锰基催化剂用于活化过硫酸盐降解有机废水的研究进展

李珏秀; 施启旭; 赵锐; 刘玥; 陈俭静; 王向飞; 刘金茗; 刘攀攀; 贾金平

doi:10.7524/j.issn.0254-6108.2023011704

锰基催化剂用于活化过硫酸盐降解有机废水的研究进展

1.
中原工学院能源与环境学院，郑州，450007
2.
郑州大学化学学院，郑州，450001
3.
郑州大学生态与环境学院，郑州，450001
4.
上海交通大学环境科学与工程学院，上海，200240

通讯作者: Tel：0371-62506813，E-mail： 6858@zut.edu.cn;

基金项目:
河南省重点研发与推广专项(科技攻关）(212102310506)，河南省自然科学基金(202300410518)，中原工学院自然科学基金(K2022QN027)，中原工学院“学科青年硕导培育计划”项目(SD202242)，中原工学院研究生教育质量提升项目(JG202217，ALK202309)，国家大学生创新训练项目(202210465037)，河南省大学生创新训练项目(202210465052)和中原工学院大学生创新训练项目(202210465121)资助.

Research progress on manganese based catalysts for activating persulfate degradation of organic wastewater

1.
School of Energy and Environment, Zhongyuan University of Technology, Zhengzhou, 450007, China
2.
College of Chemistry, Zhengzhou University, Zhengzhou , 450001, China
3.
College of Ecology and Environment, Zhengzhou University, Zhengzhou, 450001, China
4.
School of Environmental Science and Engineering, Shanghai , 200240, China

Corresponding author: LI Juexiu, 6858@zut.edu.cn ;

Fund Project: the Key Research and Development Program of Henan Province (212102310506)，Natural Science Foundation of Henan (202300410518)， Zhongyuan University of Technology Natural Science Foundation (K2022QN027)，Discipline Strength Improving Project (SD202242)，Postgraduate Education Quality Improving Project (JG202217，ALK202309)，College Students Innovation Training Program of China (202210465037)，Henan Province (202210465052) and Zhongyuan University of Technology (202210465121).

摘要: 基于过硫酸盐的高级氧化技术具有便于储运、活化方式多、pH适应范围广等优点，近年来成为有机废水处理领域的热点研究方向. 该技术可通过物理、化学及多种耦合途径活化过硫酸盐产生多种自由基和单线态氧进而实现对水中有机污染物的高效降解和矿化. 在众多过硫酸盐的活化方式中，非均相催化活化途径具有高效的活化效果，且无需引入额外能量、氧化剂投加量少. 过渡金属催化剂是优异的过硫酸盐催化活化材料，其中锰基催化剂因其自然存量高、价态和晶型丰富等优势，已被广泛用于活化过硫酸盐降解各类有机物. 本文综述了不同锰基催化剂在催化活化过硫酸盐处理有机废水方面的研究进展，分别介绍零价锰、单一锰氧化合物、复合锰氧化合物、特殊晶型锰氧化物及负载型锰氧化物的国内外研究现状，并对锰基催化剂在活化过硫酸盐方面存在的问题和应用前景进行了展望.
- 高级氧化 /
- 锰基催化剂 /
- 过硫酸盐 /
- 有机废水 /
- 活化 /
- 降解.
Abstract: Persulfate (PS) activation based advanced oxidation process is featuring of easy storage and transportation, various activation approach and wide pH value range, which has been a hot issue on organic wastewater treatment in recent years. PS can be activated by physical, chemical and hybrid technologies, thus generating various reactive oxidation species (ROS) and singlet oxygen to efficiently degrade and mineralize organic compounds. Among various PS activation methods, heterogeneous catalytic activation has the advantages of high catalytic activity, none energy consumption and less oxidant dosage. Transition metal catalysts are excellent PS activation candidates. Among them, manganese (Mn)- based catalysts are characterized by abundant natural reserves, variable valence states and multiple crystal forms, which have been widely applied in PS activation for degradation of various organic pollutants. Herein, recent progress on different Mn-based catalysts for PS activation on degradation of organic wastewater were reviewed. Research on zero valence Mn, single manganese oxides, composite manganese oxides, special crystalline manganese oxides and supporting material were discussed respectively. Finally, the remaining challenges and future direction on Mn based catalysts for PS activation were prospected.
- advanced oxidation /
- manganese based catalyst /
- persulfate /
- organic wastewater /
- activation /
- degradation.

图 1 2000—2021年锰基催化剂活化过硫酸盐相关论文发表数量

Figure 1. The number of publications related to persulfate activation by Mn-based catalysts from 2000 to 2021

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图 2 α-、β-和γ-MnO₂的理化性质与反应速率（k_obs）之间的关系

Figure 2. Relationships between the reaction rate （kobs） and physicochemical properties of α-, β-, and γ-MnO₂

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图 3 α-MnO₂（a），β-MnO₂（b），γ-MnO₂（c）和δ-MnO₂（d）的SEM图像；α-MnO₂@Co₃O₄（e），β-MnO₂@Co₃O₄（f），γ-MnO₂@Co₃O₄（g）和δ-MnO₂@Co₃O₄（h）的SEM图像^[79]

Figure 3. SEM images ofα-MnO₂（a）,β-MnO₂（b）,γ-MnO₂（c）, andδ-MnO₂（d）; SEM images ofα-MnO₂@Co₃O₄（e）,β-MnO₂@Co₃O₄（f）,γ-MnO₂@Co₃O₄（g） andδ-MnO₂@Co₃O₄（h）^[79]

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图 4 NCM催化剂的XRD谱图（a），活化PMS机理示意图（b），NCM-650的SEM图像（c）和Co、Mn元素分布（d, e）^[54]

Figure 4. NCM XRD patterns（a）, PMS activation mechanism （b）, SEM images （c）, cobalt and manganese elements mapping distribution of NCM-650 （d, e）^[54]

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图 5 LaMnO₃和Cu-LaMnO₃钙钛矿的循环伏安曲线（a），La 3d、Mn 3s、Mn 2p和Cu 2p的XPS谱图（b），SMX在Cu-LaMnO₃/PMS体系中的降解机理（c）^[95]

Figure 5. Cyclic voltammetry curve of LaMnO₃ and Cu-LaMnO₃ （a）, XPS spectra of La 3d, Mn 3s, Mn 2p and Cu 2p in LaMnO₃ and Cu-LaMnO₃ （b） and degradation mechanism of SMX in Cu-LaMnO₃/PMS system （c）^[95]

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图 6 CMO（a），HNT（b），40-CMO/HNT（c）的TEM图像，CMO和40-CMO/HNT的XPS光谱（d），40-CMO/HNT活化PMS产生自由基的机理示意图（e）^[99]

Figure 6. TEM images of bare CMO （a）, HNT （b） and 40-CMO/HNT （c），XPS spectra of survey for bare CMO and 40-CMO/HNT （d）， Schematic illustration of radical generation mechanism through PMS activated by 40-CMO/HNT （e）^[99]

