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

这项研究工作旨在设计和开发使用有组织的纳米孔作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）催化剂促进尺寸接近催化剂孔的分子的选择性转化。这种催化特性可用于将尺寸接近催化剂孔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a。催化剂表面吸附良好的分子的选择性转化，可用于将吸附良好的分子选择性转化为吸附较少的分子：例如，成功促进苯直接羟基化为苯酚，选择性>80%。我们还发现，超级笼内含有有机光敏剂的沸石，当被可见光和分子氧激活时，会促进烯烃选择性转化为羰基化合物具有 >99% 的选择性。我们还通过精确设计光催化活性物质来实现选择性有机转化，我们发现含钛介孔二氧化硅（介观钛硅酸盐）在用分子氧进行紫外线照射时可催化选择性光环氧化。我们还发现含铬二氧化硅在被可见光和分子氧活化时可以选择性催化。此外，我们合成了新型含V介孔二氧化硅，其含有“限制”在二氧化硅层内的V-氧化物物质，该V-氧化物物质对水稳定并表现出高光催化性。我们还针对有机聚合物催化剂的选择性有机转化，合成了一种含有光敏剂的两亲性树枝状聚合物光催化剂。我们还合成了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。水中氧化的光催化活性较小。

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