Exploration of functionalizing graphene and the subsequent impact on PFAS adsorption capabilities via molecular dynamics

Per- and polyfluoroalkyl substances (PFAS) are extremely stable compounds due to their strong C–F bonds. They are used in water and stain proof coatings, aqueous film forming foams for fire suppression, cosmetics, paints, adhesives, etc. PFAS have been found in soils and waterways around the world due to their widespread usage and recalcitrance to degradation. Development of selective adsorbent materials is necessary to effectively capture a vast family of PFAS structures in order to remediate PFAS contamination in the environment. The work herein is focused on extracting design principles from molecular dynamics simulations of PFAS with functionalized graphene materials. Simulations examined how PFBA, PFOA, and PFOS interact with graphene, graphene oxide, nitrogen group-functionalized graphene oxide, partially fluorinated graphene flakes, and fully fluorinated flakes. Five flakes were used in each simulation to examine how interactions between flakes may lead to competitive interactions with respect to PFAS or formation of pores. Our study revealed that both the clustering mechanisms of the flakes and functional groups on the flake play a role in PFAS adsorption. The most effective functionalizations for PFAS adsorption are as follows: pristine graphene ≈ fully fluorinated > graphene oxide ≈ partially fluorinated > amine and amide functionalized graphene oxide flake. Long chain PFAS and sulfonate PFAS had higher propensity to adsorb to the materials compared to short chain PFAS and carboxylic head groups.