Abstract
Advanced oxidation processes (AOPs) based on peroxymonosulfate (PMS) activation have attracted much attention in wastewater treatment. Here, a series of (NH4)2Mo3S13/MnFe2O4 (MSMF) composites were prepared and used as PMS activators to remove tetracycline (TC) for the first time. When the mass ratio of (NH4)2Mo3S13 to MnFe2O4 was 4.0 (MSMF4.0), the composite showed remarkable catalytic efficiency for activating PMS to remove TC. Over 93% of TC was removed in MSMF4.0/PMS system in 20 min. The aqueous •OH as well as the surface SO4•− and •OH were the primary reactive species for TC degradation in MSMF4.0/PMS system, and the comprehensive experimental results excluded the contributions of aqueous SO4•−, O2•−, and 1O2, high-valent metal-oxo species, and surface-bound PMS. The Mn(II)/Mn(III), Fe(II)/Fe(III), Mo(IV)/Mo(VI), and S2−/SOx2− all contributed to the catalytic process. MSMF4.0 also showed excellent activity and stability after five cycles and significant degradation efficiency for a variety of pollutants. This work will provide theoretical basis for applying MnFe2O4-based composites in PMS-based AOPs.
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The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request.
References
Ali J, Shahzad A, Wang J, Ifthikar J, Lei W, Aregay G, Chen Z, Chen Z (2021) Modulating the redox cycles of homogenous Fe(III)/PMS system through constructing electron rich thiomolybdate centres in confined layered double hydroxides. Chem Eng J 408:127242. https://doi.org/10.1016/j.cej.2020.127242
Bai R, Yan W, **ao Y, Wang S, Tian X, Li J, **ao X, Lu X, Zhao F (2020) Acceleration of peroxymonosulfate decomposition by a magnetic MoS2/CuFe2O4 heterogeneous catalyst for rapid degradation of fluoxetine. Chem Eng J 397:125501. https://doi.org/10.1016/j.cej.2020.125501
Bai Z, Wang S, Tian J, Gao S, Zhang R, Liu X (2022) Aluminum-based layered metal oxides activating peroxymonosulfate for bisphenol A degradation via surface-bound sulfate radicals and singlet oxygen. J Hazard Mater 424:127515. https://doi.org/10.1016/j.jhazmat.2021.127515
Chen J, Zhang L, Huang T, Li W, Wang Y, Wang Z (2016) Decolorization of azo dye by peroxymonosulfate activated by carbon nanotube: radical versus non-radical mechanism. J Hazard Mater 320:571–580. https://doi.org/10.1016/j.jhazmat.2016.07.038
Chen G, Zhang X, Gao Y, Zhu G, Cheng Q, Cheng X (2019) Novel magnetic MnO2/MnFe2O4 nanocomposite as a heterogeneous catalyst for activation of peroxymonosulfate (PMS) toward oxidation of organic pollutants. Sep Purif Technol 213:456–464. https://doi.org/10.1016/j.seppur.2018.12.049
Deng J, Xu M, Qiu C, Chen Y, Ma X, Gao N, Li X (2018) Magnetic MnFe2O4 activated peroxymonosulfate processes for degradation of bisphenol A: performance, mechanism and application feasibility. Appl Surf Sci 459:138–147. https://doi.org/10.1016/j.apsusc.2018.07.198
Ding S, Zhou B, Chen C, Huang Z, Li P, Wang S, Cao G, Zhang M (2020) Sulfur-rich (NH4)2Mo3S13 as a highly reversible anode for sodium/potassium-ion batteries. ACS Nano 14:9626–9636. https://doi.org/10.1021/acsnano.0c00101
Dong H, Guo X, Yin Y (2018) A facile synthesis of goethite-modified g-C3N4 composite for photocatalytic degradation of tylosin in an aqueous solution. Res Chem Intermediat 44:3151–3167. https://doi.org/10.1007/s11164-018-3298-z
Fu H, Ma S, Zhao P, Xu S, Zhan S (2019a) Activation of peroxymonosulfate by graphitized hierarchical porous biochar and MnFe2O4 magnetic nanoarchitecture for organic pollutants degradation: structure dependence and mechanism. Chem Eng J 360:157–170. https://doi.org/10.1016/j.cej.2018.11.207
Fu H, Zhao P, Xu S, Cheng G, Li Z, Li Y, Li K, Ma S (2019) Fabrication of Fe3O4 and graphitized porous biochar composites for activating peroxymonosulfate to degrade p-hydroxybenzoic acid: Insights on the mechanism. Chem Eng J 375:121980. https://doi.org/10.1016/j.cej.2019.121980
