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

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

摘要/Abstract

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

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

中图分类号:

X703.1
TQ426

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.

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.

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

图/表 8

图1 HMO的SEM（a）、XPS（b）、XRD（c）、吸附/脱附等温线和孔径分布（d）、FTIR（e）及其Zeta电位（f）

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

图2 HMO吸附（a）、PMS氧化（b）、HMO/PMS（c）、静态吸附+HMO/PMS（d） 4种反应体系中带有不同电荷的有机污染物的去除效果

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）

图3 DMPO（a）、TEMP（b）作为自旋捕获剂时不同反应体系的EPR谱图，以及TBA、MeOH和FFA对HMO/PMS体系去除亚甲基蓝的影响（c）

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）

图4 反应前后HMO的Mn 2p（a）和O 1s（b）的XPS谱图

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

图5 HMO/PMS体系去除亚甲基蓝的机制

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

图6 溶液初始pH（a）、亚甲基蓝初始浓度（b）、PMS投加量（c）和HMO投加量（d）对HMO/PMS体系去除亚甲基蓝的影响

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

图7 水体共存基质对HMO/PMS体系去除亚甲基蓝的影响

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

图8 HMO/PMS体系循环重复实验结果（a）及反应前后HMO的吸附-脱附等温线和孔径分布（b）、XRD（c）和FTIR（d）

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

参考文献 30

[1]	SHAH A ALI， WALIA S， KAZEMIAN H. Advancements in combined electrocoagulation processes for sustainable wastewater treatment：A comprehensive review of mechanisms，performance，and emerging applications［J］. Water Research，2024，252：121248. doi:10.1016/j.watres.2024.121248
[2]	Weiwei BEN， ZHU Bing， YUAN Xiangjuan，et al. Occurrence，removal and risk of organic micropollutants in wastewater treatment plants across China：Comparison of wastewater treatment processes［J］. Water Research，2018，130：38-46. doi:10.1016/j.watres.2017.11.057
[3]	ZHANG Yishuo， CHEN Xinjia， HUANG Xintong，et al. Enhanced peroxone reaction with amphoteric oxide modulation for efficient decontamination of challenging wastewaters：Comparative performance，economic evaluation，and pilot-scale implementation［J］. Water Research，2025，274：123058. doi:10.1016/j.watres.2024.123058
[4]	LIU Suo， SI Ting， FAN Jiahui，et al. Ultrafast decomposition of refractory organics by electric field enhanced permanganate/peroxymonosulfate process［J］. Chemical Engineering Journal，2025，504：158744. doi:10.1016/j.cej.2024.158744
[5]	REN Tengfei， LU Kechao， YIN Mengxi，et al. Single-atom cobalt enables efficient catalytic ozonation for advanced wastewater treatment：Mechanisms and application［J］. Chemical Engineering Journal，2024，500：156805. doi:10.1016/j.cej.2024.156805
[6]	YANG Zhichao， QIAN Jieshu， SHAN Chao，et al. Toward selective oxidation of contaminants in aqueous systems［J］. Environmental Science & Technology，2021，55（21）：14494-14514. doi:10.1021/acs.est.1c05862
[7]	GIANNAKIS S， LIN K A， GHANBARI F. A review of the recent advances on the treatment of industrial wastewaters by sulfate radical-based advanced oxidation processes（SR-AOPs）［J］. Chemical Engineering Journal，2021，406：127083. doi:10.1016/j.cej.2020.127083
[8]	SHARMA J， MISHRA I M， DIONYSIOU D D，et al. Oxidative removal of bisphenol A by UV-C/peroxymonosulfate（PMS）：Kinetics，influence of co-existing chemicals and degradation pathway［J］. Chemical Engineering Journal，2015，276：193-204. doi:10.1016/j.cej.2015.04.021
[9]	YANG Shiying， WANG Ping， YANG Xin，et al. Degradation efficiencies of azo dye Acid orange 7 by the interaction of heat，UV and anions with common oxidants：Persulfate，peroxymonosulfate and hydrogen peroxide［J］. Journal of Hazardous Materials，2010，179（1/2/3）：552-558. doi:10.1016/j.jhazmat.2010.03.039
[10]	范秀磊，王申鹏，张舒，等. 铜改性生物炭的制备及催化过硫酸盐去除水体中四环素的研究［J］. 工业水处理，2024，44（10）：133-142.
	FAN Xiulei， WANG Shenpeng， ZHANG Shu，et al. Preparation of copper modified biochar and its effect on catalyzing persulfate to remove the tetracycline from water［J］. Industrial Water Treatment，2024，44（10）：133-142.
[11]	ZHU Shijun， LI Haojie， WANG Lei，et al. Oxygen vacancies-rich α@ δ-MnO₂ mediated activation of peroxymonosulfate for the degradation of CIP：The role of electron transfer process on the surface［J］. Chemical Engineering Journal，2023，458：141415. doi:10.1016/j.cej.2023.141415
[12]	LI Meng， LI Yanwen， YU Pengfei，et al. Exploring degradation mechanism of tetracycline via high-effective peroxymonosulfate catalysts of montmorillonite hybridized CoFe composites and safety assessment［J］. Chemical Engineering Journal，2022，427：130930. doi:10.1016/j.cej.2021.130930
[13]	庄玲玲，姜瑞瑾，陈斯，等. 锰氧化物/碳活化过硫酸盐选择性生成单线态氧降解水中氟苯尼考［J］. 环境化学，2025，44（2）：712-720.
