Materials research is key to enable synthetic membranes for large-scale, energy-efficient molecular separations. Materials with rigid, engineered pore structures add an additional degree of freedom to create advanced membranes by providing entropically moderated selectivities. Scalability - the capability to efficiently and economically pack membranes into practical modules - is a critical yet often neglected factor to take into account for membrane materials screening. In this Progress Article, we highlight continuing developments and identify future opportunities in scalable membrane materials based on these rigid features, for both gas and liquid phase applications. These advanced materials open the door to a new generation of membrane processes beyond existing materials and approaches.

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Understanding the crystal-size dependence of both guest adsorption and structural transitions of nanoporous solids is crucial to the development of these materials. We find that nano-sized metal–organic framework (MOF) crystals have significantly different guest adsorption properties compared to the bulk material. A new methodology is developed to simulate the adsorption and transition behavior of entire MOF nanoparticles. Our simulations predict that the transition pressure significantly increases with decreasing particle size, in agreement with crystal-size-dependent experimental measurements of the N2-ZIF-8 system. We also propose a simple core–shell model to examine this effect on length scales that are inaccessible to simulations and again find good agreement with experiments. This study is the first to examine particle size effects on structural transitions in ZIFs and provides a thermodynamic framework for understanding the underlying mechanism.

Ethylene/ethane separation via cryogenic distillation is extremely energy‐intensive, and membrane separation may provide an attractive alternative. In this paper, ethylene/ethane separation performance using polymeric membranes is summarized, and an experimental ethylene/ethane polymeric upper bound based on literature data is presented. A theoretical prediction of the ethylene/ethane upper bound is also presented, and shows good agreement with the experimental upper bound. Further, two ways to overcome the ethylene/ethane upper bound, based on increasing the sorption or diffusion selectivity, is also discussed, and a review on advanced membrane types such as facilitated transport membranes, zeolite and metal organic framework based membranes, and carbon molecular sieve membranes is presented. Of these, carbon membranes have shown the potential to surpass the polymeric ethylene/ethane upper bound performance. Furthermore, a convenient, potentially scalable method for tailoring the performance of carbon membranes for ethylene/ethane separation based on tuning the pyrolysis conditions has also been demonstrated. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3475–3489, 2013

Characterization techniques beyond microscopy, scattering and spectroscopy approaches are needed to understand and improve sub-angstrom discrimination between penetrants in carbon molecular sieve (CMS) membranes. Here we use a method based on molecular scale gas diffusion probes to understand relevant membrane properties at the required level of detail. We further use this method to consider hypotheses about the evolution of structure responsible for fundamental properties of CMS materials derived from a high performance CMS precursor polymer, 6FDA:BPDA-DAM. While 6FDA:BPDA-DAM derived CMS membranes display a ~230 % improvement in CO 2 permeability when compared to Matrimid ® derived CMS formed under the same conditions, the diffusional selectivity for these two materials are very similar at 35 and 38.5, respectively. These results indicate a non-trivial connection between CMS precursor material structure and resulting performance. Linking hypotheses about structural changes likely to occur during pyrolysis with the probe data provides insights regarding transformation of the random coil polyimide into ultra-rigid CMS, with exquisite size and shape diffusion selectivity. The results provide a framework for understanding and tuning properties of this special class of materials with important technological advantages in energy-intensive gas separations.