This tutorial review highlights representative examples of ionic liquid (IL)-based (bio)catalytic systems integrating reaction and separation, as a tool for the development of sustainable chemical processes (e.g.IL/scCO₂biphasic reactors, membrane reactors, nanodrop systems, microfluidic devices, supported IL phases, sponge-like ILs,etc.).

Supported ionic liquid-like phases (SILLPs) are able to efficiently catalyse the cyanosilylation of carbonyl compounds using trimethylsilyl cyanide under solvent-free conditions. These organic catalysts were efficient for various carbonyl compounds including aromatic, aliphatic and α,β-unsaturated. This process perfectly conforms to the features of green chemistry: no waste regarding side-products and unconverted reactants, solvent-free, excellent catalytic activity, and no requirement for separation. Furthermore the supported nature of the SILLPs allows for the development of continuous flow synthesis of cyanohydrin trimethylsilyl ethers. The effect of the morphology of the polymer (gel-type or macroporous bead resins or, alternatively, a monolithic polymer) has also been studied, which has allowed selecting suitable materials for the efficient continuous flow single pass synthesis of cyanohydrin trimethylsilyl ethers.

Supported ionic liquid-like phases (SILLPs) containing Rose Bengal (RB) units are used to develop organocatalytic systems for the cycloaddition of CO₂ to epoxides. The activity of the supported RB fragments can be fine-tuned by controlling the nature of the SILLPs (i.e., substitution at the imidazolium ring, cross-linking degree of the polymeric matrix, loading, etc.). Such a catalytic system prepared from cheap, simple, and commercially available components provides high activity and stability, with no decay in activity for at least 10 days of continuous use under flow conditions.