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，高度功能化的异质性催化剂的设计有助于开发具有分子氧和过氧化氢的环保化学过程，例如烃的选择性氧化物，二氧化碳的固定和C-C-C键形成反应。 The results are summarized as below.Selective OxidationsFor preparation of high performance oxide catalysts, we extensively utilized unique characters of crystalline Metal hydroxides, i.e, hydrotalcite and hydroxapatite, and metal clusters.Ruthenium cation could be immobilized in the Brucite layer of the hydrotalcite as monomeric species based on the cation-exchange ability.通过RU和CO阳离子之间的氧化还原相互作用，通过在布鲁克特层中引入CO阳离子来大大增强氧化催化。这些功能化的材料有效地催化了各种醇和芳香烃的氧化作用，这些材料在相应的羰基化合物中在……更多的存在分子氧的存在中。隔离的RU物种也是由简单的离子 - 脱糖过程在羟基磷灰石的表面上创建的，由简单的离子 - 脱糖过程，作为一种有效的异质式氧化型氧化型氧化型和氧化物的氧化物氧化物的氧化物氧化作用。提出了与RU阳离子的单体结构相关的诺贝尔氧化机制。还发现，水力局的基础位点促进了使用过氧化氢作为氧化物的烯烃和吡啶胺的单氧化类型反应。FURTHER。我们开发了高质体caltustry of Acetoxyl of Acetoxyl of Acetsym of Acetsym of Acetsy of Acetsym of Acetsym of Acetsy of Acety clustersy的Acetsym of Acety clustersy的actasic clustrasty soctic clustrasty的动物群体的均应量。分子氧。 The prominent catalysis of the above Pd cluster is assigned 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 Calculation of hydrotalcites shown acid-base bifunctional properties and unique catalysis for the cycloaddition of carbon dioxide to various epoxides under mild reaction conditions.根据XAFS测量，讨论了MG-AL混合氧化物表面上的酸碱位点的产生。（iii）C-C键形成反应反应阳离子阳离子阳离子阳离子的蒙脱石是强固固体催化剂，可用于芳族醇的芳族醇，可用于合成有价值的原料的芳族化合物，可用于特殊材料。我们发现Hydrotalcite催化了各种醛与相应的醛醇化合物的缩合。上述固体催化剂很容易与反应混合物分离，并可回收可循环效果，以保持其高活性和选择性。较少的