An overview of natural mineral catalytic oxidation of refractory organic contaminants in wastewater

doi:10.16085/j.issn.1000-6613.2022-0586

Abstract

Abstract:

Catalytic oxidation is one of the most effective water treatment technology to remove refractory organic pollutants, which has strong oxidation capacity and high mineralization efficiency, and the application and research of catalysts are the hotspots. Natural mineral catalysts have incomparable advantages over other catalysts owing to their abundant reserves and low price. In this paper, the mechanism and research progress of natural mineral catalysts in the treatment of refractory organic pollutants in wastewater by Fenton, catalytic ozonation and activated persulfate catalytic oxidation are reviewed. The corresponding reaction conditions, treatment results and catalytic active sites were analyzed. Natural minerals rich in metal elements and thus can be used as catalysts for Fenton oxidation and persulfate oxidation, some natural minerals can be used as metal carriers to participate in oxidation reactions, and natural minerals with active sites such as surface hydroxyl groups can be catalysts for Fenton oxidation and ozone oxidation. Furthermore, natural mineral catalysts can significantly increase the oxidation capacity of ROCs by Fenton, ozone and persulfate, having a promising application prospect in wastewater treatment. This review hopes to provide useful reference for the development of natural mineral catalysts and the future application in advanced oxidation technology for water treatment.

Key words: natural mineral, catalyst, catalysis, organic compounds, radical

摘要：

催化氧化技术具有氧化性强、矿化效率高等优点，是去除水中难降解有机污染物最有效的处理技术之一，催化剂的应用和研究是关注的热点，天然矿物催化剂储量大、价格低，在使用成本方面具有其他催化剂无可比拟的优势。本文综述了天然矿物催化剂在Fenton法、催化臭氧氧化法、活化过硫酸盐催化氧化法处理水中难降解有机污染物的研究进展和作用机理，分析了其反应条件、处理效果和催化活性位点等，指出含有丰富的金属元素的天然矿物可作为芬顿氧化和过硫酸盐氧化的催化剂，有些天然矿物可作为金属负载载体参与氧化反应，而存在表面羟基等活性位点的天然矿物可催化臭氧氧化和芬顿氧化反应，天然矿物催化剂能明显提高Fenton、臭氧、过硫酸盐氧化难降解有机物（ROCs）的能力，在污水处理方面具有应用前景。以期能够为今后天然矿物催化剂的开发和在水处理高级氧化技术中的应用提供有益参考。

关键词: 天然矿物, 催化剂, 催化作用, 有机化合物, 自由基

CLC Number:

X506

WANG Qinghong, JIANG Chenxu, WANG Xin, YU Meiqi, ZHU Shuai, LI Yiming, CHEN Chunmao. An overview of natural mineral catalytic oxidation of refractory organic contaminants in wastewater[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 417-434.

王庆宏, 姜晨旭, 王鑫, 余美琪, 朱帅, 李一鸣, 陈春茂. 天然矿物催化氧化水中难降解有机污染物研究进展[J]. 化工进展, 2023, 42(1): 417-434.

Figures/Tables 8

催化剂	优点	缺点
金属氧化物	催化活性高	金属溶出问题
碳材料	比表面积较高；催化活性高；成本低	容易失活
新型纳米结构碳材料	比表面积高；催化活性高	制备条件苛刻；成本高
天然矿石	催化活性较高；储量大；成本低	活性组分溶出

