The advanced oxidation process based on persulfate has a broad application prospect in the remediation of organic pollutants. As an effective, low-cost and environmentally friendly material, nano-zero-valent iron (nZVI) can effectively activate persulfate (nZVI/PS) to generate strongly oxidizing sulfate radical for removing organic pollutants in the environment. In this review, we first clarify the activation pathway of nZVI activated persulfate including direct activation and indirect activation. Direct activation means that the electrons released by nZVI directly participate in the activation of PS; indirect activation means that Fe0 corrodes to generate Fe2+, and Fe2+ further activate the persulfate. Then, the mechanism of nZVI/PS system to degrade organic pollutants including electron transfer, hydrogen extraction and addition reactions are also discussed. Finally, combined with the activation pathway and the mechanism of degrading organic pollutants, we propose several prospects for the future research direction of nZVI activated persulfate. As a result, this review provides a theoretical basis for the nZVI/PS advanced oxidation system to remediate actual sites contaminated with organic pollutants.
Li Q, Chen ZS, Wang HH, Yang H, Wen T, Wang SQ, Hu BW, Wang XK, Removal of organic compounds by nanoscale zero-valent iron and its composites, Sci Total Environ 2021; 792: 148546. https://doi.org/10.1016/j.scitotenv.2021.148546.
Zhu F, He SY, Shang ZF, Effect of vegetables and nano-particle hydroxyapatite on the remediation of cadmium and phosphatase activity in rhizosphere soil through immobilization, International Journal Of Phytoremediation 2019; 21: 610-616. https://doi.org/10.1080/15226514.2018.1546276.
Qin Y, Xue CL, Yu HR, Wen YT, Zhang LN, Li Y, The construction of bio-inspired hierarchically porous graphene aerogel for efficiently organic pollutants absorption, Journal Of Hazardous Materials 2021; 419: 126441. https://doi.org/10.1016/j.jhazmat.2021.126441.
Fu LN, Li J, Wang GY, Luan YN, Dai W, Adsorption behavior of organic pollutants on microplastics, Ecotoxicology And Environmental Safety 2021; 217: 112207. https://doi.org/10.1016/j.ecoenv.2021.112207
Li BY, Wei DN, Li ZQ, Zhou YM, Li YJ, Huang CH, Long JM, Huang HL, Tie BQ, Lei M, Mechanistic insights into the enhanced removal of roxsarsone and its metabolites by a sludge-based, biochar supported zerovalent iron nanocomposite: Adsorption and redox transformation, Journal Of Hazardous Materials 2020; 389: 122091.https://doi.org/10.1016/j.jhazmat.2020.122091.
Rajeswari A., Christy E. Jackcina Stobel, Mary G. Ida Celine, Jayaraj K, Pius Anitha, Cellulose acetate based biopolymeric mixed matrix membranes with various nanoparticles for environmental remediation-A comparative study, Journal Of Environmental Chemical Engineering 2019; 7: 103278. https://doi.org/10.1016/j.jece.2019.103278.
Chang XQ, Lin T, Chen W, Xu H, Tao H, Wu YH, Zhang QW, Yao SZ, A new perspective of membrane fouling control by ultraviolet synergic ferrous iron catalytic persulfate (UV/Fe(II)/PS) as pretreatment prior to ultrafiltration, Sci Total Environ 2020; 737: 139711.https://doi.org/10.1016/j.scitotenv.2020.139711.
Zheng JT, Zhu CS, Jiang B, Uses of activated carbon fibers and advanced oxidation technologies in the remediation of water, New Carbon Materials 2015; 30: 519-532. https://doi.org/10.19869/j.ncm.1007-8827.2015.06.003.
Ma S, Lee S, Kim K, Im J, Jeon H, Purification of organic pollutants in cationic thiazine and azo dye solutions using plasma-based advanced oxidation process via submerged multi-hole dielectric barrier discharge, Separation And Purification Technology 2021; 255: 117715. https://doi.org/10.1016/j.seppur.2020.117715.
Behin J, Akbari A, Mahmoudi M, Khajeh M, Sodium hypochlorite as an alternative to hydrogen peroxide in Fenton process for industrial scale, Water Research 2017; 121: 120-128. https://doi.org/10.1016/j.watres.2017.05.015.
