Highly efficient supramolecular photocatalysts for CO2 reduction using visible light
Highly efficient supramolecular photocatalysts for CO2 reduction using visible light
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DOI：
10.1039/b613419j
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发表时间：
2007-01-01
影响因子：
3.1
通讯作者：
Ishitani, Osamu
中科院分区：
文献类型：
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作者：
Sato, Shunsuke;Koike, Kazuhide;Ishitani, Osamu
我们报告了最有效的均相光催化剂，但使用宽范围的可见光波长的CO2还原。我们合成了以1，3-双（4 '-甲基[2，2']联吡啶-4-基）-丙-2-醇（bpyC 3bpy）为桥配体的新型Ru（II）-Re（I）双核配合物，具体地说是[Ru-ReP（OEt）（3）]（3+）和[Ru-Repy]（3+），其中P（OEt）（3）或吡啶配体配位在Re位点上。它们的光催化活性与[Ru-ReCl]（2+）进行了比较，[Ru-ReCl]（2+）在Re位点上具有Cl-配体，并且最近被报道为比相应的Ru（II）和Re（I）单核配合物的1：1混合体系好得多的光催化剂（Phi = 0.12，TNCO = 160）。最佳的光催化剂是[Ru-ReP（OEt）（3）]（3+），其Phi = 0.21，TNCO = 232。机理研究清楚地表明，[Ru-ReP（OEt）（3）]（3+）迅速转化为溶剂复合物[Ru-ReSol]（3+），（Sol = DMF或TEOA），这是实际的光催化剂。虽然类似的快速配体取代发生与其他超分子，吡啶和Cl-阴离子加速分解的超分子光催化剂。
We report the most efficient homogeneous photocatalyst yet for CO2 reduction using a wide range of visible-light wavelength. We synthesized new Ru(II)-Re(I) binuclear complexes with 1,3-bis(4'-methyl[2,2']bipyridinyl-4-yl)-propan-2-ol (bpyC3bpy) as a bridge ligand, specifically [Ru-ReP(OEt)(3)](3+) and [Ru-Repy](3+) where a P(OEt)(3) or pyridine ligand coordinates on the Re site. Their photocatalytic activities were compared with [Ru-ReCl](2+), which has a Cl- ligand on the Re site and has recently been reported as a much better photocatalyst (Phi = 0.12, TNCO = 160) than a 1 : 1 mixed system of the corresponding Ru(II) and Re(I) mononuclear complexes. The best photocatalyst was [Ru-ReP(OEt)(3)](3+), for which Phi = 0.21 and TNCO = 232. A mechanistic study clearly showed that [Ru-ReP(OEt)(3)](3+) is rapidly converted into the solvento complex [Ru-ReSol](3+), (Sol = DMF or TEOA) which is the actual photocatalyst. Although similar rapid ligand substitution occurs with other supramolecules, the pyridine and Cl- anions accelerate the decomposition of the supramolecular photocatalysts.