Skip to main content
SpringerLink
Log in

Fe-based dual-center heterogeneous catalyst assisted with reduced graphene oxide for the activation of peroxymonosulfate

  • Research
  • Published:
Advanced Composites and Hybrid Materials Aims and scope Submit manuscript

Abstract

Transition metal-based (M = Fe, Cu, etc.) catalytic systems are generally popular in advanced oxidation processes; however, the difficulty in restoring their active oxidation state, i.e., Mn +1 → Mn+, limits their performance during the degradation of organic pollutants. Here, a novel strategy of constructing an electron-rich center via systematic intercalation of ultrathin-reduced graphene oxide (rGO) sheets into hydroxide-based materials was introduced to accelerate M(n +1)/Mn+ redox cycles of transition metal-based (M = Fe, Cu) heterogeneous catalysts (M-Hydroxide/rGO). According to the first-order kinetic model, the fabricated M-Hydroxide/rGO was more reactive than the corresponding hydroxides or rGO during peroxymonosulfate (PMS) activation. The first-order observed degradation rates (kobs) of 4-chlorophenol (4-CP) were found in the order of Fe-Hydroxide/rGO (kobs = 0.152 min−1) > Cu-Hydroxide/rGO (kobs = 0.091 min−1) > Zn-Hydroxide/rGO (kobs = 0.021 min−1). Moreover, the prepared best Fe-Hydroxide/rGO catalyst exhibited 6–43-fold high pollutant removal reactivity than catalyst precursors (Fe-Hydroxide/NO3 and rGO), conventional benchmark catalysts (CuO, Co3O4, CuOFe3O4, and Fe3O4), and various Fe3+-based co-catalytic systems (such as Fe3+/WS2 and Fe3+/MoS2). The better efficiency was ascribed to the electron-rich domain (C = O, O–C = O) of interlayered rGO, allowing the constant regeneration of Fe2+ via efficient electron transfer and the production of diverse reactive species, i.e., sulfate radicals (•SO4−), hydroxyl (•OH) radicals, and singlet oxygen (1O2). Moreover, a suitable degradation pathway of 4-CP, passing through diverse reactive species, was proposed. This study highlights the vital role of rGO in improving the activity and stability of Fe-based hydroxide catalysts by accelerating Fe3+/Fe2+ redox cycle through regular feeding of electrons.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Scheme 1
Fig. 7

Similar content being viewed by others

Data availability

The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information files.

References

  1. Zeng J, Xie W, Guo Y et al (2023) Magnetic field facilitated electrocatalytic degradation of tetracycline in wastewater by magnetic porous carbonized phthalonitrile resin. Appl Catalys B: Environ 123225

  2. Ruchi N, Anwar A, Bamne J, et al (2022) Synthesis of titania/silica nanocomposite for enhanced photodegradation of methylene blue and methyl orange dyes under UV and mercury lights. ES Materials & Manufacturing 16:78–88

    Google Scholar 

  3. Kang F, Jiang X, Wang Y et al (2023) Electron-rich biochar enhanced Z-scheme heterojunctioned bismuth tungstate/bismuth oxyiodide removing tetracycline. Inorg Chem Front

  4. Barzegar G, Jorfi S, Zarezade V et al (2018) 4-Chlorophenol degradation using ultrasound/peroxymonosulfate/nanoscale zero valent iron: reusability, identification of degradation intermediates and potential application for real wastewater. Chemosphere 201:370–379

    CAS  Google Scholar 

  5. Rebosura M Jr, Salehin S, Pikaar I et al (2020) The impact of primary sedimentation on the use of iron-rich drinking water sludge on the urban wastewater system. J Hazard Mater 402:124051

    Google Scholar 

  6. Hube S, Eskafi M, Hrafnkelsdóttir KF et al (2020) Direct membrane filtration for wastewater treatment and resource recovery: a review. Sci Total Environ 710:136375

    CAS  Google Scholar 

  7. Yang S, Shi C, Qu K et al (2023) Electrostatic self-assembly cellulose nanofibers/MXene/nickel chains for highly stable and efficient seawater evaporation and purification. Carbon Letters: 1–12

  8. Shahzad A, Ali J, Wajid Ullah M et al (2022) Interlayered modified hydroxides for removal of graphene oxide from water: mechanism and secondary applications. Sep Purif Technol 284:120305

