Structuring Metal–Organic Framework Materials into Hierarchically Porous Composites through One-Pot Fabrication Strategy

Graphical “All-in-one” porous structure : In this work, we introduce a straightforward one-pot fabrication strategy to prepare a robust and flexible hierarchically macro-meso-micro porous HKUST-1 / polyvinylidene fluoride composite by solvent evaporation, in which MOF crystallization and polymer precipitation are combined. The obtained composite showed an enhanced CO 2 adsorption rate and high gas adsorption capacity. Controlled synthesis of metal–organic framework (MOF)-based materials with multiple levels of porous structures across different length scales is of great interest in various applications but it still remains challenging. Most of the current strategies are time consuming and labor intensive, and not readily scaled-up. In this work, we introduce a straightforward one-pot fabrication strategy to prepare a robust and flexible hierarchically macro-meso-micro porous HKUST-1/polyvinylidene fluoride (PVDF) composite through solvent evaporation, in which MOF crystallization and polymer precipitation are combined together. The effect of the MOF precursor and the polymer initial amount on the morphology of the final composite was thoroughly studied. The interaction between the MOF and the polymer during the evaporation process is the key factor, which would limit the mobility of the polymer chains and cause instability in the MOF growth, thus endowing the composite with a hierarchically macro-meso-micro porous structure. This “all-in-one” porous structure could enhance the mass transport property of molecules within the composite. The obtained HKUST-1/PVDF composite showed an enhanced CO 2 adsorption rate constant of 0.821 min −1 (298 K, 1 bar), which was 3.5 times higher than that of the pristine MOF. In addition, the composite showed an equivalent gas adsorption capacity under all tested pressures and greatly improved water stability.