Citation: Yu-Ke ZHU, Xiao-Jia JIANG, Jia-Yi CHEN, Xiao-Hang FU, Li-Guang WU, Ting WANG. Mechanism and pathways for degrading tetracycline via photocatalytic synergistic peroxysulfate-activated catalytic oxidation[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(10): 1857-1868. doi: 10.11862/CJIC.2023.164 shu

Mechanism and pathways for degrading tetracycline via photocatalytic synergistic peroxysulfate-activated catalytic oxidation

Yu-Ke ZHU ¹ ,
Xiao-Jia JIANG ^{1, 2} ,
Jia-Yi CHEN ¹ ,
Xiao-Hang FU ¹ ,
Li-Guang WU ¹ ,
Ting WANG ^{1, 2,,}

1.
School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310012, China
2.
Instrumental Analysis Center, Zhejiang Gongshang University, Hangzhou 310012, China

Corresponding author: Ting WANG, zjwtwaiting@hotmail.com
Received Date: 26 May 2023
Revised Date: 22 June 2023

Figures(10)

Aiming at enhancing the degradation efficiency of antibiotics in slightly polluted water bodies, the photocatalytic synergistic sodium peroxysulfate (PDS)-activated catalytic oxidation using chiral mesoporous TiO₂ under irradiation of visible light (PDS/vis-TiO₂) was employed to degrade tetracycline (TC). The differences in active species and degradation pathways of PDS activation (PDS/TiO₂), visible light photocatalysis (vis-TiO₂), and PDS/vis-TiO₂ systems using mesoporous TiO₂ as catalysts for TC degradation were comparatively studied. The results showed that the asymmetric helical stacking structure introduced abundant Ti³⁺ into chiral mesoporous TiO₂, not only improving its visible light response but also activating PDS by Ti³⁺/Ti⁴⁺ couples to form free radicals. Both the photogenerated holes h⁺ and the free radicals (like ·OH) in the PDS/vis-TiO₂ system could simultaneously participate in TC degradation. Within 5 h, the removal rate of TC (the concentration of TC in the solution was 5 mg·L^-1) using the PDS/vis-TiO₂ system could reach over 95%, far exceeding that of the PDS/TiO₂ system (with a TC removal rate of 48.9%) and the vis-TiO₂ system (with a TC removal rate of 71.1%). PDS/vis-TiO₂ system had a high removal rate of TC in solutions with different concentrations, and the degradation all followed a first-order kinetic reaction process. Even when the initial concentration of TC reached 15 mg·L^-1, the 5 h removal rate of TC by PDS/vis-TiO₂ system could still reach 67.2%, which further indicated that the PDS synergistic photocatalysis had an effective ability to degrade TC. However, the removal rate of TC at low concentrations by PDS/vis-TiO₂ was faster than using the same amount of TiO₂ catalyst and PDS. Added PDS in the photocatalytic system would be activated by the photo-generated electrons to generate free radicals, which then consume photo-generated electrons to improve the separation rate of photo-generated holes and electrons, thus achieving synergistic enhancement on the pollutant degradation. Additionally, the free radicals after PDS activation would also enhance TC degradation. The density functional theory calculation and intermediate product analysis results indicate that the degradation pathway of TC in the PDS/vis-TiO₂ system includes the degradation pathway of attacking TC by h⁺, as well as the degradation pathway of TC after the free radicals attack.
- chiral mesoporous TiO₂,
- visible light photocatalysis,
- peroxysulfate activation,
- tetracycline,
- degradation pathway
1. [1]
