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

作者：Leiqing Hu, Won‐Il Lee, Kai Chen, Soumyabrata Roy, Kieran Fung, Kim Kisslinger, Erda Deng, Yifu Ding, Pulickel M. Ajayan, Chang‐Yong Nam, Haiqing Lin · 发表于：ACS Nano · 年份：2025 · DOI：10.1021/acsnano.4c15126 · 被引用次数：18 · 研究领域：Membrane Separation and Gas Transport、Graphene research and applications、Fuel Cells and Related Materials

Polymeric membranes with great processability are attractive for the H 2 /CO 2 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 H 2 from CO 2 . 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 H 2 /CO 2 selectivity from 9.6 to 83 at 100 °C, surpassing Robeson’s upper bound. The CMS demonstrates a stable H 2 /CO 2 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.