The Critical Role Played by the Catalytic Moiety in the Early‐Time Photodynamics of Hydrogen‐Generating Bimetallic Photocatalysts |
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| Authors: | Qing Pan Francesco Mecozzi Jeroen P Korterik Prof?Dr Johannes G Vos Prof?Dr Wesley R Browne Dr Annemarie Huijser |
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| Institution: | 1. MESA+Institute for Nanotechnology, University of Twente, Enschede, The Netherlands;2. Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, University of Groningen, The Netherlands;3. SRC for Solar Energy Conversion, School of Chemical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland |
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| Abstract: | The effect of the catalytic moiety on the early‐time photodynamics of Ru/M (M=Pt or Pd) bimetallic photocatalysts is studied by ultrafast transient absorption spectroscopy. In comparison to the Ru/Pd photocatalyst described earlier, the Ru/Pt analogue shows complex excited‐state dynamics with three distinct kinetic components ranging from sub‐ps to 102 ps, requiring a more sophisticated photophysical model than that developed earlier for the Ru/Pd complex. In the Pu/Pt photocatalyst, an additional lower‐lying excited state is proposed to quench the hot higher‐lying triplet metal‐to‐ligand charge‐transfer states. Furthermore, a strong excitation wavelength dependence on the population of excited states is observed for both the Ru/Pt and Ru/Pd complexes, indicating a non‐equilibrated distribution even on the 102 ps timescale. These insights shed light on the significant impact of the catalytic moiety on the fundamental early‐time photophysics of Ru‐based photocatalysts. |
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| Keywords: | molecular photocatalysis non-equilibrated excited states photodynamics ruthenium transient absorption |
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