Mixed matrix membranes containing MOF@COF hybrid fillers for efficient CO₂/CH₄ separation

Membrane technology has aroused great attention for gas separations due to its high energy efficiency, small capital investment, easy and continuous operation. Mixed matrix membranes (MMMs) constructed from a continuous polymer phase and a dispersed filler phase offer new opportunities to achieve a breakthrough in fabricating high-performance membranes. Metal–organic frameworks (MOFs) have been regarded as potential fillers to boost the MMM separation performance. However, MOFs occasionally exhibit limited compatibility with the polymer matrixes owing to their partially inorganic structure and tendency of agglomeration in the membranes. Here, an interfacial design strategy is demonstrated by coating size-selective MOF cores with covalent organic framework (COF) layers to construct MOF@COF hybrids as fillers in MMMs for enhanced polymer-filler compatibility. The pure organic COF layers exhibit high affinity to the polymer matrix, thereby preventing the formation of nonselective interfacial voids and alleviating filler agglomeration. With the incorporation of only 5 wt% of MOF@COF fillers, the resultant MMM exhibits 48% and 79% enhancements in CO₂ permeability and CO₂/CH₄ selectivity, respectively, with better operational stability compared to that of the pure polymeric membrane. These results reveal a novel filler design strategy for the tailored synthesis of high-performance MMMs for natural gas and biogas purification.