Skip to main content
Log in

Effective removal of antibiotics from water by Cu2O/Co3O4-catalyzed peroxymonosulfate oxidation: catalytic performance and degradation mechanism

  • Published:
Journal of Materials Science: Materials in Electronics Aims and scope Submit manuscript

Abstract

The development of efficient peroxymonosulfate (PMS) activated catalysts is important for the degradation and mineralization of organic pollutants. Metal-organic frameworks derived cobalt oxide modified cuprous oxide (Cu2O/Co3O4) with carbon bone were constructed by driving a dual-precursors of zeolitic imidazolate framework (ZIF-67) and Cu2O, activating PMS for organic degradation. XRD, FT-IR, EDS analyses and XPS were used to demonstrate phase purity while SEM and HR-TEM were used to discover the shape of the synthesised material. EIS, transient current and LSV were used to enquire about the conductivity of the samples and change in current density accordingly. The degradation efficiency of Cu2O/Co3O4-10 for TC reached 89.8% within 60 min under dark conditions. Its activated degradation of oxytetracycline (OTC), levofloxacin (LEV) and ciprofloxacin (CIP) was 89.4%, 81.32% and 54.09%, respectively. Spherical cuprous oxide loaded on cubic cobalt oxide. Furthermore, the effective activation of PMS was achieved by increasing the electron donor capacity of Co and redox cycling of Cu. The single linear state of oxygen (1O2) produced by Cu2O/Co3O4 is well adapted to H2PO4 and is active at pH = 7. Notably, Cu2O/Co3O4 utilized hydrogen persulfate (HSO5) to generate superoxide radicals (·O2) and 1O2 in the PMS system by Co3+/Co2+ and Cu2+/Cu+ cyclic conversion. The strong interaction and electron transfer between Cu2O/Co3O4 and PMS and the synergistic effect of the bimetallic oxide redox cycle accelerated improved the catalytic activity. In conclusion, this study provides a new perspective that is conducive to improving the practical application of sulfate radical-based advanced oxidation processes (SR-AOPs).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Scheme 1

Similar content being viewed by others

Explore related subjects

Discover the latest articles, news and stories from top researchers in related subjects.

Data availability

All data included in this study are available upon request by contact with the corresponding author.

References

  1. J. Zhang, M. Si, L. Jiang, X. Yuan, H. Yu, Z. Wu, Y. Li, J. Guo, Core-shell Ag@nitrogen-doped carbon quantum dots modified BiVO4 nanosheets with enhanced photocatalytic performance under Vis-NIR light: Synergism of molecular oxygen activation and surface plasmon resonance. Chem. Eng. J. 410, 128336 (2021)

    Article  CAS  Google Scholar 

  2. M. Xiang, Y. Zhou, J. Zhang, W. He, Y. Xiao, Q. Li, Y. Zhou, Z. Chen, G. Huang, D. Feng, Synergy of radical and nonradical degradations triggered by self-floating MnO2/cotton hydrogels with photothermal effect and oxygen vacancy. Chem. Eng. J. 476, 146468 (2023)

    Article  CAS  Google Scholar 

  3. L. Liu, C. Han, G. Ding, M. Yu, Y. Li, S. Liu, Y. Xie, J. Liu, Oxygen vacancies-enriched Cu/Co bimetallic oxides catalysts for high-efficiency peroxymonosulfate activation to degrade TC: insight into the increase of Cu+ triggered by Co doping. Chem. Eng. J. 450, 138302 (2022)

    Article  CAS  Google Scholar 

  4. M. Amiri, M. Salavati-Niasari, A. Akbari, T. Gholami, Removal of malachite green (a toxic dye) from water by cobalt ferrite silica magnetic nanocomposite: Herbal and green sol-gel autocombustion synthesis. Int. J. Hydrog. Energy. 42(39), 24846–24860 (2017)

