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⁻¹ vs. 2.97 × 10⁻² min⁻¹) and a much lower accumulation of total organic chlorinated products (1.42 mg L⁻¹ vs. 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.

^{在含氯废水的}电化学氧化（EO）过程中产生氯化副产物是一个重要的问题。我们旨在提出通过添加H ₂ O ₂将活性物质（例如，电解产生的活性氯和HO ^{• ）转化为1} O ₂的概念，这大大减轻了氯化有机物的形成。当苯酚用作模型有机化合物时，结果表明，包含 H _{2 O} 2_的EO 系统在^更高的速率常数（5.95 × 10 _-2 min ^-1 与2.97 × 10 ^-2 min ^-1相比）和在 60 分钟操作期间总有机氯化产物的积累要低得多（1.42 mg L ^-1 对8.18 mg L ^{-1 ）。}多种酚类化合物的消失速率常数与哈米特常数 ( σ ) 呈正相关，表明活性物质更喜欢具有富电子基团的氧化酚。在利用电子顺磁共振和计算动力学模拟鉴定了本体溶液中丰富的¹ O _2之后， ¹ O _2的路线一代被揭露。_{尽管对 H 2} O ₂和 ClO ^-之间的反应对¹ O ₂形成的贡献达成共识，但我们得出的结论是，主要途径是通过 H ₂ O ₂与电生成的 HO ^•或氯自由基（Cl ^•和 Cl ₂ ^{• −} ) 产生O ₂ ^{• −}，然后进行自结合。密度泛函理论计算从理论上表明¹ O _{2难以形成氯化副产物}在Cl ^-存在下-引发的苯酚氧化，相比之下，对于Cl ^• - 或HO ^• -引发的苯酚反应很容易发生。使用含有高浓度酚类的真实焦化废水进行的实验进一步证明了包含 H ₂ O ₂的 EO 系统的优越性。研究结果表明，这种处理含氯有机废水的独特方法^有望广泛用于将 EO 技术推广到环境应用中。