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A Self-Improved Water-Oxidation Catalyst: Is One Site Really Enough?

Authors

  • Isidoro López,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
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  • Dr. Mehmed Z. Ertem,

    1. Department of Chemistry, Brookhaven National Laboratory, Building 555A, Upton, NY 11973 (USA)
    2. Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520-8107 (USA)
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  • Dr. Somnath Maji,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
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  • Dr. Jordi Benet-Buchholz,

    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
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  • Anke Keidel,

    1. Technische Universität Berlin, Institut für Chemie, Sekr. PC14, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Dr. Uwe Kuhlmann,

    1. Technische Universität Berlin, Institut für Chemie, Sekr. PC14, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Prof. Peter Hildebrandt,

    1. Technische Universität Berlin, Institut für Chemie, Sekr. PC14, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Prof. Christopher J. Cramer,

    Corresponding author
    1. Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455-0431 (USA)
    • Christopher J. Cramer, Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455-0431 (USA)

      Victor S. Batista, Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520-8107 (USA)

      Antoni Llobet, Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)

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  • Prof. Victor S. Batista,

    Corresponding author
    1. Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520-8107 (USA)
    • Christopher J. Cramer, Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455-0431 (USA)

      Victor S. Batista, Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520-8107 (USA)

      Antoni Llobet, Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)

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  • Prof. Antoni Llobet

    Corresponding author
    1. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)
    • Christopher J. Cramer, Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455-0431 (USA)

      Victor S. Batista, Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520-8107 (USA)

      Antoni Llobet, Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain)

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  • Support from MINECO (CTQ2010–21497 and PRI-PIBIN-2011-1278), an FPU grant to I.L., and a Torres Quevedo contract to S.M. are gratefully acknowledged. Support has also been received from the Cluster of Excellence (UniCat) and the US Department of Energy (DOE) (Grant DE-SC0001423 to V.S.B.). M.Z.E. received funding from a Computational Materials and Chemical Sciences (CMCSN) project at Brookhaven National Laboratory under contract DE-AC02-98CH10886 with the US DOE and was supported by its Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences. C.J.C. acknowledges support from the US National Science Foundation (CHE-0952054).

Abstract

The homogeneous catalysis of water oxidation by transition-metal complexes has experienced spectacular development over the last five years. Practical energy-conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water-oxidation catalyst that is generated by self-assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water-oxidation catalyst that does not decompose over extended periods of time.

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