Ge L, Yue Y, Wang W, Tan F, Zhang S, Wang X, Qiao X, Wong P (2021) Efficient degradation of tetracycline in wide pH range using MgNCN/MgO nanocomposites as novel H2O2 activator. Water Res 198:117149. https://doi.org/10.1016/j.watres.2021.117149
Guo Y, Yan L, Li X, Yan T, Song W, Hou T, Tong C, Mu J, Xu M (2021) Goethite/biochar-activated peroxymonosulfate enhances tetracycline degradation: inherent roles of radical and non-radical processes. Sci Total Environ 783:147102. https://doi.org/10.1016/j.scitotenv.2021.147102
He M, Zhao P, Duan R, Xu S, Cheng G, Li M, Ma S (2022) Insights on the electron transfer pathway of phenolic pollutant degradation by endogenous N-doped carbonaceous materials and peroxymonosulfate system. J Hazard Mater 424:127568. https://doi.org/10.1016/j.jhazmat.2021.127568
He Y, Qian J, Wang P, Wu J, Lu B, Tang S, Gao P (2022) Acceleration of levofloxacin degradation by combination of multiple free radicals via MoS2 anchored in manganese ferrite doped perovskite activated PMS under visible light. Chem Eng J 431:133933. https://doi.org/10.1016/j.cej.2021.133933
Holzapfel P, Buhler M, Escalera-Lopez D, Bierling M, Speck F, Mayrhofer K, Cherevko S, Pham C, Thiele S (2020) Fabrication of a robust PEM water electrolyzer based on non-noble metal cathode catalyst: [Mo3S13]2− clusters anchored to N-doped carbon nanotubes. Small 16:2003161. https://doi.org/10.1002/smll.202003161
Hu P, Long M (2016) Cobalt-catalyzed sulfate radical-based advanced oxidation: a review on heterogeneous catalysts and applications. Appl Catal B Environ 181:103–117. https://doi.org/10.1016/j.apcatb.2015.07.024
Jiang N, Xu H, Wang L, Jiang J, Zhang T (2020) Nonradical oxidation of pollutants with single-atom-Fe(III)-activated persulfate: Fe(V) being the possible intermediate oxidant. Environ Sci Technol 54:14057–14065. https://doi.org/10.1021/acs.est.0c04867
** Q, Zhang S, Wen T, Wang J, Gu P, Zhao G, Wang X, Chen Z, Hayat T, Wang X (2018) Simultaneous adsorption and oxidative degradation of Bisphenol A by zero-valent iron/iron carbide nanoparticles encapsulated in N-doped carbon matrix. Environ Pollut 243:218–227. https://doi.org/10.1016/j.envpol.2018.08.061
Lei Y, Yang M, Hou J, Wang F, Cui E, Kong C, Min S (2018) Thiomolybdate [Mo3S13]2- nanocluster: a molecular mimic of MoS2 active sites for highly efficient photocatalytic hydrogen evolution. Chem Commun 54:603–606. https://doi.org/10.1039/c7cc08178b
Li X, Hou T, Yan L, Shan L, Meng X, Zhao Y (2020) Efficient degradation of tetracycline by CoFeLa-layered double hydroxides catalyzed peroxymonosulfate: synergistic effect of radical and nonradical pathways. J Hazard Mater 398:122884. https://doi.org/10.1016/j.jhazmat.2020.122884
Li Y, Ma S, Xu S, Fu H, Li Z, Li K, Sheng K, Du J, Lu X, Li X, Liu S (2020) Novel magnetic biochar as an activator for peroxymonosulfate to degrade bisphenol A: emphasizing the synergistic effect between graphitized structure and CoFe2O4. Chem Eng J 387:124094. https://doi.org/10.1016/j.cej.2020.124094
Li K, Ma S, Xu S, Fu H, Li Z, Li Y, Liu S, Du J (2021) The mechanism changes during bisphenol A degradation in three iron functionalized biochar/peroxymonosulfate systems: the crucial roles of iron contents and graphitized carbon layers. J Hazard Mater 404:124145. https://doi.org/10.1016/j.jhazmat.2020.124145
Li Z, Li K, Ma S, Dang B, Li Y, Fu H, Du J, Meng Q (2021b) Activation of peroxymonosulfate by iron-biochar composites: comparison of nanoscale Fe with single-atom Fe. J Colloid Interface Sci 582:598–609. https://doi.org/10.1016/j.jcis.2020.08.049
Li H, Yuan N, Qian J, Pan B (2022a) Mn2O3 as an electron shuttle between peroxymonosulfate and organic pollutants: the dominant role of surface reactive Mn(IV) species. Environ Sci Technol 56:4498–4506. https://doi.org/10.1021/acs.est.1c08790
