Supercritical carbon dioxide (scCO2) microemulsion containing ionic liquids (ILs) 1-ethyl-3-methylimidazolium acetate ([Emim]Ac) were prepared under mild operating conditions with the help of surfactant branched secondary alcohol ethoxylates (TMN-6) and cosolvents (water and ethanol). Phase equilibrium experiments and molecular dynamics (MD) simulations were conducted from gas-phase system, two-phase system to supercritical system. The conditions of constructing supercritical microemulsion were studied by using self-made phase equilibrium device. The effects of temperature, surfactant concentration, and cosolvent concentration on cloud point pressure (CPP) were studied. The results showed that the transparent and uniform microemulsion could not be formed in gas-phase and two-phase systems. In supercritical system, the proper addition of cosolvent water and ethanol contributed to the formation of microemulsion and the dissolution of ILs. However, the reduction effect of CPP was not obvious or even increased when only water was added. After added water and ethanol simultaneously, not only did the maximum WIL increase to 0.26, but CPP also significantly decreased. MD simulation was conducted to characterize the microstructure of three systems. Furthermore, the gyration radius, radial distribution function (RDF), and hydrogen bond dynamics were calculated to analyze the strengthening mechanism of cosolvents on self-assembly. The simulation results revealed that, water promoted the interaction between hydrophilic groups of surfactants and ionic liquids, while ethanol constructed a hydrogen bonding network between continuous and dispersed phases. Water and ethanol have synergistic effect on the preparation of supercritical microemulsion, which has a good effect on improving the self-assembly rate and aggregate stability.
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