. The proposal of this reaction pathway redefines the mechanistic scenario and, importantly, generates a promising avenue for designing more efficient water oxidation catalysts based on first row transition metals.</p> |
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