In-situ etching MOF nanoparticles for constructing enhanced interface in hybrid membranes for gas separation

Metal-organic frameworks (MOFs) based hybrid membranes have great potential for energy-efficient gas separation. However, the defective interface structure greatly depresses their separation performance. In this work, a distinctive interfacial design strategy via in-situ etching ZIF-8 nanoparticles is proposed to construct hybrid membranes with nearly defect-free interfaces. The nanoscale etching of ZIF-8 nanoparticles in polymer matrix with acid group (PI-COOHx) is well controlled by the amount of carboxyl group and reaction time. Owing to the strong coordination interaction between Zn2+ ions and -COOH groups, the residual ZIF-8 nanoparticles are tightly wrapped by polymer matrix. Molecular simulation was performed to study the in-situ etching ZIF-8 in PICOOHx matrix in molecular level. The resulted hybrid membranes (PI-COOHx/E-ZIF-8) exhibit simultaneously enhanced permeability and selectivity with increasing filler loading content. Benefiting from the rational interfacial design, the effective loading content of ZIF-8 nanoparticles is up to 50 wt% for PI-COOH20/E-ZIF-8 membrane. The H2, CO2, and O2 permeability of the membrane are 3058.6, 1429.0, and 459.0 Barrer, increasing by 468.5%, 288.3% and 348.2%, respectively, of pristine PI-COOH20 membrane, and the gas selectivity for H2/ N2, H2/CH4, O2/N2, and CO2/CH4 gas pairs are greatly improved from 20.3, 23.4, 3.9 and 16.0 of pristine PICOOH20 membrane to 30.7, 37.6, 4.6 and 17.6. The comprehensive separation performance for H2/N2, H2/CH4, and O2/N2 gas pairs surpass the 2008 upper bound and approach the 2015 upper bound. Meanwhile, the CO2 plasticization resistance of PI-COOH20/E-ZIF-8 membrane also achieves significant improvement from 6 bar of PI-COOH20 membrane to 27 bar. This work provides an effective and robust strategy to effectively enhance the interfacial compatibility of hybrid membranes.

Automated summary

Metal-organic frameworks (MOFs) based hybrid membranes with nearly defect-free interfaces were constructed through a distinctive interfacial design strategy via in-situ etching ZIF-8 nanoparticles. The hybrid membranes exhibited enhanced permeability and selectivity, surpassing the upper bound of 2008 and approaching the upper bound of 2015 for several gas pairs. The CO2 plasticization resistance also achieved significant improvement. This work provides an effective and robust strategy to enhance the interfacial compatibility of hybrid membranes.