    Article  CAS  Google Scholar 

  5. J. Dan, Q. Wang, P. Rao, L. Dong, M. Zhang, X. Zhang, Z. He, N. Gao, Bimetallic oxides with package structure for enhanced degradation of bisphenol a through peroxymonosulfate activation. Chem. Eng. J. 429, 132189 (2022)

    Article  CAS  Google Scholar 

  6. W. Wang, M. Chen, D. Wang, M. Yan, Z. Liu, Different activation methods in sulfate radical-based oxidation for organic pollutants degradation: Catalytic mechanism and toxicity assessment of degradation intermediates. Sci. Total Environ. 772, 145522 (2021)

    Article  CAS  PubMed  Google Scholar 

  7. B. Bouzayani, E. Rosales, M. Pazos, S.C. Elaoud, M.A. Sanromán, Homogeneous and heterogeneous peroxymonosulfate activation by transition metals for the degradation of industrial leather dye. J. Clean. Prod. 228, 222–230 (2019)

    Article  CAS  Google Scholar 

  8. Y.-Y. Ahn, H. Bae, H.-I. Kim, S.-H. Kim, J.-H. Kim, S.-G. Lee, J. Lee, Surface-loaded metal nanoparticles for peroxymonosulfate activation: efficiency and mechanism reconnaissance. Appl. Catal. B 241, 561–569 (2019)

    Article  CAS  Google Scholar 

  9. M.-X. Gu, Y. Kou, S.-C. Qi, M.-Q. Shao, M.B. Yue, X.-Q. Liu, Sun. Highly Dispersive Cobalt Oxide constructed in Confined Space for Oxygen Evolution reaction. ACS Sustain. Chem. Eng. 7(2), 2837–2843 (2019)

    Article  CAS  Google Scholar 

  10. X. Du, M. Zhou, Strategies to enhance catalytic performance of metal–organic frameworks in sulfate radical-based advanced oxidation processes for organic pollutants removal. Chem. Eng. J. 403, 126346 (2021)

    Article  CAS  Google Scholar 

  11. H. Chen, J. Wang, MOF-derived Co3O4-C@FeOOH as an efficient catalyst for catalytic ozonation of norfloxacin. J. Hazard. Mater. 403, 123697 (2021)

    Article  CAS  PubMed  Google Scholar 

  12. J. Wang, H. Zhou, M. Zhu, A. Yuan, X. Shen, Metal-organic framework-derived Co3O4 covered by MoS2 nanosheets for high-performance lithium-ion batteries. J. Alloys Compd. 744, 220–227 (2018)

    Article  CAS  Google Scholar 

  13. X.L. Chen, F. Li, M. Zhang, B. Liu, H. Chen, H. Wang, Highly dispersed and stabilized Co3O4/C anchored on porous biochar for bisphenol a degradation by sulfate radical advanced oxidation process. Sci. Total Environ. 777, 145794 (2021)

    Article  CAS  PubMed  Google Scholar 

  14. S. Shao, X. Li, Z. Gong, B. Fan, J. Hu, J. Peng, K. Lu, Gao. A new insight into the mechanism in Fe3O4@CuO/PMS system with low oxidant dosage. Chem. Eng. J. 438, 135474 (2022)

    Article  CAS  Google Scholar 

  15. H. Li, J. Tian, F. Xiao, R. Huang, S. Gao, F. Cui, S. Wang, X. Duan, Structure-dependent catalysis of cuprous oxides in peroxymonosulfate activation via nonradical pathway with a high oxidation capacity. J. Hazard. Mater. 385, 121518 (2020)

    Article  CAS  PubMed  Google Scholar 

  16. Q. Zhou, P. Hong, X. Shi, Y. Li, K. Yao, W. Zhang, C. Wang, J. He, K. Zhang, L. Kong, Efficient degradation of tetracycline by a novel nanoconfinement structure Cu2O/Cu@MXene composite. J. Hazard. Mater. 448, 130995 (2023)

