Nanospace Engineering of Metal-Organic Frameworks through Dynamic Spacer Installation of Multifunctionalities for Efficient Separation of Ethane from Ethane/Ethylene Mixtures.

Herein, a dynamic spacer installation (DSI) strategy has been implemented to construct a series of multifunctional metal-organic frameworks (MOFs), LIFM-61/31/62/63, with optimized pore space and pore environment for ethane/ethylene separation. In this respect, a series of linear dicarboxylic acids were deliberately installed in the prototype MOF, LIFM-28, leading to a dramatically increased pore volume (from 0.41 to 0.82 cm  g ) and reduced pore size (from 11.1×11.1 Å to 5.6×5.6 Å ). The increased pore volume endows the multifunctional MOFs with much higher ethane adsorption capacity, especially for LIFM-63 (4.8 mmol g ), representing nearly three times as much ethane as the prototypical counterpart (1.7 mmol g ) at 273 K and 1 bar. Meanwhile, the reduced pore size imparts enhanced ethane/ethylene selectivity of the multifunctional MOFs. Theoretical calculations and dynamic breakthrough experiments confirm that the DSI is a promising approach for the rational design of multifunctional MOFs for this challenging task.