Research progress of heterogeneous iron-based ozone catalysts for degradation of pollutants in water

doi:10.16085/j.issn.1000-6613.2024-1804

Abstract

Abstract:

Catalytic ozonation has been widely used in water treatment processes due to its advantages of environmental friendliness and high mineralization efficiency. Catalysts are one of the key factors determining the process stability and efficiency. Among numerous catalysts, heterogeneous iron-based catalysts have attracted widespread attention due to their extensive sources, low cost, excellent catalytic performance, and low toxicity. A comprehensive investigation of their preparation process, types, catalytic effects, and reaction mechanisms will be of great significance for further improving wastewater treatment efficiency and promoting technological development. This article first introduced the commonly used preparation methods of iron-based catalysts, including precipitation method, hydrothermal synthesis method, and impregnation calcination method, and discussed the catalytic effects of different types of iron-based catalysts on organic pollutants. In addition, the influence of main parameters such as active sites, reactant concentration, and mass transfer efficiency on the catalytic ozonation degradation of organic pollutants by iron-based catalysts was elucidated. And the catalytic mechanism of iron-based catalysts was explored from the aspects of ozone oxidation, reactive oxygen species, and catalytic components. Finally, the stability of iron-based catalysts was analyzed from the perspectives of deactivation causes and regeneration methods. Finally, future research directions were proposed, such as the analysis of the intrinsic relationship between water pollutant composition and preparation method of iron-based catalyst, environmental impact analysis, and quantitative analysis of reaction mechanisms.

Key words: advanced oxidation, catalyst, ozone, waste water, degradation

摘要：

臭氧催化氧化工艺具有环境友好和矿化效率高等优点，已被广泛应用于水处理过程。催化剂是决定工艺稳定性和高效性的关键因素之一。在众多催化剂中，由于非均相铁基催化剂来源广泛、催化性能强、廉价无毒等特点受到广泛关注，全面考察其制备过程、种类、催化效果和反应机理等将对进一步改善废水处理效果和推动技术进步具有重要意义。本文介绍了包括沉淀法、水热合成法、浸渍煅烧法等铁基催化剂常用的制备方法，讨论了不同种类铁基催化剂的催化效果。此外，阐述了活性位点、反应物浓度、传质效果等主要参数对铁基催化剂催化臭氧化降解有机污染物的效果，并从臭氧化作用、活性氧作用、催化活性组分作用等方面探讨了铁基催化剂的催化机理。从失活原因和再生方法等角度分析了铁基催化剂的稳定性，并提出了基于水质成分与铁基催化剂制备方法的内在联系、环境影响和反应机理等量化分析作为未来潜在的研究方向。

关键词: 高级氧化, 催化剂, 臭氧, 废水, 降解

CLC Number:

TQ09

YUAN Run, QIN Yihe, HE Xuwen. Research progress of heterogeneous iron-based ozone catalysts for degradation of pollutants in water[J]. Chemical Industry and Engineering Progress, 2025, 44(12): 6885-6905.

员润, 秦燚鹤, 何绪文. 非均相铁基臭氧催化剂催化降解水中污染物的研究进展[J]. 化工进展, 2025, 44(12): 6885-6905.

