(77f) Structuring Metal-Organic Framework Materials into Hierarchically Porous Composites Via One-Pot Fabrication Strategy

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 while 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 robust and flexible hierarchically macro-meso-micro porous HKUST-1/polyvinylidene fluoride (PVDF) composite via solvent evaporation, in which MOF crystallization and polymer precipitation are combined together. The effect of MOF precursor and polymer initial amount on the morphology of final composite was thoroughly studied. The interaction between MOF and polymer during the evaporation process is the key factor, which would limit mobility of the polymer chains and cause instability in the MOF growth, thus endowing the composite with 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 CO₂ 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 the tested pressures.