Interfacial quantum chemical characterization of aromatic organic matter adsorption on oxidized microplastic surfaces

Examining the adsorption efficiency of individual contaminants on microplastics (MPs) is resource-intensive and time-consuming. To address this challenge, combined laboratory adsorption experiments with model simulations were performed to investigate the adsorption capacities and mechanisms of MPs before and after aging. Our adsorption experiments revealed that aged polyethylene (PE) and polyvinyl chloride (PVC) MPs exhibited increased adsorption capacity for benzene, phenol, and naphthalene. Additionally, density functional theory (DFT) simulations provided insights into changes in adsorption sites, adsorption energy, and charge density on MPs. The π bond of the benzene ring emerged as a pivotal factor in the adsorption process, with van der Waals forces exerting dominant influence. For instance, the adsorption energy of benzene on pristine PE was −0.01879 eV. When oxidized groups, such as hydroxyl, carbonyl, and carboxyl, on the surface of aged PE became the adsorption sites, the adsorption energy increased to −0.06976, −0.04781, and −0.04903 eV, respectively. Regions with unoxidized functional groups also exhibited higher adsorption energies than pristine PE. These results indicated that aged PE had a stronger affinity for benzene compared to pristine PE, enhancing its adsorption. Charge density difference and energy density of states corroborated this observation, revealing larger π-bond charge accumulation areas for benzene on aged PE, suggesting stronger dipole interactions and enhanced adsorption. Similar trends were observed for phenol and naphthalene. In summary, the DFT calculations aligned with the adsorption experiment findings, confirming the effectiveness of simulation methods in predicting changes in the adsorption performance of aged MPs.