Selective adsorption of malachite green (MG) and fuchsin acid (FA) by ZIF-67 hybridized polyvinylidene fluoride (PVDF) membranes.

MOF/polymer hybrid membranes integrate the surface activity of MOFs and the advantages of PVDF membranes, and can be used as adsorption membranes in the efficient removal of target organics. In this work, a new hybrid membrane of ZIF-67/PVDF with varying ZIF-67 dosages has been fabricated through a facile mechanical blending followed by a lyotropic phase transition. Methods including field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), FT-IR analyses and surface hydrophobicity/hydrophilicity measurements are applied to characterize the structure, physicochemical properties and membrane performances. Two synthetic triarylmethane dyes, cationic malachite green (MG) and anionic fuchsin acid (FA), are chosen as the main adsorption targets to evaluate the adsorption capacities of the resulting ZIF-67/PVDF hybrid membranes. Interestingly, all of the ZIF-67/PVDF hybrid membranes exhibit distinctly favorable efficiencies and selectivities toward MG and FA compared to pristine PVDF, which proves the positive roles of ZIF-67 in the adsorption ability of the hybrid membranes. The adsorption conditions are optimized and the adsorption kinetics and thermodynamics are analysed to study the adsorption mechanism. The reusability and the structural stability of the hybrid membranes undergoing cyclic adsorption processes are also discussed. To the best of our knowledge, this is the first time that good adsorption capacities for MG and FA for these MOF/PVDF membranes have been reported. This work highlights the prospective applications of MOF/PVDF hybrid membranes in the rapid and effective removal of target organics in the treatment of waste water.