Phosphoric Acid Doped Polybenzimidazole (PBI)/Zeolitic Imidazolate Framework Composite Membranes with Significantly Enhanced Proton Conductivity under Low Humidity Conditions

The preparation and characterization of composite polybenzimidazole (PBI) membranes containing zeolitic imidazolate framework 8 (ZIF-8) and zeolitic imidazolate framework 67 (ZIF-67) is reported. The phosphoric acid doped composite membranes display proton conductivity values that increase with increasing temperatures, maintaining their conductivity under anhydrous conditions. The addition of ZIF to the polymeric matrix enhances proton transport relative to the values observed for PBI and ZIFs alone. For example, the proton conductivity of PBI@ZIF-8 reaches 3.1 × 10-3 S·cm-1 at 200 °C and higher values were obtained for PBI@ZIF-67 membranes, with proton conductivities of up to 4.1 × 10-2 S·cm-1. Interestingly, a composite membrane containing a 5 wt.% binary mixture of ZIF-8 and ZIF-67 yielded a proton conductivity of 9.2 × 10-2 S·cm-1, showing a synergistic effect on the proton conductivity.