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Covalent organic frameworks (COFs), with two dimensional (2D-) or three dimensional (3D-) structures, have accessible open channels or nanopores, with uniform sizes ranging from angstroms to nanometers and have emerged as an excellent and promising platform for designing catalysts or catalyst carriers. Herein, a 2D-COF grafted with a 1-alkyl-3-methylimidazolium-based ionic liquid (AMIMBr@H2P-DHPh COF) on the channel walls was synthesized and utilized as a highly efficient heterogeneous catalyst for the chemical fixation of CO2 via a reaction with epoxides under solvent-free and co-catalyst-free conditions. The as-synthesized AMIMBr@H2P-DHPh COF shows excellent catalytic activity in promoting the cycloaddition reactions between epoxide and CO2; the excellent catalytic activity was maintained for up to five cycles. Advantages like high porosity, functional versatility, easy modification of COFs, and high catalytic activity of ionic liquids, have been realized in a single material.

As an emerging class of crystalline porous materials, covalent organic frameworks (COFs) have been widely used as catalysts or catalyst supports. Flexible regulation of the pores and easy introduction of functional active sites onto the skeleton of COFs make them promising platforms for many catalysis applications. However, only a single function is generally observed in these COFs. Herein, we synthesized a negatively charged ionic COF (I-COF) and successfully incorporated functionalized counter ions, that is, metallic Mn2+ and a coordination complex of manganese(II) bipyridine complexes ([Mn(bpy)2]2+), via a simple ion exchange process. The resulting I-COFs can act as effective heterogeneous catalysts for epoxidation reactions. We envisage that with this type of ionic architecture, a variety of other functional cations could be exchanged into the frameworks, thus making the COF a versatile platform for different applications.

Covalent organic frameworks (COFs), established as an emerging class of crystalline porous polymers with high surface area, structural diversity, and designability, attract much interest and exhibit potential applications in catalysis. In this review, we summarize the use of COFs as a versatile platform to develop heterogeneous catalysts for a variety of chemical reactions. Catalytic COFs are categorized in accordance with the types of active sites, involving single functional active sites, bifunctional active sites, and metal nanoparticles (NPs) embedded in pores. Special emphasis is placed on the deliberate or incidental synthesis strategies, the stability, the heterogeneity, and the shape/size selectivity for COF catalysis. Moreover, a description of the application of COFs as photocatalysts and electrocatalysts is presented. Finally, the prospects of COFs in catalysis and remaining issues in this field are indicated.