催化剂	污染物	反应条件	处理效率	反应机理	文献
针铁矿	双酚A （BPA）	[BPA]：20μmol/L [催化剂]：0.25g/L [H₂O₂]：0.1mmol pH：6.2 [EDDS]：0.1mmol	反应时间：550 min [BPA]：80%	螯合剂EDDS在针铁矿表面形成Fe-EDDS配合物，中性环境下生成 $O 2 · -$ 和·OH，将Fe(Ⅲ)-EDDS还原为Fe(Ⅱ)-EDDS。形成·OH 为控制步骤	[43]
磁铁矿	双酚A （BPA）	[BPA]：20μmol/L [催化剂]：0.2g/L [H₂O₂]：0.5mmol/L pH：6.2 [EDDS]：0.1mmol/L	反应时间：600min [BPA]：70%	中性pH处形成 $O 2 · -$ 和·OH 自由基，将Fe(Ⅲ)-EDDS还原为Fe(Ⅱ)-EDDS。形成·OH 为控制步骤	[44]
黄铁矿	双氯芬酸（DCF）	[DCF]：0.017mmol/L [催化剂]：0.5~4.0mmol/L [H₂O₂]：1.0mmol/L pH：3 [反应温度]：25℃	反应时间：120s [DCF]：100%	Fe²⁺溶出形成均相Fenton体系，与加入的H₂O₂发生均相Fenton反应	[45]
针铁矿	扑热息痛（PC）	[PC]：1×10^-4mol/L [催化剂]：1 g/L [H₂O₂] ：5×10^-3mol/L pH：3 [草酸]：5×10^-4mol/L	反应时间：4h [PC]：78%	草酸和Fe(Ⅲ)生成络合物，在催化剂表面通过光子生成Fe(Ⅱ)草酸络合物，与H₂O₂反应生成·OH	[46]
合成层状黏土锂皂石	苯酚（Phenol）	[Phenol]：1mmol/L [催化剂]：1.0g/L [H₂O₂]：50mmol/L pH：3.0 [反应温度]：30℃	反应时间：5min [Phenol]：100%	未探究	[47]
纳米零价铁负载高岭土	偶氮染料直接黑（DBG）	[DBG]：100mg/L [催化剂]：0.6g/L [H₂O₂]：33mmol pH：7.06 [反应温度]：30℃	[DBG]：87.22% TOC：54.06%	具有高吸附性，催化剂表面裸露金属离子催化H₂O₂分解产生·OH	[40]
Fe负载硅藻土	碱性品红	[碱性品红]：15mmol/L [催化剂]：0.7g [H₂O₂]：5mmol/L pH：3.0 [反应温度]：50℃	反应时间：60min 碱性品红： 98.3%	催化剂表面金属离子非均相催化H₂O₂产生·OH	[41]
La-Fe MMT	亚甲基蓝(MB)、罗丹明B(RhB)	[MB]：100mg/L [RhB]：100mg/L [催化剂]：1.0g/L [H₂O₂]：30mmol pH：7.07	[MB]：97% [RhB]：96%	镧氧化物在二元催化剂体系同时具有碱和酸两种性质，Fe³⁺/Fe²⁺和La²⁺/La³⁺循环促进·OH 自由基产生	[42]
Fe负载球黏土	蒽醌染料活性蓝4(RB4)	[RB4]：50mg/L [催化剂]：5g/L [H₂O₂]：8mmol pH：3.0 [反应温度]：30℃	反应时间：140min [RB4]：99%	未探究	[48]

