Porous silica nanosheets in PIM-1 membranes for CO2 separation

PIM-1-based freestanding mixed matrix membranes (MMMs) and thin film nanocomposites (TFNs) were prepared by incorporating porous silica nanosheets (SN) and exfoliated SN (E-SN) derived from natural vermiculite (Verm) in the PIM-1 polymer matrix. In addition, SN were functionalized by sulfonic acid and amine groups (S-SN and N-SN, respectively) and were also used as fillers for the preparation of MMMs. The gas separation performance was evaluated using CO2/CH4 and CO2/N2 (1:1, v:v) binary gas mixtures. Among freestanding membranes, fresh ones (i.e. tested right after preparation) containing 0.05 wt% functionalized SN and E-SN outperformed the neat PIM-1, surpassing the 2008 Robeson upper bound. At the same filler concentration, fresh MMMs with sulfonic acid-functionalized SN (S-SN) exhibited 40% higher CO2 permeability, 20% higher CO2/N2 selectivity and almost the same CO2/CH4 selectivity as neat PIM-1 membranes. Moreover, after 150 days of aging, these membranes were capable of maintaining up to 68% of their initial CO2 permeability (compared to 37% for neat PIM-1). When prepared as TFN membranes, the incorporation of 0.05 wt% of S-SN led to 35% higher initial CO2 permeance and five times higher CO2 permeance after 28 days.