Tan J, Li ZF, Li J, Wu JX, Yao XL, Zhang TT, Graphitic carbon nitride-based materials in activating persulfate for aqueous organic pollutants degradation: A review on materials design and mechanisms, Chemosphere 2021; 262: 127675. https://doi.org/10.1016/j.chemosphere.2020.127675.
Zhou Z, Ma J, Liu XT, Lin CY, Sun K, Zhang HJ, Li XW, Fan GX, Activation of peroxydisulfate by nanoscale zero-valent iron for sulfamethoxazole removal in agricultural soil: Effect, mechanism and ecotoxicity, Chemosphere 2019; 223: 196-203. https://doi.org/10.1016/j.chemosphere.2019.02.074.
Wang SL, Wu JF, Lu XQ, Xu WX, Gong Q, Ding JQ, Dan BS, Xie PC, Removal of acetaminophen in the Fe2+/persulfate system: Kinetic model and degradation pathways, Chemical Engineering Journal 2019; 358: 1091-1100. https://doi.org/10.1016/j.cej.2018.09.145.
Ma J, Ding Y, Chi LP, Yang X, Zhong YJ, Wang ZH, Shi Q, Degradation of benzotriazole by sulfate radical-based advanced oxidation process, Environmental Technology 2021; 42: 238-247. https://doi.org/10.1080/09593330.2019.1625959.
Liu YQ, He XX, Fu YS, Dionysiou DD, Kinetics and mechanism investigation on the destruction of oxytetracycline by UV-254 nm activation of persulfate, Journal of Hazardous Materials 2016; 305: 229-239. https://doi.org/10.1016/j.jhazmat.2015.11.043.
Monteagudo JM, Duran A, Gonzalez R, Exposito AJ, In situ chemical oxidation of carbamazepine solutions using persulfate simultaneously activated by heat energy, UV light, Fe2+ ions, and H2O2, Appl. Catal. B-Environ. 2015; 176: 120-129. https://doi.org/10.1016/j.apcatb.2015.03.055.
Liang CJ, Bruell Clifford J, Marley Michael C, Sperry Kenneth L, Persulfate oxidation for in situ remediation of TCE. I. Activated by ferrous ion with and without a persulfate-thiosulfate redox couple, Chemosphere 2004; 55: 1213-1223. https://doi.org/10.1016/j.chemosphere.2004.01.029.
He DQ, Cheng Y, Zeng YF, Luo HW, Luo K, Li J, Pan XL, Barcelo D, Crittenden JC, Synergistic activation of peroxymonosulfate and persulfate by ferrous ion and molybdenum disulfide for pollutant degradation: Theoretical and experimental studies, Chemosphere 2020; 240: 124979. https://doi.org/10.1016/j.chemosphere.2019.124979.
Waldemer RH, Tratnyek PG, Johnson RL, Nurmi JT, Oxidation of chlorinated ethenes by heat-activated persulfate: Kinetics and products, Environmental Science & Technology 2007; 41: 1010-1015. https://doi.org/10.1021/es062237m.
Wei CM, Zhang J, Zhang YL, Zhang GC, Zhou P, Li WS, Liang J, Liu Y, Zhang W, Ultrasound enhanced heterogeneous activation of peroxymonosulfate by a Co-NiOx catalyst, Water Sci. Technol. 2017; 76: 1436-1446. https://doi.org/10.2166/wst.2017.316.
Gao YQ, Gao NY, Wang W, Kang SF, Xu JH, Xiang HM, Yin DQ, Ultrasound-assisted heterogeneous activation of persulfate by nano zero-valent iron (nZVI) for the propranolol degradation in water, Ultrasonics sonochemistry 2018; 49: 33-40.https://doi.org/10.1016/j.ultsonch.2018.07.001.
Liang CJ, Lei JH, Identification of Active Radical Species in Alkaline Persulfate Oxidation, Water Environment Research 2015; 87: 656-659. https://doi.org/10.2175/106143015x14338845154986.
Zhu F, Li LW, Ma SY, Shang ZF, Effect factors, kinetics and thermodynamics of remediation in the chromium contaminated soils by nanoscale zero valent Fe/Cu bimetallic particles, Chemical Engineering Journal 2016; 302: 663-669. https://doi.org/10.1016/j.cej.2016.05.072.