    CAS  Google Scholar 

  9. Jawad A, Liao Z, Zhou Z et al (2017) Fe-MoS4: an effective and stable LDH-based adsorbent for selective removal of heavy metals. ACS Appl Mater Interfaces 9(34):28451–28463

    CAS  Google Scholar 

  10. Sun Z, Qu K, Cheng Y et al (2021) Corncob-derived activated carbon for efficient adsorption dye in sewage. ES Food & Agroforestry 4:61–74

    CAS  Google Scholar 

  11. Li D, Ali J, Shahzad A et al (2022) Persulfate coupled with Cu2+/LDH-MoS4: a novel process for the efficient atrazine abatement, mechanism and degradation pathway. Chem Eng J 436:134933

    CAS  Google Scholar 

  12. Lv H, Liu Y, Bai Y et al (2023) Recent combinations of electrospinning with photocatalytic technology for treating polluted water. Catalysts 13(4):758

    CAS  Google Scholar 

  13. Wang C, Liu X, Yang T et al (2023) An overview of metal-organic frameworks and their magnetic composites for the removal of pollutants. Sep Purif Technol 124144

  14. Rayaroth MP, Marchel M, Boczkaj G (2023) Advanced oxidation processes for the removal of mono and polycyclic aromatic hydrocarbons – a review. Sci Total Environ 857:159043

    CAS  Google Scholar 

  15. Jawad A, Zhan K, Wang H et al (2020) Tuning of persulfate activation from a free radical to a nonradical pathway through the incorporation of non-redox magnesium oxide. Environ Sci Technol 54(4):2476–2488

    CAS  Google Scholar 

  16. Zhang T, Chen Y, Wang Y et al (2014) Efficient peroxydisulfate activation process not relying on sulfate radical generation for water pollutant degradation. Environ Sci Technol 48(10):5868–5875

    CAS  Google Scholar 

  17. Wang J, Duan X, Gao J et al (2020) Roles of structure defect, oxygen groups and heteroatom doping on carbon in nonradical oxidation of water contaminants. Water Res 185:116244

    CAS  Google Scholar 

  18. Waldemer RH, Tratnyek PG, Johnson RL et al (2007) Oxidation of chlorinated ethenes by heat-activated persulfate: kinetics and products. Environ Sci Technol 41(3):1010–1015

    CAS  Google Scholar 

  19. Liu Y, Wang Y, Wang Q et al (2018) Simultaneous removal of NO and SO2 using vacuum ultraviolet light (VUV)/heat/peroxymonosulfate (PMS). Chemosphere 190:431–441

    CAS  Google Scholar 

  20. Jawad A, Lang J, Liao Z et al (2018) Activation of persulfate by CuOx@Co-LDH: a novel heterogeneous system for contaminant degradation with broad pH window and controlled leaching. Chem Eng J 335:548–559

    CAS  Google Scholar 

  21. Guo S, Yang Z, Zhang H et al (2021) Enhanced photocatalytic degradation of organic contaminants over CaFe2O4 under visible LED light irradiation mediated by peroxymonosulfate. J Mater Sci Technol 62:34–43

    CAS  Google Scholar 

  22. Wang Y, Cao H, Chen L et al (2018) Tailored synthesis of active reduced graphene oxides from waste graphite: structural defects and pollutant-dependent reactive radicals in aqueous organics decontamination. Appl Catal B 229:71–80

    CAS  Google Scholar 

  23. Zhang B, Han Z, Xin Y et al (2022) Peroxymonosulfate activation by vacuum ultraviolet and trace copper ions: a new way to boost Cu (II)/Cu (I) redox cycle. Chem Eng J 450:138097

    CAS  Google Scholar 

  24. Ding Y, Zhu L, Wang N et al (2013) Sulfate radicals induced degradation of tetrabromobisphenol A with nanoscaled magnetic CuFe2O4 as a heterogeneous catalyst of peroxymonosulfate. Appl Catal B 129:153–162

    CAS  Google Scholar 

  25. Fang D, Yu Y, Xu Z et al (2018) Enhanced catalytic performance of β-FeOOH by coupling with single-walled carbon nanotubes in a visible-light-Fenton-like process. Sci Eng Compos Mater 25(1):9–15

    CAS  Google Scholar 

  26. Chen N, Wang X, Wan Y et al (2020) Simulated solar light driven Fe(III)/Fe(II) redox cycle for roxarsone degradation and simultaneous arsenate immobilization. J Hazard Mater 394:121635

