Pervaporation has been regarded as a promising separation technology in separating azeotropic mixtures, solutions with similar boiling points, thermally sensitive compounds, organic-organic mixtures as well as in removing dilute organics from aqueous solutions. As the pervaporation membrane is one of the crucial factors in determining the overall efficiency of the separation process, this article reviews the research and development (R&D) of polymeric pervaporation membranes from the perspective of membrane fabrication procedures and materials.

High‐performance zeolitic imidazolate frameworks (ZIFs)/polybenzimidazole (PBI) nanocomposites are molecularly designed for hydrogen separation at high temperatures, and demonstrate it in a useful configuration as dual‐layer hollow fibers for the first time. By incorporating as‐synthesized nanoporous ZIF‐8 nanoparticles into the high thermal stability but extremely low permeability polybenzimidazole (PBI), the resultant mixed matrix membranes show an impressive enhancement in H2 permeability as high as a hundred times without any significant deduction in H2/CO2 selectivity. The 30/70 ZIF‐8/PBI dense membrane has a H2 permeability of 105.4 Barrer and a H2/CO2 selectivity of 12.3. This performance is far superior to ZIF‐7/PBI membranes and is the best ever reported data for H2‐selective polymeric materials in the literature. Meanwhile, defect‐free ZIF‐8‐PBI/Matrimid dual‐layer hollow fibers are successfully fabricated, without post‐annealing and coating, by optimizing ZIF‐8 nanoparticle loadings, spinning conditions, and solvent‐exchange procedures. Two types of hollow fibers targeted at either high H2/CO2 selectivity or high H2 permeance are developed: i) PZM10‐I B fibers with a medium H2 permeance of 64.5 GPU (2.16 ×10−8 mol m−2 s−1 Pa−1) at 180°C and a high H2/CO2 selectivity of 12.3, and, ii) PZM33‐I B fibers with a high H2 permeance of 202 GPU (6.77 ×10−8 mol m−2 s−1 Pa−1) at 180°C and a medium H2/CO2 selectivity of 7.7. This work not only molecularly designs novel nanocomposite materials for harsh industrial applications, such as syngas and hydrogen production, but also, for the first time, synergistically combines the strengths of both ZIF‐8 and PBI for energy‐related applications.

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