Figures/Tables 16

References 64

[65]	AHMADI Mehdi, KAKAVANDI Babak, JAAFARZADEH Nemat, et al. Catalytic ozonation of high saline petrochemical wastewater using PAC@Fe^ⅡFe₂ ^ⅢO₄: Optimization, mechanisms and biodegradability studies[J]. Separation and Purification Technology, 2017,177: 293-303.
[66]	Xianghong LYU, ZHANG Qiuyun, YANG Wenqing, et al. Catalytic ozonation of 2,4-dichlorophenoxyacetic acid over novel Fe-Ni/AC[J]. RSC Advances, 2015, 5(14): 10537-10545.
[67]	BAI Zhiyong, YANG Qi, WANG Jianlong. Catalytic ozonation of dimethyl phthalate using Fe₃O₄/multi-wall carbon nanotubes[J]. Environmental Technology, 2017, 38(16): 2048-2057.
[68]	ZHANG Shuo, WANG Dong, QUAN Xie, et al. Multi-walled carbon nanotubes immobilized on zero-valent iron plates (Fe⁰-CNTs) for catalytic ozonation of methylene blue as model compound in a bubbling reactor[J]. Separation and Purification Technology, 2013, 116: 351-359.
[69]	BING Jishuai, HU Chun, NIE Yulun, et al. Mechanism of catalytic ozonation in Fe₂O₃/Al₂O₃@SBA-15 aqueous suspension for destruction of ibuprofen [J]. Environmental Science & Technology, 2015, 49(3): 1690-1697.
[70]	CHEN Weirui, LI Xukai, TANG Yiming, et al. Mechanism insight of pollutant degradation and bromate inhibition by Fe-Cu-MCM-41 catalyzed ozonation[J]. Journal of Hazardous Materials, 2018, 346: 226-233.
[71]	LAN Bingyan, HUANG Ruihuan, LI Laisheng, et al. Catalytic ozonation of p-chlorobenzoic acid in aqueous solution using Fe-MCM-41 as catalyst[J]. Chemical Engineering Journal, 2013, 219: 346-354.
[72]	HUANG Ruihuan, YAN Huihua, LI Laisheng, et al. Catalytic activity of Fe/SBA-15 for ozonation of dimethyl phthalate in aqueous solution[J]. Applied Catalysis B: Environmental, 2011, 106(1/2): 264-271.
[73]	Dilek GÜMÜŞ, AKBAL Feryal. A comparative study of ozonation, iron coated zeolite catalyzed ozonation and granular activated carbon catalyzed ozonation of humic acid[J]. Chemosphere, 2017, 174: 218-231.
[74]	Katia GONZÁLEZ-LABRADA, RICHARD Romain, ANDRIANTSIFERANA Caroline, et al. Enhancement of ciprofloxacin degradation in aqueous system by heterogeneous catalytic ozonation[J]. Environmental Science and Pollution Research International, 2020, 27(2): 1246-1255.
[75]	LI Xue, WANG Dong, ZHANG Shuo. Evaluation of Fe-functionalized 4A zeolite as ozone catalyst for an enhancement of hydroxyl radical pathway in a multiphase reactor[J]. Ozone: Science & Engineering, 2019, 41(2): 156-165.
[76]	TONG Xinyuan, LI Zhidong, CHEN Weirui, et al. Efficient catalytic ozonation of diclofenac by three-dimensional iron (Fe)-doped SBA-16 mesoporous structures[J]. Journal of Colloid and Interface Science, 2020, 578: 461-470.
[77]	CHEN Weirui, LI Xukai, LIU Meiqi, et al. Effective catalytic ozonation for oxalic acid degradation with bimetallic Fe-Cu-MCM-41: Operation parameters and mechanism[J]. Journal of Chemical Technology & Biotechnology, 2017, 92(11): 2862-2869.
[78]	LI Xukai, CHEN Weirui, TANG Yiming, et al. Relationship between the structure of Fe-MCM-48 and its activity in catalytic ozonation for diclofenac mineralization[J]. Chemosphere, 2018, 206: 615-621.
[79]	YAN Huihua, CHEN Weirui, LIAO Gaozu, et al. Activity assessment of direct synthesized Fe-SBA-15 for catalytic ozonation of oxalic acid[J]. Separation and Purification Technology, 2016, 159: 1-6.
[80]	CHEN Chunmao, LI Yang, MA Wenfeng, et al. Mn-Fe-Mg-Ce loaded Al₂O₃ catalyzed ozonation for mineralization of refractory organic chemicals in petroleum refinery wastewater[J]. Separation and Purification Technology, 2017, 183: 1-10.
[81]	TONG Shao-Ping, SHI Rui, ZHANG Hua, et al. Kinetics of Fe₃O₄-CoO/Al₂O₃ catalytic ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid[J]. Journal of Hazardous Materials, 2011, 185(1): 162-167.
[82]	SABLE Shailesh S, SHAH Kinjal J, CHIANG Pen-Chi, et al. Catalytic oxidative degradation of phenol using iron oxide promoted sulfonated-ZrO₂ by Advanced Oxidation Processes (AOPs)[J]. Journal of the Taiwan Institute of Chemical Engineers, 2018, 91: 434-440.
[83]	NIE Yulun, XING Shengtao, HU Chun, et al. Efficient removal of toxic pollutants over Fe-Co/ZrO₂ bimetallic catalyst with ozone[J]. Catalysis Letters, 2012, 142(8): 1026-1032.
[84]	YANG Zhendong, Aihua LYU, NIE Yulun, et al. Catalytic ozonation performance and surface property of supported Fe₃O₄ catalysts dispersions[J]. Frontiers of Environmental Science & Engineering, 2013, 7(3): 451-456.
[85]	GAO Guoying, KANG Jing, SHEN Jimin, et al. Heterogeneous catalytic ozonation of sulfamethoxazole in aqueous solution over composite iron-manganese silicate oxide[J]. Ozone: Science & Engineering, 2017, 39(1): 24-32.
[86]	CHEN Chunmao, YOZA Brandon A, WANG Yandan, et al. Catalytic ozonation of petroleum refinery wastewater utilizing Mn-Fe-Cu/Al₂O₃ catalyst[J]. Environmental Science and Pollution Research International, 2015,22(7): 5552-5562.
[87]	PARK Hosik, KIM Jun, JUNG Haeryong, et al. Iron oxide nanoparticle-impregnated alumina for catalytic ozonation of Para-chlorobenzoic acid in aqueous solution[J]. Water, Air, & Soil Pollution, 2014, 225(6): 1975.
[88]	GAO Guoying, CHU Wei, CHEN Zhonglin, et al. Catalytic ozonation of diclofenac with iron silicate-loaded pumice in aqueous solution[J]. Water Supply, 2017, 17(5): 1458-1467.
[1]	YANG Linyan, SHENG Mei, LI Yejin, et al. A hybrid process of Fe-based catalytic ozonation and biodegradation for the treatment of industrial wastewater reverse osmosis concentrate[J]. Chemosphere, 2020, 238: 124639.
[2]	WANG Fan, LUO Yuangfeng, RAN Gang, et al. Sequential coagulation and Fe⁰-O₃/H₂O₂ process for removing recalcitrant organics from semi-aerobic aged refuse biofilter leachate: Treatment efficiency and degradation mechanism[J]. Science of the Total Environment, 2020, 699: 134371.
[3]	CHEN Keyong, ZHANG Xiaobing, LI Jun. Advanced treatment of oilfield production wastewater by an integration of coagulation/flotation, catalytic ozonation and biological processes[J]. Environmental Technology, 2016, 37(19): 2536-2544.
[4]	Qurat Ul AIN, RASHEED Usman, YASEEN Muhammad, et al. Superior dye degradation and adsorption capability of polydopamine modified Fe₃O₄-pillared bentonite composite[J]. Journal of Hazardous Materials, 2020, 397: 122758.
[5]	WAN Zhong, HU Jun, WANG Jianlong. Removal of sulfamethazine antibiotics using CeFe-graphene nanocomposite as catalyst by Fenton-like process[J]. Journal of Environmental Management, 2016,182: 284-291.
[6]	ZHU Hongyuan, GUO Zhenyu, YU Wei, et al. Illuminating for purity: Photocatalytic and photothermal membranes for sustainable oil-water separation[J]. Water Research, 2025, 272: 122919.
[7]	YANG Wenhua, DONG Hongyu, TIAN Yonglan, et al. Electrochemistry enhanced multi-stage biological contact oxidation treating sulfamethoxazole wastewater: Performance, degradation pathway and microbial community[J]. Separation and Purification Technology, 2025, 357: 130044.
[8]	ALORAINI Dalal A, ALMUQRIN Aljawhara H, SAYYED M I, et al. Analysis of potential waste materials of protection capacity against ionizing radiation using innovative methods[J]. Journal of Radiation Research and Applied Sciences, 2024,17(3): 101030.
[9]	YIN Baohe, LI Chenxi, TIAN Zhifu, et al. Effective catalytic ozonation of Orange G by supported Ce-Fe-Co oxides on Al₂O₃: Performance, mechanism and selective oxidation[J]. Journal of Water Process Engineering, 2025, 69: 106752.
[10]	TANG Min, WU Dong, NIE Yulun, et al. Efficiently catalytic ozonation of 2,4-dichlorophenoxyacetic acid by natural ferrihydrite: A pH dependent and surface-OH group involved reaction mechanism[J]. Environmental Research, 2025, 264: 120410.
[11]	ZHAN Shujuan, LI Yiqing, SUN Lianpeng, et al. Construction of solid frustrated-Lewis-pairs in porous nanoceria for boosting catalytic ozonation of refractory organic pollutants[J]. Separation and Purification Technology, 2025, 359: 130613.
[12]	CHENG Yizhen, CHEN Zhonglin, BI Jinhong, et al. Surface coordination species in heterogeneous catalytic ozonation for water purification[J]. Cell Reports Physical Science, 2024, 5(11): 102269.
[89]	ALVER Alper, Ahmet KıLıÇ. Catalytic ozonation by iron coated pumice for the degradation of natural organic matters[J]. Catalysts, 2018, 8(5): 219.
[90]	BAI Zhiyong, WANG Jianlong, YANG Qi. Iron doped fibrous-structured silica nanospheres as efficient catalyst for catalytic ozonation of sulfamethazine[J]. Environmental Science and Pollution Research International, 2018, 25(10): 10090-10101.
[91]	QI Fei, XU Bingbing, ZHAO Lun, et al. Comparison of the efficiency and mechanism of catalytic ozonation of 2,4,6-trichloroanisole by iron and manganese modified bauxite[J]. Applied Catalysis B: Environmental, 2012, 121: 171-181.
[92]	CHEN Weirui, BAO Yixiang, LI Xukai, et al. Mineralization of salicylic acid via catalytic ozonation with Fe-Cu@SiO₂ core-shell catalyst: A two-stage first order reaction[J]. Chemosphere, 2019, 235: 470-480.
[93]	OPUTU Ogheneochuko, CHOWDHURY Mahabubur, NYAMAYARO Kudzanai, et al. A novel β-FeOOH/NiO composite material as a potential catalyst for catalytic ozonation degradation of 4-chlorophenol[J]. RSC Advances, 2015, 5(73): 59513-59521.
[94]	HE Hongping, LIU Ying, WU Deli, et al. Ozonation of dimethyl phthalate catalyzed by highly active Cu _x O-Fe₃O₄ nanoparticles prepared with zero-valent iron as the innovative precursor[J]. Environmental Pollution, 2017, 227: 73-82.
[95]	YANG Li, HU Chun, NIE Yulun, et al. Surface acidity and reactivity of β-FeOOH/Al₂O₃ for pharmaceuticals degradation with ozone: In situ ATR-FTIR studies[J]. Applied Catalysis B: Environmental, 2010, 97(3/4): 340-346.
[96]	LIN Kun-Yi Andrew, LIN Tienyu, CHEN Yu-Chien, et al. Ferrocene as an efficient and recyclable heterogeneous catalyst for catalytic ozonation in water[J]. Catalysis Communications, 2017, 95: 40-45.
