Acid-tailored self-assembled perylene diimide supramolecular for visible-light-driven activation of peroxymonosulfate towards efficient degradation of iohexol

Abstract

The presence of iohexol (IOX) in the environment has attracted widespread attention. Acetic acid, hydrochloric acid, and nitric acid tailored self-assembled perylene diimides (PA, PC and PN) were prepared and utilized in different visible-light-driven activation of peroxymonosulfate (PMS/Vis) systems for the degradation of IOX. As an electron acceptor, PMS can significantly hinder the recombination of photogenerated electron-hole pairs. The removal rate of 5 mg/L IOX by PC/PMS/Vis system reached 99.1% at 30 min, which was 2.0 times and 1.3 times higher than that of PA/PMS/Vis and PN/PMS/Vis system. The boosted oxidation activity with PC was due to the pH dependence of perylene diimide (PDI) self-assembly and the small amount of Cl− (0.56%) absorbed on PC, which can promote the transfer of electron-hole pairs, change the surface charge distribution and energy band position, and enhance π-electron conjugation. Based on density functional theory and electrostatic potential calculation, the Cl− adsorbed on the surface of PDI brings an effect on the electrostatic potential distribution. Furthermore, the built-in intermolecular electric field leads to accelerated charge transfer of PDI. In the PC/PMS/Vis system, holes, singlet oxygen and superoxide radical were perceived as the dominant contributors. The degradation of IOX carried out via pathways of amide hydrolysis, amino oxidation, hydrogen abstraction, deiodination reaction, and OH attack. This work provides a new method for the pollution control of IOX and scientific guidance for the tailored self-assembly of organic supramolecules.