Photocatalytic Water Reduction and Study of the Formation of FeIFe0 Species in Diiron Catalyst Sytems

Authors

  • Xueqiang Li,

    1. State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Centre on Molecular Devices, Dalian University of Technology (DUT), 116012 Dalian (PR China), Fax: (+86) 411-83702185
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  • Prof. Mei Wang,

    Corresponding author
    1. State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Centre on Molecular Devices, Dalian University of Technology (DUT), 116012 Dalian (PR China), Fax: (+86) 411-83702185
    • State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Centre on Molecular Devices, Dalian University of Technology (DUT), 116012 Dalian (PR China), Fax: (+86) 411-83702185
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  • Lin Chen,

    1. State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Centre on Molecular Devices, Dalian University of Technology (DUT), 116012 Dalian (PR China), Fax: (+86) 411-83702185
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  • Xiuna Wang,

    1. State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Centre on Molecular Devices, Dalian University of Technology (DUT), 116012 Dalian (PR China), Fax: (+86) 411-83702185
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  • Jingfeng Dong,

    1. State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Centre on Molecular Devices, Dalian University of Technology (DUT), 116012 Dalian (PR China), Fax: (+86) 411-83702185
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  • Prof. Licheng Sun

    Corresponding author
    1. State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Centre on Molecular Devices, Dalian University of Technology (DUT), 116012 Dalian (PR China), Fax: (+86) 411-83702185
    2. Department of Chemistry, Royal Institute of Technology (KTH), 10044 Stockholm (Sweden)
    • State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Centre on Molecular Devices, Dalian University of Technology (DUT), 116012 Dalian (PR China), Fax: (+86) 411-83702185
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Abstract

Noble-metal-free systems with bio-inspired diiron dithiolate mimics of the [FeFe]-hydrogenase active site, namely, [(μ-pdt)Fe2(CO)5L] [pdt=propanedithiolate; L=P(CH2OH)3 (1), P(CH3)3 (2)], as water reduction catalysts with xanthene dyes as photosensitizers and triethylamine as a sacrificial electron donor were studied for visible-light-driven water reduction to hydrogen. These systems display good catalytic activities with the efficiencies in hydrogen evolution of up to 226 turnovers for 1, if Eosin Y was used as the photosensitizer in an environmentally benign solvent (EtOH/H2O) after 15 h of irradiation (λ>450 nm) under optimal conditions. Under all of the conditions adopted, 1 that has a water soluble phosphine ligand, P(CH2OH)3 displayed a higher efficiency than 2, which bears a PMe3 ligand. The photoinduced electron transfer in the systems was studied using fluorescence, transient absorption, time-resolved UV/Vis, and in situ electron paramagnetic resonance (EPR) spectroscopy. A new electron-transfer mechanism is proposed for hydrogen evolution by these iron-based photocatalytic systems.

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