Bimetallic MOF-74-based mixed matrix membrane for efficient CO2 separation

Abstract

The bimetallic Ni(Zn)-MOF-74 nanoparticles were fabricated by the metal substitution method and doped into a polyether-polyamide block copolymer (Pebax 1657) matrix to obtain mixed matrix membrane (MMM) for CO2/CH4 separation. The pore structure and chemical properties of Ni(Zn)-MOF-74 nanoparticles were controlled by changing the molar ratio of Ni/Zn, and the effect of heterometallic on the gas separation performance of MMMs was studied. In particular, when the molar ratio of Ni/Zn was 2:1, the Pebax/Ni(Zn)-MOF-74-21 MMMs has the optimal CO2 separation performance. The main reason was that Ni(Zn)-MOF-74-21 has the smallest pore size (0.68 nm) and abundant CO2 adsorption sites, which could effectively prevent the entry of CH4 molecules after preferentially adsorbing one or two CO2 molecules, and improve the selectivity of CO2/CH4 molecules. Furthermore, the unreplaced pore size of 1.48 nm and the increased polymer chain spacing in Ni(Zn)-MOF-74-21 nanoparticles could provide a fast transport channel for CO2 and improve the permeability of MMMs. The developed Pebax/Ni(Zn)-MOF-74-21 MMMs loaded with 2 wt% filler displayed a CO2/CH4 selectivity of 33.7 and a high CO2 permeability of 719.9 barrer, exceeding the gas separation performance of many previously reported MOF-74-based MMMs. The results showed that the development and design of bimetallic organic framework was an important way to obtain high performance MOF-74-based MMM.