[97]	YU Deyou, WU Minghua, HU Qian, et al. Iron-based metal-organic frameworks as novel platforms for catalytic ozonation of organic pollutant: Efficiency and mechanism[J]. Journal of Hazardous Materials, 2019, 367: 456-464.
[98]	LI Ying, YEUNG King Lun. Polymeric catalytic membrane for ozone treatment of DEET in water[J]. Catalysis Today, 2019, 331: 53-59.
[99]	ZHU Hao, MA Wencheng, HAN Hongjun, et al. Degradation characteristics of two typical N-heterocycles in ozone process: Efficacy, kinetics, pathways, toxicity and its application to real biologically pretreated coal gasification wastewater[J]. Chemosphere, 2018, 209: 319-327.
[100]	LI Xufang, CHEN Weiyu, MA Luming, et al. Industrial wastewater advanced treatment via catalytic ozonation with an Fe-based catalyst[J]. Chemosphere, 2018, 195: 336-343.
[13]	MENG Hongying, CHANG Jing, WANG Shaopo, et al. Fabrication of MOF-carbonized materials as ozone catalysts for water purification: Exploration of catalytic mechanisms[J]. Journal of Environmental Chemical Engineering, 2024, 12(6): 114632.
[14]	WANG Jianlong, BAI Zhiyong. Fe-based catalysts for heterogeneous catalytic ozonation of emerging contaminants in water and wastewater[J]. Chemical Engineering Journal, 2017, 312: 79-98.
[15]	SHARMA Virender K, ZBORIL Radek, VARMA Rajender S. Ferrates: Greener oxidants with multimodal action in water treatment technologies[J]. Accounts of Chemical Research, 2015, 48(2): 182-191.
[16]	JIA Ziyu, YANG Yuming, YANG Chunwei, et al. Magnetic γ-Fe₂O₃/ZnO@CNTs synthesized by a green precipitation method for the degradation of aniline through photocatalysis coupling catalytic ozonation[J]. Applied Surface Science, 2024, 659: 159866.
[17]	LIU Xinghao, ZHU Wenxiu, YANG Zhaoguang, et al. Efficient ozone catalysis by manganese iron oxides/activated carbon for sulfamerazine degradation[J]. Journal of Water Process Engineering, 2022, 49: 103050.
[18]	WANG Zhicheng, XU Tao, TANG Dingding, et al. Catalytic ozonation with γ-Al₂O₃ sphere supported highly dispersed iron species: Preparation, performance and catalytic mechanism[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 658: 130560.
[19]	SUN Yongjun, CHENG Yueqian, XIE Shuqian, et al. Catalytic ozonation of 2,4-dichlorophenoxyacetic acid wastewater by Fe-La@ZE catalyst[J]. Journal of Water Process Engineering, 2024, 61: 105362.
[20]	WANG Xiao, WU Shuhui, YAO Xue, et al. Catalytic ozone oxidation performance of Fe-Ce@γ-Al₂O₃ in reverse osmosis concentrate treatment[J]. Journal of Water Process Engineering, 2024, 68: 106449.
[21]	ZHANG Nianbo, ZHANG Baoyong, HE Ao, et al. Activation of ozone by CoFe-LDO-BC heterogeneous catalyst for efficient mineralization of methylene blue: The role of oxygen vacancies and acidic sites[J]. Journal of Environmental Chemical Engineering, 2023, 11(5): 110717.
[22]	REZVANI Bardia, NABAVI Seyed Reza, GHANI Milad. Magnetic nanohybrid derived from MIL-53(Fe) as an efficient catalyst for catalytic ozonation of cefixime and process optimization by optimal design[J]. Process Safety and Environmental Protection, 2023, 177: 1054-1071.
[23]	YAN Pengwei, SHEN Jimin, ZHOU Yanchi, et al. Interface mechanism of catalytic ozonation in an α-Fe_0.9Mn_0.1OOH aqueous suspension for the removal of iohexol[J]. Applied Catalysis B: Environmental, 2020, 277: 119055.
[24]	QIANG Dilong, JIN Hongyang, QING Qishun, et al. Iron-doped manganese oxide octahedral molecular sieve catalysts for ozone decomposition[J]. Journal of Environmental Chemical Engineering, 2024, 12(5): 113769.
[101]	GAO Guoying, KANG Jing, SHEN Jimin, et al. Investigation on the kinetics of heterogeneous catalytic ozone decomposition in aqueous solution over composite iron-manganese silicate oxide[J]. Ozone: Science & Engineering, 2016, 38(6): 434-442.
[102]	MALIK Sameena N, GHOSH Prakash C, VAIDYA Atul N, et al. Catalytic ozone pretreatment of complex textile effluent using Fe²⁺ and zero valent iron nanoparticles[J]. Journal of Hazardous Materials, 2018,357: 363-375.
[103]	MA Jieting, CHEN Yunlu, NIE Jianxin, et al. Pilot-scale study on catalytic ozonation of bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst[J]. Scientific Reports, 2018, 8(1): 7555.
[104]	YUAN Yuting, XING Guowei, GARG Shikha, et al. Mechanistic insights into the catalytic ozonation process using iron oxide-impregnated activated carbon[J]. Water Research, 2020,1 77: 115785.
[105]	WANG Da, XU Haodan, MA Jun, et al. Enhanced mineralization of atrazine by surface induced hydroxyl radicals over light-weight granular mixed-quartz sands with ozone[J]. Water Research, 2019, 149: 136-148.
[106]	ZHENG Tianlong, WANG Qunhui, ZHANG Tao, et al. Microbubble enhanced ozonation process for advanced treatment of wastewater produced in acrylic fiber manufacturing industry[J]. Journal of Hazardous Materials, 2015, 287: 412-420.
[107]	AZEVEDO A, OLIVEIRA H, RUBIO J. Bulk nanobubbles in the mineral and environmental areas: Updating research and applications[J]. Advances in Colloid and Interface Science, 2019, 271: 101992.
[108]	XIA Zhiran, HU Liming. Treatment of organics contaminated wastewater by ozone micro-nano-bubbles[J]. Water, 2019, 11(1): 55.
[109]	AZEVEDO A, ETCHEPARE R, CALGAROTO S, et al. Aqueous dispersions of nanobubbles: Generation, properties and features[J]. Minerals Engineering, 2016, 94: 29-37.
[110]	HUANG Xiaoxue, CHENG Wen, QUAN Xuejun, et al. Catalytic ozonation of biologically treated leachate from municipal solid waste in a microbubble reactor[J]. Ozone: Science & Engineering, 2019, 41(5): 415-426.
[111]	AGUILAR CORONADO Miguel, BABAZADEH Mohammad, REZAEI Ebrahim, et al. Complete oxidation of trans-4-pentylcyclohexanecarboxylic acid by catalytic ozonation using alumina supported bi-metallic copper-magnesium oxides[J]. Chemical Engineering Journal, 2024, 497: 154365.
[112]	LI Wenbin, SHAO Yuanyuan, ZHU Jesse. Anisotropic turbulent mass transfer model and its application to a gas-particle bubbling fluidized bed[J]. Industrial & Engineering Chemistry Research, 2018, 57(5): 1671-1678.
[25]	XIAO Siqi, MA Luming, AN Wenhui, et al. Stability optimization of iron-based catalysts: Application of Cr-enriched alloy steel catalyst in ozonation pharmaceutical wastewater[J]. Separation and Purification Technology, 2025, 354: 129007.
[26]	PENG Jiali, YAN Jianfei, CHEN Qixuan, et al. Natural mackinawite catalytic ozonation for N,N-dimethylacetamide (DMAC) degradation in aqueous solution: Kinetic, performance, biotoxicity and mechanism[J]. Chemosphere, 2018, 210: 831-842.
[27]	PELALAK Rasool, ALIZADEH Reza, GHARESHABANI Eslam. Enhanced heterogeneous catalytic ozonation of pharmaceutical pollutants using a novel nanostructure of iron-based mineral prepared via plasma technology: A comparative study[J]. Journal of Hazardous Materials, 2020, 392: 122269.
[28]	YUAN Lei, SHEN Jimin, YAN Pengwei, et al. Catalytic ozonation of 4-chloronitrobenzene by goethite and Fe²⁺-modified goethite with low defects: A comparative study[J]. Journal of Hazardous Materials, 2019, 365: 744-750.
[29]	LIU Yue, CHEN Zhonglin, DUAN Xuejun, et al. Mechanism of heterogeneous catalytic ozonation of p-chloronitrobenzene in aqueous solution with iron silicate dried at different temperatures[J]. Desalination and Water Treatment, 2016, 57(40): 19002-19009.
[30]	OPUTU Ogheneochuko, CHOWDHURY Mahabubur, NYAMAYARO Kudzanai, et al. Catalytic activities of ultra-small β-FeOOH nanorods in ozonation of 4-chlorophenol[J]. Journal of Environmental Sciences, 2015, 35: 83-90.
[31]	YUAN Lei, SHEN Jimin, YAN Pengwei, et al. Interface mechanisms of catalytic ozonation with amorphous iron silicate for removal of 4-chloronitrobenzene in aqueous solution[J]. Environmental Science & Technology, 2018, 52(3): 1429-1434.
[32]	MOUSSAVI Gholamreza, KHOSRAVI Rasoul, OMRAN Nematollah Rashidnejad. Development of an efficient catalyst from magnetite ore: Characterization and catalytic potential in the ozonation of water toxic contaminants[J]. Applied Catalysis A: General, 2012, 445: 42-49.
[33]	WANG Yu-Hsiang, CHEN Kuan-Chung. Removal of disinfection by-products from contaminated water using a synthetic goethite catalyst via catalytic ozonation and a biofiltration system[J]. International Journal of Environmental Research and Public Health, 2014, 11(9): 9325-9344.
[34]	SUI Minghao, SHENG Li, LU Kexiang, et al. FeOOH catalytic ozonation of oxalic acid and the effect of phosphate binding on its catalytic activity[J]. Applied Catalysis B: Environmental, 2010, 96(1/2): 94-100.
[35]	HUANG Yuanxing, JIANG Jiewen, MA Luming, et al. Iron foam combined ozonation for enhanced treatment of pharmaceutical wastewater[J]. Environmental Research, 2020, 183: 109205.
[36]	HUANG Yuanxing, LUO Mengyu, XU Zhihua, et al. Catalytic ozonation of organic contaminants in petrochemical wastewater with iron-nickel foam as catalyst[J]. Separation and Purification Technology, 2019, 211: 269-278.
[113]	WEI Chaohai, ZHANG Fengzhen, HU Yun, et al. Ozonation in water treatment: The generation, basic properties of ozone and its practical application[J]. Reviews in Chemical Engineering, 2017, 33(1): 49-89.
[114]	WANG He, LIN Xiaozi, HUANG Yuanxing, et al. Two advanced oxidation pathways of modified iron-shavings participation in ozonation[J]. Separation and Purification Technology, 2020, 244: 116838.
[115]	SU Li, FENG Jie, ZHOU Ximin, et al. Colorimetric detection of urine glucose based ZnFe₂O₄ magnetic nanoparticles[J]. Analytical Chemistry, 2012, 84(13): 5753-5758.
[116]	ZHAO Hui, DONG Yuming, JIANG Pingping, et al. ZnAl₂O₄ as a novel high-surface-area ozonation catalyst: One-step green synthesis, catalytic performance and mechanism[J]. Chemical Engineering Journal, 2015, 260: 623-630.
[117]	YU Deyou, LI Lubiao, WU Minghua, et al. Enhanced photocatalytic ozonation of organic pollutants using an iron-based metal-organic framework[J]. Applied Catalysis B: Environmental, 2019, 251: 66-75.
