Atomically Fine-Tuning Organic-Inorganic Carbon Molecular Sieve Membranes for Hydrogen Production

Polymeric membranes with great processability are attractive for the H₂/CO₂ separation required for hydrogen production from renewable biomass with carbon capture for utilization and sequestration. However, it remains elusive to engineer polymer architectures to obtain desired sub-3.3 Å ultramicropores to efficiently sieve H₂ from CO₂. Herein, we demonstrate a scalable way of carbonizing polybenzimidazole (PBI) at low temperatures, followed by vapor phase infiltration (VPI) to atomically narrow ultramicropores throughout the films, forming hybrid organic-inorganic carbon molecular sieves (CMSs). One VPI cycle (100 s) for the PBI carbonized at 500 °C remarkably increases H₂/CO₂ selectivity from 9.6 to 83 at 100 °C, surpassing Robeson's upper bound. The CMS demonstrates a stable H₂/CO₂ separation performance when challenged with simulated syngas streams and can be fabricated into thin-film composite membranes, outperforming state-of-the-art membranes. The scalable approach can be ubiquitous to molecularly fine-tune ultramicropores of leading polymeric membranes to further improve their size-sieving ability and thus separation efficiency.