Efficiency and mechanism of hydrated manganese oxide-activated peroxymonosulfate for selective removal of organic pollutants

doi:10.19965/j.cnki.iwt.2025-0236

Abstract

Abstract:

Hydrated manganese oxide(HMO) was successfully prepared by direct oxidation of sodium hypochlorite. Characterization showed that HMO had an irregular aggregate structure with low crystallinity, large specific surface area, and negative charge at pH>4.8. Under neutral conditions, HMO activated peroxymonosulfate(PMS) could selectively remove positively charged organic pollutants such as methylene blue, methyl violet, crystal violet, and corydine, mainly because such organic pollutants could be adsorbed through electrostatic effect. Meanwhile, HO·, SO₄ ^•- and ¹O₂ produced during the reaction made a little contribution to the degradation of methylene blue, and the direct electron transfer process induced by the valence cycle transformation of Mn(Ⅲ)/Mn(Ⅳ) driven by PMS was the main cause of the oxidative degradation of methylene blue. Therefore, the HMO/PMS system had good resistance to water matrix interference. In addition, the experiments of regeneration and recycling showed that HMO activated PMS had good stability in the removal of methylene blue. These results suggested that HMO could be used as a highly efficient material to selectively remove positively charged organic pollutants from aqueous environment by activating PMS.

Key words: hydrated manganese oxide, peroxymonosulfate, organic pollutants, selective oxidation, direct electron transfer

摘要：

通过次氯酸钠直接氧化法成功制备了水合氧化锰（HMO），表征分析表明，HMO为不规则的团聚体结构，其结晶度较低、比表面积较大，且pH>4.8时表面带负电荷。在中性条件下，HMO活化过一硫酸盐（PMS）可选择性去除亚甲基蓝、甲基紫、结晶紫、柯衣定等带正电荷的有机污染物，主要是由于其可以通过静电引力吸附该类有机污染物。反应过程中产生的HO·、SO₄ ^•-和¹O₂对亚甲基蓝降解的贡献较小，PMS驱动Mn（Ⅲ）/Mn（Ⅳ）价态循环转化诱发的直接电子转移过程是亚甲基蓝氧化降解的主要原因，因而HMO/PMS体系具有良好的抗水体基质干扰性能。此外，再生和循环利用实验表明HMO活化PMS去除亚甲基蓝的稳定性良好。这些研究结果表明，HMO可作为一种高效材料通过活化PMS选择性去除水环境中带正电荷的有机污染物。

关键词: 水合氧化锰, 过一硫酸盐, 有机污染物, 选择性氧化, 直接电子转移

CLC Number:

X703.1
TQ426

Hongling JIANG, Guangxiang HE, Meng ZHU, Shiwen ZHANG. Efficiency and mechanism of hydrated manganese oxide-activated peroxymonosulfate for selective removal of organic pollutants[J]. Industrial Water Treatment, 2026, 46(2): 53-61.

蒋红玲, 何广翔, 朱萌, 张世文. 水合氧化锰活化过一硫酸盐选择性去除有机污染物的效能与机制[J]. 工业水处理, 2026, 46(2): 53-61.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2025-0236

https://www.iwt.cn/EN/Y2026/V46/I2/53

Figures/Tables 8

Fig.1 SEM image（a），XPS spectrum（b），XRD pattern（c），adsorption-desorption isotherm and pore size distribution（d），FTIR spectrum （e） and Zeta potential diagram （f） of HMO

Fig.2 Removal efficiency of organics with different charges in four reaction systems： HMO adsorption （a）， PMS oxidation （b）， HMO/PMS （c）， and static adsorption + HMO/PMS （d）

Fig.3 EPR spectra of DMPO（a） and TEMP （b）as a spin trap in different reaction systems，and the effect of TBA，MeOH and FFA on the removal of methylene blue in the HMO/PMS system（c）

Fig.4 Mn 2p（a） and O 1s（b） XPS spectra of HMO before and after reaction

Fig.5 Removal mechanism of methylene blue in the HMO/PMS system

Fig.6 Initial pH of the solution（a），initial concentration of methylene blue（b），PMS dosage（c） and HMO dosage（d） on the removal of methylene blue in the HMO/PMS system

Fig.7 Effect of coexisting substances in water on the removal of methylene blue in the HMO/PMS system

Fig.8 HMO/PMS system cyclic repetition experimental results（a），adsorption-desorption isotherms and pore size distribution（b）， XRD（c）， and FTIR（d） of HMO before and after the reaction

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