Highly Selective Organic Synthesis within Organized Nanopores as a Photocatalytic Reactor

本研究旨在设计和开发以有序纳米孔为光催化反应器的选择性有机转化过程，我们发现含钛多孔二氧化硅（钛硅酸盐）催化剂可促进尺寸接近催化剂孔的分子的选择性转化。该催化性质可用于将具有接近催化剂孔的尺寸的分子选择性转化为具有较小尺寸的分子。我们还发现，介孔二氧化钛催化剂表面吸附良好的分子的选择性转化。这种催化性能可用于选择性地将吸附良好的分子转化为吸附较少的分子：例如，成功地促进了苯直接羟基化为苯酚，选择性>80%。我们还发现，在超笼中含有有机光敏剂的沸石，当被具有分子氧的可见光激活时， ...更多信息 通过对光催化活性物种的精确设计，实现了烯烃的选择性转化，选择性大于99%。我们发现，含钛介孔二氧化硅（中孔钛硅酸盐）在分子氧紫外照射下活化时，可以非常高选择性地催化烯烃的选择性光环氧化。我们还发现，含铬的二氧化硅，当用可见光与分子氧激活，催化环己烷选择性转化为环己酮和烯烃的部分氧化。此外，我们合成了新的含V的介孔二氧化硅，其中包含V-氧化物物种“限制”在二氧化硅层内。V-氧化物物种对水稳定，表现出很高的光催化活性。我们合成了一种两亲性树枝状大分子光催化剂，它在疏水环境中含有光敏核心，周围是亲水树枝状分子。该光催化剂有效地催化硫化物光氧化成亚砜。我们还合成了一种由有机光敏分子和聚N-异丙基丙烯酰胺组成的无规聚合物光催化剂。我们发现，该催化剂显示出前所未有的温度依赖性的光催化活性在水中的氧化。少

This research work aims at the design and development of selective organic transformation processes using organized nanopores as the photocatalytic reactor.We have found that Ti-containing porous silica (titanosilicate) catalysts promote a selective conversion of molecules having a size close to the catalyst pores. This catalytic property can be applied for selective transformation of molecules having a size close to the catalyst pores to molecules having a smaller size. We also found that mesoporous titanium dioxide catalyzes a selective conversion of molecules adsorbed well on the catalyst surface. This catalytic property can be applied for selective transformation of well-adsorbed molecule to less-adsorbed molecule : for example, a direct hydroxylation of benzene to phenol was successfully promoted with >80% selectivity. We also found that a zeolite containing an organic photosensitizer within the supercage, when activated by a visible light with molecular oxygen, promote a selectiv … More e transformation of olefins to carbonyl compounds with >99% selectivity.We also aimed at the selective organic transformation through the precise designing of the photocatalytic active species. We found that Ti-containing mesoporous silica (meso-titanosilicate), when activated by UV irradiation with molecular oxygen, catalyzes selective photoepoxidation of olefins with very high selectivity. We also found that Cr-containing silica, when activated by visible light with molecular oxygen, catalyzes selective transformation of cyclohexane to cyclohexanone and partial oxidation of olefins. In addition, we synthesized new V-containing mesoporous silica, which contains V-oxide species "confined" within the silica layer. The V-oxide species are stable against water and show high photocatalytic activity.We also aimed at the selective organic transformation with organic polymer catalysts. We synthesized an amphiphilic dendrimer photocatalyst containing a photosensitizing core within the hydrophobic environment surrounded by hydrophilic dendrons. The photocatalyst efficiently catalyzes a photooxygenation of sulfides to sulfoxides. We also synthesized a random polymer photocatalyst comprised of an organic photosensitizing molecule and poly-N-isopropylacrylamide. We found that the catalyst shows unprecedented temperature-dependent photocatalytic activity for oxygenation in water. Less