催化剂	污染物	反应条件	处理效率	反应机理	文献
针铁矿	双酚A （BPA）	[BPA]：20μmol/L [催化剂]：0.25g/L [H₂O₂]：0.1mmol pH：6.2 [EDDS]：0.1mmol	反应时间：550 min [BPA]：80%	螯合剂EDDS在针铁矿表面形成Fe-EDDS配合物，中性环境下生成 $O 2 · -$ 和·OH，将Fe(Ⅲ)-EDDS还原为Fe(Ⅱ)-EDDS。形成·OH 为控制步骤	[43]
磁铁矿	双酚A （BPA）	[BPA]：20μmol/L [催化剂]：0.2g/L [H₂O₂]：0.5mmol/L pH：6.2 [EDDS]：0.1mmol/L	反应时间：600min [BPA]：70%	中性pH处形成 $O 2 · -$ 和·OH 自由基，将Fe(Ⅲ)-EDDS还原为Fe(Ⅱ)-EDDS。形成·OH 为控制步骤	[44]
黄铁矿	双氯芬酸（DCF）	[DCF]：0.017mmol/L [催化剂]：0.5~4.0mmol/L [H₂O₂]：1.0mmol/L pH：3 [反应温度]：25℃	反应时间：120s [DCF]：100%	Fe²⁺溶出形成均相Fenton体系，与加入的H₂O₂发生均相Fenton反应	[45]
针铁矿	扑热息痛（PC）	[PC]：1×10^-4mol/L [催化剂]：1 g/L [H₂O₂] ：5×10^-3mol/L pH：3 [草酸]：5×10^-4mol/L	反应时间：4h [PC]：78%	草酸和Fe(Ⅲ)生成络合物，在催化剂表面通过光子生成Fe(Ⅱ)草酸络合物，与H₂O₂反应生成·OH	[46]
合成层状黏土锂皂石	苯酚（Phenol）	[Phenol]：1mmol/L [催化剂]：1.0g/L [H₂O₂]：50mmol/L pH：3.0 [反应温度]：30℃	反应时间：5min [Phenol]：100%	未探究	[47]
纳米零价铁负载高岭土	偶氮染料直接黑（DBG）	[DBG]：100mg/L [催化剂]：0.6g/L [H₂O₂]：33mmol pH：7.06 [反应温度]：30℃	[DBG]：87.22% TOC：54.06%	具有高吸附性，催化剂表面裸露金属离子催化H₂O₂分解产生·OH	[40]
Fe负载硅藻土	碱性品红	[碱性品红]：15mmol/L [催化剂]：0.7g [H₂O₂]：5mmol/L pH：3.0 [反应温度]：50℃	反应时间：60min 碱性品红： 98.3%	催化剂表面金属离子非均相催化H₂O₂产生·OH	[41]
La-Fe MMT	亚甲基蓝(MB)、罗丹明B(RhB)	[MB]：100mg/L [RhB]：100mg/L [催化剂]：1.0g/L [H₂O₂]：30mmol pH：7.07	[MB]：97% [RhB]：96%	镧氧化物在二元催化剂体系同时具有碱和酸两种性质，Fe³⁺/Fe²⁺和La²⁺/La³⁺循环促进·OH 自由基产生	[42]
Fe负载球黏土	蒽醌染料活性蓝4(RB4)	[RB4]：50mg/L [催化剂]：5g/L [H₂O₂]：8mmol pH：3.0 [反应温度]：30℃	反应时间：140min [RB4]：99%	未探究	[48]

[橙Ⅱ] ：1g/L

[催化剂]：1.0g/L；[H₂O₂]：10mmol

pH：3

[反应温度]：30℃

1×8W UVC

反应时间：120min

[橙Ⅱ]：接近100%

TOC：接近100%

催化剂表面Fe(Ⅲ)与光子反应生成Fe(Ⅱ)，激活H₂O₂反应生成·OH，污染物吸附在催化剂表面，发生表面反应

[60]

Fe负载锂皂石

偶氮染料橙Ⅱ

[橙Ⅱ]：0.1mmol

[催化剂]：1.0g/L；[H₂O₂]：4.8mmol

pH：3

1×8W UVC

反应时间：120min

[橙Ⅱ]：100%

TOC：75%

[HE-3B]：100mg/L

[催化剂]：1.0g/L；[H₂O₂]：500mg/L

pH：3.0

2×8W UVC

反应时间：120min

[活性红HE-3B]：100%

TOC：70%

催化剂表面Fe(Ⅲ)与光子反应生成Fe(Ⅱ)，激活H₂O₂反应生成·OH，H₂O₂与催化剂产生·OH

[54]