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表 1 锰基催化剂分类及特性

Table 1. Classification and characteristics of manganese based catalysts

类别 Classification	催化活性组分 Active catalytic components	制备方法 Preparation method	反应条件 Reaction condition	目标污染物 Target contaminants	主要ROS Major reactive oxygen species	污染物去除率 Pollutants removal efficiency	特点 Features	参考文献 Reference
零价锰	NZVIM	一步液相还原法	Ccata=75.0 mg·L⁻¹、 C_PMS=1.0 mmol·L⁻¹ C_SMT=5.0 mg·L⁻¹、 M_Fe/M_Mn=2:1、1:1、 pH₀=3.0、 T=30±0.5 °C、 t=60 min	磺胺甲基嘧啶（sulfamethazine, SMT）	·OH	＞95%	粒径小、活性位点多、吸附和还原能力强	[45]
零价锰	nZVMn	化学还原法	C_Mn⁰=1.0 g·L⁻¹、 C_PDS=50 mg·L⁻¹、 pH₀=2.0 C_CIP=10 mg·L⁻¹、 t=80 min	环丙沙星（ciprofloxacin,CIP）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH	95%	粒径小、活性位点多、吸附和还原能力强	[46]
单一锰氧化物	α-MnO₂	水热法	Ccata=0.05 g·L⁻¹、 C_OI=5 mg·L⁻¹ C_PMS=25 μmol·L⁻¹、 pH₀=7.0、T=25±2 °C	橙I （OrangeI,OI）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH、 ${\text{O}}_{2}^{\cdot –} $ ¹O₂	86.2%	较好的活性和持久性	[47]
	MnOOH	水热法	Ccata=0.4 g·L⁻¹、 C_PMS=2.5 mmol·L⁻¹、 pH₀=3—9、 C_PCA=0.5 mmol·L⁻¹、 T=25 °C、t=180 min	对氯苯胺（p-chloroaniline, PCA）	¹O₂	100%		[48]
	α-MnO₂	水热法	Ccata=100 mg·L⁻¹、 C_PMS=100 mg·L⁻¹、 t=25 h、 C_DIN=2.09 μmol、 pH₀=3.9、T=25 °C	二唑（diniconazole, DIN）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH	89.3%		[49]
复合锰氧化物	CuMnFe LDHs	水热法	Ccata=0.6 g·L⁻¹、 C_PMS=0.4 mmol·L⁻¹ C_BPA=20 mg·L⁻¹、 t=15 min、光照	双酚A （bisphenol A,BPA）	h⁺ $ {\text{O}}_{\text{2}}^{\text{·–}} $	93.5%	高活性、耐水性和稳定性	[50]
	MnFeO	水热法	Ccata=0.1 g·L⁻¹、 C_PMS=0.4 mmol·L⁻¹、 t=60 min C_BPA=40 μmol·L⁻¹、 pH₀₌6.5±0.1、 T=（25±0.5） °C、	双酚A （bisphenol A,BPA）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH ¹O₂	＞96%		[51]
	Fe-Mn	溶胶-凝胶法	Ccata=0.5 g·L⁻¹、 C_PMS=2.0 g·L⁻¹ C_Phenol=30 mg·L⁻¹、 pH₀=5、T=25 ℃、 t=90 min	苯酚（Phenol, PhOH）	·OH	90.59%		[12]
	Mn₃O₄ /ZIF-8	溶剂热法	Ccata=0.4 g·L⁻¹、 C_PMS=0.3 g·L⁻¹ C_RhB=10 mg·L⁻¹、 T=23 °C	罗丹明B （rhodamine B,RhB）	·OH	96%		[52]
	MnO₂/ MnFe₂O₄	水热法	Ccata=0.2 g·L⁻¹、 C_PMS=0.4 g·L⁻¹、 pH₀=5.4、 C_RhB=0.01 g·L⁻¹、 T=30 °C	罗丹明B （rhodamine B,RhB）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $	99%		[53]
	（LiNi_0.5Co_0.2Mn_0.3O₂, NCM）	热合成	Ccata=0.5 g·L⁻¹、 C_PMS=1 mmol·L⁻¹、 C_RhB=20 mg·L⁻¹、 pH₀=3、T=25 °C、 t=20 min	罗丹明B （rhodamine B,RhB）	¹O₂	100%		[54]
	α-MnO₂/ MnFe₂O₄	水热法	Ccata=0.2 g·L⁻¹、 C_PMS=1 mmol·L⁻¹ C_NOF=20 mg·L⁻¹、 pH₀=7、T=25 °C、 t=20 min	氟沙星（Norfloxacin, NOF）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH、 $ {\text{O}}_{\text{2}}^{\text{·–}} $	100%		[55]
特殊晶型锰氧化物	La_0.5Sr_0.5Co_0.8Mn_0.2O_3-δ	煅烧法	Ccata=0.1 g·L⁻¹、 C_PMS=0.12 g·L⁻¹ C_TBBPA0=20 mg·L⁻¹、 pH₀=6.7、T=25 °C、 t=40 min	四溴双酚A （tetrrabromobisphenol A ,TBBPA）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $	＞95%	低成本、高热稳定性、高孔隙度、优良的导电性	[56]
	LaMnO₃	溶胶-凝胶法	Ccata=40 mg·L⁻¹、 C_PMS=0.2 g·L⁻¹ C_OFX=10 mg·L⁻¹、 pH₀=5.0、t=15 min	氧氟沙星（ofloxacin, OFX）	¹O₂	96.3%		[57]
	MFO-LIBs	溶胶-凝胶法	Ccata=0.3 g·L⁻¹、 C_PMS=0.1 g·L⁻¹ C_BPA=20 mg·L⁻¹、 pH₀=6.2、T=25 °C、 t=15 min	双酚A （bisphenol A,BPA）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH、 $ {\text{O}}_{\text{2}}^{\text{·–}} $ ¹O₂	100%		[58]
负载型锰氧化物	MnFe₂O₄/ （CM-600）	煅烧法	Ccata=0.4 g·L⁻¹、 n_AO7/n_PMS=1:15 C_AO7=50 g·L⁻¹、 pH₀=6.5±0.05、 T=25±0.5 °C	酸性橙7 （Orange7, AO7）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $	99.0%	热稳定性、价格低廉、比表面积大	[59]
负载型锰氧化物	MMBC	共热解	Ccata=0.2 g·L⁻¹、 C_PDS=8 mmol·L⁻¹ C_TC=20 mg·L⁻¹、 pH₀=3、t=180 min	四环素（tetracycline, TC）	·OH	93%	热稳定性、价格低廉、比表面积大	[60]
负载型锰氧化物	MCC	浸渍法	Ccata=1.0 g·L⁻¹、 C_PMS=1.0 mmol·L⁻¹、 T=25 °C C_BPA=20 mg·L⁻¹、 pH₀=6.5±0.2、 t=120 min	双酚A （bisphenol A,BPA）	¹O₂	90%	热稳定性、价格低廉、比表面积大	[61]
	α-MnO₂/Pal	水热法	Ccata=0.1 g·L⁻¹、 C_PMS=0.1 g·L⁻¹ C_RhB=20 mg·L⁻¹、 pH₀=5.5±0.1、 T=300 min	罗丹明B （rhodamine B,RhB）	$ {\text{O}}_{\text{2}}^{\text{·–}} $ ¹O₂	100%		[62]
	MnO₂/C@CNT	一锅法	Ccata=0.10 g·L⁻¹、 C_PMS=3.0 mmol·L⁻¹ C_TC=10 mg·L⁻¹、 pH₀=5.2、T=20 °C、 t=10 min	四环素（tetracycline, TC）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $	85.6%		[63]
（注：Ccata：催化剂添加量；C_PMS：过硫酸盐浓度；pH₀：初始pH值；T：温度；t：反应时间）　　（Note: C_cata: catalyst concentration; C_PMS: persulfate concentration; pH₀: initial pH value; T: temperature; t: reaction time）