  Makkaew P, Kongprajug A, Chyerochana N, Sresung M, Precha N, Mongkolsuk S, Sirikanchana K. Persisting antibiotic resistance gene pollution and its association with human sewage sources in tropical marine beach waters[J]. Int. J. Hyg. Environ. Health, 2021,238113859. doi: 10.1016/j.ijheh.2021.113859
2. [2]
  GAO H, LI B, YAO Z W. Advances in research on the presence and environmental behavior of antibiotics in the marine environment[J]. Huanjing Huaxue-Environmental Chemistry, 2023,42(3):779-791.
3. [3]
  Lyu J, Yang L S, Zhang L, Ye B X, Wang L. Antibiotics in soil and water in China - A systematic review and source analysis[J]. Environ. Pollut., 2020,266(1)115147.
4. [4]
  Li S S, Gao H, Zhang H B, Wei G K, Shu Q, Li R J, Jin S C, Na G S, Shi Y L. The fate of antibiotic resistance genes in the coastal lagoon with multiple functional zones[J]. J. Environ. Sci., 2023,128:93-106. doi: 10.1016/j.jes.2022.07.021
5. [5]
  Hiller C X, Hubner U, Fajnorova S, Schwartz T, Drewes J E. Antibiotic microbial resistance (AMR) removal efficiencies by conventional and advanced wastewater treatment processes: A review[J]. Sci. Total Environ., 2019,685:596-608. doi: 10.1016/j.scitotenv.2019.05.315
6. [6]
  Wei Z D, Liu J Y, Shangguan W. A review on photocatalysis in antibiotic wastewater: Pollutant degradation and hydrogen production[J]. Chin. J. Catal., 2020,41(10):1440-1450. doi: 10.1016/S1872-2067(19)63448-0
7. [7]
  Zhu T T, Su Z X, Lai W X, Zhang Y B, Liu Y W. Insights into the fate and removal of antibiotics and antibiotic resistance genes using biological wastewater treatment technology[J]. Sci. Total Environ., 2021,776145906. doi: 10.1016/j.scitotenv.2021.145906
8. [8]
  WANG J L, DONG M R, ZHANG Q C, LIN W S, XING Y. Preparation of Bi₂MoO₆ microspheres with hollow structure and degradation performance of ofloxacin antibiotic[J]. Chinese J. Inorg. Chem., 2020,36(5):827-834.
9. [9]
  Lee J, von Gunten U, Kim J H. Persulfate-based advanced oxidation: Critical assessment of opportunities and roadblocks[J]. Environ. Sci. Technol., 2020,54(6):3064-3081. doi: 10.1021/acs.est.9b07082
10. [10]
  Mohamed R M, Kadi M W, Ismail A A. A facile synthesis of mesoporous α-Fe₂O ₃/TiO₂ nanocomposites for hydrogen evolution under visible light[J]. Ceram. Int., 2020,46(10):15604-15612. doi: 10.1016/j.ceramint.2020.03.107
11. [11]
  Ding Y B, Fu L B, Peng X Q, Lei M, Wang C J, Jiang J Z. Copper catalysts for radical and nonradical persulfate based advanced oxidation processes: Certainties and uncertainties[J]. Chem. Eng. J., 2022,427131776. doi: 10.1016/j.cej.2021.131776
12. [12]
  ZHA F J, LIU Q, WANG J Y, LIN Y H, WANG C Y, LI Y X. One-dimensional TiO₂ anatase/rutile heterophase junctions: Preparation and photocatalytic properties for degrading formaldehyde[J]. Chinese J. Inorg. Chem., 2022,38(3):510-518.
13. [13]
  Liu J Z, Tang J, Wan J J, Wu C X, Graham B, Kerr P G, Wu Y H. Functional sustainability of periphytic biofilms in organic matter and Cu²⁺ removal during prolonged exposure to TiO₂ nanoparticles[J]. J. Hazard. Mater., 2019,370:4-12. doi: 10.1016/j.jhazmat.2017.08.068
14. [14]
  Sharma S, Shree B, Aditika , Sharma A, Irfan M, Kumar P. Nanoparticle-based toxicity in perishable vegetable crops: Molecular insights, impact on human health and mitigation strategies for sustainable cultivation[J]. Environ. Res., 2022,212113168. doi: 10.1016/j.envres.2022.113168
15. [15]
  Jafari S, Mahyad B, Hashemzadeh H, Janfaza S, Gholikhani T, Tayebi L. Biomedical applications of TiO₂ nanostructures: Recent advances[J]. Int. J. Nanomed., 2020,15:3447-3470. doi: 10.2147/IJN.S249441