[118]	XIONG Zhaokun, LAI Bo, YANG Ping, et al. Comparative study on the reactivity of Fe/Cu bimetallic particles and zero valent iron (ZVI) under different conditions of N₂, air or without aeration[J]. Journal of Hazardous Materials, 2015, 297: 261-268.
[119]	LI Xufang, CHEN Weiyu, MA Luming, et al. Characteristics and mechanisms of catalytic ozonation with Fe-shaving-based catalyst in industrial wastewater advanced treatment[J]. Journal of Cleaner Production, 2019, 222: 174-181.
[120]	NAWROCKI Jacek, Barbara KASPRZYK-HORDERN. The efficiency and mechanisms of catalytic ozonation[J]. Applied Catalysis B: Environmental, 2010, 99(1/2): 27-42.
[121]	YUAN Run, QIN Yihe, HE Can, et al. Fe-Mn-Cu-Ce/Al₂O₃ as an efficient catalyst for catalytic ozonation of bio-treated coking wastewater: Characteristics, efficiency, and mechanism[J]. Arabian Journal of Chemistry, 2023, 16(1): 104415.
[122]	ZHOU Dandan, LI Shilong, CHAI Luyi, et al. Constructing fast mass-transfer channels with efficient catalytic ozonation activity in 2D manganese dioxide membranes by intercalating Fe/Mn bimetallic MOF[J]. Chinese Journal of Chemical Engineering, 2024, 74: 272-286.
[123]	YU Liwei, ZHANG Yue, LI Fengmin, et al. Efficient catalytic ozonation for hexazinone degradation by Fe/Ce-doped MOF derivatives[J]. Separation and Purification Technology, 2024, 344: 127277.
[124]	XU Anlin, FAN Siyan, MENG Tong, et al. Catalytic ozonation with biogenic Fe-Mn-Co oxides: Biosynthesis protocol and catalytic performance[J]. Applied Catalysis B: Environmental, 2022, 318: 121833.
[37]	WEN Chen, XU Xiaoyi, FAN Yunshuang, et al. Pretreatment of water-based seed coating wastewater by combined coagulation and sponge-iron-catalyzed ozonation technology[J]. Chemosphere, 2018,206: 238-247.
[38]	XIONG Zhaokun, LAI Bo, YUAN Yue, et al. Degradation of p-nitrophenol (PNP) in aqueous solution by a micro-size Fe⁰/O₃ process (mFe⁰/O₃): Optimization, kinetic, performance and mechanism[J]. Chemical Engineering Journal, 2016, 302: 137-145.
[39]	OLEA-MEJIA O, FERNÁNDEZ-MONDRAGÓN M, BARRERA-DÍAZ C, et al. Effect of the Fe nanoparticles generated by pulsed plasma in liquid in the catalyzed ozone removal of phenolphthalein[J]. International Journal of Photoenergy, 2017, 2017(1): 9314764.
[40]	BAI Zhiyong, WANG Jianlong, YANG Qi. Catalytic ozonation of dimethyl phthalate by Ce-substituted goethite[J]. International Journal of Environmental Science and Technology, 2017, 14(11): 2379-2388.
[41]	XU Zhenzhen, XIE Meiling, Yue BEN, et al. Efficiency and mechanism of atenolol decomposition in Co-FeOOH catalytic ozonation[J]. Journal of Hazardous Materials, 2019, 365: 146-154.
[42]	ZHANG Fengzhen, WEI Chaohai, HU Yun, et al. Zinc ferrite catalysts for ozonation of aqueous organic contaminants: Phenol and bio-treated coking wastewater[J]. Separation and Purification Technology, 2015,156: 625-635.
[43]	ZHAO Hui, DONG Yuming, WANG Guangli, et al. Novel magnetically separable nanomaterials for heterogeneous catalytic ozonation of phenol pollutant: NiFe₂O₄ and their performances[J]. Chemical Engineering Journal, 2013, 219: 295-302.
[44]	ZHANG Gucheng, ZHANG Jing, ZHANG Yongli, et al. Effect of the composition and surface functional groups of Fe-Ni bimetal oxides catalysts in catalytic ozonation process[J]. Journal of Water Supply: Research and Technology-Aqua, 2018, 67(2): 119-126.
[45]	GOUNDEN Asogan N, JONNALAGADDA Sreekanth B, SINGH Sooboo. Debromination of 2,4,6-Tribromophenol and bromate ion minimization in water by catalytic ozonation[J]. Journal of Water Process Engineering, 2019, 31: 100893.
[46]	HUANG Yuanxing, YANG Tingting, LIANG Manli, et al. Ni-Fe layered double hydroxides catalized ozonation of synthetic wastewater containing bisphenol A and municipal secondary effluent[J]. Chemosphere, 2019, 235: 143-152.
[47]	BAI Zhiyong, YANG Qi, WANG Jianlong. Catalytic ozonation of sulfamethazine antibiotics using Ce_0.1Fe_0.9OOH: Catalyst preparation and performance[J]. Chemosphere, 2016, 161: 174-180.
[48]	LIU Yue, WANG Shiyuan, GONG Weijin, et al. Heterogeneous catalytic ozonation of p-chloronitrobenzene (pCNB) in water with iron silicate doped hydroxylation iron as catalyst[J]. Catalysis Communications, 2017, 89: 81-85.
[49]	WU Jin, MA Luming, CHEN Yunlu, et al. Catalytic ozonation of organic pollutants from bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst: Removal and pathways[J]. Water Research, 2016, 92: 140-148.
[50]	WU Deli, LIU Ying, HE Hongping, et al. Magnetic pyrite cinder as an efficient heterogeneous ozonation catalyst and synergetic effect of deposited Ce[J]. Chemosphere, 2016, 155: 127-134.
[51]	MARTINS Rui C, RAMOS Carina M, QUINTA-FERREIRA Rosa M. Low-cost catalysts to enhance ozone action on the depuration of olive mill wastewaters[J]. Industrial & Engineering Chemistry Research, 2014, 53(40): 15357-15368.
[52]	IKHLAQ Amir, MUNIR Hafiz Muhammad Shahzad, KHAN Asifa, et al. Comparative study of catalytic ozonation and Fenton-like processes using iron-loaded rice husk ash as catalyst for the removal of methylene blue in wastewater[J]. Ozone: Science & Engineering, 2019, 41(3): 250-260.
[53]	LU Siying, LIU Yongze, FENG Li, et al. Characterization of ferromagnetic sludge-based activated carbon and its application in catalytic ozonation of p-chlorobenzoic acid[J]. Environmental Science and Pollution Research, 2018, 25(6): 5086-5094.
[54]	VAN Huu Tap, NGUYEN Lan Huong, HOANG Trung Kien, et al. Using FeO-constituted iron slag wastes as heterogeneous catalyst for Fenton and ozonation processes to degrade Reactive Red 24 from aqueous solution[J]. Separation and Purification Technology, 2019, 224: 431-442.
[55]	MENG Fanqing, MA Wei, ZONG Panpan, et al. Synthesis of a novel catalyst based on Fe(Ⅱ)/Fe(Ⅲ) oxide and high alumina coal fly ash for the degradation of o-methylphenol[J]. Journal of Cleaner Production, 2016, 133: 986-993.
[56]	HOU Sen, JIA Shengyong, JIA Jinjin, et al. Fe₃O₄ nanoparticles loading on cow dung based activated carbon as an efficient catalyst for catalytic microbubble ozonation of biologically pretreated coal gasification wastewater[J]. Journal of Environmental Management, 2020, 267: 110615.
[57]	WU Jie, GAO Hong, YAO Shuo, et al. Degradation of Crystal Violet by catalytic ozonation using Fe/activated carbon catalyst[J]. Separation and Purification Technology, 2015, 147: 179-185.
[58]	XIONG Wei, CHEN Nan, FENG Chuanping, et al. Ozonation catalyzed by iron- and/or manganese-supported granular activated carbons for the treatment of phenol[J]. Environmental Science and Pollution Research, 2019, 26(20): 21022-21033.
[59]	BAI Zhiyong, YANG Qi, WANG Jianlong. Fe₃O₄/multi-walled carbon nanotubes as an efficient catalyst for catalytic ozonation of p-hydroxybenzoic acid[J]. International Journal of Environmental Science and Technology, 2016, 13(2): 483-492.
[60]	CHEN Chunmao, CHEN Hongshuo, GUO Xuan, et al. Advanced ozone treatment of heavy oil refining wastewater by activated carbon supported iron oxide[J]. Journal of Industrial and Engineering Chemistry, 2014, 20(5): 2782-2791.
[125]	YAN Liqiang, BING Jishuai, WU Hecheng. The behavior of ozone on different iron oxides surface sites in water[J]. Scientific Reports, 2019, 9(1): 14752.
[126]	WANG Cheng, LI Aimin, SHUANG Chendong. The effect on ozone catalytic performance of prepared-FeOOH by different precursors[J]. Journal of Environmental Management, 2018, 228: 158-164.
[127]	ZHANG Tao, LI Chunjuan, MA Jun, et al. Surface hydroxyl groups of synthetic α-FeOOH in promoting OH generation from aqueous ozone: Property and activity relationship[J]. Applied Catalysis B: Environmental, 2008, 82(1/2): 131-137.
[128]	ZHANG Yanqing, LI Meng, ZHANG Qian. Silicon-modified ferric hydroxide for catalytic ozonation of nitrobenzene in aqueous solution[J]. Desalination and Water Treatment, 2015, 54(10): 2902-2908.
[129]	REN Yueming, CHEN Yu, ZENG Teng, et al. Influence of Bi-doping on Mn_1- _x Bi _x Fe₂O₄ catalytic ozonation of di-n-butyl phthalate[J]. Chemical Engineering Journal, 2016, 283: 622-630.
[130]	LIU Dan, WANG Chunrong, SONG Yifan, et al. Effective mineralization of quinoline and bio-treated coking wastewater by catalytic ozonation using CuFe₂O₄/Sepiolite catalyst: Efficiency and mechanism[J]. Chemosphere, 2019, 227: 647-656.
[131]	CHENG Chen, LI Jianping, WEN Yuzhen, et al. Deactivation mechanism of Fe/Al₂O₃ catalyst during the ozonation of reverse osmosis concentrates (ROCs): Effect of silicate[J]. Chemical Engineering Journal Advances, 2020, 1: 100003.
[132]	TAN Xuefei, WANG Shengzhe, MA Lei, et al. Catalytic ozone oxidation of m-cresol by spirulina biochar-modified perovskite: Catalyst deactivation and in situ regeneration[J]. Separation and Purification Technology, 2024, 329: 124994.
[133]	KONG Xiangtong, GARG Shikha, CHEN Guifeng, et al. Investigation of the deactivation and regeneration of an Fe₂O₃/Al₂O₃·SiO₂ catalyst used in catalytic ozonation of coal chemical industry wastewater[J]. Journal of Hazardous Materials, 2023, 451: 131194.
[61]	LI Xukai, CHEN Weirui, LI Laisheng. Catalytic ozonation of oxalic acid in the presence of Fe₂O₃-loaded activated carbon[J]. Ozone: Science & Engineering, 2018, 40(6): 448-456.
[62]	HUANG Yuanxing, CUI Chenchen, ZHANG Daofang, et al. Heterogeneous catalytic ozonation of dibutyl phthalate in aqueous solution in the presence of iron-loaded activated carbon[J]. Chemosphere, 2015, 119: 295-301.
[63]	TANG Shoufeng, YUAN Deling, ZHANG Qi, et al. Fe-Mn bi-metallic oxides loaded on granular activated carbon to enhance dye removal by catalytic ozonation[J]. Environmental Science and Pollution Research International, 2016, 23(18): 18800-18808.
[64]	BAI Zhiyong, YANG Qi, WANG Jianlong. Catalytic ozonation of sulfamethazine antibiotics using Fe₃O₄/multiwalled carbon nanotubes[J]. Environmental Progress & Sustainable Energy, 2018, 37(2): 678-685.