类别 Classification	催化活性组分 Active catalytic components	制备方法 Preparation method	反应条件 Reaction condition	目标污染物 Target contaminants	主要ROS Major reactive oxygen species	污染物去除率 Pollutants removal efficiency	特点 Features	参考文献 Reference
零价锰	NZVIM	一步液相还原法	Ccata=75.0 mg·L⁻¹、 C_PMS=1.0 mmol·L⁻¹ C_SMT=5.0 mg·L⁻¹、 M_Fe/M_Mn=2:1、1:1、 pH₀=3.0、 T=30±0.5 °C、 t=60 min	磺胺甲基嘧啶（sulfamethazine, SMT）	·OH	＞95%	粒径小、活性位点多、吸附和还原能力强	[45]
零价锰	nZVMn	化学还原法	C_Mn⁰=1.0 g·L⁻¹、 C_PDS=50 mg·L⁻¹、 pH₀=2.0 C_CIP=10 mg·L⁻¹、 t=80 min	环丙沙星（ciprofloxacin,CIP）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH	95%	粒径小、活性位点多、吸附和还原能力强	[46]
单一锰氧化物	α-MnO₂	水热法	Ccata=0.05 g·L⁻¹、 C_OI=5 mg·L⁻¹ C_PMS=25 μmol·L⁻¹、 pH₀=7.0、T=25±2 °C	橙I （OrangeI,OI）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH、 ${\text{O}}_{2}^{\cdot –} $ ¹O₂	86.2%	较好的活性和持久性	[47]
	MnOOH	水热法	Ccata=0.4 g·L⁻¹、 C_PMS=2.5 mmol·L⁻¹、 pH₀=3—9、 C_PCA=0.5 mmol·L⁻¹、 T=25 °C、t=180 min	对氯苯胺（p-chloroaniline, PCA）	¹O₂	100%		[48]
	α-MnO₂	水热法	Ccata=100 mg·L⁻¹、 C_PMS=100 mg·L⁻¹、 t=25 h、 C_DIN=2.09 μmol、 pH₀=3.9、T=25 °C	二唑（diniconazole, DIN）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH	89.3%		[49]
复合锰氧化物	CuMnFe LDHs	水热法	Ccata=0.6 g·L⁻¹、 C_PMS=0.4 mmol·L⁻¹ C_BPA=20 mg·L⁻¹、 t=15 min、光照	双酚A （bisphenol A,BPA）	h⁺ $ {\text{O}}_{\text{2}}^{\text{·–}} $	93.5%	高活性、耐水性和稳定性	[50]
	MnFeO	水热法	Ccata=0.1 g·L⁻¹、 C_PMS=0.4 mmol·L⁻¹、 t=60 min C_BPA=40 μmol·L⁻¹、 pH₀₌6.5±0.1、 T=（25±0.5） °C、	双酚A （bisphenol A,BPA）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH ¹O₂	＞96%		[51]
	Fe-Mn	溶胶-凝胶法	Ccata=0.5 g·L⁻¹、 C_PMS=2.0 g·L⁻¹ C_Phenol=30 mg·L⁻¹、 pH₀=5、T=25 ℃、 t=90 min	苯酚（Phenol, PhOH）	·OH	90.59%		[12]
	Mn₃O₄ /ZIF-8	溶剂热法	Ccata=0.4 g·L⁻¹、 C_PMS=0.3 g·L⁻¹ C_RhB=10 mg·L⁻¹、 T=23 °C	罗丹明B （rhodamine B,RhB）	·OH	96%		[52]
	MnO₂/ MnFe₂O₄	水热法	Ccata=0.2 g·L⁻¹、 C_PMS=0.4 g·L⁻¹、 pH₀=5.4、 C_RhB=0.01 g·L⁻¹、 T=30 °C	罗丹明B （rhodamine B,RhB）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $	99%		[53]
	（LiNi_0.5Co_0.2Mn_0.3O₂, NCM）	热合成	Ccata=0.5 g·L⁻¹、 C_PMS=1 mmol·L⁻¹、 C_RhB=20 mg·L⁻¹、 pH₀=3、T=25 °C、 t=20 min	罗丹明B （rhodamine B,RhB）	¹O₂	100%		[54]
	α-MnO₂/ MnFe₂O₄	水热法	Ccata=0.2 g·L⁻¹、 C_PMS=1 mmol·L⁻¹ C_NOF=20 mg·L⁻¹、 pH₀=7、T=25 °C、 t=20 min	氟沙星（Norfloxacin, NOF）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH、 $ {\text{O}}_{\text{2}}^{\text{·–}} $	100%		[55]
特殊晶型锰氧化物	La_0.5Sr_0.5Co_0.8Mn_0.2O_3-δ	煅烧法	Ccata=0.1 g·L⁻¹、 C_PMS=0.12 g·L⁻¹ C_TBBPA0=20 mg·L⁻¹、 pH₀=6.7、T=25 °C、 t=40 min	四溴双酚A （tetrrabromobisphenol A ,TBBPA）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $	＞95%	低成本、高热稳定性、高孔隙度、优良的导电性	[56]
	LaMnO₃	溶胶-凝胶法	Ccata=40 mg·L⁻¹、 C_PMS=0.2 g·L⁻¹ C_OFX=10 mg·L⁻¹、 pH₀=5.0、t=15 min	氧氟沙星（ofloxacin, OFX）	¹O₂	96.3%		[57]
	MFO-LIBs	溶胶-凝胶法	Ccata=0.3 g·L⁻¹、 C_PMS=0.1 g·L⁻¹ C_BPA=20 mg·L⁻¹、 pH₀=6.2、T=25 °C、 t=15 min	双酚A （bisphenol A,BPA）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $ ·OH、 $ {\text{O}}_{\text{2}}^{\text{·–}} $ ¹O₂	100%		[58]
负载型锰氧化物	MnFe₂O₄/ （CM-600）	煅烧法	Ccata=0.4 g·L⁻¹、 n_AO7/n_PMS=1:15 C_AO7=50 g·L⁻¹、 pH₀=6.5±0.05、 T=25±0.5 °C	酸性橙7 （Orange7, AO7）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $	99.0%	热稳定性、价格低廉、比表面积大	[59]
负载型锰氧化物	MMBC	共热解	Ccata=0.2 g·L⁻¹、 C_PDS=8 mmol·L⁻¹ C_TC=20 mg·L⁻¹、 pH₀=3、t=180 min	四环素（tetracycline, TC）	·OH	93%	热稳定性、价格低廉、比表面积大	[60]
负载型锰氧化物	MCC	浸渍法	Ccata=1.0 g·L⁻¹、 C_PMS=1.0 mmol·L⁻¹、 T=25 °C C_BPA=20 mg·L⁻¹、 pH₀=6.5±0.2、 t=120 min	双酚A （bisphenol A,BPA）	¹O₂	90%	热稳定性、价格低廉、比表面积大	[61]
	α-MnO₂/Pal	水热法	Ccata=0.1 g·L⁻¹、 C_PMS=0.1 g·L⁻¹ C_RhB=20 mg·L⁻¹、 pH₀=5.5±0.1、 T=300 min	罗丹明B （rhodamine B,RhB）	$ {\text{O}}_{\text{2}}^{\text{·–}} $ ¹O₂	100%		[62]
	MnO₂/C@CNT	一锅法	Ccata=0.10 g·L⁻¹、 C_PMS=3.0 mmol·L⁻¹ C_TC=10 mg·L⁻¹、 pH₀=5.2、T=20 °C、 t=10 min	四环素（tetracycline, TC）	$ {\text{SO}}_{\text{4}}^{\text{·–}} $	85.6%		[63]
（注：Ccata：催化剂添加量；C_PMS：过硫酸盐浓度；pH₀：初始pH值；T：温度；t：反应时间）　　（Note: C_cata: catalyst concentration; C_PMS: persulfate concentration; pH₀: initial pH value; T: temperature; t: reaction time）