    Article  CAS  PubMed  Google Scholar 

  17. Y. Jeon, J. Lee, H. Jo, H. Hong, L.Y.S. Lee, Y. Piao, Co/Co3O4-embedded N-doped hollow carbon composite derived from a bimetallic MOF/ZnO Core-shell template as a sulfur host for Li-S batteries. Chem. Eng. J. 407, 126967 (2021)

    Article  CAS  Google Scholar 

  18. A. Jafarinejad, M. Salavati-Niasari, R. Monsef, H. Bashiri, Flower-shaped magnetically recyclable ZnS/ZnIn2S4/Fe2O3 nanocomposites towards decolorization of colored pollutants. Int. J. Hydrog. Energy. 48(9), 3440–3455 (2023)

    Article  CAS  Google Scholar 

  19. N. Mir, M. Salavati-Niasari, Preparation of TiO2 nanoparticles by using tripodal tetraamine ligands as complexing agent via two-step sol–gel method and their application in dye-sensitized solar cells. Mater. Res. Bull. 48(4), 1660–1667 (2013)

    Article  CAS  Google Scholar 

  20. Z. Li, X. Tang, G. Huang, X. Luo, D. He, Q. Peng, J. Huang, M. Ao, K. Liu, Bismuth MOFs based hierarchical Co3O4-Bi2O3 composite: an efficient heterogeneous peroxymonosulfate activator for azo dyes degradation. Sep. Purif. Technol. 242, 116825 (2020)

    Article  CAS  Google Scholar 

  21. H. Li, P. Zhang, Y. Guo, J. Jia, S. Wang, X. Duan, F. Cui, S. Gao, Tian. Iron-doped cuprous oxides toward accelerated nonradical oxidation: doping induced controlled facet transformation and optimized electronic structure. Chem. Eng. J. 407, 127172 (2021)

    Article  CAS  Google Scholar 

  22. M. Salavati-Niasari, M. Dadkhah, F. Davar, Pure cubic ZrO2 nanoparticles by thermolysis of a new precursor. Polyhedron. 28(14), 3005–3009 (2009)

    Article  CAS  Google Scholar 

  23. M. Panahi-Kalamuei, M. Salavati-Niasari, S.M. Hosseinpour-Mashkani, Facile microwave synthesis, characterization, and solar cell application of selenium nanoparticles. J. Alloys Compd. 617, 627–632 (2014)

    Article  CAS  Google Scholar 

  24. A. Karami, R. Monsef, I. Waleed, H.L. Kareem, I.T. Ibrahim, M. Salavati-Niasari, Microwave synthesized erbium vanadate nano-photocatalyst: application for enhanced degradation of contaminated water. Int. J. Hydrog. Energy. 48(23), 8499–8513 (2023)

    Article  CAS  Google Scholar 

  25. S. Zinatloo-Ajabshir, M. Baladi, M. Salavati-Niasari, Enhanced visible-light-driven photocatalytic performance for degradation of organic contaminants using PbWO4 nanostructure fabricated by a new, simple and green sonochemical approach. Ultrason. Sonochem. 72, 105420 (2021)

    Article  CAS  PubMed  Google Scholar 

  26. H. Teymourinia, M. Salavati-Niasari, O. Amiri, H. Safardoust-Hojaghan, Synthesis of graphene quantum dots from corn powder and their application in reduce charge recombination and increase free charge carriers. J. Mol. Liq. 242, 447–455 (2017)

    Article  CAS  Google Scholar 

  27. H. Khojasteh, M. Salavati-Niasari, H. Safajou, H. Safardoust-Hojaghan, Facile reduction of graphene using urea in solid phase and surface modification by N-doped graphene quantum dots for adsorption of organic dyes. Diam. Relat. Mater. 79, 133–144 (2017)

    Article  CAS  Google Scholar 

  28. Y. Liu, H. Zou, H. Ma, J. Ko, W. Sun, K. Andrew Lin, S. Zhan, H. Wang, Highly efficient activation of peroxymonosulfate by MOF-derived CoP/CoOx heterostructured nanoparticles for the degradation of tetracycline. Chem. Eng. J. 430, 132816 (2022)

