Creation of heterogeneous catalysts based on hierarchical macrostructures of porous coordination polymers

这项研究的目的是创造新的整体宏观结构，具有致力于连续流动催化的分级孔隙率。靶向结构是由多孔配位聚合物(PCPs)构成的，这是一种由有机连接物和无机连接物在分子尺度上组装而成的新型结晶材料。它们是通过应用申请人小组开发的方法合成的，即所谓的“配位-复制”，该方法能够通过溶解-重结晶过程精确地控制PCP的结晶位置，在该过程中牺牲的金属氧化物溶解，从而提供构建PCP晶体所需的金属阳离子。到目前为止，这一过程只以一种独特的金属组成的金属氧化物相作为牺牲模板，如纯铝。在本项目中，申请人选择了掺杂氧化还原活性金属中心(M‘)的混合金属氧化物相MOX-M’Ox或由具有催化活性的过渡金属组成的金属氧化物相作为牺牲模板。用不同类型的有机连接物成功地合成了具有催化活性的PCP晶体的单晶和多晶宏观结构，并对其进行了表征，考察了这些材料的催化活性。

The purpose of the research was the creation of new monolithic macrostructures with a hierarchical porosity dedicated to continuous flow catalysis. The targeted structures are made of porous coordination polymers (PCPs), a new class of crystalline materials assembled by organic linkers and inorganic joints at the molecular scale. They are synthesized by applying a method developed in the applicant's group, so-called "coordination-replication", which enables to precisely control the PCP crystallization location through a dissolution-recrystallization process, where a sacrificial metal oxide dissolves and therefore provides the metal cation required to built the PCP crystals. So far, this process was only carried out with metal oxide phases composed of one unique type of metal as sacrificial template, such as pure alumina.In this project, the applicant selected as sacrificial template a mixed metal oxide phase MOx-M’Ox doped with redox active metal centers (M’) or metal oxide phase made of catalytically active transition metals.In this project, the sacrificial template used were vanadium doped alumina aerogels and copper hydroxide macro porous monoliths. Monolithic and polycrystalline macrostructures made of catalytically active PCP crystals were successfully synthesized with different types of organic linkers and characterized.The catalytic activity of these materials are under investigation.