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[1]	杜明辉, 王勇, 高群丽, 等. 臭氧微气泡处理有机废水的效果与机制 [J]. 化工进展, 2021, 40(12): 6907-6915. DU M H, WANG Y, GAO Q L, et al. Mechanism and efficiency of ozone microbubble treatment of organic wastewater [J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6907-6915(in Chinese).
[2]	李珏秀, 刘纪林, 杨草原, 等. 微生物燃料电池辅助转盘液膜光催化降解染料废水 [J]. 中原工学院学报, 2022, 33(2): 51-57. LI J X, LIU J L, YANG C Y, et al. Degradation of dye wastewater by microbial fuel cell assisting rotating disk thin-film photocatalysis integrated system [J]. Journal of Zhongyuan University of Technology, 2022, 33(2): 51-57(in Chinese).
[3]	申大伟. 锰基催化剂对印染废水的降解研究 [J]. 印染助剂, 2022, 39(5): 21-26. SHEN D W. Degradation of printing and dyeing wastewater by Manganese based catalyst [J]. Textile Auxiliaries, 2022, 39(5): 21-26(in Chinese).
[4]	王渊源, 阎鑫, 艾涛, 等. 碳化泡沫负载Co₃O₄活化过硫酸盐降解罗丹明B [J]. 环境科学, 2022, 43(4): 2039-2046. WANG Y Y, YAN X, AI T, et al. Carbonized foam supported Co₃O₄ activated peroxymonosulfate towards rhodamine B degradation [J]. Environmental Science, 2022, 43(4): 2039-2046(in Chinese).
[5]	吴健森, 孟耀庭, 潘月燕, 等. 亚临界水氧化技术处理高盐难降解有机废水研究进展 [J]. 能源环境保护, 2022, 36(3): 30-36. doi: 10.3969/j.issn.1006-8759.2022.03.005 WU J S, MENG Y T, PAN Y Y, et al. Research progress in the treatment of refractory organic wastewater with high salinity by subcritical water oxidation technology [J]. Energy Environmental Protection, 2022, 36(3): 30-36(in Chinese). doi: 10.3969/j.issn.1006-8759.2022.03.005
[6]	马博雅, 孙立坤, 杨春维. 碳中和背景下我国污水处理技术思考 [J]. 应用化工, 2022, 51(10): 2997-3000. MA B Y, SUN L K, YANG C W. The feasible wastewater treatment technology in China under the background of carbon neutrality [J]. Applied Chemical Industry, 2022, 51(10): 2997-3000(in Chinese).
[7]	孙小淇, 郝泽伟, 陈家斌, 等. 碳中和背景下高盐废水中盐分的高效分离和资源化 [J]. 工业水处理, 2023, 43(2): 14-22. SUN X Q, HAO Z W, CHEN J B, et al. Efficient separation and resource recovery technology of salts in highly saline wastewater in the context of carbon neutrality [J]. Industrial Water Treatment, 2023, 43(2): 14-22(in Chinese).
[8]	吴百苗, 张一梅, 栗帅, 等. 基于LCA的污水处理方案碳中和综合影响评价 [J]. 环境工程, 2022, 40(6): 130-137. WU B M, ZHANG Y M, LI S, et al. Comprehensive impact assessment on carbon neutralization of wastewater treatment plants based on hybrid LCA [J]. Environmental Engineering, 2022, 40(6): 130-137(in Chinese).
[9]	GLAZE W H, KANG J W, CHAPIN D H. The chemistry of water treatment processes involving ozone, hydrogen peroxide and ultraviolet radiation [J]. Ozone:Science & Engineering, 1987, 9(4): 335-352.
[10]	WEI Y, MIAO J, GE J X, et al. Ultrahigh peroxymonosulfate utilization efficiency over CuO nanosheets via heterogeneous Cu(III) formation and preferential electron transfer during degradation of phenols [J]. Environmental Science & Technology, 2022, 56(12): 8984-8992.
[11]	齐亚兵. 活化过硫酸盐高级氧化法降解抗生素的研究进展 [J]. 化工进展, 2022, 41(12): 6627-6643. QI Y B. Research progress on degradation of antibiotics by activated persulfate advanced oxidation [J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6627-6643(in Chinese).
[12]	邵强, 郭轶琼. 铁锰催化剂活化过硫酸盐去除水中苯酚的研究 [J]. 工业水处理, 2020, 40(7): 94-97. SHAO Q, GUO Y Q. Removal of phenol from water by activation of persulfate with Fe-Mn catalyst [J]. Industrial Water Treatment, 2020, 40(7): 94-97(in Chinese).
[13]	王庆宏, 李思雨, 牛皓, 等. 活化过硫酸盐氧化处理难降解废水的技术研究进展 [J]. 工业水处理, 2022, 42(8): 8-16,26. WANG Q H, LI S Y, NIU H, et al. An overview of activated persulfate oxidation processes in treatment of refractory wastewaters [J]. Industrial Water Treatment, 2022, 42(8): 8-16,26(in Chinese).
[14]	杨鹤云, 郑兴. 高级氧化法降解有机污染物的应用及研究进展 [J]. 水处理技术, 2021, 47(12): 13-18. YANG H Y, ZHENG X. Application and research progress of advanced oxidation process for degradation of organic pollutants [J]. Technology of Water Treatment, 2021, 47(12): 13-18(in Chinese).
[15]	杨淼淼. 高级氧化技术处理印染废水的研究进展 [J]. 生物化工, 2022, 8(1): 149-152. YANG M M. Research progress of advanced oxidation process for dyeing wastewater treatment based on free radical [J]. Biological Chemical Engineering, 2022, 8(1): 149-152(in Chinese).
[16]	JIANG S F, LING L L, CHEN W J, et al. High efficient removal of bisphenol A in a peroxymonosulfate/iron functionalized biochar system: Mechanistic elucidation and quantification of the contributors [J]. Chemical Engineering Journal, 2019, 359: 572-583. doi: 10.1016/j.cej.2018.11.124
[17]	OLMEZ-HANCI T, ARSLAN-ALATON I. Comparison of sulfate and hydroxyl radical based advanced oxidation of phenol [J]. Chemical Engineering Journal, 2013, 224: 10-16. doi: 10.1016/j.cej.2012.11.007
[18]	ZHANG X W, LAN M Y, WANG F, et al. ZIF-67-based catalysts in persulfate advanced oxidation processes (PS-AOPs) for water remediation [J]. Journal of Environmental Chemical Engineering, 2022, 10(3): 107997. doi: 10.1016/j.jece.2022.107997
[19]	LIU Y H, KUO Y S, LIU W C. et al. Photoelectrocatalytic activity of perovskite YFeO₃/carbon fiber composite electrode under visible light irradiation for organic wastewater treatment [J]. Journal of the Taiwan Institute of Chemical Engineers, 2021, 128: 227-236. doi: 10.1016/j.jtice.2021.08.029
[20]	马祯, 宋小三, 张轩. 紫外/过硫酸盐高级氧化技术在饮用水处理中的研究进展 [J]. 应用化工, 2022, 51(5): 1466-1471. MA Z, SONG X S, ZHANG X. Research progress of ultraviolet/persulfate advanced oxidation technology in drinking water treatment [J]. Applied Chemical Industry, 2022, 51(5): 1466-1471(in Chinese).
[21]	王静, 邓黎玲, 薛罡, 等. 物化-生化-高级氧化处理涂料废渣热催化废液 [J]. 水处理技术, 2019, 45(10): 100-105. WANG J, DENG L L, XUE G, et al. Physicochemical-biochemical advanced treatment for paint sludge thermocatalytic waste liquor [J]. Technology of Water Treatment, 2019, 45(10): 100-105(in Chinese).
[22]	吴秀, 方迪, 危亚云, 等. 热活化过一硫酸盐调理强化厌氧消化污泥脱水的研究 [J]. 环境科学学报, 2021, 41(11): 4547-4553. WU X, FANG D, WEI Y Y, et al. Improved dewaterability of anaerobically digested sewage sludge by thermally activated peroxymonosulfate [J]. Acta Scientiae Circumstantiae, 2021, 41(11): 4547-4553(in Chinese).
[23]	LONG L L, BAI C W, ZHOU X Y, et al. A novel strategy for promoting PMS activation: Enhanced utilization of side reactions [J]. Separation and Purification Technology, 2022, 297: 121432. doi: 10.1016/j.seppur.2022.121432
[24]	程佳鑫, 李荣兴, 杨海涛, 等. 三维电催化氧化处理难生化降解有机废水研究进展 [J]. 环境化学, 2022, 41(1): 288-304. doi: 10.7524/j.issn.0254-6108.2020082804 CHENG J X, LI R X, YANG H T, et al. Review of three-dimensional electrodes for bio-refractory organic wastewater treatment [J]. Environmental Chemistry, 2022, 41(1): 288-304(in Chinese). doi: 10.7524/j.issn.0254-6108.2020082804
[25]	左静, 秦丰林, 方国东. 电化学活化过硫酸盐修复土壤有机污染研究进展 [J]. 现代农业科技, 2021(13): 179-185. ZUO J, QIN F L, FANG G D. Research progress on remediation of soil organic pollution by electrochemical activation of persulfate [J]. Modern Agricultural Science and Technology, 2021(13): 179-185(in Chinese).
[26]	杨晴, 孙昕, 李鹏飞, 等. 超声活化过硫酸盐降解甲基橙的影响因素研究 [J]. 环境科学学报, 2020, 40(8): 2715-2721. YANG Q, SUN X, LI P F, et al. Influencing factors of methyl orange degradation by ultrasound activated persulfate [J]. Acta Scientiae Circumstantiae, 2020, 40(8): 2715-2721(in Chinese).
[27]	张楠, 陈蕾. 超声活化过硫酸盐降解废水中有机污染物的研究进展 [J]. 应用化工, 2021, 50(10): 2805-2808,2813. ZHANG N, CHEN L. Research progress of ultrasonic activated persulfate for degradation of organic pollutants in wastewater [J]. Applied Chemical Industry, 2021, 50(10): 2805-2808,2813(in Chinese).
[28]	朱佳, 宋慧, 高敏, 等. 超声协同MoS₂/g-C₃N₄活化过硫酸盐降解二甲基亚砜的研究 [J]. 化工新型材料, 2022, 50(9): 179-184,190. ZHU J, SONG H, GAO M, et al. Degradation of dimethyl sulfoxide by ultrasonic synergistic [J]. New Chemical Materials, 2022, 50(9): 179-184,190(in Chinese).
[29]	张磊, 祝思频, 张青青, 等. 微波活化过硫酸盐降解典型选矿药剂水杨羟肟酸 [J]. 环境化学, 2022, 41(8): 3414-3424. doi: 10.7524/j.issn.0254-6108.2021030801 ZHANG L, ZHU S P, ZHANG Q Q, et al. Degradation of salicylhydroxamic acid by microwave activated persulfate [J]. Environmental Chemistry, 2022, 41(8): 3414-3424(in Chinese). doi: 10.7524/j.issn.0254-6108.2021030801
[30]	程爱华, 马万超, 徐哲. 等离子体改性海绵铁活化过硫酸盐处理含酚废水 [J]. 化工进展, 2020, 39(2): 798-804. CHENG A H, MA W C, XU Z. Treatment of phenol wastewater with persulfate activated by plasmamodified sponge iron [J]. Chemical Industry and Engineering Progress, 2020, 39(2): 798-804(in Chinese).
[31]	李春琴, 邹亚辰, 贾小宁. 过硫酸盐高级氧化技术活化方法及降解机理的研究进展 [J]. 化学与生物工程, 2022, 39(6): 1-6,27. LI C Q, ZOU Y C, JIA X N. Research progress in activation methods of persulfate and degradation mechanism of organic pollutants by persulfate advanced oxidation process [J]. Chemistry & Bioengineering, 2022, 39(6): 1-6,27(in Chinese).
[32]	凌良雄, 陆建, 周易, 等. 铁基材料活化过硫酸盐降解水中抗生素的研究进展 [J]. 环境科学研究, 2022, 35(1): 290-298. LING L X, LU J, ZHOU Y, et al. Persulfate activated by iron-based materials for degradation of antibiotics in water: A review [J]. Research of Environmental Sciences, 2022, 35(1): 290-298(in Chinese).
[33]	田婷婷, 李朝阳, 王召东, 等. 过渡金属活化过硫酸盐降解有机废水技术研究进展 [J]. 化工进展, 2021, 40(6): 3480-3488. TIAN T T, LI C Y, WANG S D, et al. Research progress of transition metal activated persulfate to degrade organic wastewater [J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3480-3488(in Chinese).
[34]	李书典, 郑德山, 郭峰. 二氧化锰催化氧化性能的研究进展 [J]. 现代化工, 2020, 40(3): 52-56. LI S D, ZHENG D S, GUO F. Research progress on catalytic oxidation performance of Manganese dioxide [J]. Modern Chemical Industry, 2020, 40(3): 52-56(in Chinese).
[35]	周自成, 刘悦, 李英, 等. 纳米Mn₃O₄的快速制备及其对亚甲基蓝的类芬顿催化氧化性能 [J]. 矿冶工程, 2020, 40(4): 153-155,160. ZHOU Z C, LIU Y, LI Y, et al. Simple and rapid preparation of nano-Mn₃O₄ and its Fenton-like catalytic oxidation of methylene blue [J]. Mining and Metallurgical Engineering, 2020, 40(4): 153-155,160(in Chinese).
[36]	张磊, 王胜, 汪明哲, 等. CoMnO_x/Al₂O₃/monolith整体催化剂的制备及其催化臭氧分解性能 [J]. 工业催化, 2020, 28(1): 17-23. ZHANG L, WANG S, WANG M Z, et al. Preparation of CoMnOx/Al₂O₃/monolith catalyst for ozone elimination [J]. Industrial Catalysis, 2020, 28(1): 17-23(in Chinese).
[37]	FU R, ZHANG P S, JIANG Y X, et al. Wastewater treatment by anodic oxidation in electrochemical advanced oxidation process: Advance in mechanism, direct and indirect oxidation detection methods [J]. Chemosphere, 2023, 311: 136993. doi: 10.1016/j.chemosphere.2022.136993
[38]	LIN C, LI J L, LI X P, et al. In-situ reconstructed Ru atom array on α-MnO₂ with enhanced performance for acidic water oxidation [J]. Nature Catalysis, 2021, 4(12): 1012-1023. doi: 10.1038/s41929-021-00703-0
[39]	ZHOU Y, FENG S, DUAN X M, et al. MnO₂/UIO-66 improves the catalysed degradation of oxytetracycline under UV/H₂O₂/PMS system [J]. Journal of Solid State Chemistry, 2021, 300: 122231. doi: 10.1016/j.jssc.2021.122231
[40]	GUO M N, FANG R M, LIU X W, et al. Experimental study of volatile organic compounds catalytic combustion on Cu-Mn catalysts with different carriers [J]. International Journal of Energy Research, 2021, 45(6): 8749-8762. doi: 10.1002/er.6411
[41]	QIN C H, GUO M K, JIANG C C, et al. Simultaneous oxidation of toluene and ethyl acetate by dielectric barrier discharge combined with Fe, Mn and Mo catalysts [J]. Science of the Total Environment, 2021, 782: 146931. doi: 10.1016/j.scitotenv.2021.146931
[42]	向宁, 韩小金, 郑剑锋, 等. 锰改性对ZIF-67衍生Co₃O₄低温催化氧化甲醛性能的影响 [J]. 燃料化学学报, 2022, 50(7): 859-867. XIANG N, HAN X J, ZHENG J F, et al. Effect of Manganese modification on catalytic oxidation of formaldehyde at low temperature by Co₃O₄ derived from ZIF-67 [J]. Journal of Fuel Chemistry and Technology, 2022, 50(7): 859-867(in Chinese).
[43]	DING Y B, WANG X R, FU L B, et al. Nonradicals induced degradation of organic pollutants by peroxydisulfate (PDS) and peroxymonosulfate (PMS): Recent advances and perspective [J]. Science of the Total Environment, 2021, 765: 142794. doi: 10.1016/j.scitotenv.2020.142794
[44]	WACLAWEK S, LUTZE H V, GRüBEL K, et al. Chemistry of persulfates in water and wastewater treatment: A review [J]. Chemical Engineering Journal, 2017, 330: 44-62. doi: 10.1016/j.cej.2017.07.132
[45]	XIAO J Y, LI R, DONG H R, et al. Activation of sulfite via zero-valent iron-Manganese bimetallic nanomaterials for enhanced sulfamethazine removal in aqueous solution: Key roles of Fe/Mn molar ratio and solution pH [J]. Separation and Purification Technology, 2022, 297: 121479. doi: 10.1016/j.seppur.2022.121479
[46]	SHAH N S, ALI KHAN J, SAYED M, et al. Hydroxyl and sulfate radical mediated degradation of ciprofloxacin using nano zerovalent Manganese catalyzed S₂O₈²⁻ [J]. Chemical Engineering Journal, 2019, 356: 199-209. doi: 10.1016/j.cej.2018.09.009
[47]	YANG Y S, ZHAO Y, ZONG Y, et al. Activation of peroxymonosulfate by α-MnO₂ for Orange Ⅰ removal in water [J]. Environmental Research, 2022, 210: 112919. doi: 10.1016/j.envres.2022.112919
[48]	XU X M, ZHANG Y Q, ZHOU S Q, et al. Activation of persulfate by MnOOH: Degradation of organic compounds by nonradical mechanism [J]. Chemosphere, 2021, 272: 129629. doi: 10.1016/j.chemosphere.2021.129629
[49]	ZHAO M J, XU R S, CHEN Z Q, et al. Kinetics and mechanisms of diniconazole degradation by α-MnO₂ activated peroxymonosulfate [J]. Separation and Purification Technology, 2022, 281: 119850. doi: 10.1016/j.seppur.2021.119850
[50]	刘畅, 王宇寒, 胡清, 等. 太阳光/CuMnFe LDHs催化剂/过一硫酸盐体系降解双酚A [J]. 环境工程学报, 2021, 15(11): 3545-3560. LIU C, WANG Y H, HU Q, et al. Degradation of bisphenol A using CuMnFe LDHs catalyst and peroxymonosulfate under solar light [J]. Chinese Journal of Environmental Engineering, 2021, 15(11): 3545-3560(in Chinese).
[51]	李广英, 杜敏洁, 谈成英, 等. 锰铁氧体活化PMS降解双酚A的过程机制 [J]. 环境工程学报, 2021, 15(9): 2952-2962. LI G Y, DU M J, TAN C Y, et al. Mechanism of BPA degradation in a system of peroxymonosulfate activated by a Mn/Fe bimetallic oxide catalysts [J]. Chinese Journal of Environmental Engineering, 2021, 15(9): 2952-2962(in Chinese).
[52]	HU L X, DENG G H, LU W C, et al. Peroxymonosulfate activation by Mn₃O₄/metal-organic framework for degradation of refractory aqueous organic pollutant rhodamine B [J]. Chinese Journal of Catalysis, 2017, 38(8): 1360-1372. doi: 10.1016/S1872-2067(17)62875-4
