Effective and efficient transport mechanism of CO$_2$ in subnano-porous crystalline membrane of syndiotactic polystyrene

TL;DR

This study investigates the high selectivity and permeability of CO₂ in syndiotactic polystyrene crystalline membranes, revealing a mechanism based on cavity structure that enhances CO₂ transport and proposes new design criteria.

Contribution

It introduces a detailed analysis of CO₂ transport in s-PS S-I form, highlighting the role of cavity structure and proposing a novel membrane design criterion.

Findings

s-PS S-I form exhibits high CO₂ permeability and selectivity.

CO₂ molecules fit into specific cavities, increasing solubility.

Tri-atomic molecules diffuse more effectively than di-atomic ones.

Abstract

The gas permeation behavior in the single crystal of syndiotactic polystyrene (s-PS) S-I form was investigated in detail, in comparison to that in the s-PS $\varepsilon$ form. The S-I form exhibits high CO$_2$/N$_2$ and CO$_2$/CH$_4$ separation factors while preserving its high CO$_2$ permeability; a trade-off between selectivity and permeability was broken through.The mechanism of the effective and efficient transport of CO$_2$ in the S-I form was examined in relation to the cavity structure in the crystal. Because the CO$_2$ molecule is only fitted to the cavities in the S-I form, the solubility of CO$_2$ becomes high. In addition, tri-atomic molecules can more effectively diffuse in the S-I form compared with di-atomic molecules, as proved by the "long-gas" model. A novel design criterion for the CO$_2$ separation membranes is proposed based on the aspect of momentum transfer from polymer matrix to the penetrant.