Core cross-linked micelle-based nanoreactors for efficient photocatalysis.
Core cross-linked micelle-based nanoreactors for efficient photocatalysis.
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DOI：
10.1002/asia.201300668
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发表时间：
2013-08
期刊：
影响因子：
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通讯作者：
M. Zheng;Zaicheng Sun;Zhigang Xie;X. Jing
中科院分区：
文献类型：
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作者：
M. Zheng;Zaicheng Sun;Zhigang Xie;X. Jing
以单甲氧基聚乙二醇嵌段聚赖氨酸（MPEG-PLys）和[（bpy）2 Ru（fmbpy）]（PF 6）2（bpy=联吡啶，fmbpy=5-甲酰基-5 '-甲基-2，2'-联吡啶）为原料，制备了稳定的纳米级交联聚合物胶束。为了稳定胶束，使用双官能戊二醛作为交联剂与PLys嵌段的游离氨基反应。在此之后，Ru-CM在普通溶剂中显示出非常好的稳定性。Ru-CMs在硫化物的氧化反应中表现出与已知的[Ru（bpy）3（PF 6）2]配合物一样高的光催化活性和选择性，这是因为胶束在甲醇-硫化物混合物中溶胀。此外，由于颗粒的纳米尺寸和它们的高稳定性，Ru-CM光催化剂可以容易地通过超滤回收并重复使用而不损失光催化活性。这项工作突出了使用交联胶束作为开发高效多相光催化剂的平台，用于许多重要的有机转化的潜力。
Stable nanoscale cross-linked polymer micelles containing Ru complexes (Ru-CMs) were prepared from monomethoxy[poly(ethylene glycol)]-block-poly(L-lysine) (MPEG-PLys) and [(bpy)2Ru(fmbpy)](PF6)2 (bpy=bipyridine, fmbpy=5-formy-5'-methyl-2,2'-bipyridine). To stabilize the micelles, bifunctional glutaraldehyde was used as a cross-linker to react with the free amino groups of the PLys block. After that, the Ru-CMs showed very good stability in common solvents. The Ru-CMs showed photocatalytic activity and selectivity in the oxidation of sulfides that were as high as those of the well-known [Ru(bpy)3(PF6)2] complex, because the micelles were swollen in the methanol-sulfide mixture. Moreover, because of the nanoscale size of the particles and their high stability, the Ru-CM photocatalysts can be readily recovered by ultrafiltration and reused without loss of photocatalytic activity. This work highlights the potential of using cross-linked micelles as a platform for developing highly efficient heterogeneous photocatalysts for a number of important organic transformations.