No abstract

Membrane gas separation is a mature and expanding technology. However, the availability of better membrane materials would promote faster growth. In this Perspective we analyze the state of the art of membrane materials, including polymers and hybrid materials, as well as the current issues and barriers, and finally, we outline future research directions in membrane science. Development of new membrane materials for large scale separations will rely on a multidisciplinary approach that embraces the broad fields of chemical and materials engineering, polymer science, and materials chemistry.

Metal–organic frameworks (MOFs) represent the largest known class of porous crystalline materials ever synthesized. Their narrow pore windows and nearly unlimited structural and chemical features have made these materials of significant interest for membrane-based gas separations. In this comprehensive review, we discuss opportunities and challenges related to the formation of pure MOF films and mixed-matrix membranes (MMMs). Common and emerging separation applications are identified, and membrane transport theory for MOFs is described and contextualized relative to the governing principles that describe transport in polymers. Additionally, cross-cutting research opportunities using advanced metrologies and computational techniques are reviewed. To quantify membrane performance, we introduce a simple membrane performance score that has been tabulated for all of the literature data compiled in this review. These data are reported on upper bound plots, revealing classes of MOF materials that consistently demonstrate promising separation performance. Recommendations are provided with the intent of identifying the most promising materials and directions for the field in terms of fundamental science and eventual deployment of MOF materials for commercial membrane-based gas separations.

The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes. Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal-organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework-polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes.

Triptycene-containing polyimide membranes with tunable fractional free volume promoting fast gas transport and selective separations.