催化剂	污染物	反应条件	处理效率	反应机理	文献
黄铁矿	磺胺甲𫫇唑（SMX）	[SMX]：1mmol/L [阳极]：25cm²BDD板 [阴极]：碳毡阴极（15cm × 4cm × 0.5cm） [催化剂]：2.0g/L pH：3 [O₂]：1L/min [反应温度]：25℃	反应时间：8h [SMX]：100% [TOC]：95%	阴极原位生成H₂O₂，与溶液中的Fe²⁺发生均相Fenton反应	[63]
黄铁矿	四环素（TC）	[TC]：0.2mmol/L [阳极]：24cm²BDD板 [阴极]：碳毡阴极（15cm×4cm×0.5cm） [催化剂]：2.0mg/L pH：3 [O₂]：1L/min [反应温度]：25℃	反应时间：480min TOC：96%	阴极原位生成H₂O₂，与溶液中的Fe²⁺发生均相Fenton反应	[69]
黄铁矿	左氧氟沙星	[左氧氟沙星]：0.23mmol/L [阳极]：6cm²BDD薄膜电极 [阴极]：60cm²碳毡阴极 [催化剂]：2.0g/L pH：3 [O₂]：1L/min [反应温度]：25℃ [电流]：300mA	反应时间：8h TOC：95%	未探究	[70]
黄铁矿	酪醇（TY）	[TY]：0.3mmol [阳极]：6cm² BDD薄膜沉积导电硅片 [阴极]：60cm²碳毡电极 [催化剂]：1g/L pH：3.0 [反应温度]：25℃ [电流]：300mA	反应时间：6h [TY]：100% [TOC]: 89%	1.0g/L黄铁矿提供0.20mmol Fe²⁺，发生均相Fenton反应	[75]
黄铁矿	罗丹明B（RhB）	[RhB]：10mg/L [阳极]：25cm² 石墨电极 [阴极]：25cm² 石墨电极 [催化剂]：10mg/L [极板间距]：4cm pH：3 [电压]：8V	反应时间：180min [RhB]：99.2%	Fe²⁺溶出，与H₂O₂形成均相Fenton体系	[76]
黄铜矿	四环素（TC）	[TC]：0.20mmol/L [阳极]：高4.5cm、内径3cm的圆柱形Pt网或25cm²薄膜BDD置于Nb衬底上 [阴极]：三维碳毡(15cm×4cm×0.5cm) [催化剂]：1.0g/L pH：3 [反应温度]：25℃ [电流]：500mA	反应时间：360min TOC：98%	黄铜矿溶出Fe²⁺和Cu²⁺协同均相反应；·OH攻击Cu(II)-羧酸配合物	[72]
Fe₂O₃负载高岭土	依诺沙星（ENXN）	[ENXN]：0.25mmol/L [阳极]：Pt网或BDD电极（5cm×4cm） [阴极]：70cm²三维碳毡 [催化剂]：0.3g pH：2.0 [反应温度]：25℃ [电流]：300mA	反应时间：7h TOC：98%	催化剂表面形成活性铁物种，与电化学协同生成·OH的非均相反应	[73]

催化剂	污染物	反应条件	处理效率	反应机理	文献
黄铁矿	磺胺甲𫫇唑（SMX）	[SMX]：1mmol/L [阳极]：25cm²BDD板 [阴极]：碳毡阴极（15cm × 4cm × 0.5cm） [催化剂]：2.0g/L pH：3 [O₂]：1L/min [反应温度]：25℃	反应时间：8h [SMX]：100% [TOC]：95%	阴极原位生成H₂O₂，与溶液中的Fe²⁺发生均相Fenton反应	[63]
黄铁矿	四环素（TC）	[TC]：0.2mmol/L [阳极]：24cm²BDD板 [阴极]：碳毡阴极（15cm×4cm×0.5cm） [催化剂]：2.0mg/L pH：3 [O₂]：1L/min [反应温度]：25℃	反应时间：480min TOC：96%	阴极原位生成H₂O₂，与溶液中的Fe²⁺发生均相Fenton反应	[69]
黄铁矿	左氧氟沙星	[左氧氟沙星]：0.23mmol/L [阳极]：6cm²BDD薄膜电极 [阴极]：60cm²碳毡阴极 [催化剂]：2.0g/L pH：3 [O₂]：1L/min [反应温度]：25℃ [电流]：300mA	反应时间：8h TOC：95%	未探究	[70]
黄铁矿	酪醇（TY）	[TY]：0.3mmol [阳极]：6cm² BDD薄膜沉积导电硅片 [阴极]：60cm²碳毡电极 [催化剂]：1g/L pH：3.0 [反应温度]：25℃ [电流]：300mA	反应时间：6h [TY]：100% [TOC]: 89%	1.0g/L黄铁矿提供0.20mmol Fe²⁺，发生均相Fenton反应	[75]
黄铁矿	罗丹明B（RhB）	[RhB]：10mg/L [阳极]：25cm² 石墨电极 [阴极]：25cm² 石墨电极 [催化剂]：10mg/L [极板间距]：4cm pH：3 [电压]：8V	反应时间：180min [RhB]：99.2%	Fe²⁺溶出，与H₂O₂形成均相Fenton体系	[76]
黄铜矿	四环素（TC）	[TC]：0.20mmol/L [阳极]：高4.5cm、内径3cm的圆柱形Pt网或25cm²薄膜BDD置于Nb衬底上 [阴极]：三维碳毡(15cm×4cm×0.5cm) [催化剂]：1.0g/L pH：3 [反应温度]：25℃ [电流]：500mA	反应时间：360min TOC：98%	黄铜矿溶出Fe²⁺和Cu²⁺协同均相反应；·OH攻击Cu(II)-羧酸配合物	[72]
Fe₂O₃负载高岭土	依诺沙星（ENXN）	[ENXN]：0.25mmol/L [阳极]：Pt网或BDD电极（5cm×4cm） [阴极]：70cm²三维碳毡 [催化剂]：0.3g pH：2.0 [反应温度]：25℃ [电流]：300mA	反应时间：7h TOC：98%	催化剂表面形成活性铁物种，与电化学协同生成·OH的非均相反应	[73]