	ZHUANG Lingling， JIANG Ruijin， CHEN Si，et al. Research on the selective generation of singlet oxygen from manganese oxide/carbon activated persulfate for the degradation of florfenicol in water［J］. Environmental Chemistry，2025，44（2）：712-720.
[14]	邓宇辉. 二氧化锰表面缺陷调控及活化过一硫酸盐去除水中难降解有机污染物［D］. 广州：华南理工大学，2022.
	DENG Yuhui. Regulation of surface defects of manganese dioxide and removal of refractory organic pollutants from water by activated persulfate［D］. Guangzhou：South China University of Technology，2022.
[15]	HE Liuyang， YANG Shangding， LI Yulong，et al. Sludge biochar as an electron shuttle between periodate and sulfamethoxazole：The dominant role of ball mill-loaded Mn₂O₃ ［J］. Separation and Purification Technology，2023，314：123627. doi:10.1016/j.seppur.2023.123627
[16]	LI Hongchao， YUAN Na， QIAN Jieshu，et al. Mn₂O₃ as an electron shuttle between peroxymonosulfate and organic pollutants：The dominant role of surface reactive Mn（Ⅳ） species［J］. Environmental Science & Technology，2022，56（7）：4498-4506.
[17]	XIE Lan， HAO Jiajia， WU Yinsu，et al. Non-radical activation of peroxymonosulfate with oxygen vacancy-rich amorphous MnO _x for removing sulfamethoxazole in water［J］. Chemical Engineering Journal，2022，436：135260.
[18]	CHEN Lin， JIANG Xia， XIE Ruzhen，et al. A novel porous biochar-supported Fe-Mn composite as a persulfate activator for the removal of Acid red 88［J］. Separation and Purification Technology，2020，250：117232. doi:10.1016/j.seppur.2020.117232
[19]	WANG Junkai， FU Liya， CHEN Xingxing，et al. Catalytic ozonation promoted by Mn-doped sludge-based catalyst treating refractory industrial wastewater［J］. Separation and Purification Technology，2025，354：128676. doi:10.1016/j.seppur.2024.128676
[20]	ANIPSITAKIS G P， DIONYSIOU D D. Radical generation by the interaction of transition metals with common oxidants［J］. Environmental Science & Technology，2004，38（13）：3705-3712. doi:10.1021/es035121o
[21]	GUAN Chaoting， JIANG Jin， PANG Suyan，et al. Oxidation kinetics of bromophenols by nonradical activation of peroxydisulfate in the presence of carbon nanotube and formation of brominated polymeric products［J］. Environmental Science & Technology，2017，51（18）：10718-10728. doi:10.1021/acs.est.7b02271
[22]	JIANG Ning， XU Haodan， WANG Lihong，et al. Nonradical oxidation of pollutants with single-atom-Fe（Ⅲ）-activated persulfate：Fe（Ⅴ） being the possible intermediate oxidant［J］. Environmental Science & Technology，2020，54（21）：14057-14065． doi:10.1021/acs.est.0c04867
[23]	LI Xuan， HE Kai， PAN Bingcai，et al. Efficient As（Ⅲ） removal by macroporous anion exchanger-supported Fe-Mn binary oxide：Behavior and mechanism［J］. Chemical Engineering Journal，2012，193：131-138. doi:10.1016/j.cej.2012.04.036
[24]	BIESINGER M C， PAYNE B P， GROSVENOR A P，et al. Resolving surface chemical states in XPS analysis of first row transition metals，oxides and hydroxides：Cr，Mn，Fe，Co and Ni［J］. Applied Surface Science，2011，257（7）：2717-2730. doi:10.1016/j.apsusc.2010.10.051
[25]	WEI Haoxuan， ZHAO Jujiao， SHANG Bo，et al. Carbamazepine degradation through peroxymonosulfate activation by α-MnO₂ with the different exposed facets：Enhanced radical oxidation by facet-dependent surface effect［J］. Journal of Environmental Chemical Engineering，2022，10（5）：108532. doi:10.1016/j.jece.2022.108532
[26]	WANG Yan， FENG Xionghan， VILLALOBOS M，et al. Sorption behavior of heavy metals on birnessite：Relationship with its Mn average oxidation state and implications for types of sorption sites［J］. Chemical Geology，2012，292：25-34. doi:10.1016/j.chemgeo.2011.11.001
[27]	ZHANG Yimei， WANG Fei， Ping OU，et al. High efficiency and rapid degradation of bisphenol A by the synergy between adsorption and oxidization on the MnO₂@nano hollow carbon sphere［J］. Journal of Hazardous Materials，2018，360：223-232. doi:10.1016/j.jhazmat.2018.08.003
[28]	史胜利，冯佳，谢树莲，等. MnO₂-生物炭材料协同过一硫酸盐快速高效去除双酚A的行为和机理研究［J］. 环境科学学报，2023，43（2）：73-86.
	SHI Shengli， FENG Jia， XIE Shulian，et al. Behavior and mechanism of MnO₂-biochar synergistic with PMS for rapid and efficient removal of bisphenol A［J］. Acta Scientiae Circumstantiae，2023，43（2）：73-86.
[29]	LEE J， VON GUNTEN U， KIM J H. Persulfate-based advanced oxidation：Critical assessment of opportunities and roadblocks［J］. Environmental Science & Technology，2020，54（6）：3064-3081. doi:10.1021/acs.est.9b07082
[30]	HOU Shaodong， LING Li， DIONYSIOU D D，et al. Chlorate formation mechanism in the presence of sulfate radical，chloride，bromide and natural organic matter［J］. Environmental Science & Technology，2018，52（11）：6317-6325.

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