Li X, Wang L, Guo Y, Song W, Li Y, Yan L (2022) Goethite-MoS2 hybrid with dual active sites boosted peroxymonosulfate activation for removal of tetracycline: the vital roles of hydroxyl radicals and singlet oxygen. Chem Eng J 450:138104. https://doi.org/10.1016/j.cej.2022.138104
Liang J, Xu X, Qamar Zaman W, Hu X, Zhao L, Qiu H, Cao X (2019) Different mechanisms between biochar and activated carbon for the persulfate catalytic degradation of sulfamethoxazole: roles of radicals in solution or solid phase. Chem Eng J 375:121908. https://doi.org/10.1016/j.cej.2019.121908
Liu Y, Wang L, Dong Y, Peng W, Fu Y, Li Q, Fan Q, Wang Y, Wang Z (2021) Current analytical methods for the determination of persulfate in aqueous solutions: a historical review. Chem Eng J 416:129143. https://doi.org/10.1016/j.cej.2021.129143
Lyu C, He D, Mou Z, Yang X (2019) Synergetic activation of peroxymonosulfate by MnO2-loaded β-FeOOH catalyst for enhanced degradation of organic pollutant in water. Sci Total Environ 693:133589. https://doi.org/10.1016/j.scitotenv.2019.133589
Meng X, He Q, Song T, Ge M, He Z, Guo C (2022) Activation of peroxydisulfate by magnetically separable rGO/MnFe2O4 toward oxidation of tetracycline: efficiency, mechanism and degradation pathways. Sep Purif Technol 282:120137. https://doi.org/10.1016/j.seppur.2021.120137
Pan J, Gao B, Duan P, Guo K, Akram M, Xu X, Yue Q, Gao Y (2021) Improving peroxymonosulfate activation by copper ion-saturated adsorbent-based single atom catalysts for the degradation of organic contaminants: electron-transfer mechanism and the key role of Cu single atoms. J Mater Chem A 9:11604–11613. https://doi.org/10.1039/d1ta02237g
Rajagopal A, Akbarzadeh E, Li C, Mitoraj D, Krivtsov I, Adler C, Diemant T, Biskupek J, Kaiser U, Im C, Heiland M, Jacob T, Streb C, Dietzek B, Beranek R (2020) Polymeric carbon nitride coupled with a molecular thiomolybdate catalyst: exciton and charge dynamics in light-driven hydrogen evolution. Sustain Energy Fuels 4:6085–6095. https://doi.org/10.1039/d0se01366h
Song Y, Sun D, Liu C, Ma H, Ma H, Ma C (2022) Peroxymonosulfate activation through ferromagnetic bimetallic spinel sulfide composite (Fe3O4/NiCo2S4) for organic pollutant degradation. Chemosphere 307:135682. https://doi.org/10.1016/j.chemosphere.2022.135682
Su X, Guo Y, Yan L, Wang Q, Zhang W, Li X, Song W, Li Y, Liu G (2022) MoS2 nanosheets vertically aligned on biochar as a robust peroxymonosulfate activator for removal of tetracycline. Sep Purif Technol 282:120118. https://doi.org/10.1016/j.seppur.2021.120118
Sun Y, Li H, Zhang S, Hua M, Qian J, Pan B (2022) Revisiting the heterogeneous peroxymonosulfate activation by MoS2: a surface Mo–peroxymonosulfate complex as the major reactive species. ACS EST Water 2:376–384. https://doi.org/10.1021/acsestwater.1c00459
Tan C, Gao N, Fu D, Deng J, Deng L (2017) Efficient degradation of paracetamol with nanoscaled magnetic CoFe2O4 and MnFe2O4 as a heterogeneous catalyst of peroxymonosulfate. Sep Purif Technol 175:47–57. https://doi.org/10.1016/j.seppur.2016.11.016
Wang L, Xu H, Jiang N, Pang S, Jiang J, Zhang T (2021) Effective activation of peroxymonosulfate with natural manganese-containing minerals through a nonradical pathway and the application for the removal of bisphenols. J Hazard Mater 417:126152. https://doi.org/10.1016/j.jhazmat.2021.126152
Wang Q, Yan L, Wang L, Zhang W, Guo Y, Song W, Li X (2022) Enhanced peroxymonosulfate activation by (NH4)2Mo3S13 for organic pollutant removal: crucial roles of adsorption and singlet oxygen. J Environ Chem Eng 10:107966. https://doi.org/10.1016/j.jece.2022.107966
Wang X, Wang H, Li F, Hu X, **e Z, Hua T (2022) Activation of peroxymonosulfate in an electrochemical filter by MnFe2O4-rGO electro-assisted catalytic membrane for the degradation of oxytetracycline. J Environ Chem Eng 10:107008. https://doi.org/10.1016/j.jece.2021.107008
Wei H, Peng T, Wang B, Zhang Y (2022) Synthesis of conjugated polyvinyl chloride derivative coupled MnFe2O4 nanoparticles as a magnetic visible-light photocatalyst. Colloids and Surf A Physicochem Eng Asp 649:129510. https://doi.org/10.1016/j.colsurfa.2022.129510