催化剂	污染物	反应条件	处理效率	反应机理	文献
水镁石	活性艳红X-3B	[活性艳红X-3B]：50mg/L [催化剂]：0.5g [O₃]：0.3mg/min pH：6.4 [反应温度]：25℃	反应时间：15min [活性艳红X-3B]： 89% COD：32.5%	Mg(OH)₂溶解，产生大量OH^-，均相臭氧直接氧化催化机理	[87]
水镁石	苯酚	[苯酚]：100mg/L [催化剂]：0.5g [O₃]：72mg/L pH：10.8	反应时间：15min [苯酚]：50.3% COD：57.8%	Mg(OH)₂溶解，产生大量OH^-，均相臭氧直接氧化催化机理	[88]
斜发沸石、丝光沸石	亚甲基蓝（MB）	[MB]：94μmol/L [催化剂]：15g/L [O₃]：125μmol/L pH：8.0 [反应温度]：20℃	反应时间：50min [MB]：接近100%	表面羟基 (S—OH₂⁺，S—OH，S—O—) 催化臭氧分解生成·OH	[89]
铝土矿	2,4,6-三氯苯甲醚（TCA）	[TCA]：100ng/L [催化剂]：200mg/L [O₃]：0.5mg/L pH：6.0 [反应温度]：20℃	反应时间：10min [TCA]：95.2%	铝土矿Al—O、Si—O表面活性位点存在表面羟基，催化臭氧分解生成·OH	[93]
四方硫铁矿	N, N-二甲基乙酰胺(DMAC）	[DMAC]：10mg/L [催化剂]：3.5g/L [O₃]：300mL/min pH：6.8 [反应温度]：30℃	反应时间：20min [DMAC]：96.6%	Fe金属和表面羟基活性组分促进·OH生成，S^2-作为电子供体促进体系中Fe(Ⅱ)和Fe(Ⅲ)循环	[96]
焙烧磁铁矿	活性红-120 （RR-120）	[RR-120]：100mg/L [催化剂]：0.2g [O₃]：(1±0.08)mg/min pH：11.0 [反应温度]：20℃	反应时间：10min [RR-120]：100% TOC：96.1%	焙烧后主要成分为Fe₂O₃，比表面积增大，表面羟基促进·OH生成	[99]
焙烧铝矾土（Al₂O₃、SiO₂、 Fe₂O₃、TiO₂）	对硝基苯酚	[对硝基苯酚]：300mg/L [催化剂]：5g/L [O₃]：(2.46 ± 0.1)mg/min pH：5.0 [反应温度]：25℃	反应时间：10min TOC： 73.5%	比表面积增大，表面羟基促进·OH生成	[100]
焙烧锰砂矿（MnO、Fe₂O₃、SiO₂、Al₂O₃）	苯胺	[苯胺]：200mg/L [催化剂]：3g/L [O₃]：(1.76 ± 0.1)mg/min pH：5.0 [反应温度]：25℃	反应时间：10min COD： 69.2%	比表面积增大，催化剂表面和溶液中的·OH氧化起主导作用，同时存在臭氧直接氧化	[3]
Co改性赤泥	苯扎贝特（BZF）	[BZF]：2.76μmol/L [催化剂]：50mg/L [O₃]：0.5mg/L pH：6.68	反应时间：30min [BZF]：80%	表面负载Co形成介孔，比表面积增大，生成Co—O—活性反应位点，增加表面羟基，增加臭氧分解生成·OH	[94]
Ce负载天然沸石	青霉素G (PG)	[PG]：50mg/L [催化剂]：2.0g/L [O₃]：6mg/min pH：4.5	反应时间：20min [PG]：99.5%	Ce³⁺/Ce⁴⁺电子转移促进O₃产生 $O 2 · -$ 、·OH等自由基	[102]
改性铝土矿	2,4,6-三氯苯甲醚 (TCA)	[TCA]：28.2μg/L [催化剂]：0.5g/L [O₃]：0.62mg/L pH：6.5	反应时间：40min [TCA]：90.0%	催化剂微孔吸附，表面羟基催化臭氧分解生成·OH	[105]
改性针铁矿纳米粒子	磺胺嘧啶 (SSZ)	[SSZ]：10mg/L [催化剂]：1.5g/L [O₃]：5mg/min pH：7.0 [反应温度]：25℃	反应时间：40min COD： 69.2%	比表面积增大，增加表面羟基的密度，促进表面吸附和·OH生成	[109]

