Polybenzimidazole Membranes Modified with Porous Aromatic Frameworks: Synthesis, Structure, Mechanical and Transport Properties

High-temperature proton exchange membrane systems (HT-PEM) based on polybenzimidazole (PBI) membranes are a promising technology offering significant advantages over their low-temperature counterparts. A key challenge limiting its long-term durability is the leaching of phosphoric acid (PA) from the membrane during operation. This work introduces, for the first time, the strategy of modifying polybenzimidazole (PBI) membranes with amino-functionalized porous aromatic frameworks (PAF-20-NH₂) to fundamentally enhance their PA retention and operational stability, a critical challenge for high-temperature PEM technologies. We propose that the synergistic combination of the framework’s nanoscale porosity and the specific interaction of its amino groups create an unprecedented network for acid immobilization via reinforced hydrogen bonding. A comprehensive study of the membranes’ physicochemical and structural properties reveals that PAF-20-NH₂ modification results in a significant and quantitatively demonstrated improvement in acid retention capacity, directly translating into a notable increase in proton conductivity compared to both pristine PBI and membranes modified with the non-functionalized PAF-20. These findings establish a new, highly effective pathway for the rational design of next-generation high-performance PBI-based membranes.