Few-cycle atomic layer deposition to nanoengineer polybenzimidazole for H₂/CO₂ separation

Atomic layer deposition (ALD) creates uniform sub-nanometer films on a variety of surfaces and nanopore walls and has been used to modify polymers to improve surface affinity towards specific molecules, solvent resistance, and barrier properties to gases and vapors. Here, for the first time, we demonstrate that few-cycle ALD can be used to engineer functional polymers at a sub-nanometer scale to improve both molecular size-sieving ability and counterintuitively, gas permeability. Particularly, 1-cycle ALD treatment of polybenzimidazole (PBI) by sequential exposure to trimethylaluminum (TMA) and water vapor remarkably increases H₂ permeability by 120% − 270% and H₂/CO₂ selectivity by 30% at 35–200 °C. The ALD not only deposits an AlO_x layer on the surface but also enables the TMA to infiltrate and react with the bulk PBI to form an AlO_x network, disrupting polymer chain packing and increasing chain rigidity. The membrane exhibits excellent stability when challenged with simulated syngas, overcoming the permeability/selectivity tradeoff for H₂/CO₂ separation. This study showcases a facile and scalable way of engineering polymeric membranes at a sub-nanometer level to improve molecular separation performance.