Highly Efficient Binuclear Ruthenium Catalyst for Water Oxidation

<p> Water splitting is one of the key steps in the conversion of sunlight into a usable renewable energy carrier such as dihydrogen or more complex chemical fuels. Developing rugged and highly efficient catalysts for the oxidative part of water splitting, the water oxidation reaction generatin...

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Detalles Bibliográficos
Autores: Sander, Anett C., Maji, Somnath, Francàs, Laia, Böhnisch, Torben, S. Dechert, Sebastian, Llobet, Antoni, Meyer, Franc
Tipo de recurso: artículo
Fecha de publicación:2015
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:2072/305796
Acceso en línea:http://hdl.handle.net/2072/305796
https://doi.org/10.1002/cssc.201403344
Access Level:acceso abierto
Palabra clave:artificial photosynthesi
binuclear complexes
oxygen evolving complex
ruthenium
water oxidation catalysis
Descripción
Sumario:<p> Water splitting is one of the key steps in the conversion of sunlight into a usable renewable energy carrier such as dihydrogen or more complex chemical fuels. Developing rugged and highly efficient catalysts for the oxidative part of water splitting, the water oxidation reaction generating dioxygen, is a major challenge in the field. Herein, we introduce a new, and rationally designed, pyrazolate-based diruthenium complex with the highest activity in water oxidation catalysis for binuclear systems reported to date. Single-crystal X-ray diffraction showed favorable preorganization of the metal ions, well suited for binding two water molecules at a distance adequate for O<img alt="[BOND]" height="6" src="file:///C:/Users/nmas/AppData/Local/Temp/msohtmlclip1/01/clip_image001.gif" width="17" />O bond formation; redox titrations as well as spectroelectrochemistry allowed characterization of the system in several oxidation states. Low oxidation potentials reflect the trianionic character of the elaborate compartmental pyrazolate ligand furnished with peripheral carboxylate groups. Water oxidation has been mediated both by a chemical oxidant (CeIV)&mdash;by means of manometry and a Clark electrode for monitoring the dioxygen production&mdash;and electrochemically with impressive activities.</p>