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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[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
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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