MOF Nanosheet-Based Mixed Matrix Membranes with Metal− Organic Coordination Interfacial Interaction for Gas Separation
Xiangyu Bi1, Yong’an Zhang2, Feng Zhang1, Shenxiang Zhang2, Zhenggong Wang1,*（王正宫）, and Jian Jin1, 2,*（靳健）
1College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
2i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, China
ACS Appl. Mater. Interfaces2020, 12, 49101--49110
In the mixed matrix membrane (MMM), the interface between the filler and the polymer matrix will directly affect the gas separation performance of the membranes. Reasonable interfacial design in MMMs is thus important and necessary. In this work, metal−organic coordination interaction is used to construct the interface in metal−organic framework (MOF) nanosheetbased polyimide MMMs where ultrathin Co-benzenedicarboxylate MOF nanosheets (CBMNs) with a thickness less than 5 nm and a lateral size more than 5 μm are synthesized as fillers and a carboxyl-functionalized polyimide (6FDA-durene-DABA) is used as a polymer matrix. Because of the high aspect ratio (>1000) of CBMNs, abundant metal−organic coordination bonds are formed between Co2+ in CBMNs and the −COOH group in 6FDA-durene-DABA. As a result, the 6FDA-durene-DABA/CBMN MMMs exhibit improved separation performance for the CO2/CH4 and H2/CH4 gas pairs with H2/CH4 and CO2/CH4 selectivities up to 42.0 ± 4.0 and 33.6 ± 3.0, respectively. The enhanced interfacial interaction leads to the comprehensive separation performance of CO2/CH4 and H2/CH4 gas pairs approaching or surpassing the 2008 Robeson upper bound. In addition, the CO2 plasticization pressure of the MMMs is significantly enhanced up to ∼20 bar, which is 2 times that of the pure 6FDA-durene-DABA membrane. When separating a mixed gas of CO2/CH4, the selectivity of CO2/CH4 remains stable at around 23 and the CO2 permeability keeps around 400 barrer during the long-term test.