Fabrication of Hofmann-type metal-organic framework based mixed-matrix membranes for efficient CH4/N2 separation

The analogous physical and chemical properties of methane (CH4) and nitrogen (N2) pose a great challenge for their separation. Mixed-matrix membranes (MMMs), combining the good separation performance of fillers and easy processability of polymers, are expected to address this challenging task. In this work, one Hofmann-type metal-organic framework (MOF), CoNi-DABCO, featuring abundant oppositely adjacent open metal sites, narrow pore size, and strong binding affinity toward CH4, is introduced into the polymer of polydimethylsiloxane to fabricate MMMs. The presence of CoNi-DABCO in the membranes could enhance the adsorption capacity for CH4, thus facilitating the transport of CH4 molecules through the membranes. Specially, the MMM containing 20 wt% CoNi-DABCO displays a high CH4 permeability of 1285 Barrer and maintains a good CH4/N2 mixed-gas selectivity of 3.7. Furthermore, the MMMs show good pressure resistance (up to 10 bar) and long-term stability for 30 days. This study suggests the potential of Hofmann-type MOF in the development of high-performance membranes for CH4/N2 separation. [Display omitted] •CoNi-DABCO, one Hofmann-type MOF, exhibits strong binding affinity toward CH4.•Hofmann-type MOF-based MMMs were prepared for CH4/N2 separation.•CH4 permeability increased over 100 % without sacrificing the CH4/N2 selectivity.