Photocatalytic Water Oxidation by a Mixed-Valent MnIII3MnIVO3 Manganese Oxo Core that Mimics the Natural Oxygen-Evolving Center†
Dr. Rami Al-Oweini
ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorDr. Andrea Sartorel
ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorDr. Bassem S. Bassil
Jacobs University, School of Engineering and Science, P.O. Box 750561, 28725 Bremen (Germany) http://www.jacobs-university.de/ses/ukortz
Search for more papers by this authorDr. Mirco Natali
Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare, sez. di Ferrara via Fossato di Mortara 17–19, 44121 Ferrara (Italy)
Search for more papers by this authorDr. Serena Berardi
ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorCorresponding Author
Prof. Franco Scandola
Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare, sez. di Ferrara via Fossato di Mortara 17–19, 44121 Ferrara (Italy)
Franco Scandola, Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare, sez. di Ferrara via Fossato di Mortara 17–19, 44121 Ferrara (Italy)
Ulrich Kortz, Jacobs University, School of Engineering and Science, P.O. Box 750561, 28725 Bremen (Germany) http://www.jacobs-university.de/ses/ukortz
Marcella Bonchio, ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorCorresponding Author
Prof. Ulrich Kortz
Jacobs University, School of Engineering and Science, P.O. Box 750561, 28725 Bremen (Germany) http://www.jacobs-university.de/ses/ukortz
Franco Scandola, Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare, sez. di Ferrara via Fossato di Mortara 17–19, 44121 Ferrara (Italy)
Ulrich Kortz, Jacobs University, School of Engineering and Science, P.O. Box 750561, 28725 Bremen (Germany) http://www.jacobs-university.de/ses/ukortz
Marcella Bonchio, ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorCorresponding Author
Prof. Marcella Bonchio
ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Franco Scandola, Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare, sez. di Ferrara via Fossato di Mortara 17–19, 44121 Ferrara (Italy)
Ulrich Kortz, Jacobs University, School of Engineering and Science, P.O. Box 750561, 28725 Bremen (Germany) http://www.jacobs-university.de/ses/ukortz
Marcella Bonchio, ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorDr. Rami Al-Oweini
ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorDr. Andrea Sartorel
ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorDr. Bassem S. Bassil
Jacobs University, School of Engineering and Science, P.O. Box 750561, 28725 Bremen (Germany) http://www.jacobs-university.de/ses/ukortz
Search for more papers by this authorDr. Mirco Natali
Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare, sez. di Ferrara via Fossato di Mortara 17–19, 44121 Ferrara (Italy)
Search for more papers by this authorDr. Serena Berardi
ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorCorresponding Author
Prof. Franco Scandola
Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare, sez. di Ferrara via Fossato di Mortara 17–19, 44121 Ferrara (Italy)
Franco Scandola, Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare, sez. di Ferrara via Fossato di Mortara 17–19, 44121 Ferrara (Italy)
Ulrich Kortz, Jacobs University, School of Engineering and Science, P.O. Box 750561, 28725 Bremen (Germany) http://www.jacobs-university.de/ses/ukortz
Marcella Bonchio, ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorCorresponding Author
Prof. Ulrich Kortz
Jacobs University, School of Engineering and Science, P.O. Box 750561, 28725 Bremen (Germany) http://www.jacobs-university.de/ses/ukortz
Franco Scandola, Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare, sez. di Ferrara via Fossato di Mortara 17–19, 44121 Ferrara (Italy)
Ulrich Kortz, Jacobs University, School of Engineering and Science, P.O. Box 750561, 28725 Bremen (Germany) http://www.jacobs-university.de/ses/ukortz
Marcella Bonchio, ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorCorresponding Author
Prof. Marcella Bonchio
ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Franco Scandola, Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare, sez. di Ferrara via Fossato di Mortara 17–19, 44121 Ferrara (Italy)
Ulrich Kortz, Jacobs University, School of Engineering and Science, P.O. Box 750561, 28725 Bremen (Germany) http://www.jacobs-university.de/ses/ukortz
Marcella Bonchio, ITM-CNR and Dipartimento di Scienze Chimiche, Università di Padova via Marzolo 1, 35131 Padova (Italy) http://www.chimica.unipd.it/NanoMolCat
Search for more papers by this authorThis work was supported by the Italian MIUR (FIRB “NanoSolar” RBAP11C58Y, PRIN “Hi-Phuture” 2010N3T9M4_001) and by the Fondazione Cariparo (Nanomode, progetti di eccellenza 2010). The EU COST Action program (CM1003, CM1203, and CM1205) is gratefully acknowledged. U.K. thanks the German Science Foundation (DFG, KO-2288/20-1) and Jacobs University for research support. Figure 1 was generated with Diamond Version 3.2 (copyright Crystal Impact GbR).
Abstract
The functional core of oxygenic photosynthesis is in charge of catalytic water oxidation by a multi-redox MnIII/MnIV manifold that evolves through five electronic states (Si , where i=0–4). The synthetic model system of this catalytic cycle and of its S0→S4 intermediates is the expected turning point for artificial photosynthesis. The tetramanganese-substituted tungstosilicate [MnIII3MnIVO3(CH3COO)3(A-α-SiW9O34)]6− (Mn4POM) offers an unprecedented mimicry of the natural system in its reduced S0 state; it features a hybrid organic–inorganic coordination sphere and is anchored on a polyoxotungstate. Evidence for its photosynthetic properties when combined with [Ru(bpy)3]2+ and S2O82− is obtained by nanosecond laser flash photolysis; its S0→S1 transition within milliseconds and multiple-hole-accumulating properties were studied. Photocatalytic oxygen evolution is achieved in a buffered medium (pH 5) with a quantum efficiency of 1.7 %.
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