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Nanostructured Manganese Oxide Supported on Carbon Nanotubes for Electrocatalytic Water Splitting

Authors

  • Katharina Mette,

    1. Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Arno Bergmann,

    1. Department of Chemistry, Chemical and Materials Engineering Division, The Electrochemical Energy, Catalysis and Materials Science Laboratory, Technische Universität Berlin, Strasse des 17. Juni 124, 10623 Berlin (Germany)
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  • Dr. Jean-Philippe Tessonnier,

    Corresponding author
    1. Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
    2. Present address: Department of Chemical Engineering, University of Delaware, 150 Academy Street, Newark, DE 19716 (USA)
    • Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Dr. Michael Hävecker,

    1. Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
    2. Present address: Division Solar Energy Research, Elektronenspeicherring BESSY II, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Str. 15, 12489 Berlin (Germany)
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  • Dr. Lide Yao,

    1. Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Prof. Dr. Thorsten Ressler,

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

    1. Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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  • Prof. Dr. Peter Strasser,

    Corresponding author
    1. Department of Chemistry, Chemical and Materials Engineering Division, The Electrochemical Energy, Catalysis and Materials Science Laboratory, Technische Universität Berlin, Strasse des 17. Juni 124, 10623 Berlin (Germany)
    • Department of Chemistry, Chemical and Materials Engineering Division, The Electrochemical Energy, Catalysis and Materials Science Laboratory, Technische Universität Berlin, Strasse des 17. Juni 124, 10623 Berlin (Germany)
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  • Dr. Malte Behrens

    Corresponding author
    1. Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
    • Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany), Fax: (+49) 30-8413-4405
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Abstract

Incipient wetness impregnation and a novel deposition symproportionation precipitation were used for the preparation of MnOx/CNT electrocatalysts for efficient water splitting. Nanostructured manganese oxides have been dispersed on commercial carbon nanotubes as a result of both preparation methods. A strong influence of the preparation history on the electrocatalytic performance was observed. The as-prepared state of a 6.5 wt. % MnOx/CNT sample could be comprehensively characterized by comparison to an unsupported MnOx reference sample. Various characterization techniques revealed distinct differences in the oxidation state of the Mn centers in the as-prepared samples as a result of the two different preparation methods. As expected, the oxidation state is higher and near +4 for the symproportionated MnOx compared to the impregnated sample, where +2 was found. In both cases an easy adjustability of the oxidation state of Mn by post-treatment of the catalysts was observed as a function of oxygen partial pressure and temperature. Similar adjustments of the oxidation state are also expected to happen under water splitting conditions. In particular, the 5 wt. % MnO/CNT sample obtained by conventional impregnation was identified as a promising catalytic anode material for water electrolysis at neutral pH showing high activity and stability. Importantly, this catalytic material is comparable to state-of-art MnOx catalyst operating in strongly alkaline solutions and, therefore, offers advantages for hydrogen production from waste and sea water under neutral, hence, environmentally benign conditions.

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