Self-assembly of cationic surfactants on the carbon nanotube surface: insights from molecular dynamics simulations

The insolubility of carbon nanotubes (CNTs) in aqueous media has been a limitation for the practical application of this unique material. Recent studies have demonstrated that the suspend ability of CNT can be substantially improved by employing appropriate surfactants. Although various surfactants have been tested, the exact mechanism by which carbon nanotubes and the different surfactants interact is not fully understood. To deepen the understanding of molecular interaction between CNT and surfactants, as well as to investigate the influence of the surfactant tail length on the adsorption process, we report here the first detailed large-scale all-atomistic molecular dynamics simulation study of the adsorption and morphology of aggregates of the cationic surfactants containing trimethylammonium headgroups (C12TAB and C16TAB) on single-walled carbon nanotube (SWNT) surfaces. We find that the aggregation morphology of both C12TAB and C16TAB on the SWNT is dependent upon the number of the surfactants in the simulation box. As the number of the surfactants increases the random monolayer structure gradually changes to the cylinder-like monolayer structure. Moreover, we make a comparison between the C12TAB and C16TAB adsorption onto SWNTs to clarify the role of the surfactant tail length on the adsorption process. This comparison indicates that by increasing the number of surfactant molecules, the larger number of the C16TAB molecules tend to adsorb onto SWNTs. Further, our results show that a longer chain yields the higher packed aggregates in which the surfactant heads are extended far into the aqueous phase, which in turn may increase the SWNTs stabilization in aqueous suspensions.