Supramolecular Water Oxidation with Ru-bda-Based Catalysts

<p> Extremely slow and extremely fast new water oxidation catalysts based on the Ru&ndash;bda (bda=2,2&prime;-bipyridine-6,6&prime;-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles&thinsp;s&minus;1, respectively. Detailed analys...

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Detalhes bibliográficos
Autores: Richmond, Craij J., Matheu, Roc, Poater, Albert, Falivene, Laura, . Benet-Buchholz, Jordi, Sala, Xavier, Cavallo, Luigi, Llobet, Antoni
Tipo de documento: artigo
Data de publicação:2014
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositório:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/305878
Acesso em linha:http://hdl.handle.net/2072/305878
https://doi.org/10.1002/chem.201405144
Access Level:Acceso aberto
Palavra-chave:DFT calculations
redox catalysis
ruthenium
supramolecular chemistry
water splitting
Descrição
Resumo:<p> Extremely slow and extremely fast new water oxidation catalysts based on the Ru&ndash;bda (bda=2,2&prime;-bipyridine-6,6&prime;-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles&thinsp;s&minus;1, respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system &pi;-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts.</p>