Carbon molecular sieve structure development and membrane performance relationships

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 CO2 permeability when compared to Matrimid® derived CMS formed under the same conditions, the CO2/CH4 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.