Aniline chlorination by in situ formed Ag–Cl complexes under simulated solar light irradiation

Abstract

Ag speciation in a chloride medium was dependent upon the Cl/Ag ratio after releasing into surface water. In this study, the photoreaction of in situ formed Ag-Cl species and their effects on aniline photochlorination were systematically investigated. Our results suggested that formation of chloroaniline was strongly relevant to the Cl/Ag ratio and could be interpreted using the thermodynamically expected speciation of Ag in the presence of Cl-. AgCl was the main species responsible for the photochlorination of aniline. Both photoinduced hole and •OH drove the oxidation of Cl- to radical •Cl, which promoted the chlorination of aniline. Ag0 formation was observed from the surface plasmon resonance absorption during AgCl photoreaction. This study revealed that Ag+ released into Cl--containing water may result in the formation of chlorinated intermediates of organic compounds under solar light irradiation.

Self-sensitized photochlorination of benzo[a]pyrene in saline water under simulated solar light irradiation

“…In Fe-containing saline water, a low pH facilitated the formation of chlorine radicals under photoirradiation, resulting in the production of more chlorinated product (Liu et al, 2009;Wu and Hu, 2012). In an AgCl particle system, the formation of chlorine radicals was independent of the pH (Hu et al, 2015). The amount of chlorinated product formed increased with decreasing pH because the reaction rates between the chlorine radicals and various organic compounds increased at lower pH values (Remucal and Manley, 2016).…”

“…Natural seawater is particularly rich in chloride ions, which greatly influence the transformation of various species in an aqueous environment under irradiation. To organic compounds that can not absorb solar light, chlorine radicals originating from other photosensitive substances are likely responsible for their chlorination (Vione et al, 2005;Wu and Hu, 2012;Hu et al, 2015). Our previous work investigated the photoreaction of aniline in aqueous solutions containing Ag + /Fe 3+ and Cl − under simulated sunlight irradiation (Wu and Hu, 2012;Hu et al, 2015), where chlorine radicals originating from the photolysis of Ag-Cl/Fe-Cl complex were responsible for aniline chlorination.…”

“…To organic compounds that can not absorb solar light, chlorine radicals originating from other photosensitive substances are likely responsible for their chlorination (Vione et al, 2005;Wu and Hu, 2012;Hu et al, 2015). Our previous work investigated the photoreaction of aniline in aqueous solutions containing Ag + /Fe 3+ and Cl − under simulated sunlight irradiation (Wu and Hu, 2012;Hu et al, 2015), where chlorine radicals originating from the photolysis of Ag-Cl/Fe-Cl complex were responsible for aniline chlorination. No chloroaniline was detectable in the absence of Ag + /Fe 3+ because aniline and Cl − are unable to absorb solar light effectively.…”

“…•− radicals, and thus promoted the chlorination of aniline (Vione et al, 2005;Hu et al, 2015). Aromatic ketones were reported to form charge transfer complexes with halides (exciplexes), producing reactive halogen radicals by charge separation (Parker and Mitch, 2016).…”

Cation Radical Induced Photochlorination of Naphthalene in Saline Water under UV Light Irradiation

“…A multitude of substances present in natural water can affect the photochlorination of PAHs. Some substances can either facilitate or hinder the formation of active intermediates like Cl·, − 1 PAH*, 3 PAH*, , and PAH + · . Consequently, examining the impact of environmental factors on the photochlorination of PAHs is of great significance.…”