催化剂	污染物	反应条件	处理效率	反应机理	文献
水镁石	活性艳红X-3B	[活性艳红X-3B]：50mg/L [催化剂]：0.5g [O₃]：0.3mg/min pH：6.4 [反应温度]：25℃	反应时间：15min [活性艳红X-3B]： 89% COD：32.5%	Mg(OH)₂溶解，产生大量OH^-，均相臭氧直接氧化催化机理	[87]
水镁石	苯酚	[苯酚]：100mg/L [催化剂]：0.5g [O₃]：72mg/L pH：10.8	反应时间：15min [苯酚]：50.3% COD：57.8%	Mg(OH)₂溶解，产生大量OH^-，均相臭氧直接氧化催化机理	[88]
斜发沸石、丝光沸石	亚甲基蓝（MB）	[MB]：94μmol/L [催化剂]：15g/L [O₃]：125μmol/L pH：8.0 [反应温度]：20℃	反应时间：50min [MB]：接近100%	表面羟基 (S—OH₂⁺，S—OH，S—O—) 催化臭氧分解生成·OH	[89]
铝土矿	2,4,6-三氯苯甲醚（TCA）	[TCA]：100ng/L [催化剂]：200mg/L [O₃]：0.5mg/L pH：6.0 [反应温度]：20℃	反应时间：10min [TCA]：95.2%	铝土矿Al—O、Si—O表面活性位点存在表面羟基，催化臭氧分解生成·OH	[93]
四方硫铁矿	N, N-二甲基乙酰胺(DMAC）	[DMAC]：10mg/L [催化剂]：3.5g/L [O₃]：300mL/min pH：6.8 [反应温度]：30℃	反应时间：20min [DMAC]：96.6%	Fe金属和表面羟基活性组分促进·OH生成，S^2-作为电子供体促进体系中Fe(Ⅱ)和Fe(Ⅲ)循环	[96]
焙烧磁铁矿	活性红-120 （RR-120）	[RR-120]：100mg/L [催化剂]：0.2g [O₃]：(1±0.08)mg/min pH：11.0 [反应温度]：20℃	反应时间：10min [RR-120]：100% TOC：96.1%	焙烧后主要成分为Fe₂O₃，比表面积增大，表面羟基促进·OH生成	[99]
焙烧铝矾土（Al₂O₃、SiO₂、 Fe₂O₃、TiO₂）	对硝基苯酚	[对硝基苯酚]：300mg/L [催化剂]：5g/L [O₃]：(2.46 ± 0.1)mg/min pH：5.0 [反应温度]：25℃	反应时间：10min TOC： 73.5%	比表面积增大，表面羟基促进·OH生成	[100]
焙烧锰砂矿（MnO、Fe₂O₃、SiO₂、Al₂O₃）	苯胺	[苯胺]：200mg/L [催化剂]：3g/L [O₃]：(1.76 ± 0.1)mg/min pH：5.0 [反应温度]：25℃	反应时间：10min COD： 69.2%	比表面积增大，催化剂表面和溶液中的·OH氧化起主导作用，同时存在臭氧直接氧化	[3]
Co改性赤泥	苯扎贝特（BZF）	[BZF]：2.76μmol/L [催化剂]：50mg/L [O₃]：0.5mg/L pH：6.68	反应时间：30min [BZF]：80%	表面负载Co形成介孔，比表面积增大，生成Co—O—活性反应位点，增加表面羟基，增加臭氧分解生成·OH	[94]
Ce负载天然沸石	青霉素G (PG)	[PG]：50mg/L [催化剂]：2.0g/L [O₃]：6mg/min pH：4.5	反应时间：20min [PG]：99.5%	Ce³⁺/Ce⁴⁺电子转移促进O₃产生 $O 2 · -$ 、·OH等自由基	[102]
改性铝土矿	2,4,6-三氯苯甲醚 (TCA)	[TCA]：28.2μg/L [催化剂]：0.5g/L [O₃]：0.62mg/L pH：6.5	反应时间：40min [TCA]：90.0%	催化剂微孔吸附，表面羟基催化臭氧分解生成·OH	[105]
改性针铁矿纳米粒子	磺胺嘧啶 (SSZ)	[SSZ]：10mg/L [催化剂]：1.5g/L [O₃]：5mg/min pH：7.0 [反应温度]：25℃	反应时间：40min COD： 69.2%	比表面积增大，增加表面羟基的密度，促进表面吸附和·OH生成	[109]

