Photochemical CO2-reduction catalyzed by mono- and dinuclear phenanthroline-extended tetramesityl porphyrin complexes.
Photochemical CO2-reduction catalyzed by mono- and dinuclear phenanthroline-extended tetramesityl porphyrin complexes.
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DOI：
10.1039/c4dt03846k
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发表时间：
2015-03
影响因子：
4
通讯作者：
Corinna Matlachowski;M. Schwalbe
中科院分区：
文献类型：
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作者：
Corinna Matlachowski;M. Schwalbe
我们在这里提出了一个全面的研究光诱导催化CO2还原采用一些单核和双核配合物与菲咯啉扩展的四均三甲苯卟啉配体（）。异双核配合物的逐步合成是可能的，因为配体的菲咯啉部分可以选择性地配位第二金属中心，例如Ru（tbbpy）2（2+）片段，而任何其他金属可以驻留在卟啉腔中。我们将前人的研究拓展到钴和铁的化合物，合成了配合物，并对配合物的结构进行了研究。以三乙胺（TEA）为牺牲电子给体，在DMF溶液中对所有化合物（M = 2H，Cu，Pd，Co，FeCl）的光驱动CO2还原反应进行了深入的催化研究.观察到催化性能的非常令人惊讶的波长依赖性。转换数（TONS）的CO进行了量化，并表明氧化还原活性金属（即M =钴和FeCl）在卟啉腔引起的最高催化活性。在用λ > 305 nm的光照射24小时后，我们的实验装置的TONCO达到11.4，而没有显示出太多的分解。该值是在相同条件下对CoTPP测定的TONCO（5.8）的两倍，其代表了迄今为止用于光催化CO2还原的最活性卟啉体系。
We here present a comprehensive study on the light-induced catalytic CO2 reduction employing a number of mono- and dinuclear complexes with a phenanthroline-extended tetramesityl porphyrin ligand (). A stepwise synthesis of heterodinuclear complexes is possible because the phenanthroline moiety of the ligand can selectively coordinate a second metal center, e.g. Ru(tbbpy)2(2+) fragment, while any other metal can reside in the porphyrin cavity. We expanded our former studies to cobalt and iron compounds and synthesized the complexes , and , . Thorough catalytic investigation on the light-driven CO2 reduction of all compounds (M = 2H, Cu, Pd, Co, FeCl) was performed in a DMF solution in the presence of triethylamine (TEA) as a sacrificial electron donor. A very surprising wavelength dependence of the catalytic performance was observed. Turnover numbers (TONs) of CO were quantified and showed that redox active metals (i.e.M = Co and FeCl) in the porphyrin cavity caused the highest catalytic activity. After 24 hours of illumination with light λ > 305 nm reached a TONCO of 11.4 with our experimental setup without showing much decomposition. This value is twice as high as the TONCO determined for CoTPP (5.8) under the same conditions, which represented the most active porphyrinic system so far for photocatalytic CO2 reduction.