Abstract
The adsorption and degradation capacities of dichlorodiphenyltrichloroethane (DDT) on a photocatalyst composed of TiO(2) supported on the mesoporous material MCM-41 (TiO(2)/MCM-41) were investigated using density functional theory and real-time density functional theory methods. The van der Waals interactions within the PBE functional were adjusted by using the Grimme approach. The adsorption of DDT was evaluated through analyses involving adsorption energy, Hirshfeld atomic charges, Wiberg bond orders, molecular electrostatic potential, noncovalent interaction analysis, and bond path analysis. The findings reveal that DDT undergoes physical adsorption on pristine MCM-41 or MCM-41 modified with Al or Fe due to the very small bond order (only about 0.15-0.18) as well as the change in total charge of DDT after adsorption is close to 0. However, it chemically adsorbs onto the TiO(2)/MCM-41 composite through the formation of Ti···Cl coordination bonds because the maximum bond order is very large, about 1.0 (it can be considered as a single bond). The adsorption process is significantly influenced by van der Waals interactions (accounting for approximately 30-40% of the interaction energy), hydrogen bonding, and halogen bonding. MCM-41 is demonstrated to concurrently function as a support for the TiO(2) photocatalyst, creating a synergistic effect that enhances the photocatalytic activity of TiO(2). Based on the computational results, a novel photocatalytic mechanism for the degradation of DDT on the TiO(2)/MCM-41 catalyst system was proposed.