Pore-Window Partitions in Metal-Organic Frameworks for Highly Efficient Reversed Ethylene/Ethane Separations.

Abstract

The development of paraffin-selective adsorbents is desirable but extremely challenging because adsorbents usually prefer olefin over paraffin. Herein, a new pore-window-partition strategy is proposed for the rational design of highly efficient paraffin-preferred metal-organic framework (MOF) adsorbents. The power of this strategy is demonstrated by stepwise installations of linear bidentate N-donor linkers into a prototype MOF (SNNU-201) to produce a series of partitional MOF adsorbents (SNNU-202-204). With continuous pore-window partitions from SNNU-201 to SNNU-204, the isosteric heat of adsorption can be tuned from -34.4 to -19.4 kJ mol-1 for ethylene and from -25.5 to -20.7 kJ mol-1 for ethane. Accordingly, partitional MOFs exhibit much higher ethane adsorption capacities, especially for SNNU-204 (104.6 cm3 g-1), representing nearly 4 times as much ethane as the prototypical counterpart (SNNU-201; 27.5 cm3 g-1) under ambient conditions. The C2H6/C2H4 ideal adsorbed solution theory selectivity, dynamic breakthrough experiments, and theoretical simulations further indicate that pore-window partition is a promising and universal strategy for the exploration of highly efficient paraffin-selective MOF adsorbents.