[53]	CHEN G, ZHANG X Y, GAO Y J, et al. Novel magnetic MnO₂/MnFe₂O₄ nanocomposite as a heterogeneous catalyst for activation of peroxymonosulfate (PMS) toward oxidation of organic pollutants [J]. Separation and Purification Technology, 2019, 213: 456-464. doi: 10.1016/j.seppur.2018.12.049
[54]	ZHAO Y L, WANG H, JI J Q, et al. Recycling of waste power lithium-ion batteries to prepare nickel/cobalt/Manganese-containing catalysts with inter-valence cobalt/Manganese synergistic effect for peroxymonosulfate activation [J]. Journal of Colloid and Interface Science, 2022, 626: 564-580. doi: 10.1016/j.jcis.2022.06.112
[55]	XU L S, SUN X B, HONG J M, et al. Peroxymonosulfate activation by α-MnO₂/MnFe₂O₄ for norfloxacin degradation: Efficiency and mechanism [J]. Journal of Physics and Chemistry of Solids, 2021, 153: 110029. doi: 10.1016/j.jpcs.2021.110029
[56]	毛韦达, 胡翔. La_0.5Sr_0.5Co_0.8Mn_0.2O_3-δ钙钛矿对过一硫酸盐降解水中四溴双酚A影响实验研究 [J]. 地学前缘, 2019, 26(3): 255-262. MAO W D, HU X. Exoerinentai studies of the effect of perovskite La_0.5Sr_0.5Co_0.8Mn_0.2O_3-δ on tetrabromobisphenol A degradation in water by peroxy-monosulfate [J]. Earth Science Frontiers, 2019, 26(3): 255-262(in Chinese).
[57]	NIE Y L, ZHOU H, TIAN S, et al. Anionic ligands driven efficient ofloxacin degradation over LaMnO₃ suspended particles in water due to the enhanced peroxymonosulfate activation [J]. Chemical Engineering Journal, 2022, 427: 130998. doi: 10.1016/j.cej.2021.130998
[58]	LIANG J X, GUO M M, XUE Y X, et al. Constructing magnetically separable Manganese-based spinel ferrite from spent ternary lithium-ion batteries for efficient degradation of bisphenol A via peroxymonosulfate activation [J]. Chemical Engineering Journal, 2022, 435: 135000. doi: 10.1016/j.cej.2022.135000
[59]	DU J Y, XU W S, LIU J, et al. Efficient degradation of Acid Orange 7 by persulfate activated with a novel developed carbon-based MnFe₂O₄ composite catalyst [J]. Journal of Chemical Technology & Biotechnology, 2020, 95(4): 1135-1145.
[60]	HUANG D L, ZHANG Q, ZHANG C, et al. Mn doped magnetic biochar as persulfate activator for the degradation of tetracycline [J]. Chemical Engineering Journal, 2020, 391: 123532. doi: 10.1016/j.cej.2019.123532
[61]	YANG Z, WANG Z W, LIANG G W, et al. Catalyst bridging-mediated electron transfer for nonradical degradation of bisphenol A via natural Manganese ore-cornstalk biochar composite activated peroxymonosulfate [J]. Chemical Engineering Journal, 2021, 426: 131777. doi: 10.1016/j.cej.2021.131777
[62]	HUANG C, WANG Y L, GONG M, et al. α-MnO₂/Palygorskite composite as an effective catalyst for heterogeneous activation of peroxymonosulfate (PMS) for the degradation of Rhodamine B [J]. Separation and Purification Technology, 2020, 230: 115877. doi: 10.1016/j.seppur.2019.115877
[63]	WANG Z X, HAN Y F, FAN W L, et al. Shell-core MnO₂/Carbon@Carbon nanotubes synthesized by a facile one-pot method for peroxymonosulfate oxidation of tetracycline [J]. Separation and Purification Technology, 2021, 278: 119558. doi: 10.1016/j.seppur.2021.119558
[64]	LI Y T, LI H S, LIU F L, et al. Zero-valent iron-Manganese bimetallic nanocomposites catalyze hypochlorite for enhanced thallium(I) oxidation and removal from wastewater: Materials characterization, process optimization and removal mechanisms [J]. Journal of Hazardous Materials, 2020, 386: 121900. doi: 10.1016/j.jhazmat.2019.121900
[65]	DADA A O, ADEKOLA F A, ODEBUNMI E O. Liquid phase scavenging of Cd (II) and Cu (II) ions onto novel nanoscale zerovalent Manganese (nZVMn): Equilibrium, kinetic and thermodynamic studies [J]. Environmental Nanotechnology, Monitoring & Management, 2017, 8: 63-72.
[66]	PANDA A P, ROUT P, JENA K K, et al. Core–shell structured zero-valent Manganese (ZVM): A novel nanoadsorbent for efficient removal of As(iii) and As(v) from drinking water [J]. Journal of Materials Chemistry A, 2019, 7(16): 9933-9947. doi: 10.1039/C9TA00428A
[67]	贺君, 陈思琦, 唐首锋, 等. MnO₂/EGM电极制备及电化学降解罗丹明B的研究 [J]. 环境科学学报, 2020, 40(11): 3922-3930. HE J, CHEN S Q, TANG S F, et al. Preparation of MnO₂/EGM electrode and electrochemical degradation of Rhodamine B [J]. Acta Scientiae Circumstantiae, 2020, 40(11): 3922-3930(in Chinese).
[68]	SHEN S T, ZHOU X Q, ZHAO Q D, et al. Understanding the nonradical activation of peroxymonosulfate by different crystallographic MnO₂: The pivotal role of Mn^III content on the surface [J]. Journal of Hazardous Materials, 2022, 439: 129613. doi: 10.1016/j.jhazmat.2022.129613
[69]	NDAYIRAGIJE S, ZHANG Y F, ZHOU Y Q, et al. Mechanochemically tailoring oxygen vacancies of MnO₂ for efficient degradation of tetrabromobisphenol A with peroxymonosulfate [J]. Applied Catalysis B:Environmental, 2022, 307: 121168. doi: 10.1016/j.apcatb.2022.121168
[70]	YI H L, WANG Y H, DIAO L L, et al. Ultrasonic treatment enhances the formation of oxygen vacancies and trivalent Manganese on α-MnO₂ surfaces: Mechanism and application [J]. Journal of Colloid and Interface Science, 2022, 626: 629-638. doi: 10.1016/j.jcis.2022.06.144
[71]	LI M, ZHANG H, LIU Z L, et al. Surface lattice oxygen mobility inspired peroxymonosulfate activation over Mn₂O₃ exposing different crystal faces toward bisphenol A degradation [J]. Chemical Engineering Journal, 2022, 450: 138147. doi: 10.1016/j.cej.2022.138147
[72]	OUYANG H, WU C, QIU X H, et al. New insight of Mn(III) in δ-MnO₂ for peroxymonosulfate activation reaction: Via direct electron transfer or via free radical reactions [J]. Environmental Research, 2023, 217: 114874. doi: 10.1016/j.envres.2022.114874
[73]	ZHOU Z G, DU H M, DAI Z H, et al. Degradation of organic pollutants by peroxymonosulfate activated by MnO₂ with different crystalline structures: Catalytic performances and mechanisms [J]. Chemical Engineering Journal, 2019, 374: 170-180. doi: 10.1016/j.cej.2019.05.170
[74]	王淑敏, 林海龙, 侯俊斌, 等. MnO₂的生长机理及其对罗丹明B的快速降解 [J]. 材料科学与工程学报, 2022, 40(1): 34-39. WANG S M, LIN H L, HOU J B, et al. Growth mechanism of MnO₂ and its rapid degradation of rhodamine B [J]. Journal of Materials Science and Engineering, 2022, 40(1): 34-39(in Chinese).
[75]	闵弘扬, 王赟, 冉献强, 等. Cu-Mn/ZSM-5催化剂的制备及其催化降解酸性红的研究 [J]. 工业用水与废水, 2015, 46(1): 52-56,64. MIN H Y, WANG Y, RAN X Q, et al. Study on Cu-Mn/ZSM-5 catalyst preparation and its catalytic degradation performance on acid red [J]. Industrial Water & Wastewater, 2015, 46(1): 52-56,64(in Chinese).
[76]	GHASEMI H, MOZAFFARI S, MOUSAVI S H, et al. Decolorization of wastewater by heterogeneous Fenton reaction using MnO₂-Fe₃O₄/CuO hybrid catalysts [J]. Journal of Environmental Chemical Engineering, 2021, 9(2): 105091. doi: 10.1016/j.jece.2021.105091
[77]	LIU M, YIN W, ZHAO T L, et al. High-efficient removal of organic dyes from model wastewater using Mg(OH)₂-MnO₂ nanocomposite: Synergistic effects of adsorption, precipitation, and photodegradation [J]. Separation and Purification Technology, 2021, 272: 118901. doi: 10.1016/j.seppur.2021.118901
[78]	PANIMALAR S, SUBASH M, CHANDRASEKAR M, et al. Reproducibility and long-term stability of Sn doped MnO₂ nanostructures: Practical photocatalytic systems and wastewater treatment applications [J]. Chemosphere, 2022, 293: 133646. doi: 10.1016/j.chemosphere.2022.133646
[79]	THAO L T, van NGUYEN T, NGUYEN V Q, et al. Orange G degradation by heterogeneous peroxymonosulfate activation based on magnetic MnFe₂O₄/α-MnO₂ hybrid [J]. Journal of Environmental Sciences, 2023, 124: 379-396. doi: 10.1016/j.jes.2021.10.008
[80]	SHI Q Q, PU S Y, YANG X, et al. Enhanced heterogeneous activation of peroxymonosulfate by boosting internal electron transfer in a bimetallic Fe₃O₄-MnO₂ nanocomposite [J]. Chinese Chemical Letters, 2022, 33(4): 2129-2133. doi: 10.1016/j.cclet.2021.07.063
[81]	ANUSHREE C, NANDA GOPALA KRISHNA D, PHILIP J. Efficient dye degradation via catalytic persulfate activation using iron oxide-Manganese oxide core-shell particle doped with transition metal ions [J]. Journal of Molecular Liquids, 2021, 337: 116429. doi: 10.1016/j.molliq.2021.116429
[82]	WANG Z M, WANG Z H, LI W, et al. Performance comparison and mechanism investigation of Co₃O₄-modified different crystallographic MnO₂ (α, β, γ, and δ) as an activator of peroxymonosulfate (PMS) for sulfisoxazole degradation [J]. Chemical Engineering Journal, 2022, 427: 130888. doi: 10.1016/j.cej.2021.130888
[83]	JIANG Z R, WANG P F, ZHOU Y X, et al. Fabrication of a 3D-blocky catalyst (CoMnO_x@sponge) via mooring Co-Mn bimetallic oxide on sponge to activate peroxymonosulfate for convenient and efficient degradation of sulfonamide antibiotics [J]. Chemical Engineering Journal, 2022, 446: 137306. doi: 10.1016/j.cej.2022.137306
[84]	CHEN L, MAQBOOL T, NAZIR G, et al. Peroxymonosulfate activated by composite ceramic membrane for the removal of pharmaceuticals and personal care products (PPCPs) mixture: Insights of catalytic and noncatalytic oxidation [J]. Water Research, 2023, 229: 119444. doi: 10.1016/j.watres.2022.119444
[85]	ZHAO Y, LI B, LI Y, et al. Synergistic activation of peroxymonosulfate between Co and MnO for bisphenol A degradation with enhanced activity and stability [J]. Journal of Colloid and Interface Science, 2022, 623: 775-786. doi: 10.1016/j.jcis.2022.05.105
[86]	CHEN L J, LI Y H, ZHANG J W, et al. Oxidative degradation of tetracycline hydrochloride by Mn₂O₃/Bi₂O₃ photocatalysis activated peroxymonosulfate [J]. Inorganic Chemistry Communications, 2022, 140: 109414. doi: 10.1016/j.inoche.2022.109414
[87]	WANG L H, XU H D, JIANG N, et al. Effective activation of peroxymonosulfate with natural Manganese-containing minerals through a nonradical pathway and the application for the removal of bisphenols [J]. Journal of Hazardous Materials, 2021, 417: 126152. doi: 10.1016/j.jhazmat.2021.126152
[88]	HE B, YANG Y, LIU B R, et al. Degradation of chlortetracycline hydrochloride by peroxymonosulfate activation on natural Manganese sand through response surface methodology [J]. Environmental Science and Pollution Research, 2022, 29(54): 82584-82599. doi: 10.1007/s11356-022-21556-5
[89]	CHEN T, ZHU Z L, WANG Z Y, et al. 3D hollow sphere-like Cu-incorporated LaAlO₃ perovskites for peroxymonosulfate activation: Coaction of electron transfer and oxygen defect [J]. Chemical Engineering Journal, 2020, 385: 123935. doi: 10.1016/j.cej.2019.123935
[90]	FAYYAZ A, SARAVANAKUMAR K, TALUKDAR K, et al. Catalytic oxidation of naproxen in cobalt spinel ferrite decorated Ti₃C₂T_x MXene activated persulfate system: Mechanisms and pathways [J]. Chemical Engineering Journal, 2021, 407: 127842. doi: 10.1016/j.cej.2020.127842
[91]	HUANG M J, PENG S S, XIANG W, et al. Strong metal-support interaction between carbon nanotubes and Mn-Fe spinel oxide in boosting peroxymonosulfate activation: Underneath mechanisms and application [J]. Chemical Engineering Journal, 2022, 429: 132372. doi: 10.1016/j.cej.2021.132372
[92]	MANOS D, MISERLI K, KONSTANTINOU I. Perovskite and spinel catalysts for sulfate radical-based advanced oxidation of organic pollutants in water and wastewater systems [J]. Catalysts, 2020, 10(11): 1299. doi: 10.3390/catal10111299
[93]	UTAMA P S, WIDAYATNO W B, AZHAR M R, et al. LaMnO₃ perovskite activation of peroxymonosulfate for catalytic palm oil mill secondary effluent degradation [J]. Journal of Applied Materials and Technology, 2020, 2(1): 27-35. doi: 10.31258/Jamt.2.1.27-35
[94]	WANG T, QIAN X F, YUE D T, et al. CaMnO₃ perovskite nanocrystals for efficient peroxydisulfate activation [J]. Chemical Engineering Journal, 2020, 398: 125638. doi: 10.1016/j.cej.2020.125638
[95]	GAO P P, TIAN X K, FU W, et al. Copper in LaMnO₃ to promote peroxymonosulfate activation by regulating the reactive oxygen species in sulfamethoxazole degradation [J]. Journal of Hazardous Materials, 2021, 411: 125163. doi: 10.1016/j.jhazmat.2021.125163
[96]	GUO J X, JING Y, SHEN T, et al. Effect of doped strontium on catalytic properties of La_1‒xSr_xMnO₃ for rhodamine B degradation [J]. Journal of Rare Earths, 2021, 39(11): 1362-1369. doi: 10.1016/j.jre.2020.12.017
[97]	LUO H D, GUO J X, SHEN T, et al. Study on the catalytic performance of LaMnO₃ for the RhB degradation [J]. Journal of the Taiwan Institute of Chemical Engineers, 2020, 109: 15-25. doi: 10.1016/j.jtice.2020.01.011
[98]	JIANG Z R, LI Y X, ZHOU Y X, et al. Co₃O₄-MnO₂ nanoparticles moored on biochar as a catalyst for activation of peroxymonosulfate to efficiently degrade sulfonamide antibiotics [J]. Separation and Purification Technology, 2022, 281: 119935. doi: 10.1016/j.seppur.2021.119935
[99]	YANG X, WEI G L, WU P Q, et al. Novel halloysite nanotube-based ultrafine CoMn₂O₄ catalyst for efficient degradation of pharmaceuticals through peroxymonosulfate activation [J]. Applied Surface Science, 2022, 588: 152899. doi: 10.1016/j.apsusc.2022.152899
[100]	NGUYEN T B, LE V R, HUANG C P, et al. Construction of ternary NiCo₂O₄/MnOOH/GO composite for peroxymonosulfate activation with enhanced catalytic activity toward ciprofloxacin degradation [J]. Chemical Engineering Journal, 2022, 446: 137326. doi: 10.1016/j.cej.2022.137326
[101]	WU Y H, LI Y L, HE J Y, et al. Nano-hybrids of needle-like MnO₂ on graphene oxide coupled with peroxymonosulfate for enhanced degradation of norfloxacin: A comparative study and probable degradation pathway [J]. Journal of Colloid and Interface Science, 2020, 562: 1-11. doi: 10.1016/j.jcis.2019.11.121
[102]	PAN M, WANG N, WENG Z T, et al. The synergistic activation of peroxymonosulfate for the degradation of Acid Scarlet GR by palygorskite/MnO₂/Fe₃O₄ nanocomposites [J]. Dalton Transactions (Cambridge, England:2003), 2023, 52(4): 1009-1020. doi: 10.1039/D2DT02998G
[103]	HU Y Y, SUN S Y, GUO J L, et al. In situ anchoring strategy to enhance dual nonradical degradation of sulfamethoxazole with high loading manganese doped carbon nitride [J]. Chemosphere, 2022, 303: 135035. doi: 10.1016/j.chemosphere.2022.135035
[104]	GONG Y X, WU Y N, SHEN J M, et al. Generation of interfacial high-spin Manganese intermediates as reactive oxidant during peroxymonosulfate activation mediated by amorphous MnO_x supported on polymeric substrate [J]. Applied Catalysis B:Environmental, 2022, 316: 121671. doi: 10.1016/j.apcatb.2022.121671