催化剂	处理对象	反应条件	降解效率	参考文献
α-FeOOH	磺胺嘧啶类抗生素（SMT）	初始污染物浓度为10mg/L；反应pH为7；臭氧投加量为5mg/L；催化剂投加量为1.5g/L；气体流量为1L/h	SO：D[SMT]=61.44%CO：D[SMT]=96.05%	[27]
Fe²⁺-α-FeOOH	4-氯硝基苯（4-CNB）	反应温度为25℃；反应pH为6；初始污染物浓度为50μg/L；臭氧投加量为0.6mg/L；催化剂投加量为50mg/L；反应时间为10min	SO：D[4-CNB]=34.2% CO：D[4-CNB]=57.2%	[28]
硅酸铁盐	对氯硝基苯（p-CNB）	初始污染物浓度为100μg/L；臭氧投加量为0.6mg/L；催化剂投加量为100mg/L；反应pH为7；反应时间为15min；反应温度为25℃	SO：D[p-CNB]=60% CO：D[p-CNB]=97%	[29]
β-FeOOH	对氯苯酚（4-CP）	反应温度为20℃；反应pH为3.5；初始污染物浓度为2mmol/L；臭氧投加量为0.6mg/min	SO：D[4-CP]=67% CO：D[4-CP]=99%	[30]
硅酸铁盐	4-氯硝基苯（4-CNB）	反应温度为25℃；初始污染物浓度为0.1mg/L；臭氧投加量为0.9mg/L；催化剂投加量为100mg/L	SO：D[4-CNB]=49.2%，[TOC]=27.2% CO：D[4-CNB]=82.2%，[TOC]=67.4%	[31]
改性磁铁矿	活性红120（RR-120）	初始污染物浓度为100mg/L；催化剂投加量为2g/L；臭氧投加量为1mg/min；反应温度为25℃；反应pH为11	SO：D[RR-120]=39% CO：D[RR-120]=83.4%	[32]
α-FeOOH	经农业污水和生活污水污染后的河水	气体流量为50mL/min；反应温度为20℃；催化剂投加量为1.5g/L；臭氧投加量为2.5g/L；初始TOC为9.21mg/L	SO：[TOC]=7.8% CO：[TOC]=43.54%	[33]
α-FeOOH	草酸（OA）	气体流量为0.4L/min；臭氧投加量为0.45mg/min；反应pH为7；反应时间为30min；初始污染物浓度为0.01mmol/L；催化剂投加量为2g/L；反应温度为20℃	SO：D[OA]=22% CO：D[OA]=54%	[34]

