Exfoliation and stabilization mechanism of graphene in carbon dioxide expanded organic solvents: molecular dynamics simulations

CO2 expanded organic solvents possess significant advantages in liquid-phase exfoliation to obtain monolayer/few-layer graphene from graphite. Further insights into the mechanism of graphene exfoliation in such solvents are essential to explore liquid-phase dispersion of graphene as a more potent alternative to chemical vapor deposition. In this study, dynamic processes of exfoliation and stabilization of graphene in CO2-N,N-dimethylformamide (DMF), CO2-N-methylpyrrolidone (NMP), CO2-dimethyl sulfoxide (DMSO), and CO2-ethanol (EtOH) were investigated using molecular dynamics simulations. The origin of the effect of each solvent on graphene exfoliation was analyzed quantitatively through potential mean force simulations. It has been found that the organic solvent in a CO2 expanded solvent should be chosen with proper surface tension, and there exist two different graphene exfoliation processes in the effective solvents, which can be described as "burger dissociation" and "extrusion-taking away" processes, respectively. In the former process, a characteristic "super-burger-like" conformation with a semi-exfoliated structure was formed, which was the deciding factor to obtain high ratio of monolayer/few-layer graphene in dispersion product. A theoretical explanation has also been provided at the molecular level to the earlier experimental phenomena. A predicted simulation of the CO2-3,3'-iminobis(N,N-dimethylpropylamine) (DMPA) system is also calculated. This investigation helps to avoid incompatible CO2 expanded organic solvents employed in the experimental studies and provides theoretical clues to understand the mechanism of exfoliation and stabilization of graphene in such solvents.