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Molecular Mixed-Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts

Authors

  • Sandy Suseno,

    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 127-72, Pasadena, California 91125 (USA)
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  • Dr. Charles C. L. McCrory,

    1. Joint Center for Artificial Photosynthesis, Pasadena, California 91125 (USA)
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  • Dr. Rosalie Tran,

    1. Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (USA)
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  • Dr. Sheraz Gul,

    1. Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (USA)
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  • Dr. Junko Yano,

    Corresponding author
    1. Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (USA)
    • Junko Yano, Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (USA)

      Theodor Agapie, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 127-72, Pasadena, California 91125 (USA)

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  • Prof. Theodor Agapie

    Corresponding author
    1. Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 127-72, Pasadena, California 91125 (USA)
    • Junko Yano, Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (USA)

      Theodor Agapie, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 127-72, Pasadena, California 91125 (USA)

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Abstract

Well-defined mixed-metal [CoMn3O4] and [NiMn3O4] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure-function relationships of the electrocatalysts’ heterometallic composition. Depending on preparation conditions, the Co-Mn oxide was found to change metal composition during catalysis, while the Ni–Mn oxides maintained the NiMn3 ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn3O4 cubane-like geometry was maintained in the absence of thermal treatment (2-Ni). In contrast, the thermally generated 3-Ni develops an oxide-like extended structure. Both 2-Ni and 3-Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen-evolving complex in Photosystem II, including the MMn3O4 cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides.

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