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Highly Selective Organic Synthesis within Organized Nanopores as a Photocatalytic Reactor

作为光催化反应器在有序纳米孔内进行高选择性有机合成

基本信息

批准号：
15360430
负责人：
HIRAI Takayuki
金额：
$ 6.78万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

项目摘要

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

本研究工作旨在设计和开发选择性有机转化过程，利用有组织的纳米孔作为光催化反应器。我们发现含钛的多孔二氧化硅（钛硅酸盐）催化剂促进了分子的选择性转化，这些分子的大小接近于催化剂的孔隙。这种催化性质可用于选择性地将具有接近催化剂孔大小的分子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了吸附在催化剂表面的分子的选择性转化。这种催化性质可以应用于将吸附良好的分子选择性转化为吸附较差的分子：例如，苯直接羟基化成苯酚的选择性达到80%。我们还发现，在超笼中含有有机光敏剂的沸石，当被带有分子氧的可见光激活时，促进了烯烃向羰基化合物的选择性转化，选择性为50% ~ 99%。通过对光催化活性物质的精确设计，实现选择性有机转化。我们发现含ti介孔二氧化硅（介孔硅酸钛）在分子氧紫外照射下活化时，能以非常高的选择性催化烯烃的光环氧化反应。我们还发现含cr二氧化硅在可见光和分子氧的激活下，催化环己烷选择性转化为环己酮和烯烃部分氧化。此外，我们还合成了新的含v介孔二氧化硅，它含有“局限”在二氧化硅层内的v -氧化物。v -氧化物对水稳定，具有较高的光催化活性。我们还针对有机聚合物催化剂的选择性有机转化进行了研究。我们合成了一种两亲性树状聚合物光催化剂，在疏水环境中含有一个光敏核心，周围是亲水树突。该光催化剂能有效地催化硫化物光氧化生成亚砜。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。我们发现该催化剂对水中的氧合表现出前所未有的温度依赖光催化活性。少

项目成果

期刊论文数量（29）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Size-Screening Photocatalytic Conversion within Titanosilicate Molecular Sieves

钛硅酸盐分子筛内的尺寸筛选光催化转化

DOI：
发表时间：
2004
期刊：
Proceeding of The 4th International 21century COE Symposium on Integrated EcoChemistry(COE IEC IV)
影响因子：
0
作者：
Yasuhiro Shiraishi;et al.;白石康浩ら;白石康浩;Naoya Saito
通讯作者：
Naoya Saito

チタノシリケート:分子を削る光触媒

钛硅酸盐：切割分子的光催化剂