催化剂	污染物	反应条件	处理效率	反应机理	文献
磁铁矿纳米颗粒	2,4,4'-三氯联苯（PCB28）	[PCB28]：2.5μmol [催化剂]：1.0g/L [PS]：2.0mmol pH：7.0 反应温度：25℃	反应时间：240min [PCB28]：71%	溶解和表面Fe(Ⅱ)活化PS生成 $S O 4 - ·$ ，中性pH条件下产生超氧自由基（ $O 2 · -$ ），激活PS生成 $S O 4 - ·$	[115]
磁铁矿纳米颗粒	磺胺甲氧嘧啶（SMM）	[SMM]：0.06mmol/L [催化剂]：2.4mmol [PS]：1.2 mmol pH：6.4 反应温度：25℃	反应时间：15min [SMM]：100%	溶解和表面Fe(Ⅱ)活化PS生成 $S O 4 - ·$	[125]
黄铁矿	对氯苯胺（PCA）	[PCA]：0.1mmol/L [催化剂]：0.5g/L [PS]：0.5mmol pH：7.0 反应温度：20℃	反应时间：240min [PCA]：91.02%	溶解和表面Fe(Ⅱ)活化PS生成 $S O 4 - ·$ ，有氧条件下产生超氧自由基（ $O 2 - ·$ ），激活PS生成 $S O 4 - ·$	[121]
磁黄铁矿	乙硫氨酯（IPETC）	[IPETC]：0.28mmol [催化剂]：0.8g/L [PS]：1.4mmol pH：6.0 反应温度：20℃	TOC：62.84%	溶解和表面Fe(Ⅱ)活化PS生成 $S O 4 - ·$	[126]
赤泥	对羟基苯甲酸酯	[对羟基苯甲酸酯]：0.8mg/L [催化剂]：2g/L [PS]：2g/L pH：3.0 反应温度：25℃	反应时间：120min [对羟基苯甲酸酯]：接近100%	赤泥中Fe²⁺溶解后非均相催化反应	[127]
赤泥粉	磺胺嘧啶（SDZ）	[SDZ]：4μmol [催化剂]：2g/L [PS]：1.75mmol pH：8.0 反应温度：(20 ± 2)℃	反应时间：180min [SDZ]：94.0%	溶解和表面Fe(Ⅱ)活化过硫酸盐产生 $S O 4 - ·$	[128]
磁铁矿	偶氮染料（AO7）	[AO7]：25mg/L [催化剂：0.8g/L [PDS]：10mmol pH：6.0 [阳极]：5cm ×11.9cm Ti/RuO₂-IrO₂平板 [阴极]：5cm ×11.9cm不锈钢平板电流密度：8.4mA/cm²	反应时间：60min [AO7]：100%	溶解和表面Fe(Ⅱ)活化过硫酸盐产生 $S O 4 - ·$ ，外加电流提供电子，快速将Fe(Ⅲ)还原为Fe(Ⅱ)，加速 $S O 4 - ·$ 生成	[129]
针铁矿	偶氮染料橙Ⅱ	[橙Ⅱ]：50mg/L [催化剂]：0.5g/L [PDS]：2g/L pH：7.0 Na₂SO₄：50mmol [阳极]：5cm ×11.9cm Ti/RuO₂-IrO₂平板 [阴极]：5cm ×11.9cm 不锈钢平板电流密度：8.4mA/cm²	反应时间：120min; [橙Ⅱ]：92.1% TOC：12.8%	溶解和表面Fe(Ⅱ)活化过硫酸盐产生 $S O 4 - ·$ ，外加电流提供电子快速将Fe(Ⅲ)还原为Fe(Ⅱ)，加速 $S O 4 - ·$ 生成，同时阳极产生·OH	[130]

