Design of Molecular-Imprinted Metal-Complex Catalysts at Surfaces for Shape-Selective and Asymmetric Catalysis

用于形状选择性和不对称催化的表面分子印迹金属络合物催化剂的设计

基本信息

批准号：
15206087
负责人：
IWASAWA Yasuhiro
金额：
$ 28.95万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
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

In this study, we proposed a designs of catalytically active surfaces by metal-complex attaching and molecular imprinting and succeeded in the preparation of novel supported metal-complex catalysts on oxide surfaces. A ligand of an attached metal complex is used as a template molecule and a cavity with similar shape to the template ligand is created on the active metal center, which acts as shape-selective reaction space on the surface. We prepared Pd-monomer catalysts on silica, alumina, and titania surfaces for alkene hydroamination, a series of metal-containing ionic liquid supported on silica surfaces, molecular-imprinted Rh-complex catalysts on silica, and N-interstitial Re clusters located in H-ZSM-5. The catalytic performances of these supported metal-complex catalysts were investigated.The structures of the prepared metal-complex catalysts were characterized by means of FT-IR, NMR, UV/VIS, ESR XRD, XRF, BET, ICP, Raman, XPS, XAFS and DFT calculations. The structural kinetics of the active metal catalysts were investigated by time-resolved energy-dispersive XAFS(DXAFS) with ms time resolution, and their catalytic reaction mechanism on surfaces and the relationship between the structures of active metal centers and their catalysis were demonstrated.For asymmetric catalysis on heterogeneous surfaces, we found the novel chiral self-dimerization of vanadium Schiff-base monomers on a silica surface and surface functionalizaiton with achial silane-coupling reagents promoting enantioselectivity on supported Cu-BOX catalysts on a silica surface. The obtained heterogeneous catalysts of chiral V dimers exhibited catalytic activity, 100% selectivity and high enantioselectivity for the asymmetric oxidative coupling of 2-naphthol. The surface-functionalized Cu-BOX catalyst dramatically increased enantioselectivity for asymmetric Diels-Alder reaction. These techniques are promising ways to develop asymmetric heterogeneous catalysts on oxide surfaces.

在这项研究中，我们通过金属复合物附着和分子印记提出了一种催化活性表面的设计，并成功地制备了氧化物表面上新型的支持金属复合催化剂。附着的金属络合物的配体用作模板分子，并且具有与模板配体相似的腔体在活性金属中心产生，该中心是表面上的形状选择性反应空间。我们在硅，氧化铝和钛表面上制备了PD-M-M-Sonomer催化剂，以用于烯烃氢化，这是一系列含金属的离子液体，在二氧化硅表面上支撑，二氧化硅上的分子rh-compemplex催化剂以及位于H-ZSM-5的N相关晶状体上的分子型RH-Compemplex催化剂。研究了这些受支持的金属复合物催化剂的催化性能。制备的金属复合催化剂的结构是通过FT-IR，NMR，NMR，UV/VIS，ESR XRD，XRF，BET，ICP，ICP，ICP，RAMAN，RAMAN，RAMAN，RAMAN，XPS，XP，XP，XAF和DFT计算来表征的。 The structural kinetics of the active metal catalysts were investigated by time-resolved energy-dispersive XAFS(DXAFS) with ms time resolution, and their catalytic reaction mechanism on surfaces and the relationship between the structures of active metal centers and their catalysis were demonstrated.For asymmetric catalysis on heterogeneous surfaces, we found the novel chiral self-dimerization of vanadium Schiff-base monomers在二氧化硅表面和表面功能性上，具有硅烷耦合试剂，可在二氧化硅表面上促进对映选择性的对映选择性。获得的手性V二聚体的异质催化剂表现出催化活性，100％的选择性和高的对对映选择性，用于2-萘酚的不对称氧化偶联。表面官能化的Cu-box催化剂显着提高了对非对称性主教 - alder反应的对映选择性。这些技术是在氧化物表面上开发不对称异质催化剂的有前途的方法。