    CAS  Google Scholar 

  27. Liu H, Wang C, Li X et al (2007) A novel electro-Fenton process for water treatment: reaction-controlled pH adjustment and performance assessment. Environ Sci Technol 41(8):2937–2942

    CAS  Google Scholar 

  28. Xia L, Bai J, Li J et al (2018) High-efficient energy recovery from organics degradation for neutral wastewater treatment based on radicals catalytic reaction of Fe2+/Fe3+-EDTA complexes. Chemosphere 201:59–65

    CAS  Google Scholar 

  29. Dong C, Ji J, Shen B et al (2018) Enhancement of H2O2 decomposition by the co-catalytic effect of WS2 on the Fenton reaction for the synchronous reduction of Cr (VI) and remediation of phenol. Environ Sci Technol 52(19):11297–11308

    CAS  Google Scholar 

  30. Gao P, Tian X, Fu W et al (2021) Copper in LaMnO3 to promote peroxymonosulfate activation by regulating the reactive oxygen species in sulfamethoxazole degradation. J Hazard Mater 411:125163

    CAS  Google Scholar 

  31. Ali J, Shahzad A, Wang J et al (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

    CAS  Google Scholar 

  32. Zou J, Ma J, Chen L et al (2013) Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe (III)/Fe (II) cycle with hydroxylamine. Environ Sci Technol 47(20):11685–11691

    CAS  Google Scholar 

  33. Li T, Zhao Z, Wang Q et al (2016) Strongly enhanced Fenton degradation of organic pollutants by cysteine: an aliphatic amino acid accelerator outweighs hydroquinone analogues. Water Res 105:479–486

    CAS  Google Scholar 

  34. Sheng B, Yang F, Wang Y et al (2019) Pivotal roles of MoS2 in boosting catalytic degradation of aqueous organic pollutants by Fe (II)/PMS. Chem Eng J 375:121989

    CAS  Google Scholar 

  35. Lyu Z, Xu M, Wang J et al (2022) Hierarchical nano-vesicles with bimetal-encapsulated for peroxymonosulfate activation: singlet oxygen-dominated oxidation process. Chem Eng J 433:133581

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  37. Ali J, Wenli L, Shahzad A et al (2020) Regulating the redox centers of Fe through the enrichment of Mo moiety for persulfate activation: a new strategy to achieve maximum persulfate utilization efficiency. Water Res 181:115862

    CAS  Google Scholar 

  38. Wang S, Hu J, Wang J (2022) Degradation of sulfamethoxazole using PMS activated by cobalt sulfides encapsulated in nitrogen and sulfur co-doped graphene. Sci Total Environ 827:154379

    CAS  Google Scholar 

  39. Liang J, Duan X, Xu X et al (2021) Biomass-derived pyrolytic carbons accelerated Fe(III)/Fe(II) redox cycle for persulfate activation: pyrolysis temperature-depended performance and mechanisms. Appl Catal B 297:120446

    CAS  Google Scholar 

  40. Cui Q, Li Y, Chai S et al (2022) Enhanced catalytic activation of H2O2 by CNTs/SCH through rapid Fe(III)/Fe(II) redox couple circulation: insights into the role of functionalized multiwalled CNTs. Sep Purif Technol 282:120000

    CAS  Google Scholar 

  41. Duan X, Ao Z, Sun H et al (2015) Insights into N-doping in single-walled carbon nanotubes for enhanced activation of superoxides: a mechanistic study. Chem Commun 51(83):15249–15252

    CAS  Google Scholar 

  42. Feng X-C, Xiao Z-J, Shi H-T et al (2022) How nitrogen and sulfur doping modified material structure, transformed oxidation pathways, and improved degradation performance in peroxymonosulfate activation. Environ Sci Technol 56(19):14048–14058

    CAS  Google Scholar 

  43. Liu C, Liu Y, Dang Z et al (2021) Enhancement of heterogeneous photo-Fenton performance of core-shell structured boron-doped reduced graphene oxide wrapped magnetical Fe3O4 nanoparticles: Fe(II)/Fe(III) redox and mechanism. Appl Surf Sci 544:148886

    CAS  Google Scholar 

  44. Cheng F, Zhou P, Huo X et al (2020) Enhancement of bisphenol A degradation by accelerating the Fe(III)/Fe(II) cycle in graphene oxide modified Fe(III)/peroxymonosulfate system under visible light irradiation. J Colloid Interface Sci 580:540–549

