AbstractIonene – ionic liquid (IL) composites are promising materials for CO2 separation, yet a molecular‐level understanding of their structure and its impact on CO2 speciation, solubility, rotation, and diffusivity remains unclear. Herein, using multimodal nuclear magnetic resonance (NMR), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS), atomic force microscopy (AFM), and molecular dynamics (MD) simulations, we reveal that the composites contain IL‐rich domains extending across hundreds of nanometres within the ionene matrix, and these bicontinuous domains span the entire membrane depth. CO2 also absorbs into the ionene matrix, with the distribution between two CO2 species varying with temperature and time. The rotational correlation times of these two species are on the timescale of 0.1 and 1 ns, respectively. As IL content increases, the ionic domains expand, resulting in higher CO2 solubility due to enhanced molecular dynamics and increased free volume in both ionene backbones and IL‐rich regions. Although CO2 diffusion in the membranes is an order of magnitude slower than in bulk IL, the activation energy for CO2 diffusion remains comparable. Ionene‐IL composites represent a promising platform for designing CO2 separation membranes, offering enhanced CO2diffusion and selectivity through IL‐rich domains, and increased CO2 solubility and mechanical integrity from the ionene matrix.
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