催化剂	处理对象	反应条件	降解效率	参考文献
α-FeOOH	磺胺嘧啶类抗生素（SMT）	初始污染物浓度为10mg/L；反应pH为7；臭氧投加量为5mg/L；催化剂投加量为1.5g/L；气体流量为1L/h	SO：D[SMT]=61.44%CO：D[SMT]=96.05%	[27]
Fe²⁺-α-FeOOH	4-氯硝基苯（4-CNB）	反应温度为25℃；反应pH为6；初始污染物浓度为50μg/L；臭氧投加量为0.6mg/L；催化剂投加量为50mg/L；反应时间为10min	SO：D[4-CNB]=34.2% CO：D[4-CNB]=57.2%	[28]
硅酸铁盐	对氯硝基苯（p-CNB）	初始污染物浓度为100μg/L；臭氧投加量为0.6mg/L；催化剂投加量为100mg/L；反应pH为7；反应时间为15min；反应温度为25℃	SO：D[p-CNB]=60% CO：D[p-CNB]=97%	[29]
β-FeOOH	对氯苯酚（4-CP）	反应温度为20℃；反应pH为3.5；初始污染物浓度为2mmol/L；臭氧投加量为0.6mg/min	SO：D[4-CP]=67% CO：D[4-CP]=99%	[30]
硅酸铁盐	4-氯硝基苯（4-CNB）	反应温度为25℃；初始污染物浓度为0.1mg/L；臭氧投加量为0.9mg/L；催化剂投加量为100mg/L	SO：D[4-CNB]=49.2%，[TOC]=27.2% CO：D[4-CNB]=82.2%，[TOC]=67.4%	[31]
改性磁铁矿	活性红120（RR-120）	初始污染物浓度为100mg/L；催化剂投加量为2g/L；臭氧投加量为1mg/min；反应温度为25℃；反应pH为11	SO：D[RR-120]=39% CO：D[RR-120]=83.4%	[32]
α-FeOOH	经农业污水和生活污水污染后的河水	气体流量为50mL/min；反应温度为20℃；催化剂投加量为1.5g/L；臭氧投加量为2.5g/L；初始TOC为9.21mg/L	SO：[TOC]=7.8% CO：[TOC]=43.54%	[33]
α-FeOOH	草酸（OA）	气体流量为0.4L/min；臭氧投加量为0.45mg/min；反应pH为7；反应时间为30min；初始污染物浓度为0.01mmol/L；催化剂投加量为2g/L；反应温度为20℃	SO：D[OA]=22% CO：D[OA]=54%	[34]

