Boosting Ethane/Ethylene Separation within Isoreticular Ultramicroporous Metal–Organic Frameworks

The separation of ethane from its
analogous ethylene is of great importance in the petrochemical industry,
but very challenging and energy intensive. Adsorptive separation using
C2H6-selective porous materials can directly
produce high-purity C2H4 in a single operation
but suffers from poor selectivity. Here, we report an approach to
boost the separation of C2H6 over C2H4, involving the control of pore structures in two isoreticular
ultramicroporous metal–organic framework (MOF) materials with
weakly polar pore surface for strengthened binding affinity toward
C2H6 over C2H4. Under
ambient conditions, the prototypical compound shows a very small uptake
difference and selectivity for C2H6/C2H4, whereas its smaller-pore isoreticular analogue exhibits
a quite large uptake ratio of 237% (60.0/25.3 cm3 cm–3), remarkably increasing the C2H6/C2H4 selectivity. Neutron powder diffraction
studies clearly reveal that the latter material shows self-adaptive
sorption behavior for C2H6, which enables it
to continuously maintain close van der Waals contacts with C2H6 molecules in its optimized pore structure, thus preferentially
binds C2H6 over C2H4.
Gas sorption isotherms, crystallographic analyses, molecular modeling,
selectivity calculation, and breakthrough experiment comprehensively
demonstrate this unique MOF material as an efficient C2H6-selective adsorbent for C2H4 purification.