16. [16]
  Wang T, Li Y, Wu W T, Zhang Y L, Wu L G, Chen H L. Effect of chiral-arrangement on the solar adsorption of black TiO₂-SiO₂ mesoporous materials for photodegradation and photolysis[J]. Appl. Surf. Sci., 2021,537148025. doi: 10.1016/j.apsusc.2020.148025
17. [17]
  Dong Z Y, Zhang Q, Chen B Y, Hong J M. Oxidation of bisphenol A by persulfate via Fe₃O₄-α-MnO₂ nanoflower-like catalyst: Mechanism and efficiency[J]. Chem. Eng. J., 2019,357:337-347. doi: 10.1016/j.cej.2018.09.179
18. [18]
  Zhou J, Cheng H, Ma J F, Peng M G, Kong Y, Komarneni S. Persulfate activation by MnCuS nanocomposites for degradation of organic pollutants[J]. Sep. Purif. Technol., 2021,261118290. doi: 10.1016/j.seppur.2020.118290
19. [19]
  FU X H, WANG L X, LI Y, WU L G, WANG T. Chiral TiO₂-based photocatalysts with visible light response and their photo-degradation of organic pollutants[J]. Acta Scientiae Circumstantiae, 2021,41(12):4862-4870.
20. [20]
  Wang T, Li B R, Wu L G, Yin Y B, Jiang B Q, Lou J Q. Enhanced performance of TiO₂/reduced graphene oxide doped by rare-earth ions for degrading phenol in seawater excited by weak visible light[J]. Adv. Powder Technol., 2019,30(9):1920-1931. doi: 10.1016/j.apt.2019.06.011
21. [21]
  LIU X T, ZHU H C, LI Y, WANG F, ZHANG Y T, JIN G P, WEI F Y. A high-efficiency visible-light-driven mesoporous AgI@Fe-MIL-88B-NH₂ photocatalyst via Z-scheme mechanism[J]. Chinese J. Inorg. Chem., 2019,35(7):1255-1266.
22. [22]
  Du Y E, Li W X, Bai Y, Huangfu Z W, Wang W J, Chai R D, Chen C D, Yang X J, Feng Q. Facile synthesis of TiO₂/Ag₃PO₄ composites with co-exposed high-energy facets for efficient photodegradation of rhodamine B solution under visible light irradiation[J]. RSC Adv., 2020,10(41):24555-24569. doi: 10.1039/D0RA04183A
23. [23]
  Duan L L, Hung C T, Wang J X, Wang C Y, Ma B, Zhang W, Ma Y Z, Zhao Z W, Yang C C, Zhao T C, Peng L, Liu D, Zhao D Y, Li W. Synthesis of fully exposed single-atom-layer metal clusters on 2D ordered mesoporous TiO₂ nanosheets[J]. Angew. Chem. Int. Ed., 2022,61(43)e202211307. doi: 10.1002/anie.202211307
24. [24]
  Sabri M, Habibi-Yangjeh A, Chand H, Krishnan V. Activation of persulfate by novel TiO₂/FeOCl photocatalyst under visible light: Facile synthesis and high photocatalytic performance[J]. Sep. Purif. Technol., 2020,250117268. doi: 10.1016/j.seppur.2020.117268
25. [25]
  Chen Y, Bai X, Ji Y, Chen D. Enhanced activation of peroxymonosulfate using ternary MOFs-derived MnCoFeO for sulfamethoxazole degradation: Role of oxygen vacancies[J]. J. Hazard. Mater., 2023,441129912. doi: 10.1016/j.jhazmat.2022.129912
26. [26]
  LIANG M J, DENG N, XIANG X Y, MEI Y, YANG Z Y, YANG Y, YANG S J. Bi/BiVO₄ & Bi₄V₂O₁₁ composite catalysts: Preparation and photocatalytic performance[J]. Chinese J. Inorg. Chem., 2019,35(2):263-270.
27. [27]
  MAO J Y, HUANG Y W, HUANG Z Q, LIU X P, XUE H, XIAO L R. Different photocatalytic performances for tetracycline hydrochloride degradation of p-block metal oxides Ga₂O₃ and Sb₂O₃[J]. Chinese J. Inorg. Chem., 2021,37(3):509-515.
28. [28]
  Cao Y X, Yuan X Z, Chen H Y, Wang H, Chen Y, Chen J Y, Huang H M, Mou Y, Shangguan Z C, Li X. Rapid concurrent photocatalysis-persulfate activation for ciprofloxacin degradation by Bi₂S₃ quantum dots-decorated MIL-53(Fe) composites[J]. Chem. Eng. J., 2023,456140971. doi: 10.1016/j.cej.2022.140971
29. [29]
