Heteronuclear MOFs for applications in adsorption and redox catalysis

本合作项目的目标是在了解MOF材料结构相关功能的基础上，合理开发用于选择性吸附和选择性催化的MOF材料。三个研究小组结合他们在合成/结构分析，吸附和多相催化方面的经验，对具有特定技术应用功能的MOF材料有了更深入的了解。研究重点是在该计划的第一阶段开发的具有取代苯甲酸三唑酯或间苯二甲酸酯连接剂的多孔Cu-MOFs。它们将被修改以调整孔隙几何形状并产生活性位点。由于吸附剂的形状和大小不同，为了实现吸附和催化的形状选择性，将通过连接剂的设计（三唑和芳香基团的取代模式）来控制孔和孔窗的大小和几何形状。mof中的活性中心将通过在框架中引入第二种金属离子而产生。这种异核mof可以通过同构取代法合成。将研究吸附和氧化还原催化中产生的选择性，例如，烷烃/烯烃分离和烯烃氧化反应。研究具有不同连接剂和金属位点的MOF上的反应物（如CO、O2、碳氢化合物）的吸附行为与其催化性能的相关性，将有助于我们更深入地了解MOF材料的基于框架的功能。

Aim of this joint project is the rational development of MOF materials for applications in selective adsorption and selective catalysis based on a fundamental understanding of their structure-related functions. Three research groups combine their experience in synthesis/structural analysis, sorption and heterogeneous catalysis to achieve a deeper knowledge on MOF materials with specific functions for technical applications.The investigations focus on porous Cu-MOFs with substituted triazolyl benzoate or isophthalate linkers, developed in the first period of this program. They will be modified in order to adjust the pore geometry and to generate active sites. Size and geometry of the pores and the pore windows will be controlled by linker design (substitution pattern of the triazole and aromatic groups) in order to achieve shape selectivity in adsorption and catalysis, due to differences in shape and size of the adsorptives. Active centres in the MOFs will be generated by introducing a second type of metal ions into the framework. Such heteronuclear MOFs can be synthesized by isomorphous substitution. The resulting selectivity in adsorption and redox catalysis will be studied, e.g., for alkane/alkene separation and alkene oxidation reactions. The correlation of the sorption behavior of the reactants (e.g. CO, O2, hydrocarbons) on MOFs with different linkers and metal sites to their catalytic properties will provide a deeper understanding of the framework-based functions of MOF materials.