    CAS  Google Scholar 

  45. Wang H, Liu S, Liu Y et al (2022) Fe3N nanoparticles embedded in N-doped porous magnetic graphene for peroxymonosulfate activation: radical and nonradical mechanism. Chemosphere 305:135317

    CAS  Google Scholar 

  46. Zhang H, Feng X, Cheng L et al (2019) Non-noble Co anchored on nanoporous graphene oxide, as an efficient and long-life catalyst for hydrogen generation from sodium borohydride. Colloids Surf, A 563:112–119

    CAS  Google Scholar 

  47. Iyi N, Matsumoto T, Kaneko Y et al (2004) A novel synthetic route to layered double hydroxides using hexamethylenetetramine. Chem Lett 33(9):1122–1123

    CAS  Google Scholar 

  48. Iyi N, Matsumoto T, Kaneko Y et al (2004) Deintercalation of carbonate ions from a hydrotalcite-like compound: enhanced decarbonation using acid−salt mixed solution. Chem Mater 16(15):2926–2932

    CAS  Google Scholar 

  49. Marcano DC, Kosynkin DV, Berlin JM et al (2010) Improved synthesis of graphene oxide. ACS Nano 4(8):4806–4814

    CAS  Google Scholar 

  50. Asif M, Aziz A, Wang H et al (2019) Superlattice stacking by hybridizing layered double hydroxide nanosheets with layers of reduced graphene oxide for electrochemical simultaneous determination of dopamine, uric acid and ascorbic acid. Microchim Acta 186(2):1–11

    CAS  Google Scholar 

  51. Jawad A, Peng L, Liao Z et al (2019) Selective removal of heavy metals by hydrotalcites as adsorbents in diverse wastewater: different intercalated anions with different mechanisms. J Clean Prod 211:1112–1126

    CAS  Google Scholar 

  52. Mei X, Wang J, Yang R et al (2015) Synthesis of Pt doped Mg–Al layered double oxide/graphene oxide hybrid as novel NOx storage–reduction catalyst. RSC Adv 5(95):78061–78070

    CAS  Google Scholar 

  53. Khataee A, Rad TS, Nikzat S et al (2019) Fabrication of NiFe layered double hydroxide/reduced graphene oxide (NiFe-LDH/rGO) nanocomposite with enhanced sonophotocatalytic activity for the degradation of moxifloxacin. Chem Eng J 375:122102

    CAS  Google Scholar 

  54. Chen Y, Cui K, Liu T et al (2022) Enhanced degradation of sulfamethoxazole by non-radical-dominated peroxymonosulfate activation with Co/Zn co-doped carbonaceous catalyst: Synergy between Co and Zn. Sci Total Environ 850:158055

    CAS  Google Scholar 

  55. Tong M, Sun F, Xie Y et al (2021) Operando cooperated catalytic mechanism of atomically dispersed Cu− N4 and Zn− N4 for promoting oxygen reduction reaction. Angew Chem Int Ed 60(25):14005–14012

    CAS  Google Scholar 

  56. Fan L, Zheng Y, Li J et al (2022) Improving catalytic degradation of organic pollutants through highly efficient non-radical peroxymonosulfate activation using interlayer-expanded mesoporous nitrogen-doped graphene. Chem Eng J 450:138278

    CAS  Google Scholar 

  57. Wang J, Wang S (2018) Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants. Chem Eng J 334:1502–1517

    CAS  Google Scholar 

  58. Lindsey ME, Tarr MA (2000) Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter. Environ Sci Technol 34(3):444–449

    CAS  Google Scholar 

  59. Jaafarzadeh N, Ghanbari F, Ahmadi M (2017) Efficient degradation of 2,4-dichlorophenoxyacetic acid by peroxymonosulfate/magnetic copper ferrite nanoparticles/ozone: a novel combination of advanced oxidation processes. Chem Eng J 320:436–447

    CAS  Google Scholar 

  60. Duan X, Sun H, Shao Z et al (2018) Nonradical reactions in environmental remediation processes: uncertainty and challenges. Appl Catal B 224:973–982

    CAS  Google Scholar 

  61. Shao P, Tian J, Yang F et al (2018) Identification and regulation of active sites on nanodiamonds: establishing a highly efficient catalytic system for oxidation of organic contaminants. Adv Func Mater 28(13):1705295

