Polyimide/Ionic Liquids Hybrid Membranes with NH3-Philic Channels for Ammonia-Based CO2 Separation Processes

An efficient separation technology involving ammonia (NH3) and carbon dioxide (CO2) is of great importance for achieving low-carbon economy, environmental protection, and resource utilization. However, directly separating NH3 and CO2 for ammonia-based CO2 capture processes is still a great challenge. Herein, we propose a new strategy for selective separation of NH3 and CO2 by functional hybrid membranes that integrate polyimide (PI) and ionic liquids (ILs). The incorporated protic IL [Bim][NTf2] is confined in the interchain segment of PI, which decreases the fractional free volume and narrows the gas transport channel, benefiting the high separation selectivity of hybrid membranes. At the same time, the confined IL also provides high NH3 affinity for transport channels, promoting NH3 selective and fast transport owing to strong hydrogen bonding interaction between [Bim][NTf2] and NH3 molecules. Thus, the optimal hybrid membrane exhibits an ultrahigh NH3/CO2 ideal selectivity of up to 159 at 30 °C without sacrificing permeability, which is 60 times higher than that of the neat PI membrane and superior to the state-of-the art reported values. Moreover, the introduction of [Bim][NTf2] also reduces the permeation active energy of NH3 and reverses the hybrid membrane toward “NH3 affinity”, as understood by studying the effect of temperature. Also, NH3 molecules are much easier to transport at high temperature, showing great application potential in direct NH3/CO2 separation. Overall, this work provides a promising ultraselective membrane material for ammonia-based CO2 capture processes.