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一种带有钌三联吡啶光敏剂的聚合离子液体负载型B12催化剂,用于离子液体中的光催化脱氯反应。

A polymerized ionic liquid-supported B12 catalyst with a ruthenium trisbipyridine photosensitizer for photocatalytic dechlorination in ionic liquids.

作者信息

Zhang Wei, Shimakoshi Hisashi, Houfuku Noriyuki, Song Xi-Ming, Hisaeda Yoshio

机构信息

Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Motooka, Fukuoka 819-0395, Japan.

出版信息

Dalton Trans. 2014 Oct 7;43(37):13972-8. doi: 10.1039/c4dt01360c. Epub 2014 Aug 12.

Abstract

By immobilizing a B12 complex and a Ru(ii) trisbipyridine photosensitizer in a polymerized ionic liquid (PIL), a visible light-driven photocatalyst was developed. The synthesized copolymer was characterized by GPC and DLS, and using UV-vis absorption spectra and luminescence spectra. The Ru(ii) trisbipyridine photosensitizer in the copolymer showed an enhanced emission compared to that of the monomer in the ionic liquid, 1-butyl-4-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C4mim][NTf2]). Formation of the Co(i) species of the B12 complex in the copolymer was confirmed by the UV-vis spectral change in [C4mim][NTf2] containing a sacrificial reductant (triethanolamine) under irradiation with visible light. The copolymer showed a high photocatalytic activity in various ionic liquids for 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) dechlorination with ∼99% conversion after visible light irradiation for 2 h. Furthermore, both the B12 catalyst and photosensitizer in the polymer were easily recycled for use with the ionic liquid solvent without any loss of catalytic activity.

摘要

通过将维生素B12配合物和钌(II)三联吡啶光敏剂固定在聚合离子液体(PIL)中,开发了一种可见光驱动的光催化剂。通过凝胶渗透色谱(GPC)和动态光散射(DLS)对合成的共聚物进行了表征,并使用紫外可见吸收光谱和发光光谱进行分析。与离子液体1-丁基-4-甲基咪唑双(三氟甲磺酰)酰胺([C4mim][NTf2])中的单体相比,共聚物中的钌(II)三联吡啶光敏剂发射增强。通过在含有牺牲还原剂(三乙醇胺)的[C4mim][NTf2]中在可见光照射下的紫外可见光谱变化,证实了共聚物中维生素B12配合物的Co(I)物种的形成。该共聚物在各种离子液体中对1,1-双(4-氯苯基)-2,2,2-三氯乙烷(DDT)脱氯表现出高光催化活性,可见光照射2小时后转化率约为99%。此外,聚合物中的维生素B12催化剂和光敏剂都很容易回收,可与离子液体溶剂一起使用,而不会损失任何催化活性。

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