    Article  CAS  Google Scholar 

  29. Y. Wang, L. Zhang, R. Li, H. He, H. Wang, L. Huang, MOFs-based coating derived Me-ZIF-67@CuOx materials as low-temperature NO-CO catalysts. Chem. Eng. J. 381, 122757 (2020)

    Article  CAS  Google Scholar 

  30. Q. Chen, X. Zhang, S. Li, J. Tan, C. Xu, Y. Huang, MOF-derived Co3O4@Co-Fe oxide double-shelled nanocages as multi-functional specific peroxidase-like nanozyme catalysts for chemo/biosensing and dye degradation. Chem. Eng. J. 395, 125130 (2020)

    Article  CAS  Google Scholar 

  31. Y. Zhu, D. Li, S. Zuo, Z. Guan, S. Ding, D. Xia, X. Li, Cu2O/CuO induced non-radical/radical pathway toward highly efficient peroxymonosulfate activation. J. Environ. Chem. Eng. 9(6), 106781 (2021)

    Article  CAS  Google Scholar 

  32. C. Jin, M. Wang, Z. Li, J. Kang, Y. Zhao, J. Han, Wu. Two dimensional Co3O4/g-C3N4 Z-scheme heterojunction: Mechanism insight into enhanced peroxymonosulfate-mediated visible light photocatalytic performance. Chem. Eng. J. 398, 125569 (2020)

    Article  CAS  Google Scholar 

  33. B. Dai, Y. Li, J. Xu, C. Sun, S. Li, W. Zhao, Photocatalytic oxidation of tetracycline, reduction of hexavalent chromium and hydrogen evolution by Cu2O/g-C3N4 S-scheme photocatalyst: performance and mechanism insight. Appl. Surf. Sci. 592, 153309 (2022)

    Article  CAS  Google Scholar 

  34. Y. Guo, Y. Dai, W. Zhao, H. Li, B. Xu, C. Sun, Highly efficient photocatalytic degradation of naphthalene by Co3O4/ Bi2O2CO3 under visible light: a novel p–n heterojunction nanocomposite with nanocrystals/lotus-leaf-like nanosheets structure. Appl. Catal. B 237, 273–287 (2018)

    Article  CAS  Google Scholar 

  35. S. Zuo, D. Li, F. Yang, H. Xu, M. Huang, Z. Guan, D. Xia, Copper oxide/graphitic carbon nitride composite for bisphenol a degradation by boosted peroxymonosulfate activation: mechanism of Cu-O covalency governs. J. Colloid Interface Sci. 603, 85–93 (2021)

    Article  CAS  PubMed  Google Scholar 

  36. X. Zhou, A. Jawad, M. Luo, C. Luo, T. Zhang, H. Wang, J. Wang, S. Wang, Z. Chen, Z. Chen, Regulating activation pathway of Cu/persulfate through the incorporation of unreducible metal oxides: pivotal role of surface oxygen vacancies. Appl. Catal. B 286, 119914 (2021)

    Article  CAS  Google Scholar 

  37. Y. Ding, C. Pan, X. Peng, Q. Mao, Y. Xiao, L. Fu, J. Huang, Deep mineralization of bisphenol A by catalytic peroxymonosulfate activation with nano CuO/Fe3O4 with strong Cu-Fe interaction. Chem. Eng. J. 384, 123378 (2020)

    Article  CAS  Google Scholar 

  38. Z. Wu, Y. Wang, Z. Xiong, Z. Ao, S. Pu, G. Yao, B. Lai, Core-shell magnetic Fe3O4@Zn/Co-ZIFs to activate peroxymonosulfate for highly efficient degradation of carbamazepine. Appl. Catal. B 277, 119136 (2020)

