Ionic liquids have attracted the attention of the industry and research community as versatile solvents with unique properties, such as ionic conductivity, low volatility, high solubility of gases and vapors, thermal stability, and the possibility to combine anions and cations to yield an almost endless list of different structures. These features open perspectives for numerous applications, such as the reaction medium for chemical synthesis, electrolytes for batteries, solvent for gas sorption processes, and also membranes for gas separation. In the search for better-performing membrane materials and membranes for gas and vapor separation, ionic liquids have been investigated extensively in the last decade and a half. This review gives a complete overview of the main developments in the field of ionic liquid membranes since their first introduction. It covers all different materials, membrane types, their preparation, pure and mixed gas transport properties, and examples of potential gas separation applications. Special systems will also be discussed, including facilitated transport membranes and mixed matrix membranes. The main strengths and weaknesses of the different membrane types will be discussed, subdividing them into supported ionic liquid membranes (SILMs), poly(ionic liquids) or polymerized ionic liquids (PILs), polymer/ionic liquid blends (physically or chemically cross-linked ‘ion-gels’), and PIL/IL blends. Since membrane processes are advancing as an energy-efficient alternative to traditional separation processes, having shown promising results for complex new separation challenges like carbon capture as well, they may be the key to developing a more sustainable future society. In this light, this review presents the state-of-the-art of ionic liquid membranes, to analyze their potential in the gas separation processes of the future.

Over the last decade, membrane-based CO₂ capture using ionic liquids (ILs) has been demonstrated as a promising technology. However, elaborative synthesis of monomers and long-term instability of IL-based composite membranes have so far limited their industrial relevance. In this paper, novel membranes are introduced for CO₂ separation using poly(ionic liquids) (PILs) based on polyvinylbenzyl chloride (PVBC). Three PIL-based membranes were prepared as thin-film composites (TFC) by solvent casting with subsequent sealing. They were tested for the CO₂ removal from synthetic flue gas. An ammonium-derivatised PVBC-analogue was prepared as a first PIL-type by polymerisation of an IL monomer, whereas two other PILs, respectively with hydroxyethyl ammonium and pyrrolidinium cations, were obtained using a modification of commercial PVBC. Introduction of bis(trifluoromethylsulfonyl)imide (Tf₂N) anions was accomplished by metathesis. A thorough characterisation of the material structure, composition, membrane morphology and gas separation properties demonstrates that the presence of hydroxyl groups in the polycation enhanced the interaction with CO₂ molecules. The mixed-gas selectivity increases with the higher positive charge on the cation species (hydroxyethyl-dimethylammonium > trimethylammonium > pyrrolidinium). More importantly, experiments performed in humidified conditions particularly revealed a doubled CO₂ permeance and a 20–30% increased selectivity in comparison to dry conditions. These developments are spurring the application of PIL-based TFC membranes for CO₂ capture from flue gas streams.

Polymer-based CO₂ selective membranes offer an energy efficient method to separate CO₂ from flue gas. ‘Top-down’ polyelectrolytes represent a particularly interesting class of polymer materials based on their vast synthetic flexibility, tuneable interaction with gas molecules, ease of processability into thin films, and commercial availability of precursors. Recent developments in their synthesis and processing are reviewed herein. The four main groups of post-synthetically modified polyelectrolytes discern ionised neutral polymers, cation and anion functionalised polymers, and methacrylate-derived polyelectrolytes. These polyelectrolytes differentiate according to the origin and chemical structure of the precursor polymer. Polyelectrolytes are mostly processed into thin-film composite (TFC) membranes using physical and chemical layer deposition techniques such as solvent-casting, Langmuir-Blodgett, Layer-by-Layer, and chemical grafting. While solvent-casting allows manufacturing commercially competitive TFC membranes, other methods should still mature to become cost-efficient for large-scale application. Many post-synthetically modified polyelectrolytes exhibit outstanding selectivity for CO₂ and some overcome the Robeson plot for CO₂/N₂ separation. However, their CO₂ permeance remain low with only grafted and solvent-casted films being able to approach the industrially relevant performance parameters. The development of polyelectrolyte-based membranes for CO₂ separation should direct further efforts at promoting the CO₂ transport rates while maintaining high selectivities with additional emphasis on environmentally sourced precursor polymers.