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

该研究的目的是创造新的整体宏观结构，具有分层孔隙度，专门用于连续流动催化。目标结构是由多孔配位聚合物（pcp）制成的，这是一种在分子尺度上由有机连接剂和无机连接剂组装的新型晶体材料。它们是通过应用申请人小组开发的一种方法合成的，即所谓的“配位复制”，该方法能够通过溶解-再结晶过程精确控制PCP结晶位置，其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，该工艺只使用由一种独特类型的金属组成的金属氧化物相作为牺牲模板，如纯氧化铝。在本项目中，申请人选择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或由催化活性过渡金属制成的金属氧化物相作为牺牲模板。在本项目中，使用的牺牲模板是掺钒氧化铝气凝胶和氢氧化铜大孔整体。用不同类型的有机连接剂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。这些材料的催化活性正在研究中。

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.