Multivariate Porous Aromatic Frameworks with High Porosity and Hierarchical Structures for Enzyme Immobilization.

As materials with permanently porous structures and readily modifying availability, porous aromatic frameworks (PAFs) are considered as promising porous materials with versatile functionality. Currently the designable synthesis of PAFs with the desired surface area and pore size is still a challenge, and instead kinetically irreversible coupling reactions for PAFs synthesis has resulted in the unpredictable connection of building units. Herein, a series of PAFs with highly porous and hierarchical structures were successfully synthesized through a multivariate inspired strategy, where multiple building units with various topologies and sizes were selected for PAFs synthesis. All the PAFs synthesized through this strategy possessed hierarchical structures and high specific surface areas at the same time. Encouraged by their high surface area and hierarchical structures, we loaded lipase onto one of the multivariate PAFs. The enzyme loading content of the obtained lipase@PAF-147 was as high as 1456 mg g-1, which surpassed any other currently reported enzyme loading materials. The lipase@PAF-147 also exhibited favorable catalytic activity and stability to a model reaction of p-nitrophenyl caprylate (p-NPC) hydrolysis. This multivariate strategy inspired synthetic method broadens the selection of building units for PAFs design and opens a new avenue for the design of functional porous materials.