Adsorption space for microporous polymers with diverse adsorbate species

Abstract

Abstract The enormous number of combinations of adsorbing molecules and porous materials that exist is known as adsorption space. The adsorption space for microporous polymers has not yet been systematically explored, especially when compared with efforts for crystalline adsorbents. We report molecular simulation data for the adsorptive and structural properties of polymers of intrinsic microporosity with a diverse set of adsorbate species with 345 distinct adsorption isotherms and over 240,000 fresh and swollen structures. These structures and isotherms were obtained using a sorption-relaxation technique that accounts for the critical role of flexibility of the polymeric adsorbents. This enables us to introduce a set of correlations that can estimate adsorbent swelling and fractional free volume dilation as a function of adsorbate uptake based on readily characterized properties. The separation selectivity of the 276 distinct binary molecular pairs in our data is reported and high-performing adsorbent systems are identified.