MOF‐Based Hierarchically Porous Monoliths Prepared via High Internal Phase Emulsion Template: Morphology, Thermal Stability, Mechanical Property, and MOF Accessibility

Abstract In this work, hierarchically macro/microporous monolithic MOF composite materials are fabricated through the HIPE template. The effects of MOF loading on the pore structure, thermal stability, mechanical property, and MOF accessibility are systematically investigated. As the MOF loading increased, the average pore size and mechanical property decreased while the thermal stability increased. Meanwhile, when the MOF loading is low, the monolith exhibited a low BET surface area, suggesting a low MOF accessibility due to the clogging of MOF pores by polymer and the embedment of MOF particles inside the polymer matrix, while at high MOF loadings, the accessibility can be increased to ≈80% owing to the formation of percolation network of MOF particles inside the polymer matrix. Finally, the obtained monolith exhibited good catalytic performance and can be easily regenerated and reused. This work provides some fundamental understandings of the effect of MOF loading on the properties of HIPE‐based porous monoliths and can facilitate the further development of MOFs and their composites.