  Wu Y Q, Zhao X Y, Tian J T, Liu S X, Liu W Y, Wang T Y. Heterogeneous catalytic system of photocatalytic persulfate activation by novel Bi₂WO ₆ coupled magnetic biochar for degradation of ciprofloxacin[J]. Colloid Surf. A-Physicochem. Eng. Asp., 2022,651129667. doi: 10.1016/j.colsurfa.2022.129667
30. [30]
  XU H T, FU X H, FENG W H, WANG T. Photo-degradation mechanism and pathway for tetracycline in simulated seawater under irradiation of visible light[J]. Environmental Science, 2023,44(6):3260-3269. doi: 10.13227/j.hjkx.202206237
31. [31]
  Shi W L, Hao C C, Fu Y M, Guo F, Tang Y B, Yan X. Enhancement of synergistic effect photocatalytic/persulfate activation for degradation of antibiotics by the combination of photo-induced electrons and carbon dots[J]. Chem. Eng. J., 2022,433(3)133741.
32. [32]
  XIE K, YE J M, SUN P, WANG H, MA D Z. Non-radical degradation of paracetamol by persulfate activation with modified ordered mesoporous carbon[J]. Acta Scientiae Circumstantiae, 2022,42(4):149-156.
33. [33]
  Liu X N, Li F, Liu Y, Li P S, Chen L, Li B, Qian T W, Liu W. Degradation of diclofenac in a photosensitization-like photocatalysis process using palladium quantum dots deposited graphite carbon nitride under solar light[J]. J. Environ. Chem. Eng., 2022,10(3)107545. doi: 10.1016/j.jece.2022.107545
34. [34]
  Qi J, Yang X, Pan P Y, Huang T, Yang X, Wang C C, Liu W. Interface engineering of Co(OH)₂ nanosheets growing on the KNbO₃ perovskite based on electronic structure modulation for enhanced peroxymonosulfate activation[J]. Environ. Sci. Technol., 2022,56:5200-5212. doi: 10.1021/acs.est.1c08806
35. [35]
  Kong W J, Gao Y, Yue Q Y, Li Q, Gao B Y, Kong Y, Wang X D, Zhang P, Wang Y. Performance optimization of CdS precipitated graphene oxide/polyacrylic acid composite for efficient photodegradation of chlortetracycline[J]. J. Hazard. Mater., 2020,388121780.
36. [36]
  Ji H D, Liu W, Sun F B, Huang T B, Chen L, Liu Y, Qi J J, Xie C H, Zhao D Y. Experimental evidences and theoretical calculations on phenanthrene degradation in a solar-light-driven photocatalysis system using silica aerogel supported TiO₂ nanoparticles: Insights into reactive sites and energy evolution[J]. Chem. Eng. J., 2021,419129605.
37. [37]
  Ma L L, Xu J Y, Liu Y C, An Y T, Pan Z C, Yang B, Li L L, Hu T, Lai B. Improved degradation of tetracycline by Cu-doped MIL-101 (Fe) in a coupled photocatalytic and persulfate oxidation system: Efficiency, mechanism, and degradation pathway[J]. Sep. Purif. Technol., 2023,305112450.
38. [38]
  Zhang Y, Zhou J B, Chen J H, Feng X Q, Cai W Q. Rapid degradation of tetracycline hydrochloride by heterogeneous photocatalysis coupling persulfate oxidation with MIL-53(Fe) under visible light irradiation[J]. J. Hazard. Mater., 2020,392122315.
1. [1]
  Jiahui YU , Jixian DONG , Yutong ZHAO , Fuping ZHAO , Bo GE , Xipeng PU , Dafeng ZHANG . The morphology control and full-spectrum photodegradation tetracycline performance of microwave-hydrothermal synthesized BiVO₄:Yb³⁺,Er³⁺ photocatalyst. Journal of Fuel Chemistry and Technology, 2025, 53(3): 348-359. doi: 10.1016/S1872-5813(24)60514-1
2. [2]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
3. [3]
  Qiang ZHAO , Zhinan GUO , Shuying LI , Junli WANG , Zuopeng LI , Zhifang JIA , Kewei WANG , Yong GUO . Cu₂O/Bi₂MoO₆ Z-type heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 885-894. doi: 10.11862/CJIC.20230435
4. [4]
  Yaping ZHANG , Tongchen WU , Yun ZHENG , Bizhou LIN . Z-scheme heterojunction β-Bi₂O₃ pillared CoAl layered double hydroxide nanohybrid: Fabrication and photocatalytic degradation property. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 531-539. doi: 10.11862/CJIC.20240256
