随着水质标准和检测技术的提高，新污染物的控制逐渐成为了研究热点。本研究通过引入电场提高了Mn2+对过一硫酸盐（PMS）的活化能力，构建E-Mn2+-PMS协同体系去除水中难降解有机污染物双氯芬酸（DCF）。首先，考察了电流密度、PMS浓度、Mn2+浓度、溶液pH值以及水体背景物质（NO3-、Cl-、HA）等对水中DCF去除的影响。结果表明，在电流密度为11.42 mA cm-2、PMS浓度为1 mM、Mn2+浓度为150 μM的条件下，反应20 min内E-Mn2+-PMS体系协同系数为10.88，其反应速率常数为19.250×10-2 min-1，反应180 min对DCF的矿化率为67.4%，酸性条件比碱性条件更有利于DCF去除，最佳条件为pH=3。NO3-对DCF的去除几乎没有影响，Cl-、HA对DCF的去除有明显的促进作用。随后，通过自由基捕获实验、电子顺磁共振（EPR）测试以及锰中间价态物质分析证明，E-Mn2+-PMS体系中非自由基路径（Mn(III)氧化和1O2氧化）占据主导地位。与Mn2+-PMS体系相比，电场条件下原位生成的无定形MnO2可快速活化PMS产生1O2，实现对污染物的高效去除。

With the improvement of water quality standards and detection technology, the control of new pollutants has gradually become a research hotspot. The activation ability of divalent manganese to peroxymonosulfate (PMS) was improved by introducing an electric field, and the E-Mn2+-PMS synergistic process was constructed to remove the refractory organic pollutant diclofenac (DCF) in water. Firstly, the effects of current density, PMS concentration, Mn2+ concentration, solution pH value and water matrix (NO3-、Cl-、HA) on the removal of DCF in water were discussed, respectively. The results indicated that the synergy indices of the E-Mn2+-PMS process was 10.88 within 20 min of reaction, and its reaction rate constant was 19.250×10-2 min-1. The mineralization rate of DCF was 67.4% in 180 min, under the experimental conditions: current density was 11.42 mA cm-2, PMS concentration was 1 mM and Mn2+ concentration was 150 μM. Acidic conditions facilitated the removal of DCF, and the optimal pH value was 3. NO3- had almost no effect on the removal of DCF, and Cl- and HA promoted the removal of DCF significantly. Subsequently, it was demonstrated by radical scavenger experiment, electron paramagnetic resonance (EPR) tests, and analysis of manganese intermediate valence substances. The non-radical pathways (Mn(III) oxidation and 1O2 oxidation) dominated in the E-Mn2+-PMS process. Compared with Mn2+-PMS process, the amorphous MnO2 generated in situ under electric field conditions could quickly activate PMS to produce 1O2, achieving efficient removal of pollutants.

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国家自然科学基金项目（面上项目，重点项目，重大项目）