Supramolecular Water Oxidation with Ru–bda‐Based Catalysts |
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| Authors: | Craig J Richmond Roc Matheu Dr Albert Poater Dr Laura Falivene Dr Jordi Benet‐Buchholz Dr Xavier Sala Prof Luigi Cavallo Prof Antoni Llobet |
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| Institution: | 1. Institute of Chemical Research of Catalonia (ICIQ), Av. Pa?sos Catalans 16‐43007, Tarragona (Spain);2. Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus de Motilivi, 17071 Girona (Spain);3. KAUST Catalysis Center, Chemical and Life Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal 23955‐6900 (Saudi Arabia);4. Departament de Química, Universitat Autonoma de Barcelona, Cerdanyola del Vallès, 08193 Barcelona (Spain) |
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| Abstract: | Extremely slow and extremely fast new water oxidation catalysts based on the Ru–bda (bda=2,2′‐bipyridine‐6,6′‐dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s?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 π‐stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts. |
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| Keywords: | DFT calculations redox catalysis ruthenium supramolecular chemistry water splitting |
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