A Molecular Approach to Self-Supported Cobalt-Substituted ZnO Materials as Remarkably Stable Electrocatalysts for Water Oxidation

Authors

  • Johannes Pfrommer,

    1. Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Dr. Michael Lublow,

    1. Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Anahita Azarpira,

    1. Institut für Solare Brennstoffe, Helmholtz Zentrum für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin (Germany)
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  • Dr. Caren Göbel,

    1. Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Marcel Lücke,

    1. Institut für Solare Brennstoffe, Helmholtz Zentrum für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin (Germany)
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  • Dr. Alexander Steigert,

    1. Institut für Solare Brennstoffe, Helmholtz Zentrum für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin (Germany)
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  • Martin Pogrzeba,

    1. Institut für Solare Brennstoffe, Helmholtz Zentrum für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin (Germany)
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  • Dr. Prashanth W. Menezes,

    1. Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Dr. Anna Fischer,

    Corresponding author
    1. Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)
    • Anna Fischer, Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)===

      Thomas Schedel-Niedrig, Institut für Solare Brennstoffe, Helmholtz Zentrum für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin (Germany)===

      Matthias Driess, Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)===

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  • Dr. Thomas Schedel-Niedrig,

    Corresponding author
    1. Institut für Solare Brennstoffe, Helmholtz Zentrum für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin (Germany)
    • Anna Fischer, Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)===

      Thomas Schedel-Niedrig, Institut für Solare Brennstoffe, Helmholtz Zentrum für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin (Germany)===

      Matthias Driess, Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)===

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  • Prof. Dr. Matthias Driess

    Corresponding author
    1. Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)
    • Anna Fischer, Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)===

      Thomas Schedel-Niedrig, Institut für Solare Brennstoffe, Helmholtz Zentrum für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin (Germany)===

      Matthias Driess, Department of Chemistry, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany)===

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  • We thank the BMBF (Light2Hydrogen project, L2H), the Cluster of Excellence UniCat (Exc 314 financed by the DFG and administered by the TU Berlin) and the DFG (SPP1613 project; SolarH2) for financial support. We thank the ZELMI team (TU Berlin) and especially Dr. Dirk Berger and Sören Selve for the FIB preparation and TEM micrographs of the Co:ZnO EPD layers.

Abstract

In regard to earth-abundant cobalt water oxidation catalysts, very recent findings show the reorganization of the materials to amorphous active phases under catalytic conditions. To further understand this concept, a unique cobalt-substituted crystalline zinc oxide (Co:ZnO) precatalyst has been synthesized by low-temperature solvolysis of molecular heterobimetallic Co4−xZnxO4 (x=1–3) precursors in benzylamine. Its electrophoretic deposition onto fluorinated tin oxide electrodes leads after oxidative conditioning to an amorphous self-supported water-oxidation electrocatalyst, which was observed by HR-TEM on FIB lamellas of the EPD layers. The Co-rich hydroxide-oxidic electrocatalyst performs at very low overpotentials (512 mV at pH 7; 330 mV at pH 12), while chronoamperometry shows a stable catalytic current over several hours.

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