He SY, Zhu F, Li LW, Ren WT, Box-Behnken design for the optimization of the removal of Cr(VI) in soil leachate using nZVI/Ni bimetallic particles, Soil & Sediment Contamination 2018; 27: 658-673. https://doi.org/10.1080/15320383.2018.1502744.
Zhu F, Li LW, Ren WT, Deng XQ, Liu T, Effect of pH, temperature, humic acid and coexisting anions on reduction of Cr(VI) in the soil leachate by nZVI/Ni bimetal material, Environmental Pollution 2017; 227: 444-450. https://doi.org/10.1016/j.envpol.2017.04.074.
Shan A, Idrees A, Zaman WQ, Abbas Z, Ali M, Rehman MSU, Hussain S, Danish M, Gu XG, Lyu SG, Synthesis of nZVI-Ni@BC composite as a stable catalyst to activate persulfate: Trichloroethylene degradation and insight mechanism, Journal Of Environmental Chemical Engineering 2021; 9: 104808. https://doi.org/10.1016/j.jece.2020.104808.
Yan JC, Han L, Gao WG, Xue S, Chen MF, Biochar supported nanoscale zerovalent iron composite used as persulfate activator for removing trichloroethylene, Bioresource Technology 2015; 175: 269-274. https://doi.org/10.1016/j.biortech.2014.10.103.
Ahmad A, Gu XG, Li L, Lv SG, Xu YS, Guo XH, Efficient degradation of trichloroethylene in water using persulfate activated by reduced graphene oxide-iron nanocomposite, Environ. Sci. Pollut. Res. 2015; 22: 17876-17885. https://doi.org/10.1007/s11356-015-5034-1.
Hussain I, Li MY, Zhang YQ, Li YC, Huang SB, Du XD, Liu GQ, Hayat W, Anwar N, Insights into the mechanism of persulfate activation with nZVI/BC nanocomposite for the degradation of nonylphenol, Chemical Engineering Journal 2017; 311: 163-172. https://doi.org/10.1016/j.cej.2016.11.085.
Huang JY, Yi SP, Zheng CM, Lo IMC, Persulfate activation by natural zeolite supported nanoscale zero-valent iron for trichloroethylene degradation in groundwater, Sci Total Environ 2019; 684: 351-359. https://doi.org/10.1016/j.scitotenv.2019.05.331.
Gu MB, Sui Q, Farooq U, Zhang X, Qiu ZF, Lyu SG, Degradation of phenanthrene in sulfate radical based oxidative environment by nZVI-PDA functionalized rGO catalyst, Chemical Engineering Journal 2018; 354: 541-552. https://doi.org/10.1016/j.cej.2018.08.039.
Chen XY, Wang WP, Xiao H, Hong CL, Zhu FX, Yao YL, Xue ZY, Accelerated TiO2 photocatalytic degradation of Acid Orange 7 under visible light mediated by peroxymonosulfate, Chemical Engineering Journal 2012; 193: 290-295. https://doi.org/10.1016/j.cej.2012.04.033.
Wang Y, Chen SY, Yang X, Huang XF, Yang YH, He EK, Wang SQ, Qiu RL, Degradation of 2,2 ',4,4 '-tetrabromodiphenyl ether (BDE-47) by a nano zerovalent iron-activated persulfate process: The effect of metal ions, Chemical Engineering Journal 2017; 317: 613-622. https://doi.org/10.1016/j.cej.2017.02.070.
Wang JL, Wang SZ, Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants, Chemical Engineering Journal 2018; 334: 1502-1517. https://doi.org/10.1016/j.cej.2017.11.059.
Rahmani AR, Poormohammadi A, Zamani F, Birgani YT, Jorfi S, Gholizadeh S, Mohammadi MJ, Almasi H, Activated persulfate by chelating agent Fe /complex for in situ degradation of phenol: intermediate identification and optimization study, Research on Chemical Intermediates 2018; 44: 5501-5519. https://doi.org/10.1007/s11164-018-3436-7.
