A porous aromatic framework with mesopores was used as a platform for an immobilized Pd catalyst with superb catalytic activity and size selectivity for the Suzuki–Miyaura coupling reaction.

Porous aromatic frameworks (PAFs) with robust structure, high stability, and high surface area have attracted intense interest from scientists in diverse fields. However, there are still very few reports on the adsorption of organic dyes by PAFs. In this work, four new PAFs have been facilely synthesized by the polymerization of a tetrahedral‐shaped (four‐node) monomer with a series of three‐node monomers through Suzuki–Miyaura coupling reactions. All the obtained materials possess hierarchical porous structures and show high thermal and chemical stability. The Brunauer–Emmett–Teller (BET) surface areas of these PAFs were determined to be 857 m2 g−1 for PAF‐111, 526 m2 g−1 for PAF‐112A, 725 m2 g−1 for PAF‐112B, and 598 m2 g−1 for PAF‐113. Rhodamine B was selected as a model organic dye to test the adsorption capacities of the obtained PAF materials. PAF‐111 showed a maximum adsorption capacity of 1666 mg g−1 (167 wt %) for Rhodamine B, which is among the highest values reported to date for porous organic materials. It is noteworthy that PAF‐111 could be reused in at least ten cycles under the adsorption conditions without any loss of adsorption capacity. Our study has revealed the great potential and advantages of PAFs as ultrastable adsorption materials for the removal of organic dyes.

An amine-tagged hierarchical porous aromatic framework PAF70-NH2 with ultra-stability and narrowly distributed mesopores was synthesized. PAF70-NH2 has high potential for covalently immobilizing a relatively large-sized catalyst inside its pores. This work gave a perfect example of using PAF70-NH2 as a platform for completely recyclable heterogeneous organocatalysis.

High density of phenyl rings makes PAF-1 have robust structure and highly lipophilic pore, which make it very suitable for organocatalysis. However, there is no report about using PAF-1 as platform for enantioselective organocatalysis. In this paper, using PAF-1 as the platform, a chiral prolinamide catalytic site was introduced onto the framework of PAF-1 via a series of stepwise post-synthetic modifications, obtaining a novel PAF-supported chiral catalyst named PAF-1-NHPro. Then its enantioselective catalytic performance was studied by subjecting it to catalyze the model Aldol reaction between p-nitrobenzaldehyde and cyclohexanone. PAF-1-NHPro showed good diastereoselectivity and enantioselectivity with excellent and easy recyclability.

Porous aromatic frameworks (PAFs) that feature a high density of phenyl rings in their robust frameworks are attractive platforms for catalysis because of their extremely high stability, high surface area, and adjustable pore size. In this paper, two PAF‐supported ionic liquids were constructed by introducing ionic liquid units onto the framework of a PAF material PAF‐111 using a series of stepwise post‐synthetic modifications. The basic PAF‐supported ionic liquid with a hydroxy anion exhibited high catalytic activity and high stability, and could undergo at least 10 cycles without any activity loss when catalyzing Knoevenagel condensation reaction under aqueous conditions. It is expected that our study will further promote the development of designing and applying functional PAF materials for catalysis in aqueous systems.