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Photoinduced Biphasic Hydrogen Evolution: Decamethylosmocene as a Light-Driven Electron Donor

Authors

  • Peiyu Ge,

    1. Laboratoire d'Electrochimie Physique et Analytique (LEPA), Ecole Polytechnique Fédérale de Lausanne (EPFL), Station 6, 1015 Lausanne (Switzerland), Fax: (+41) 21-6933667
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  • Astrid J. Olaya,

    1. Laboratoire d'Electrochimie Physique et Analytique (LEPA), Ecole Polytechnique Fédérale de Lausanne (EPFL), Station 6, 1015 Lausanne (Switzerland), Fax: (+41) 21-6933667
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  • Dr. Micheál D. Scanlon,

    1. Laboratoire d'Electrochimie Physique et Analytique (LEPA), Ecole Polytechnique Fédérale de Lausanne (EPFL), Station 6, 1015 Lausanne (Switzerland), Fax: (+41) 21-6933667
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  • Dr. Imren Hatay Patir,

    1. Department of Chemistry, Selcuk University, 42031 Konya (Turkey)
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  • Heron Vrubel,

    1. Laboratory of Inorganic Synthesis and Catalysis (LISC), Ecole Polytechnique Fédérale de Lausanne (EPFL), BCH 3305, Av. Forel 2, 1015 Lausanne (Switzerland)
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  • Prof. Hubert H. Girault

    Corresponding author
    1. Laboratoire d'Electrochimie Physique et Analytique (LEPA), Ecole Polytechnique Fédérale de Lausanne (EPFL), Station 6, 1015 Lausanne (Switzerland), Fax: (+41) 21-6933667
    • Laboratoire d'Electrochimie Physique et Analytique (LEPA), Ecole Polytechnique Fédérale de Lausanne (EPFL), Station 6, 1015 Lausanne (Switzerland), Fax: (+41) 21-6933667

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Abstract

Excitation of the weak electron donor decamethylosmocene on illumination with white light produces an excited-state species capable of reducing organically solubilized protons under biphasic conditions. Insight into the mechanism and kinetics of light-driven biphasic hydrogen evolution are obtained by analysis with gas chromatography, cyclic voltammetry, and UV/Vis and 1H NMR spectroscopy. Formation of decamethylosmocenium hydride, which occurs prior to hydrogen evolution, is a rapid step relative to hydrogen release and takes place independently of light activation. Remarkably, hydride formation occurs with greater efficiency (ca. 90 % conversion) under biphasic conditions than when the reaction is carried out in an acidified single organic phase (ca. 20 % conversion). Cyclic voltammetry studies reveal that decamethylosmocene has a higher proton affinity than either decamethylferrocene or osmocene.

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