Hydroxyl-functionalized linker endows an ultra-microporous aluminum based metal–organic framework with electronegative site for enhancing ethane/ethylene separation

Efficient purification of ethylene (C2H4) from the cracking gas containing a small amount of ethane (C2H6) by selective adsorption of C2H6 is meaningful but remains challenging. Aluminum-based metal–organic frameworks (Al-MOFs) with ultra-microporous structure show preferential adsorption of C2H6 over C2H4, relying on the existence of multiple hydrogen bonding acceptors (e.g., AlO6 polyhedra) for C2H6 molecule in the confined pores. However, most Al-MOFs exhibit limited C2H6/C2H4 selectivity (<2), which lack other strong preferential binding sites for C2H6. Here we report that a hydroxyl functionalized Al-MOF (i.e., CAU-1-OH) exhibits notably improved C2H6/C2H4 selectivity (2.13) and C2H6 uptake (3.95 mmol g−1) at 298 K and 1 bar compared to its amino-functionalized counterpart, CAU-1-NH2. Prior to experiment, theoretical calculations were performed, revealing that O atom from hydroxyl group in CAU-1-OH acts as a fairly strong hydrogen bond acceptor due to its more negative charge than N atom in CAU-1-NH2. The in-situ infrared experiment further confirmed the formation of multiple hydrogen bonds (C–H⋅⋅⋅O) between CAU-1-OH and C2H6 molecules, which plays vital role for C2H6-selective capture. The actual potential for C2H4 purification was fully demonstrated by dynamic breakthrough experiments, in which CAU-1-OH displayed excellent separative performance from C2H6/C2H4 (1/15, v/v) mixture. Moreover, the structural stability and excellent recyclability suggested and the promise for cost-effective industrial application in C2H6/C2H4 separation.