Wu L, Guo P, Wang X, Li H, Zhang X, Chen K, Zhou P (2022) The synergy of sulfur vacancies and heterostructure on CoS@FeS nanosheets for boosting the peroxymonosulfate activation. Chem Eng J 446:136759. https://doi.org/10.1016/j.cej.2022.136759
Wu Z, Song W, Xu X, Yuan J, Lv W, Yao Y (2022) High 1T phase and sulfur vacancies in C-MoS2@Fe induced by ascorbic acid for synergistically enhanced contaminants degradation. Sep Purif Technol 286:120511. https://doi.org/10.1016/j.seppur.2022.120511
** T, Li X, Zhang Q, Liu N, Niu S, Dong Z, Lyu C (2021) Enhanced catalytic oxidation of 2,4-dichlorophenol via singlet oxygen dominated peroxymonosulfate activation on CoOOH@Bi2O3 composite. Front Environ Sci Eng 15:55. https://doi.org/10.1007/s11783-020-1347-5
Yang L, Chen H, Jia F, Peng W, Tian X, **a L, Wu X, Song S (2021a) Emerging hexagonal Mo2C nanosheet with (002) facet exposure and Cu incorporation for peroxymonosulfate activation toward antibiotic degradation. ACS Appl Mater Interfaces 13:14342–14354. https://doi.org/10.1021/acsami.1c03601
Yang T, Ma T, Yang L, Dai W, Zhang S, Luo S (2021) A self-supporting UiO-66 photocatalyst with Pd nanoparticles for efficient degradation of tetracycline. Appl Surf Sci 544:148928. https://doi.org/10.1016/j.apsusc.2021.148928
Zhang H, Wang X, Li Y, Zuo K, Lyu C (2021) A novel MnOOH coated nylon membrane for efficient removal of 2,4-dichlorophenol through peroxymonosulfate activation. J Hazard Mater 414:125526. https://doi.org/10.1016/j.jhazmat.2021.125526
Zhang X, Yang Y, Hao Ngo H, Guo W, Long T, Wang X, Zhang J, Sun F (2022) Enhancement of urea removal from reclaimed water using thermally modified spent coffee ground biochar activated by adding peroxymonosulfate for ultrapure water production. Bioresource Technol 349:126850. https://doi.org/10.1016/j.biortech.2022.126850
Zhou X, Kong L, **g Z, Wang S, Lai Y, **e M, Ma L, Feng Z, Zhan J (2020) Facile synthesis of superparamagnetic β-CD-MnFe2O4 as a peroxymonosulfate activator for efficient removal of 2,4-dichlorophenol: structure, performance, and mechanism. J Hazard Mater 394:122528. https://doi.org/10.1016/j.jhazmat.2020.122528
Funding
This work was funded by the National Natural Science Foundation of China (22206057), Shandong Provincial Natural Science Foundation (ZR2020QB142), and the Science and Technology Program of University of **an (No. XKY1810).
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Xuguang Li: conceptualization, methodology, formal analysis, writing—original draft, funding acquisition; Qiaodi Wang: investigation, conceptualization, data curation, writing—original draft; **aoyu Zheng: methodology, data curation, writing—review and editing; Le Wang: investigation, methodology, formal analysis; Wei Zhang: investigation, methodology; Wen Song: formal analysis, writing—review and editing; Yanfei Li: conceptualization, formal analysis; Weiyan Pan: investigation, methodology; Tianyang Zhao: investigation, methodology; Liangguo Yan: conceptualization, project administration, funding acquisition, supervision, writing—review and editing.
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Highlights
• (NH4)2Mo3S13/MnFe2O4 composites were efficient PMS activators.
• Both aqueous and surface reactive species contributed to TC degradation.
• Mn, Fe, Mo, and S were involved in the activation of PMS.
• The catalyst still showed excellent activity and stability after five cycles.
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Li, X., Wang, Q., Zheng, X. et al. (NH4)2Mo3S13/MnFe2O4 hybrid with multiple active sites boosted activation of peroxymonosulfate for removal of tetracycline. Environ Sci Pollut Res 30, 67485–67498 (2023). https://doi.org/10.1007/s11356-023-26967-6
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DOI: https://doi.org/10.1007/s11356-023-26967-6