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

这项研究工作的目的是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的设计和开发。我们发现，含Ti的多孔二氧化硅（钛硅酸盐）催化剂促进了具有尺寸接近催化剂孔的分子的选择性转换。该催化特性可用于选择性转化，该分子的大小接近催化剂孔，向具有较小尺寸的分子转化。我们还发现，介孔二氧化钛催化了在催化剂表面充满吸附的分子的选择性转化。该催化特性可以用于选择性化值良好的分子到较低的吸附分子：例如，以> 80％的选择性成功促进了苯向苯酚的直接羟基化。我们还发现，当通过具有分子氧的可见光激活时，在超元素中含有有机光敏剂的沸石，促进烯烃对烯烃的转化，以> 99％的选择性转化为羰基化合物。我们还针对精选的有机转化，通过精确的有机化设计，通过精确的有机物设计。我们发现，当用分子氧通过紫外线照射激活含Ti的介孔二氧化硅（中苯甲尼硅酸盐），催化具有很高选择性的烯烃的选择性光氧化。我们还发现，当用分子氧通过可见光激活含CR的二氧化硅时，会催化环己烷的选择性转化为环己酮和烯烃的部分氧化物。此外，我们合成了新的含V的介孔二氧化硅，其中包含二氧化硅层中“限制”的V-氧化物物种。 V-氧化物物质稳定在水中，并显示出高光催化活性。我们还针对有机聚合物催化剂的选择性有机转化。我们合成了一种两亲硫酸一氢聚合物的光催化剂，该光催化剂含有光敏核心在疏水环境中，围绕着亲水性树突。光催化剂有效地催化了硫化物的光氧化为亚硫酸。我们还合成了一个随机聚合物光催化剂，其中包括有机光敏分子和聚-N-异丙烯酰胺。我们发现催化剂显示出水中氧合的空前温度依赖性光催化活性。较少的

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