Molecular clusters played an important role in the adsorption of polycyclic aromatic hydrocarbons (PAHs) on carbonaceous materials.

Polycyclic aromatic hydrocarbons (PAHs) are one of the most frequently detected hydrophobic organic contaminants (HOCs) in the environment. They may form clusters because of the strong hydrophobic and π-π electron-donor-acceptor (EDA) interactions among PAHs molecules. However, previous experimental studies and theoretical simulations generally ignored the impact of molecular clusters on the adsorption, which may result in the misunderstanding of the environmental fate and risk. In this work, naphthalene (NAP), phenanthrene (PHE), and pyrene (PYR) were selected to investigate intermolecular interaction as well as the consequent impact on their adsorption on graphene. The density field of C atoms in equilibrium configurations of self-interacted PAHs suggested that the formation of PAHs molecular clusters was a spontaneous process, and was favored in solvents with stronger polarity and for PAHs with more benzene rings. It should be noted that the molecular dynamics simulations with the initial state of molecular clusters matched better with the published experimental results compared with those of individual PAHs. The formed compact PAHs clusters in polar solvents increased the apparent PAHs adsorption, because of their higher hydrophobic and π-π EDA interactions. This study emphasized that the self-interaction of PAHs should be carefully considered in both experimental and theoretical simulation studies.