Metal–Organic Framework (MOF)‐Based Materials as Heterogeneous Catalysts for C−H Bond Activation

Abstract Converting light hydrocarbons such as methane, ethane, propane, and cyclohexane into value‐added chemicals and fuel products by means of direct C−H functionalization is an attractive method in the petrochemical industry. As they emerge as a relatively new class of porous solid materials, metal–organic frameworks (MOFs) are appealing as single‐site heterogeneous catalysts or catalytic supports for C−H bond activation. In contrast to the traditional microporous and mesoporous materials, MOFs feature high porosity, functional tunability, and molecular‐level characterization for the study of structure–property relationships. These virtues make MOFs ideal platforms to develop catalysts for C−H activation with high catalytic activity, selectivity, and recyclability under relatively mild reaction conditions. This review highlights the research aimed at the implementation of MOFs as single‐site heterogeneous catalysts for C−H bond activation. It provides insight into the rational design and synthesis of three types of stable MOF catalysts for C−H bond activation, that is, i) metal nodes as catalytic sites, ii) the incorporation of catalytic sites into organic struts, and iii) the incorporation of catalytically active guest species into pores of MOFs. Here, the rational design and synthesis of MOF catalysts that lead to the distinct catalytic property for C−H bond activation are discussed along with the post‐synthesis of MOFs, intriguing functions with MOF catalysts, and microenvironments that lead to the distinct catalytic properties of MOF catalysts.