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Developing a facile strategy to synthesize free-standing defect-free metal–organic framework (MOF) membranes with high separation selectivity and good mechanical stability is very appealing but challenging. Herein, by confining the reaction of metal and ligand at the quasi-interface, a representative membrane composed of a continuous ZIF-8 layer and poly(vinyl alcohol) (PVA) was fabricated. The continuous ZIF-8 layer endowed the membrane with high separation efficiency, while PVA acted as a filler to eliminate the defection, synergistically achieving high selective ion transport and good mechanical stability. The continuous defect-free ZIF-8/PVA membrane showed excellent separation performance of selective ion transport with high Li+permeance of 17.83 mol·m–2·h–1as well as decent Li+/Mg2+and Li+/Ca2+selectivities of 24.60 and 244.58, respectively. The separation performance of the ZIF-8/PVA membrane remained stable after 10% strain, indicating its good mechanical stability. This work will promote the development of MOF-based membranes in practical applications.

In human life and production, excessive oily wastewaters containing detergents are produced and discharged, causing severe environmental pollution and water resource problems. A metal–organic framework (MOF)-based membrane is an economical and environmentally friendly tool for emulsion separation but is limited by a complex preparation process and poor flexibility. Herein, we developed a simple method to synthesize a MOF-based mixed-matrix membrane (MMM) by spray and fabricated the membrane on poly(vinylidene fluoride) (PVDF) fibers via postdeposition and in situ growth manners. The prepared ZIF-8/PVA MMMs have uniform distribution of ZIF-8 particles and poly(vinyl alcohol) (PVA) on the PVDF fibers. PVA improved the adhesion between the ZIF-8 particles and between the MOF layer and PVDF fiber, endowing the separation membrane with high flexibility and bendability. The prepared ZIF-8/PVA membrane exhibited hydrophilicity and underwater superoleophobicity, which showed high separation efficiency and considerable water flux for emulsions, emulsion containing dye, and surfactant-stabilized emulsion. In addition, the fabricated ZIF-8/PVA/PVDF fibers exhibited good antifouling property and flexibility and can maintain stable separation efficiency after working several times and even under bending, demonstrating the stability and potentiality of the ZIF-8/PVA/PVDF fibers in practical applications. This work paves a new avenue for the synthesis and application of MOF-based MMMs.