催化剂	污染物	反应条件	处理效率	反应机理	文献
磁铁矿纳米颗粒	2,4,4'-三氯联苯（PCB28）	[PCB28]：2.5μmol [催化剂]：1.0g/L [PS]：2.0mmol pH：7.0 反应温度：25℃	反应时间：240min [PCB28]：71%	溶解和表面Fe(Ⅱ)活化PS生成 $S O 4 - ·$ ，中性pH条件下产生超氧自由基（ $O 2 · -$ ），激活PS生成 $S O 4 - ·$	[115]
磁铁矿纳米颗粒	磺胺甲氧嘧啶（SMM）	[SMM]：0.06mmol/L [催化剂]：2.4mmol [PS]：1.2 mmol pH：6.4 反应温度：25℃	反应时间：15min [SMM]：100%	溶解和表面Fe(Ⅱ)活化PS生成 $S O 4 - ·$	[125]
黄铁矿	对氯苯胺（PCA）	[PCA]：0.1mmol/L [催化剂]：0.5g/L [PS]：0.5mmol pH：7.0 反应温度：20℃	反应时间：240min [PCA]：91.02%	溶解和表面Fe(Ⅱ)活化PS生成 $S O 4 - ·$ ，有氧条件下产生超氧自由基（ $O 2 - ·$ ），激活PS生成 $S O 4 - ·$	[121]
磁黄铁矿	乙硫氨酯（IPETC）	[IPETC]：0.28mmol [催化剂]：0.8g/L [PS]：1.4mmol pH：6.0 反应温度：20℃	TOC：62.84%	溶解和表面Fe(Ⅱ)活化PS生成 $S O 4 - ·$	[126]
赤泥	对羟基苯甲酸酯	[对羟基苯甲酸酯]：0.8mg/L [催化剂]：2g/L [PS]：2g/L pH：3.0 反应温度：25℃	反应时间：120min [对羟基苯甲酸酯]：接近100%	赤泥中Fe²⁺溶解后非均相催化反应	[127]
赤泥粉	磺胺嘧啶（SDZ）	[SDZ]：4μmol [催化剂]：2g/L [PS]：1.75mmol pH：8.0 反应温度：(20 ± 2)℃	反应时间：180min [SDZ]：94.0%	溶解和表面Fe(Ⅱ)活化过硫酸盐产生 $S O 4 - ·$	[128]
磁铁矿	偶氮染料（AO7）	[AO7]：25mg/L [催化剂：0.8g/L [PDS]：10mmol pH：6.0 [阳极]：5cm ×11.9cm Ti/RuO₂-IrO₂平板 [阴极]：5cm ×11.9cm不锈钢平板电流密度：8.4mA/cm²	反应时间：60min [AO7]：100%	溶解和表面Fe(Ⅱ)活化过硫酸盐产生 $S O 4 - ·$ ，外加电流提供电子，快速将Fe(Ⅲ)还原为Fe(Ⅱ)，加速 $S O 4 - ·$ 生成	[129]
针铁矿	偶氮染料橙Ⅱ	[橙Ⅱ]：50mg/L [催化剂]：0.5g/L [PDS]：2g/L pH：7.0 Na₂SO₄：50mmol [阳极]：5cm ×11.9cm Ti/RuO₂-IrO₂平板 [阴极]：5cm ×11.9cm 不锈钢平板电流密度：8.4mA/cm²	反应时间：120min; [橙Ⅱ]：92.1% TOC：12.8%	溶解和表面Fe(Ⅱ)活化过硫酸盐产生 $S O 4 - ·$ ，外加电流提供电子快速将Fe(Ⅲ)还原为Fe(Ⅱ)，加速 $S O 4 - ·$ 生成，同时阳极产生·OH	[130]

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