Density Functional Theory Insight in Photocatalytic Degradation of Dichlorvos Using Covalent Triazine Frameworks Modified by Various Oxygen-Containing Acid Groups.

Dichlorvos (2,2-dichlorovinyl dimethyl phosphate, DDVP) is a highly toxic organophosphorus insecticide, and its persistence in air, water, and soil poses potential threats to human health and ecosystems. Covalent triazine frameworks (CTFs), with their sufficient visible-light harvesting capacity, ameliorated charge separation, and exceptional redox ability, have emerged as promising candidates for the photocatalytic degradation of DDVP. Nevertheless, pure CTFs lack effective oxidative active sites, resulting in elevated reaction energy barriers during the photodegradation of DDVP. In this work, density functional theory (DFT) calculations were employed to investigate the impact of various oxygen-containing acid groups (-COOH, -HSO₃, -H₂PO₃) on DDVP photodegradation performance. First, simulations of the structure and optical properties of modified CTFs reveal that oxygen-containing acid groups induce surface distortion and result in a redshift in the absorption edge. Subsequently, analysis of the density of states, frontier molecular orbitals, surface electrostatic potential, work function, and dipole moment demonstrates that oxygen-containing acid groups enhance CTF polarization, facilitate charge separation, and ameliorate their oxidative capability. Additionally, the free-energy diagram of DDVP degradation uncovers that oxygen-containing acid groups lower the energy barrier by elevating the adsorption and activation capability of DDVP. Notably, -H₂PO₃ presents optimal potential for the photodegradation of DDVP by unique electronic structure and activation capability. This work offers a valuable reference for the development of oxygen-containing acid CTF-based photocatalysts applied in degrading toxic organophosphate pesticides.