Reactive species conversion into 1O2 promotes substantial inhibition of chlorinated byproduct formation during electrooxidation of phenols in Cl--laden wastewater

Abstract

The generation of chlorinated byproducts during the electrochemical oxidation (EO) of Cl^--laden wastewater is a significant concern. We aim to propose a concept of converting reactive species (e.g., reactive chlorines and HO^• resulting from electrolysis) into ¹O₂ via the addition of H₂O₂, which substantially alleviates chlorinated organic formation. When phenol was used as a model organic compound, the results showed that the H₂O₂-involving EO system outperformed the H₂O₂-absent system in terms of higher rate constants (5.95 × 10^-2 min^-1vs. 2.97 × 10^-2 min^-1) and a much lower accumulation of total organic chlorinated products (1.42 mg L^-1vs. 8.18 mg L^-1) during a 60 min operation. The rate constants of disappearance of a variety of phenolic compounds were positively correlated with the Hammett constants (σ), suggesting that the reactive species preferred oxidizing phenols with electron-rich groups. After the identification of ¹O₂ that was abundant in the bulk solution with the use of electron paramagnetic resonance and computational kinetic simulation, the routes of ¹O₂ generation were revealed. Despite the consensus as to the contribution of reaction between H₂O₂ and ClO^- to ¹O₂ formation, we conclude that the predominant pathway is through H₂O₂ reaction with electrogenerated HO^• or chlorine radicals (Cl^• and Cl₂^•-) to produce O₂^•-, followed by self-combination. Density functional theory calculations theoretically showed the difficulty in forming chlorinated byproducts for the ¹O₂-initiated phenol oxidation in the presence of Cl^-, which, by contrast, easily occurred for the Cl^•-or HO^•-initiated phenol reaction. The experiments run with real coking wastewater containing high-concentration phenols further demonstrated the superiority of the H₂O₂-involving EO system. The findings imply that this unique method for treating Cl^--laden organic wastewater is expected to be widely adopted for generalizing EO technology for environmental applications.

Keywords: Chlorinated byproducts; Degradation of phenols; Electrochemical oxidation; Halide wastewater treatment; Reactive chlorine species; Reactive oxygen species.