Microporous polymers with cascaded cavities for controlled transport of small gas molecules

In membrane-based separation, molecular size differences relative to membrane pore sizes govern mass flux and separation efficiency. In applications requiring complex molecular differentiation, such as in natural gas processing, cascaded pore size distributions in membranes allow different permeate molecules to be separated without a reduction in throughput. Here, we report the decoration of microporous polymer membrane surfaces with molecular fluorine. Molecular fluorine penetrates through the microporous interface and reacts with rigid polymeric backbones, resulting in membrane micropores with multimodal pore size distributions. The fluorine acts as angstrom-scale apertures that can be controlled for molecular transport. We achieved a highly effective gas separation performance in several industrially relevant hollow-fibrous modular platform with stable responses over 1 year.