    Google Scholar 

  62. Cheng X, Guo H, Zhang Y et al (2017) Non-photochemical production of singlet oxygen via activation of persulfate by carbon nanotubes. Water Res 113:80–88

    CAS  Google Scholar 

  63. Lee J, Hong S, Mackeyev Y et al (2011) Photosensitized oxidation of emerging organic pollutants by Tetrakis C60 aminofullerene-derivatized silica under visible light irradiation. Environ Sci Technol 45(24):10598–10604

    CAS  Google Scholar 

  64. Tian Y, Wu Y, Yi Q et al (2021) Singlet oxygen mediated Fe2+/peroxymonosulfate photo-Fenton-like reaction driven by inverse opal WO3 with enhanced photogenerated charges. Chem Eng J 425:128644

    CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge the analysis and testing center of Huazhong University of Science and Technology, Wuhan, China, and the support of the Fundamental Research Funds for Central Universities, the Open Research Fund of the State Key Laboratory of Polymer Physics and Chemistry, and the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences. The authors extend their appreciation to the Deanship of Scientific Research at King Khalid University, Saudi Arabia, for funding this work through the Large Groups Project under grant number RGP2/447/44. The authors also acknowledge the support of the Unit of Bee Research and Honey Production at King Khalid University, Abha, Saudi Arabia.

Funding

This work was supported by the BRICS STI Framework Programme 3rd call 2019 (2018YFE0123700), the National Natural Science Foundation of China (21774039, 51973076), and the Deanship of Scientific Research at King Khalid University Saudi Arabia through the Large Group Project (RGP2/447/44).

Author information

Authors and Affiliations

  1. Department of Biomedical Engineering, Huazhong University of Science and Technology, 430074, Wuhan, People’s Republic of China

    Ajmal Shahzad, Weam Abdul Raheem M & Guang Yang

  2. School of Environmental and Biological Engineering, Wuhan Technology and Business University, Wuhan, 430065, People’s Republic of China

    Jawad Ali

  3. School of the Environment and Safety Engineering, Biofuels Institute, Jiangsu University, Zhenjiang, 212013, People’s Republic of China

    Muhammad Wajid Ullah & Sehrish Manan

  4. College of Earth and Environmental Sciences, University of the Punjab, Lahore, Pakistan

    Kazim Aziz & Muhammad Asif Javed

  5. Department of Chemical and Energy Engineering, Institute of Applied Science and Technology, Pak-Austria FachhochschuleHaripur, Pakistan

    Fida Hussain

  6. Mahala Campus and the Unit of Bee Research and Honey Production/Research Center for Advanced Materials Science (RCAMS), Applied College, King Khalid University, 61413, Abha, Saudi Arabia

    Khalid Ali Khan

  7. Department of Physics, Faculty of Applied Science, Umm Al-Qura University, 21955, Makkah, Saudi Arabia

    Thamer Alomayri

Authors
  1. Ajmal Shahzad
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jawad Ali
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Muhammad Wajid Ullah
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kazim Aziz
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Muhammad Asif Javed
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Fida Hussain
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Sehrish Manan
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Khalid Ali Khan
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Thamer Alomayri
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Weam Abdul Raheem M
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Guang Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

All authors contributed to the study’s conception and design. Material preparation, data collection, and analysis were performed by Ajmal Shahzad, Jawad Ali, and Muhammad Wajid Ullah. The first draft of the manuscript was written by Ajmal Shahzad, and all authors commented on previous versions of the manuscript. Muhammad Asif Javed, Fida Hussain, Sehrish Manan, Khalid Ali Khan, Thamer Alomayri, and Weam Abdul Raheem M contributed to the data curation and preparation of figures. Guang Yang and Khalid Ali Khan acquired funding. Muhammad Wajid Ullah and Guang Yang edited and proofread the manuscript. All authors read and approved the final version of the manuscript.

Corresponding authors

Correspondence to Muhammad Wajid Ullah or Guang Yang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Conflict of interest

The authors declare no conflict of interest.

Additional information

Ajmal Shahzad and Jawad Ali contributed equally to this manuscript.

Publisher's Note

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

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 986 KB)

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

Shahzad, A., Ali, J., Ullah, M.W. et al. Fe-based dual-center heterogeneous catalyst assisted with reduced graphene oxide for the activation of peroxymonosulfate. Adv Compos Hybrid Mater 6, 185 (2023). https://doi.org/10.1007/s42114-023-00757-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s42114-023-00757-7

Keywords

Search

Navigation