Molecular-Scale Design of Hydrocarbon Surfactant Self-Assembly in Supercritical CO₂

Forming wormlike reverse micelles (RMs) by hydrocarbon surfactant self-assembly is an economic and environmental strategy to improve the physicochemical properties of supercritical carbon dioxide (scCO₂), but it remains challenging. Introducing cosurfactant in hydrocarbon surfactant self-assembly system is a potential method to generate wormlike RMs. Here, adopting molecular dynamics simulations, we performed hydrocarbon surfactant (TC14) self-assembly with introducing cosurfactants (C₈Benz). It is found that adding the C₈Benz molecules will induce the spherical RMs to a short rodlike form. In this case, the microstructure of the short rodlike RMs shows a dumbbell-like form that is composed by three parts including a middle part of C₈Benz and two parts of TC14 aggregation at both ends of rodlike RMs, which is regarded as the origin of RMs shape transition. Further, the analysis of free energy for RMs fusion indicates that the high fusion ability of C₈Benz aggregation drives the formation of the dumbbell-like RMs. Accordingly, enhancing the affinity of the C₈Benz is found to be effective strategy to further fusion of rodlike RMs in end-to-end manner, yielding a wormlike RMs with a beads-on-a-string structure. It is expected that this work will provide a valuable information for design the hydrocarbon wormlike RMs and facilitate the potential application of scCO₂.