Kang YG, Yoon H, Lee W, Kim EJ, Chang YS, Comparative study of peroxide oxidants activated by nZVI: Removal of 1,4-Dioxane and arsenic(III) in contaminated waters, Chemical Engineering Journal 2018; 334: 2511-2519. https://doi.org/10.1016/j.cej.2017.11.076.
Qu GZ, Chu RJ, Wang H, Wang TC, Zhang ZQ, Qiang H, Liang DL, Hu SB, Simultaneous removal of chromium(VI) and tetracycline hydrochloride from simulated wastewater by nanoscale zero-valent iron/copper-activated persulfate, Environmental Science And Pollution Research 2020; 27: 40826-40836. https://doi.org/10.1007/s11356-020-10120-8.
Wang QF, Rao PH, Li GH, Dong L, Zhang X, Shao YS, Gao NY, Chu WH, Xu B, An N, Deng J, Degradation of imidacloprid by UV-activated persulfate and peroxymonosulfate processes: Kinetics, impact of key factors and degradation pathway, Ecotoxicology And Environmental Safety 2020; 187: 109779. https://doi.org/10.1016/j.ecoenv.2019.109779.
Dhaka S, Kumar R, Lee SH, Kurade MB, Jeon BH, Degradation of ethyl paraben in aqueous medium using advanced oxidation processes: Efficiency evaluation of UV-C supported oxidants, Journal Of Cleaner Production 2018; 180: 505-513. https://doi.org/10.1016/j.jclepro.2018.01.197.
Fedorov K, Plata-Gryl M, Khan JA, Boczkaj G, Ultrasound-assisted heterogeneous activation of persulfate and peroxymonosulfate by asphaltenes for the degradation of BTEX in water, Journal Of Hazardous Materials 2020; 397: 122804. https://doi.org/10.1016/j.jhazmat.2020.122804.
Wang ZH, Ai LY, Huang Y, Zhang JK, Li ST, Chen JW, Yang F, Degradation of azo dye with activated peroxygens: when zero-valent iron meets chloride, Rsc Advances 2017; 7: 30941-30948. https://doi.org/10.1039/c7ra03872k.
Kilic MY, Abdelraheem WH, He XX, Kestioglu K, Dionysiou DD, Photochemical treatment of tyrosol, a model phenolic compound present in olive mill wastewater, by hydroxyl and sulfate radical-based advanced oxidation processes (AOPs), Journal Of Hazardous Materials 2019; 367: 734-742. https://doi.org/10.1016/j.jhazmat.2018.06.062.
Rehman F, Sayed M, Khan JA, Shah NS, Khan HM, Dionysiou DD, Oxidative removal of brilliant green by UV/S2O82-, UV/HSO5- and UV/H2O2 processes in aqueous media: A comparative study, Journal Of Hazardous Materials 2018; 357: 506-514. https://doi.org/10.1016/j.jhazmat.2018.06.012.
Zuo SY, Li DY, Xu HM, Xia DS, An integrated microwave-ultraviolet catalysis process of four peroxides for wastewater treatment: Free radical generation rate and mechanism, Chemical Engineering Journal 2020; 380: 122434. https://doi.org/10.1016/j.cej.2019.122434.
Yan JC, Qian LB, Gao WG, Chen Y, Ouyang D, Chen MF, Enhanced Fenton-like Degradation of Trichloroethylene by Hydrogen Peroxide Activated with Nanoscale Zero Valent Iron Loaded on Biochar, Scientific Reports 2017; 7: 43051. https://doi.org/10.1038/srep43051.
Liang CJ, Su HW, Identification of Sulfate and Hydroxyl Radicals in Thermally Activated Persulfate, Industrial & Engineering Chemistry Research 2009; 48: 5558-5562. https://doi.org/10.1021/ie9002848.
Dong HR, Wang B, Li L, Wang YY, Ning Q, Tian R, Li R, Chen J, Xie QQ, Activation of persulfate and hydrogen peroxide by using sulfide-modified nanoscale zero-valent iron for oxidative degradation of sulfamethazine: A comparative study, Separation And Purification Technology 2019; 218: 113-119. https://doi.org/10.1016/j.seppur.2019.02.052.