催化剂	处理对象	反应条件	降解效率	参考文献
泡沫铁	制药废水	臭氧投加量为9mg/L；催化剂投加量为80g/L；初始TOC为40~50mg/L；初始COD为120~150mg/L；反应pH为8.4；反应时间为120min	SO：[TOC]=32%，[COD]=73% CO：[TOC]=53%，[COD]=73%	[35]
泡沫铁镍	石化废水	臭氧投加量为12.2mg/L；催化剂投加量为110g/L；初始TOC为31~35mg/L；初始COD为116~143mg/L；反应pH为8.3；反应时间为120min	SO：[TOC]=11%，[COD]=65% CO：[TOC]=43%，[COD]=65%	[36]
泡沫铁	农药废水	臭氧投加量为5.3mg/L；催化剂投加量为20g/L；初始COD为900mg/L；反应pH为9；反应时间为30min	SO：[COD]=14.3% CO：[COD]=28.9%	[37]
纳米零价铁	对硝基苯酚	初始污染物浓度为500mg/L；初始COD为833mg/L；催化剂投加量为40mg/L；反应pH为5.3；气体流量为1.5L/min；臭氧投加量为7.6mg/L；反应时间为60min	SO：[COD]=29.4% CO：[COD]=89.5%	[38]
纳米零价铁	酚酞（PHL）	臭氧投加量为5mg/L；初始污染物浓度为60mg/L；反应pH为3；反应时间为60min；催化剂投加量为1.8g/L	SO：[TOC]=49%，D[PHL]=84% CO：[TOC]=96%，D[PHL]=100%	[39]

