Competitive adsorption of methanol co-solvent and dioctyl phthalate on functionalized graphene sheet: Integrated investigation by molecular dynamics simulations and quantum chemical calculations

Abstract

Hypothesis: Organic co-solvents, which are universally employed in adsorption studies of hydrophobic organic chemicals (HOCs), can inhibit HOC adsorption by competing for active sites on the adsorbent. The adsorbent structure can influence co-solvent interference of HOC adsorption; however, this effect remains unclear, leading to an incomplete understanding of the adsorption mechanism.

Experiments: In this study, dioctyl phthalate (DOP) was used to investigate competitive adsorption on functionalized graphene sheet in a water-methanol co-solvent system through molecular dynamics simulations and quantum chemical calculations.

Findings: The simulations showed that the functional groups in the graphene defects had a strong adsorption affinity for methanol. The adsorbed methanol occupied a large number of active sites at the graphene center, thereby weakening DOP adsorption. However, the methanol adsorbed at the graphene edges could not compete with DOP for the active sites. -COOH had the strongest binding affinity for methanol among the functional groups and thus predominantly controlled the interaction between graphene and methanol. This study makes an innovative contribution toward understanding the competitive adsorption of methanol and DOP on functionalized graphene sheet, especially in visualizing the competition for active sites, and provides theoretical guidance for the removal of HOCs and practical application of graphene.

Keywords: Active sites; Co-solvent; Competitive adsorption; Defect structures; Graphene.