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近年来我国有机废水排放量仍居高位，据统计2021年我国有机废水排放量突破589. 64亿m³，对水体环境和水生态平衡均造成巨大威胁. 不同行业的有机废水中主要成分为各自工艺流程带入的特征有机物，如农药、医药中间体、抗生素、高分子染料、芳香族化合物以及含硫、氮等有机化合物，具有COD高、生物毒害效应、处理难度大、生物难降解等特点，未经有效处理后排放会造成水体富营养化等环境问题^[1-5]. 因此，有机废水的高效治理是从源头上遏制水体富营养化、改善水质和饮水安全的必要途径. 此外，在碳中和碳达峰的目标要求下，对有机废水的高效降解和深度治理符合我国双碳目标的发展路径^[6-8].

在有机废水处理方法方面，典型水处理工艺（如吸附、膜过滤等）仅能实现水中有机污染物转移，易造成产生固废等二次污染，不能实现有机成分的深度降解. 高级氧化技术（advanced oxidation processes, AOPs）自1987年被Glaze^[9]提出以来各种高级氧化方式不断得到开发，而以过硫酸盐（persulfate, PS）为氧化剂的高级氧化技术近年来引起了更多关注，其特点在于可通过多种活化方式产生活性氧物种（reactive oxygen species, ROS），进而无选择性地将有机污染物降解并矿化为CO₂、无机盐和水等产物，具有高效、易储运等优点^[10-15]. 通过活化过硫酸盐产生的ROS主要包括硫酸根自由基（ $ {\text{SO}}_{\text{4}}^{\text{·–}} $ ）（2.5—3.1 eV, 30—40 μs）、羟基自由基（·OH）（1.8—2.7 eV, 20 ns）、超氧自由基 $ {\text{O}}_{\text{2}}^{\text{·–}} $ （2.4 eV）和单态氧¹O₂（1.52 eV）等，在较宽的pH值范围（2—8）均可有效降解和矿化各类有机污染物^[16-18].

