权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Development of Nobel Catalytic Process Aimed at Green Chemistry by Functionalization of Solid Surface

通过固体表面功能化开发旨在绿色化学的诺贝尔催化工艺

基本信息

批准号：
11450307
负责人：
KANEDA Kiyotomi
金额：
$ 8.7万
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：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450307/
关键词：
Green Chemistry Molecular Oxygen Selective Oxidations Fixation of Carbon Dioxide C-C Bond Formation Reactions Hydrotalcite Hydroxyapatite Metal Cluster 層状化合物 CO_2 固定化過酸化水素

项目摘要

This research demonstrated that the design of highly-functionalized heterogeneous catalysts contributes to developing environmentally-acceptable chemical processes such as selective oxidations of hydrocarbons using molecular oxygen and hydrogen peroxide, fixation of carbon dioxide, and C-C bond formation reactions. The results are summarized as below.Selective OxidationsFor preparation of high performance oxidation catalysts, we extensively utilized unique characters of crystalline metal hydroxides, i.e, hydrotalcite and hydroxyapatite, and metal clusters.Ruthenium cation could be immobilized in the Brucite layer of the hydrotalcite as monomeric species based on the cation-exchange ability. The oxidation catalysis was greatly enhanced by introducing Co cation in the Brucite layer through Redox interactions between Ru and Co cations. These functionalized materials efficiently catalyzed oxidations of various alcohols and aromatic hydrocarbons to the corresponding carbonyl compounds in th … More e presence of molecular oxygen.The isolated Ru species are also created on the surface of hydroxyapatite by a simple ion-exchange procedure, which acted as an effective heterogeneous catalyst for aerobic oxidation of alcohols and amines. A nobel oxidation mechanism was proposed in relation to the monomeric structure of the Ru cations.It was also found that base sites of hydrotalcites promotes monooxygenation type reactions of olefins and pyridines using hydrogen peroxide as an oxidant.Further, we developed preparation method of the giant palladium cluster as a highly active catalyst for the acetoxylation of aromatic hydrocarbons in the presence of molecular oxygen. The prominent catalysis of the above Pd cluster is ascribed to specific ensemble sites composed of metallic Pd and neighboring Pd cations on its surface.Fixation of Carbon DioxideThe surface of Mg-Al mixed oxides obtained by calcination of hydrotalcites showed acid-base bifunctional properties and unique catalysis for the cycloaddition of carbon dioxide to various epoxides under mild reaction conditions. The generation of acid-base sites on the surface of the Mg-Al mixed oxide was discussed on the basis of XAFS measurements.(iii) C-C Bond Formation ReactionsTitanium cation-exchanged montmorillonite acted as a strong solid acid catalyst for aromatic alkylations with carbonyl compounds to synthesize valuable raw materials for speciality polymers. We found hydrotalcite-catalyzed the condensation of various aldehydes to the corresponding aldol compounds.The above solid catalysts were easily separated from the reaction mixture and recyclable keeping their high activities and selectivities. Less

这项研究表明，高度官能化的多相催化剂的设计有助于开发环境可接受的化学过程，如使用分子氧和过氧化氢的烃的选择性氧化，二氧化碳的固定和C-C键形成反应。主要研究结果如下：选择性氧化在制备高性能氧化催化剂方面，我们广泛利用了金属氢氧化物（水滑石和羟基磷灰石）和金属簇的独特性质，利用其阳离子交换能力，将钌阳离子作为单体物种固定在水滑石的水镁石层中。通过Ru和Co阳离子之间的氧化还原相互作用，在水镁石层中引入Co阳离子，大大增强了氧化催化作用。这些功能化的材料有效地催化了各种醇和芳烃氧化成相应的羰基化合物， ...更多信息通过简单的离子交换过程，在羟基磷灰石表面上也产生了分离的Ru物种，其作为醇和胺的有氧氧化的有效的多相催化剂。提出了与Ru离子单体结构有关的Nobel氧化机理，并发现水滑石的碱位促进了烯烃和吡啶在H_2O_2氧化下的单加氧反应，进而发展了大钯簇催化剂的制备方法，该催化剂可用于分子氧存在下芳烃的乙酰氧基化反应.上述Pd簇的突出催化作用归因于其表面上由金属Pd和相邻Pd阳离子组成的特定系综位点。二氧化碳的固定通过煅烧水滑石得到的Mg-Al混合氧化物表面显示出酸碱双功能性质，在温和的反应条件下对二氧化碳与各种环氧化物的环加成反应具有独特的催化作用。利用XAFS研究了镁铝复合氧化物表面酸碱位的形成。(iii)C-C键形成反应钛阳离子交换蒙脱土作为强固体酸催化剂，用于芳香族化合物与羰基化合物的烷基化反应，合成有价值的特种聚合物原料。我们发现水滑石可以催化各种醛的缩合反应，而且这些固体催化剂易于分离，可以循环使用，保持了较高的活性和选择性。少