催化活化C-H键金属有机骨架的设计构筑及其作用机理

As a new class of inorganic/organic hybrid materials with well-defined pores, MOFs had been applied in gas adsorption, separation and catalysis. However the catalytic reactions that had been investigated using MOFs as the catalysts are still limited and only few reports on some challenging reactions, i.e. C-H activation. We are planning to use organic compounds with similar topology while missing at least one chelating functionality as the organic links as the structural directing agents to synthesize new MOFs with distinct structure and unique coordination environments. Thus-obtained MOFs will have open metal cites and multi-valence metal centers and therefore can be seen as bi-functional catalysts. We will explore their catalytic activity in C-H activation and investigate the relationship between the structures and the performance. We will focus on catalytic activation of benzylic C-H bond and oxidation of benzyl alcohols and related tandem reactions.

MOFs作为一类新型的具有特定开放孔道结构的无机有机杂化材料，已经在气体储存、分离、碳捕捉和催化等领域得到了应用。然而，MOF催化反应的类型仍相当有限，一些重要的催化过程，例如C-H活化，则少有报道。本项目拟通过与目标有机配体具有类似拓扑学结构但缺少至少一个配位官能团的有机物作为模板剂，诱导生长具有新颖结构和特殊配位环境的新型MOFs材料。通过这一缺位模板法设计合成的MOFs将具有开放金属位点和变价金属中心，是一类具有酸性和氧化性的双功能绿色催化剂。我们拟探索这些MOFs催化活化C-H键的特性与机理，发现和揭示它们在目标催化反应中的构效关系规律。围绕寻找活化二苯甲烷衍生物C-H键和醇分子中C-H键的高效绿色双功能MOFs催化剂，提高C-H键活化的转化率，进而实现高效转换二苯甲烷成二苯甲酮和醇氧化成醛继而发生串联反应。这将为开辟MOFs催化化学研究新领域提供新思路和理论依据。