5. [5]
  Yurong Tang , Yunren Shi , Yi Xu , Bo Qin , Yanqin Xu , Yunfei Cai . Innovative Experiment and Course Transformation Practice of Visible-Light-Mediated Photocatalytic Synthesis of Isoquinolinone. University Chemistry, 2024, 39(5): 296-306. doi: 10.3866/PKU.DXHX202311087
6. [6]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187
7. [7]
  Fugui XI , Du LI , Zhourui YAN , Hui WANG , Junyu XIANG , Zhiyun DONG . Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 683-694. doi: 10.11862/CJIC.20240291
8. [8]
  Ping ZHANG , Chenchen ZHAO , Xiaoyun CUI , Bing XIE , Yihan LIU , Haiyu LIN , Jiale ZHANG , Yu'nan CHEN . Preparation and adsorption-photocatalytic performance of ZnAl@layered double oxides. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1965-1974. doi: 10.11862/CJIC.20240014
9. [9]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
10. [10]
  Jinwang Wu , Qijing Xie , Chengliang Zhang , Haifeng Shi . 自旋极化增强ZnFe_1.2Co_0.8O₄/BiVO₄ S型异质结光催化性能降解四环素. Acta Physico-Chimica Sinica, 2025, 41(5): 100050-. doi: 10.1016/j.actphy.2025.100050
11. [11]
  Qin Li , Huihui Zhang , Huajun Gu , Yuanyuan Cui , Ruihua Gao , Wei-Lin Dai . In situ Growth of Cd_0.5Zn_0.5S Nanorods on Ti₃C₂ MXene Nanosheet for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2025, 41(4): 100031-. doi: 10.3866/PKU.WHXB202402016
12. [12]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
13. [13]
  Xinzhe HUANG , Lihui XU , Yue YANG , Liming WANG , Zhangyong LIU , Zhongjian WANG . Preparation and visible light responsive photocatalytic properties of BiSbO₄/BiOBr. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 284-292. doi: 10.11862/CJIC.20240212
14. [14]
  Zhinan GUO , Junli WANG , Qiang ZHAO , Zhifang JIA , Zuopeng LI , Kewei WANG , Yong GUO . Cu₂O/Bi₂CrO₆ Z-scheme heterojunction: Construction and photocatalytic degradation properties for tetracycline. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 741-752. doi: 10.11862/CJIC.20240403
15. [15]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
16. [16]
  Jie Li , Huida Qian , Deyang Pan , Wenjing Wang , Daliang Zhu , Zhongxue Fang . Efficient Synthesis of Anethaldehyde Induced by Visible Light. University Chemistry, 2024, 39(4): 343-350. doi: 10.3866/PKU.DXHX202310076
17. [17]
  Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang . Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst. Acta Physico-Chimica Sinica, 2025, 41(4): 100038-. doi: 10.3866/PKU.WHXB202408015
18. [18]
  Zhen Yao , Bing Lin , Youping Tian , Tao Li , Wenhui Zhang , Xiongwei Liu , Wude Yang . Visible-Light-Mediated One-Pot Synthesis of Secondary Amines and Mechanistic Exploration. University Chemistry, 2024, 39(5): 201-208. doi: 10.3866/PKU.DXHX202311033
19. [19]
  Huan ZHANG , Jijiang WANG , Guang FAN , Long TANG , Erlin YUE , Chao BAI , Xiao WANG , Yuqi ZHANG . A highly stable cadmium(Ⅱ) metal-organic framework for detecting tetracycline and p-nitrophenol. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 646-654. doi: 10.11862/CJIC.20230291
20. [20]
  Yang Xia , Kangyan Zhang , Heng Yang , Lijuan Shi , Qun Yi . 构建双通道路径增强iCOF/Bi₂O₃ S型异质结在纯水体系中光催化合成H₂O₂性能. Acta Physico-Chimica Sinica, 2024, 40(11): 2407012-. doi: 10.3866/PKU.WHXB202407012

Get Citation

PDF

XML

Metrics

PDF Downloads(36)
Abstract views(2151)
HTML views(685)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142