Wang W, Li SL, Lei H, Pan BC, Zhang WX, Enhanced separation of nanoscale zero-valent iron (nZVI) using polyacrylamide: Performance, characterization and implication, Chemical Engineering Journal 2015; 260: 616-622. https://doi.org/10.1016/j.cej.2014.09.042.
Zhu F, He SY, Liu T, Effect of pH, temperature and co-existing anions on the Removal of Cr(VI) in groundwater by green synthesized nZVI/Ni, Ecotoxicology And Environmental Safety 2018; 163: 544-550. https://doi.org/10.1016/j.ecoenv.2018.07.082.
Zhu F, Liu T, Zhang ZC, Liang WJ, Remediation of hexavalent chromium in column by green synthesized nanoscale zero-valent iron/nickel: Factors, migration model and numerical simulation, Ecotoxicology And Environmental Safety 2021; 207: 111572. https://doi.org/10.1016/j.ecoenv.2020.111572.
Kim C, Ahn JY, Kim TY, Shin WS, Hwang I, Activation of Persulfate by Nanosized Zero-Valent Iron (NZVI): Mechanisms and Transformation Products of NZVI, Environmental Science & Technology 2018; 52: 3625-3633. https://doi.org/10.1021/acs.est.7b05847.
Wu LB, Lin QT, Fu HY, Luo HY, Zhong QF, Li JQ, Chen YJ, Role of sulfide-modified nanoscale zero-valent iron on carbon nanotubes in nonradical activation of peroxydisulfate, Journal Of Hazardous Materials 2022; 422: 126949. https://doi.org/10.1016/j.jhazmat.2021.126949.
Li H, Song L, Han BH, Song HW, Improved sludge dewaterability using persulfate activated by humic acid supported nanoscale zero-valent iron: effect on sludge characteristics and reaction mechanisms, Environmental Science-Water Research & Technology 2018; 4: 1480-1488. https://doi.org/10.1039/c8ew00379c.
Zhang YL, Su YM, Zhou XF, Dai CM, Keller Arturo A., A new insight on the core-shell structure of zerovalent iron nanoparticles and its application for Pb(II) sequestration, Journal Of Hazardous Materials 2013; 263: 685-693. https://doi.org/10.1016/j.jhazmat.2013.10.031.
Lin CC, Chen YH, Feasibility of using nanoscale zero-valent iron and persulfate to degrade sulfamethazine in aqueous solutions, Separation And Purification Technology 2018; 194: 388-395. https://doi.org/10.1016/j.seppur.2017.10.073.
Rodriguez-Chueca J, Guerra-Rodriguez S, Raez JM., Lopez-Munoz MJ, Rodriguez E, Assessment of different iron species as activators of S2O82- and HSO5- for inactivation of wild bacteria strains, Applied Catalysis B-Environmental 2019; 248: 54-61. https://doi.org/10.1016/j.apcatb.2019.02.003.
Li LX, Zhang SS, Lu B, Zhu F, Cheng J, Sun ZH, Nitrobenzene reduction using nanoscale zero-valent iron supported by polystyrene microspheres with different surface functional groups, Environmental Science And Pollution Research 2018; 25: 7916-7923. https://doi.org/10.1007/s11356-017-0854-9.
Wu JX, Wang B, Blaney L, Peng GL, Chen P, Cui YZ, Deng SB, Wang YJ, Huang J, Yu G, Degradation of sulfamethazine by persulfate activated with organo-montmorillonite supported nano- zero valent iron, Chemical Engineering Journal 2019; 361: 99-108. https://doi.org/10.1016/j.cej.2018.12.024.
Zhang TT, Yang YL, Gao JF, Li X, Yu HK, Wang N, Du P, Yu R, Li H, Fan XY, Zhou ZW, Synergistic degradation of chloramphenicol by ultrasound-enhanced nanoscale zero-valent iron/persulfate treatment, Separation And Purification Technology 2020; 240: 116575. https://doi.org/10.1016/j.seppur.2020.116575.
Han WL, Dong LY, Activation Methods of Advanced Oxidation Processes Based on Sulfate Radical and Their Applications in The Degradation of Organic Pollutants, Progress In Chemistry 2021; 33: 1426-1439. https://doi.org/10.7536/pc200771.