    Article  CAS  Google Scholar 

  39. Y. Wang, P. Yan, X. Dou, C. Liu, Y. Zhang, Z. Song, Z. Chen, B. Xu, Qi. Degradation of benzophenone-4 by peroxymonosulfate activated with microwave synthesized well-distributed CuBi2O4 microspheres: theoretical calculation of degradation mechanism. Appl. Catal. B 290, 120048 (2021)

    Article  CAS  Google Scholar 

  40. W. Li, X. He, B. Li, B. Zhang, T. Liu, Y. Hu, J. Ma, Structural tuning of multishelled hollow microspheres for boosted peroxymonosulfate activation and selectivity: role of surface superoxide radical. Appl. Catal. B 305, 121019 (2022)

    Article  CAS  Google Scholar 

  41. T. Tang, G. Lu, W. Wang, R. Wang, K. Huang, Z. Qiu, X. Tao, Z. Dang, Photocatalytic removal of organic phosphate esters by TiO2: Effect of inorganic ions and humic acid. Chemosphere. 206, 26–32 (2018)

    Article  CAS  PubMed  Google Scholar 

  42. Y. Chen, Y. Zhou, J. Zhang, J. Li, T. Yao, A. Chen, M. Xiang, Q. Li, Z. Chen, Zhou. Plasmonic Bi promotes the construction of Z-scheme heterojunction for efficient oxygen molecule activation. Chemosphere. 302, 134527 (2022)

    Article  CAS  PubMed  Google Scholar 

  43. Y. Zhou, Q. Li, J. Zhang, M. Xiang, Y. Zhou, Z. Chen, Y. Chen, Yao. Broad spectrum driven Y doped BiO2 – x for enhanced degradation of tetracycline: synergy between singlet oxygen and free radicals. Appl. Surf. Sci. 607, 154957 (2023)

    Article  CAS  Google Scholar 

  44. R. Guo, Y. Zhu, X. Cheng, J. Li, J.C. Crittenden, Efficient degradation of lomefloxacin by Co-Cu-LDH activating peroxymonosulfate process: optimization, dynamics, degradation pathway and mechanism. J. Hazard. Mater. 399, 122966 (2020)

    Article  CAS  PubMed  Google Scholar 

  45. S. Wang, S. Gao, J. Tian, Q. Wang, T. Wang, X. Hao, F. Cui, A stable and easily prepared copper oxide catalyst for degradation of organic pollutants by peroxymonosulfate activation. J. Hazard. Mater. 387, 121995 (2020)

    Article  CAS  PubMed  Google Scholar 

  46. C. Chen, L. Liu, J. Guo, L. Zhou, Y. Lan, Sulfur-doped copper-cobalt bimetallic oxides with abundant Cu(I): a novel peroxymonosulfate activator for chloramphenicol degradation. Chem. Eng. J. 361, 1304–1316 (2019)

    Article  CAS  Google Scholar 

Download references

Funding

This work was supported by the Hunan Provincial Natural Science Foundation of China (2022JJ40505) and National Natural Science Foundation of China (No. 21671026).

Author information

Authors and Affiliations

Authors

Contributions

XS: Conceptualization, validation, Writing—original draft. YZ: Resources, Writing—review & editing, supervision, data curation. WH: Methodology, data curation. ZC: Validation, formal analysis, visualization. YX:Validation, formal analysis, visualization. GH: Validation, formal analysis, visualization. DF: Software, validation, formal analysis, visualization. JZ: Resources, conceptualization, Writing—review & editing, supervision, data curation.

Corresponding author

Correspondence to Jin Zhang.

Ethics declarations

Competing interests

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Ethical standards

The currently submitted article contains research that did not involve human or animal subjects, plagiarise the results of others, or manipulate the literature and data.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Song, X., Zhou, Y., He, W. et al. Effective removal of antibiotics from water by Cu2O/Co3O4-catalyzed peroxymonosulfate oxidation: catalytic performance and degradation mechanism. J Mater Sci: Mater Electron 35, 851 (2024). https://doi.org/10.1007/s10854-024-12491-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10854-024-12491-x

Navigation