利用外加能量如紫外光照^[19-20]、热活化^[21-22]、电化学^[23-25]、超声波^[26-28]、微波^[29]等方式均能有效活化过硫酸盐. 而通过引入外加催化剂的非均相活化方法无需外加能量即可活化过硫酸盐，具有操作方便、成本低、反应条件温和、 $ {\text{SO}}_{\text{4}}^{\text{·–}} $ 生成速率高等优点，其中过渡金属催化剂（如Co，Fe，Mn等）由于来源广泛和可变价态是优异的过硫酸盐催化活化材料^[30-33]. 在众多过渡金属中，锰基催化剂因为其高催化活性被广泛应用于环境催化方面^[34-35]，在催化臭氧分解^[36]、电化学氧化^[37-38]、光催化^[39]、VOCs热催化氧化^[40-42]以及过硫酸盐活化方面均有大量应用和报道. 近年来，国内外众多学者对锰基催化剂用于过硫酸盐活化进行了广泛而深入的研究，已成为高级氧化领域的热点研究方向. 以“锰”、“过硫酸盐”为关键词，对Scopus数据库近二十年相关论文发表进行了检索（见图1），可以看出锰基催化剂活化过硫酸盐的研究热度持续上升，其中2021年共计发表文章近400篇. 过氧一硫酸盐（peroxymonosulfate，PMS）和过氧二硫酸盐（peroxydisulfate，PDS）由于结构的不同，在活化途径和非自由基反应方面存在一定的差异. PMS比PDS更活跃^[43]，具有更高的溶解度，且PMS具有较短的键长（0.146 nm）和更高的键解离能（377 kJ mol⁻¹）^[44]. 因此，近几年锰基催化剂活化过氧PMS方面的文章发表数量高于PDS，约占论文发表总数的70%.

