Symmetric and Asymmetric Zeolitic Imidazolate Frameworks (ZIFs)/Polybenzimidazole (PBI) Nanocomposite Membranes for Hydrogen Purification at High Temperatures

Abstract 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 H 2 permeability as high as a hundred times without any significant deduction in H 2 /CO 2 selectivity. The 30/70 ZIF‐8/PBI dense membrane has a H 2 permeability of 105.4 Barrer and a H 2 /CO 2 selectivity of 12.3. This performance is far superior to ZIF‐7/PBI membranes and is the best ever reported data for H 2 ‐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 H 2 /CO 2 selectivity or high H 2 permeance are developed: i) PZM10‐I B fibers with a medium H 2 permeance of 64.5 GPU (2.16 ×10 −8 mol m −2 s −1 Pa −1 ) at 180°C and a high H 2 /CO 2 selectivity of 12.3, and, ii) PZM33‐I B fibers with a high H 2 permeance of 202 GPU (6.77 ×10 −8 mol m −2 s −1 Pa −1 ) at 180°C and a medium H 2 /CO 2 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.