Abstract
Metal organic frameworks (MOFs) are porous crystalline solids whose frameworks are constituted by metal ions/nodes with rigid organic linkers leading to the formation of materials having high surface area and pore volume. One of the unique features of MOFs is the presence of coordinatively unsaturated metal sites in their crystalline lattice that can act as Lewis acid sites promoting organic transformations, including aerobic oxidation reactions of various substrates such as hydrocarbons, alcohols, and sulfides. This review article summarizes the existing Co-based MOFs for oxidation reactions organized according to the nature of substrates like hydrocarbon, alcohol, olefin, and water. Both aerobic conditions and peroxide oxidants are discussed. Emphasis is placed on comparing the advantages of using MOFs as solid catalysts with respect to homogeneous salts in terms of product selectivity and long-term stability. The final section provides our view on future developments in this field.
Highlights
Catalysts for Oxidation Reactions.Metal-organic frameworks (MOFs) are a class of crystalline porous materials where rigid bi- or multipodal organic linkers interact with metal ions or metal oxo clusters by Coulombic attraction and/or coordinative metal ligand bonds [1,2,3]
Xamena and co-workers have reported the facile synthesis of mixed metal Co–Ni and Mn–Ni trimesate Metal organic frameworks (MOFs) by fast aqueous synthesis and their catalytic activity was investigated in the selective aerobic oxidation of cumene to cumene hydroperoxide (CHP) (Scheme 2) [46]
The experimental catalytic results have shown that the isolation of Co2+ in an inert Ni-BTC framework is a facile strategy to attain more than 90% CHP selectivity
Summary
One of the unique features of MOFs compared to silicates is their high mass and volumetric loading of Co ions, making them more convenient from an engineering point of view, since it may diminish reactor costs that are related to the volume of the reactor [2] These transition metals are highly accessible depending on the pore dimensions and geometry of the MOF [2]. Mesoporous oxides and MOFs can have accessible pores, MOFs have some additional features like tailoring surface area [18], as a suitable host for high drug loading [19], possibility to install the desired functional groups in the linker moiety [20], entrapment of a wide range of guests (metal nanoparticles, polyoxometalates, tungstic acid) [21], and the development of photoactive materials [22], among others [23].
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