【摘要】 本工作合成了两个新的含有桥联配体6,8-硫辛酸甲酯（pdte）的[2Fe2S]化合物1和2,并通过IR、¹HNMR、³¹PNMR（化合物2）、元素分析、X射线单晶衍射（化合物1）等手段表征了其结构，构建了以目标化合物1或2为光催化剂、EY^2-为光敏剂、TEA为电子给体和质子源的三组分光催化体系。结果表明：在pH=11的CH₃CN/H₂O（V（CH₃CN）/V（H₂O）=1/1）溶液中和经过3.5 h的可见光（λ>420 nm）照射的条件下，该体系的最大氢产量分别为106.5μmol （TON 13.3 vs.1）和136.2μmol （TON 17 vs.2）,对应的产氢速率分别为7 607μmol·g^-1·h^-1和6 595.6μmol·g^-1·h^-1。机理研究表明：体系失活主要归因于光催化过程中光敏剂EY^2-和催化剂的光降解。在所构建的体系中，光生电子可经两种途径由^1*EY^2-或EY^3-·转移到Fe^ⅠFe^Ⅰ中心上，形成产氢的重要中间体Fe^ⅠFe⁰物种，并通过进一步质子化产生HFe^ⅡFe^Ⅰ物种和（η²-H₂）Fe^Ⅱ-Fe^Ⅰ物种，最终释放出H₂分子并使Fe^ⅠFe^Ⅰ物种再生。这说明目标催化剂（特别是化合物2）可作为潜在的光催化产氢分子催化剂。更多还原

【Abstract】 Two new [2Fe2S] compounds 1 and 2 containing the bridging ligand 6, 8-lipoic acid methyl ester（pdte） were synthesized, and their structures were characterized by IR, ¹HNMR, ³¹PNMR（compound 2）, elemental analysis and X-ray single crystal diffraction（compound 1）, etc. A three-component photo-catalytic hydrogen production system was constructed, in which compounds 1 or 2 was used as the photo-catalyst, EY^2-as the photo-sensitizer, TEA as the electron donor and proton source, respectively. The results showed that the maximum hydrogen production was 106.5 μmol（TON 13.3 vs.1） and 136.2 μmol（TON 17 vs.2）, with corresponding hydrogen production rates 7 607 μmol·g^-1·h^-1and 6 595.6 μmol·g^-1·h^-1, respectively, under the optimal hydrogen production conditions of V（CH₃CN）/V（H₂O）=1/1, pH=11, and visible light（λ>420 nm） irradiation for 3.5 h. Probing into the mechanism of hydrogen production, it was shown that the deactivation of the system was mainly due to the photo-degradation of the photo-sensitizer EY^2-and the catalyst in the photo-catalytic process. Photogenerated electrons can be transferred from ^1*EY^2- or EY^3-· to the Fe^ⅠFe^Ⅰ center via two pathways to form the important intermediate Fe^ⅠFe⁰ species in the present system. Furthermore, the important hydrogen-producing active intermediates HFe^ⅡFe^Ⅰ species and（η²-H₂） Fe^Ⅱ-Fe^Ⅰ species were formed by further protonation, finally releasing H₂ and regenerating Fe^ⅠFe^Ⅰspecies. The result implicated that the title catalyst（especially 2） was a potential molecular catalyst for photo-catalytic hydrogen production.更多还原