Trimodal Hierarchical Porous Metal–Organic Frameworks with Tunable Mesoporous Core–Shell Architectures

The synthesis of metal–organic frameworks (MOFs) with a defined multimodal porous structure is still challenging in synthetic methodology. Herein, we report a cotemplating strategy to synthesize hierarchical Ce-based MOFs with tunable dual-mesopores and core–shell architectures using the diblock copolymer poly(ethylene oxide-b-caprolactone) (PEO-b-PCL) and the poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (F127) as soft templates. The resultant MOFs possess high surface areas and two sets of uniform mesopores with diameters of ∼9.5 and 24 nm contributed by F127 and PEO-b-PCL, respectively. The thickness of the shell can be simply tuned by adjusting the feed ratio of two templates and changing the polarity of the synthesis system. This facile cotemplating assembly approach is expected to offer new opportunities in exploring the design of MOFs with sophisticated multimodal mesostructures for various applications.