Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry & Graduate University, the Chinese Academy of Sciences, Beijing 100190, PR China.
Langmuir. 2010 Jun 15;26(12):9766-71. doi: 10.1021/la101322s.
To offer an intriguing access to photocatalytic H(2) generation in an aqueous solution, the hydrophobic photosensitizer, Re(I)(4,4'-dimethylbpy)(CO)(3)Br (1) or Re(I)(1,10-phenanthroline)(CO)(3)Br (2), and [FeFe] H(2)ases mimics, [Fe(2)(CO)(6)(mu-adt)CH(2)C(6)H(5)] (3) or [Fe(2)(CO)(6)(mu-adt)C(6)H(5)] (4) [mu-adt = N(CH(2)S)(2)], have been successfully incorporated into an aqueous sodium dodecyl sulfate (SDS) micelle solution, in which ascorbic acid (H(2)A) was used as a sacrificial electron donor and proton source. Studies on the reaction efficiency for H(2) generation reveal that both the close contact and the driving force for electron transfer from the excited Re(I) complexes and [FeFe] H(2)ases mimics are crucial for efficient H(2) generation with visible light irradiation. Steady-state and time-resolved investigations demonstrate that the electron transfer takes place from the excited Re(I) complex 1 or 2 to [FeFe] H(2)ases mimic catalyst 3, leading to the formation of the long-lived Fe(I)Fe(0) charge-separated state that can react with a proton to generate Fe(I)Fe(II).H, an intermediate for H(2) production. As a result, a reaction vessel for the photocatalytic H(2) production in an aqueous solution is established.
为了提供一种有趣的途径来研究水相中的光催化 H(2)生成，将疏水性光敏剂 Re(I)(4,4'-dimethylbpy)(CO)(3)Br(1)或 Re(I)(1,10-phenanthroline)(CO)(3)Br(2)以及[FeFe]H(2)ase 模拟物 [Fe(2)(CO)(6)(mu-adt)CH(2)C(6)H(5)] (3)或[Fe(2)(CO)(6)(mu-adt)C(6)H(5)] (4)[mu-adt = N(CH(2)S)(2)]成功地掺入到含有抗坏血酸 (H(2)A)作为牺牲电子供体和质子源的十二烷基硫酸钠 (SDS) 水溶液胶束中。对 H(2)生成反应效率的研究表明，激发态 Re(I)配合物和[FeFe]H(2)ase 模拟物之间的紧密接触和电子转移驱动力对于可见光照射下高效的 H(2)生成至关重要。稳态和时间分辨研究表明，电子从激发态 Re(I)配合物 1 或 2 转移到[FeFe]H(2)ase 模拟物催化剂 3，导致形成长寿命的 Fe(I)Fe(0)电荷分离态，该状态可以与质子反应生成 H(2)生成的中间体 Fe(I)Fe(II).H。因此，建立了一种在水溶液中进行光催化 H(2)生成的反应容器。