Xia SQ, Gu ZL, Zhang ZQ, Zhang J, Hermanowicz SW, Removal of chloramphenicol from aqueous solution by nanoscale zero-valent iron particles, Chemical Engineering Journal 2014; 257: 98-104. https://doi.org/10.1016/j.cej.2014.06.106.
Luo S, Wei ZS, Spinney R, Villamena FA, Dionysiou DD, Chen D, Tang CJ, Chai LY, Xiao RY, Quantitative structure-activity relationships for reactivities of sulfate and hydroxyl radicals with aromatic contaminants through single-electron transfer pathway, Journal Of Hazardous Materials 2018; 344: 1165-1173. https://doi.org/10.1016/j.jhazmat.2017.09.024.
Ma B, Wang YY, Tong XL, Guo XN, Zheng ZF, Guo XY, Graphene-supported CoS2 particles: an efficient photocatalyst for selective hydrogenation of nitroaromatics in visible light, Catalysis Science & Technology 2017; 7: 2805-2812. https://doi.org/10.1039/c7cy00356k.
Zhang DJ, Li Y, Sun AW, Tong SQ, Jiang XB, Mu Y, Li JS, Han WQ, Sun XY, Wang LJ, Shen JY, Optimization ofS/Fe ratio for enhanced nitrobenzene biological removal in anaerobic System amended with Sulfide-modified nanoscale zerovalent iron, Chemosphere 2020; 247: 125832. https://doi.org/10.1016/j.chemosphere.2020.125832.
Wang B, Zhu C, Ai D, Fan ZP, Activation of persulfate by green nano-zero-valent iron-loaded biochar for the removal of p-nitrophenol: Performance, mechanism and variables effects, Journal Of Hazardous Materials 2021; 417: 126106. https://doi.org/10.1016/j.jhazmat.2021.126106.
Du JK, Wang Y, Faheem, Xu TT, Zheng H, Bao JG, Synergistic degradation of PNP via coupling H2O2 with persulfate catalyzed by nano zero valent iron, Rsc Advances 2019; 9: 20323-20331. https://doi.org/10.1039/c9ra02901j.
Anipsitakis, George P, Dionysiou, Dionysios D, Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt, Environmental science & technology 2003; 37: 4790-7. https://doi.org/10.1021/es0263792.
Dong HR, Hou KJ, Qiao WW, Cheng YJ, Zhang LH, Wang B, Li L, Wang YY, Ning Q, Zeng GM, Insights into enhanced removal of TCE utilizing sulfide-modified nanoscale zero-valent iron activated persulfate, Chemical Engineering Journal 2019; 359: 1046-1055. https://doi.org/10.1016/j.cej.2018.11.080.
Ding CX, Xiao SJ, Lin YJ, Yu P, Zhong ME, Yang LH, Wang H, Su L, Liao CJ, Zhou YY, Deng YC, Gong DX, Attapulgite-supported nano-Fe-0/peroxymonsulfate for quinclorac removal: Performance, mechanism and degradation pathway, Chemical Engineering Journal 2019; 360: 104-114. https://doi.org/10.1016/j.cej.2018.11.189.
Wu SH, He HJ, Li X, Yang CP, Zeng GM, Wu B, He SY, Lu L, Insights into atrazine degradation by persulfate activation using composite of nanoscale zero-valent iron and graphene: Performances and mechanisms, Chemical Engineering Journal 2018; 341: 126-136. https://doi.org/10.1016/j.cej.2018.01.136.
Li HH, Zhu F, He SY, The degradation of decabromodiphenyl ether in the e-waste site by biochar supported nanoscale zero-valent iron/persulfate, Ecotoxicology And Environmental Safety 2019; 183: 109540. https://doi.org/10.1016/j.ecoenv.2019.109540.
Huang KC, Zhao Z.Q, Hoag GE., Dahmani A, Block PA, Degradation of volatile organic compounds with thermally activated persulfate oxidation, Chemosphere 2005; 61: 551-560. https://doi.org/10.1016/j.chemosphere.2005.02.032.
Zhu F, Wu YY, Liang YK, Li HH, Liang WJ, Degradation mechanism of norfloxacin in water using persulfate activated by BC@nZVI/Ni, Chemical Engineering Journal 2020; 389: 124276. https://doi.org/10.1016/j.cej.2020.124276.
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