催化剂	处理对象	反应条件	降解效率	参考文献
泡沫铁	制药废水	臭氧投加量为9mg/L；催化剂投加量为80g/L；初始TOC为40~50mg/L；初始COD为120~150mg/L；反应pH为8.4；反应时间为120min	SO：[TOC]=32%，[COD]=73% CO：[TOC]=53%，[COD]=73%	[35]
泡沫铁镍	石化废水	臭氧投加量为12.2mg/L；催化剂投加量为110g/L；初始TOC为31~35mg/L；初始COD为116~143mg/L；反应pH为8.3；反应时间为120min	SO：[TOC]=11%，[COD]=65% CO：[TOC]=43%，[COD]=65%	[36]
泡沫铁	农药废水	臭氧投加量为5.3mg/L；催化剂投加量为20g/L；初始COD为900mg/L；反应pH为9；反应时间为30min	SO：[COD]=14.3% CO：[COD]=28.9%	[37]
纳米零价铁	对硝基苯酚	初始污染物浓度为500mg/L；初始COD为833mg/L；催化剂投加量为40mg/L；反应pH为5.3；气体流量为1.5L/min；臭氧投加量为7.6mg/L；反应时间为60min	SO：[COD]=29.4% CO：[COD]=89.5%	[38]
纳米零价铁	酚酞（PHL）	臭氧投加量为5mg/L；初始污染物浓度为60mg/L；反应pH为3；反应时间为60min；催化剂投加量为1.8g/L	SO：[TOC]=49%，D[PHL]=84% CO：[TOC]=96%，D[PHL]=100%	[39]

催化剂	处理对象	反应条件	降解效率	参考文献
铈改性针铁矿	邻苯二甲酸二甲酯（DMP）	初始污染物浓度为10mg/L；反应pH为6.8；臭氧投加量为6mg/min；催化剂投加量为0.2g/L；反应时间为60min	SO：D[DMP]=80%，[TOC]=15%CO：D[DMP]=88%，[TOC]=40%	[40]
铁镍金属氧化物	邻苯二甲酸二甲酯（DMP）	初始污染物浓度为440mg/L；臭氧（液相）投加量为0.5mg/L；催化剂投加量为0.1g/L；反应时间为10min	SO：D[DMP]=39.08% CO：D[DMP]=86.83%	[44]
铁钴金属氧化物	2,4,6-三溴苯酚（2,4,6-TBP）	反应时间为20min；臭氧投加量为100mg/L；催化剂投加量为4g/L；初始污染物浓度为50mg/L	SO：D[2,4,6-TBP]=40%，[TOC]=11%CO：D[2,4,6-TBP]=100%，[TOC]=58%	[45]
镍铁层状氢氧化物	双酚A（BPA）	催化剂投加量为0.3g/L；臭氧（液相）投加量为9mg/L；反应pH为8.2；初始污染物浓度为10mg/L	SO：[TOC]=30%，D[BPA]=100%CO：[TOC]=89%，D[BPA]=100%	[46]
Ce_0.1Fe_0.9OOH	磺胺二甲嘧啶	气体流量为0.4L/min；初始污染物浓度为0.2g/L；臭氧投加量为15mg/L；催化剂投加量为0.2g/L；反应时间为60min	SO：[TOC]=24.1% CO：[TOC]=42.1%	[47]
Co-FeOOH	阿替洛尔	初始污染物浓度为20mg/L；初始TOC浓度为14.48mg/L；臭氧投加量为2.04mg/L；催化剂投加量为0.2g/L；反应pH为7；反应时间为20min	SO：[TOC]≈16% CO：[TOC]=22%	[41]
ZnFe₂O₄	苯酚	反应时间为30min；反应温度为20℃；臭氧投加量为14mg/L；反应pH为6.38；气体流量为1L/min；初始污染物浓度为300mg/L；催化剂投加量为1g/L	SO：D[苯酚]=63.4% CO：D[苯酚]=92.6%	[42]
NiFe₂O₄	苯酚	臭氧投加量为0.75mg/min；初始污染物浓度为300mg/L；催化剂投加量为1g/L；反应pH为6.5；反应温度为20℃	SO：D[苯酚]=38.9% CO：D[苯酚]=55.2%	[43]
硅酸铁掺杂羟基氧化铁	对氯硝基苯	初始污染物浓度为100μg/L；液相臭氧投加量为0.6mg/L；反应pH为7；催化剂投加量为0.5g/L	SO：[TOC]=28.1% CO：[TOC]=61.3%	[48]