Molecular dynamics study of di-CF4 based reverse micelles in supercritical CO₂

Reverse micelles (RMs) in supercritical CO₂ (scCO₂) are promising alternatives for organic solvents, especially when both polar and non-polar components are involved. Fluorinated surfactants, particularly double-chain fluorocarbon surfactants, are able to form well-structured RMs in scCO₂. The inherent self-assembly mechanisms of surfactants in scCO₂ are still subject to discussion. In this study, molecular dynamics simulations are performed to investigate the self-aggregation behavior of di-CF4 based RMs in scCO₂, and stable and spherical RMs are formed. The dynamics process and the self-assembly structure in the RMs reveal a three-step mechanism to form the RMs, that is, small RMs, rod-like RMs and fusion of the rod-like RMs. Hydrogen-bonds between headgroups and water molecules, and salt bridges linking Na⁺ ions, headgroups and water molecules enhance the interfacial packing efficiency of the surfactant. The results show that di-CF4 molecules have a high surfactant coverage at the RM interface, implying a high CO₂-philicity. This mainly results from bending of the short chain (C-COO-CH₂-(CF2)₃-CF3) due to the flexible carboxyl group. The microscopic insight provided in this study is helpful in understanding surfactant self-assembly phenomena and designing new CO₂-philic surfactants.