Light-Driven Electron Transfer between a Photosensitizer and a Proton-Reducing Catalyst Co-adsorbed to NiO
Light-Driven Electron Transfer between a Photosensitizer and a Proton-Reducing Catalyst Co-adsorbed to NiO
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DOI：
10.1021/ja3082268
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发表时间：
2012-11-28
影响因子：
15
通讯作者：
Hammarstrom, Leif
中科院分区：
文献类型：
--
作者：
Gardner, James M.;Beyler, Maryline;Hammarstrom, Leif
虽然分子间空穴沿半导体表面沿着跳跃是已知的，但之前没有表面上分子间电子跳跃的实例。在此，我们提出的第一个证据的电子转移从光敏剂，香豆素-343（C343）的配合物1，都绑定在NiO的表面上。在溶液中，1已被证明是单核铁基质子还原催化剂。1的还原是可逆的，并且在C343激发后50 ns内发生。减少1（（-））和NiO孔之间的界面复合发生在100 μ s的时间尺度上的非指数动力学。所观察到的过程是在没有牺牲供体试剂的情况下从分子催化剂光敏生成Hz的第一个重要步骤。
While intermolecular hole-hopping along the surface of semiconductors is known, there are no previous examples of electron-hopping between molecules on a surface. Herein, we present the first evidence of electron transfer from the photoreduced sensitizer, Coumarin-343 (C343) to complex 1, both bound on the surface of NiO. In solution, 1 has been shown to be a mononuclear Fe-based proton-reducing catalyst. The reduction of 1 is reversible and occurs within 50 ns after excitation of C343. Interfacial recombination between the reduced 1((-)) and NiO hole occurs on a 100 mu s time scale by non-exponential kinetics. The observed process is the first essential step in the photosensitized generation of Hz from a molecular catalyst in the absence of a sacrificial donor reagent.