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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) nanosheet-based 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.

Interlayer coupling in two-dimensional (2D) layered materials plays an important role in controlling their properties. 2H- and 3R-MoS2 with different stacking orders and the resulting interlayer coupling have been recently discovered to have different band structures and a contrast behavior in valley physics. However, the role of carrier doping in interlayer coupling in 2D materials remains elusive. Here, based on the electric double layer interface, we demonstrated the experimental observation of carrier doping-enhanced interlayer coupling in 3R-MoS2. A remarkable tuning of interlayer Raman modes can be observed by changing the stacking sequence and carrier doping near their monolayer limit. The modulated interlayer vibration modes originated from the interlayer coupling show a doping-induced blue shift and are supposed to be associated with the interlayer coupling enhancement, which is further verified using our first-principles calculations. Such an electrical control of interlayer coupling of layered materials in an electrical gating geometry provides a new degree of freedom to modify the physical properties in 2D materials.