Amidation‐Reaction Strategy Constructs Versatile Mixed Matrix Composite Membranes towards Efficient Volatile Organic Compounds Adsorption and CO₂ Separation

Abstract Mixed matrix composite membranes (MMCMs) have shown advantages in reducing VOCs and CO₂ emissions. Suitable composite layer, substrate, and good compatibility between the filler and the matrix in the composite layer are critical issues in designing MMCMs. This work develops a high‐performance UiO‐66‐NA@PDMS/MCE for VOCs adsorption and CO₂ permea‐selectivity, based on a simple and facile fabrication of composite layer using amidation‐reaction approach on the substrate. The composite layer shows a continuous morphological appearance without interface voids. This outstanding compatibility interaction between UiO‐66‐NH₂ and PDMS is confirmed by molecular simulations. The Si─O functional group and UiO‐66‐NH₂ in the layer leads to improved VOCs adsorption via active sites, skeleton interaction, electrostatic interaction, and van der Waals force. The layer and ─CONH─ also facilitate CO₂ transport. The MMCMs show strong four VOCs adsorption and high CO₂ permeance of 276.5 GPU with a selectivity of 36.2. The existence of VOCs in UiO‐66‐NA@PDMS/MCE increases the polarity and fine‐tunes the pore size of UiO‐66‐NH₂, improving the affinity towards CO₂ and thus promoting the permea‐selectivity for CO₂, which is further verified by GCMC and EMD methods. This work is expected to offer a facile composite layer manufacturing method for MMCMs with high VOC adsorption and CO₂ permea‐selectivity.