Wu Jianying, Zou Jing, Lin Jinbin, Li Sheng, Chen Siying, Liao Xiaobin, Yang Jingxin, Yuan Baoling, Ma Jun
Xiamen Key Laboratory of Municipal and Industrial Solid Waste Utilization and Pollution Control, College of Civil Engineering, Huaqiao University, Xiamen, Fujian 361021, PR China.
Xiamen Key Laboratory of Municipal and Industrial Solid Waste Utilization and Pollution Control, College of Civil Engineering, Huaqiao University, Xiamen, Fujian 361021, PR China.
J Hazard Mater. 2023 Oct 15;460:132461. doi: 10.1016/j.jhazmat.2023.132461. Epub 2023 Sep 2.
The slow reduction of Cu(II) into Cu(I) through peracetic acid (PAA) heavily limited the widespread application of Cu(II)/PAA system. Herein, hydroxylamine (HA) was proposed to boost the oxidative capacity of Cu(II)/PAA system by facilitating the redox cycle of Cu(I)/Cu(II). HA/Cu(II)/PAA system was quite rapid in the removal of diclofenac within a broad pH range of 4.5-9.5, with a 10-fold increase in the removal rate of diclofenac compared with the Cu(II)/PAA system at an optimal initial pH of 8.5. Results of UV-Vis spectra, electron paramagnetic resonance, and alcohol quenching experiments demonstrated that CHC(O)O, CHC(O)OO, Cu(III), and OH were involved in HA/Cu(II)/PAA system, while CHC(O)OO was verified as the predominant reactive species of diclofenac elimination. Different from previously reported Cu-catalyzed PAA processes, CHC(O)OO mainly generated from the reaction of PAA with Cu(III) rather than CHC(O)O and OH. Four possible elimination pathways for diclofenac were proposed, and the acute toxicity of treated diclofenac solution with HA/Cu(II)/PAA system significantly decreased. Moreover, HA/Cu(II)/PAA system possessed a strong anti-interference ability towards the commonly existent water matrix. This research proposed an effective strategy to boost the oxidative capacity of Cu(II)/PAA system and might promote its potential application, especially in copper-contained wastewater.
过氧乙酸（PAA）将Cu（II）缓慢还原为Cu（I）严重限制了Cu（II）/PAA体系的广泛应用。在此，提出了羟胺（HA）通过促进Cu（I）/Cu（II）的氧化还原循环来提高Cu（II）/PAA体系的氧化能力。HA/Cu（II）/PAA体系在4.5-9.5的宽pH范围内对双氯芬酸的去除相当迅速，在最佳初始pH为8.5时，双氯芬酸的去除率比Cu（II）/PAA体系提高了10倍。紫外可见光谱、电子顺磁共振和醇淬灭实验结果表明，CHC（O）O、CHC（O）OO、Cu（III）和OH参与了HA/Cu（II）/PAA体系，而CHC（O）OO被证实是双氯芬酸消除的主要活性物种。与先前报道的铜催化PAA过程不同，CHC（O）OO主要由PAA与Cu（III）反应生成，而不是由CHC（O）O和OH生成。提出了双氯芬酸的四种可能消除途径，并且HA/Cu（II）/PAA体系处理后的双氯芬酸溶液的急性毒性显著降低。此外，HA/Cu（II）/PAA体系对常见的水基质具有很强的抗干扰能力。本研究提出了一种提高Cu（II）/PAA体系氧化能力的有效策略，并可能促进其潜在应用，特别是在含铜废水处理方面。