本文综述了近年来锰基催化材料在催化活化过硫酸盐降解有机废水领域的研究进展，系统总结了零价锰、单一锰氧化物、复合锰氧化物、特殊晶型锰氧化物以及负载型锰氧化物的相关报道，为针对性地设计高活性锰基过硫酸盐活化材料提供思路和借鉴，并对其存在问题和发展趋势进行了初步展望.

1. 锰基催化剂分类（Classification of manganese based catalysts）

通过梳理已报道用于活化过硫酸盐的锰基催化剂类别，可以分为零价锰、单一锰氧化物、复合锰氧化物、特殊晶型锰氧化物以及负载型锰氧化物，围绕催化剂类别、催化剂活性组分、制备方法、目标污染物、主要活性物种（ROS）及污染物去除效率等方面，对部分代表性研究进行了总结，具体见表1.

3. 单一锰氧化合物（Single manganese oxide compound）

5. 特殊晶型锰氧化物（Special crystalline manganese oxides）

锰基催化剂用于活化过硫酸盐降解有机废水的研究进展

通讯作者: Tel：0371-62506813，E-mail： 6858@zut.edu.cn;

Research progress on manganese based catalysts for activating persulfate degradation of organic wastewater

Corresponding author: LI Juexiu, 6858@zut.edu.cn ;

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锰基催化剂用于活化过硫酸盐降解有机废水的研究进展

通讯作者: Tel：0371-62506813，E-mail： 6858@zut.edu.cn;

English Abstract

Research progress on manganese based catalysts for activating persulfate degradation of organic wastewater

Corresponding author: LI Juexiu, 6858@zut.edu.cn ;

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目录

锰基催化剂用于活化过硫酸盐降解有机废水的研究进展

通讯作者: Tel：0371-62506813，E-mail： 6858@zut.edu.cn;

Research progress on manganese based catalysts for activating persulfate degradation of organic wastewater

Corresponding author: LI Juexiu, 6858@zut.edu.cn ;

计量

出版历程

锰基催化剂用于活化过硫酸盐降解有机废水的研究进展

通讯作者: Tel：0371-62506813，E-mail： 6858@zut.edu.cn;

English Abstract

Research progress on manganese based catalysts for activating persulfate degradation of organic wastewater

Corresponding author: LI Juexiu, 6858@zut.edu.cn ;

全文HTML

目录