Advertisement

Fabrication of CoFe2O4-modified and HNTs-supported g-C3N4 heterojunction photocatalysts for enhancing MBT degradation activity under visible light

  • 66 Accesses

Abstract

It is still a challenging work to realize the universality of photocatalytic materials for unselectively removing environmental pollutants in water. Here, a ternary magnetism CoFe2O4/g-C3N4/HNTs heterojunction photocatalyst is firstly prepared, and the morphology, crystalline property, surface area, and magnetic recycling capability of the photocatalyst were investigated. The CoFe2O4/g-C3N4/HNTs shows a superior degradation efficiency for degrading 2-mercaptobenzothiazole (MBT) than that of pure g-C3N4. The high degradation performance that derives from the hollow structure of halloysite nanotubes (HNTs) can inhibit stacking of g-C3N4, which results in a larger specific surface area and more abundant reaction sites. Meanwhile, the heterojunction structure between g-C3N4 and CoFe2O4 improved the separation efficiency of charge carriers. In addition, the intermediate products, degradation pathway, and reaction mechanism of representative MBT pollutant over the CoFe2O4/g-C3N4/HNTs photocatalyst are revealed in depth. This work makes an important development.

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

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Subscribe to journal

Immediate online access to all issues from 2019. Subscription will auto renew annually.

US$ 199

This is the net price. Taxes to be calculated in checkout.

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11
Figure 12
Figure 13
Figure 14
Figure 15

References

  1. 1

    Naing H, Wang K, Tun P, Zhang G (2019) Enhanced broad spectrum (Vis-NIR) responsive photocatalytic performance of Ag2O/rectorite nanoarchitectures. Appl Surf Sci 491:216–224

  2. 2

    Li C, Yu S, Dong H, Liu C, Wu H, Che H, Chen G (2018) Z-scheme mesoporous photocatalyst constructed by modification of Sn3O4 nanoclusters on g-C3N4 nanosheets with improved photocatalytic performance and mechanism insight. Appl Catal B Environ 238:284–293

  3. 3

    Wen H, Ru X, Xi T, Jie J, Wei W (2017) Interfacial amplification for graphene-based position-sensitive-detectors. Light Sci Appl 6:e17113–e17117

  4. 4

    Zhu Z, Fan W, Liu Z, Yu Y, Dong H (2018) Fabrication of the metal-free biochar-based graphitic carbon nitride for improved 2-mercaptobenzothiazole degradation activity. J Photochem Photobiol, A 358:284–293

  5. 5

    Zhu Z, Lu Z, Zhao X, Yan Y, Shi W, Wang D, Liu Y (2015) Surface imprinting of a g-C3N4 photocatalyst for enhanced photocatalytic activity and selectivity towards photodegradation of 2-mercaptobenzothiazole. RSC Adv 5:40726–40736

  6. 6

    Luo Y, Lu Z, Jiang Y, Wang D, Yang L, Huo P, Yang P (2014) Selective photodegradation of 1-methylimidazole-2-thiol by the magnetic and dual conductive imprinted photocatalysts based on TiO2/Fe3O4/MWCNTs. Chem Eng J 240:244–252

  7. 7

    Li SZ, Li XY, Cui ZF, Wang DZ (2004) Application of ultrafiltration to improve the extraction of antibiotics. Sep Purif Technol 34:115–123

  8. 8

    Moreira F, Garcia-Segura S, Rui A (2014) Degradation of the antibiotic trimethoprim by electrochemical advanced oxidation processes using a carbon-PTFE air-diffusion cathode and a boron-doped diamond or platinum anode. Appl Catal B Environ 160:492–505

  9. 9

    Lupton J (2004) Microbial degradation products influence colon cancer risk: the butyrate controversy. J Nutr 134:479–482

  10. 10

    Huang J, Wang X, Jin Q, Liu Y, Wang Y (2007) Removal of phenol from aqueous solution by adsorption onto OTMAC-modified attapulgite. J Environ Manag 84:229–236

  11. 11

    Li C, Yu S, Che H, Zhang X, Han J, Mao Y, Wang Y, Liu C, Dong H (2018) Fabrication of Z-scheme heterojunction by anchoring mesoporous γ-Fe2O3 nanospheres on g-C3N4 for degrading tetracycline hydrochloride in water. ACS Sustain Chem Eng 6:16437–16447

  12. 12

    Yatsui T, Tsuboi T, Yamaguchi M (2016) Optically controlled magnetic-field etching on the nano-scale. Light Sci Appl 5:e16054–e16061

  13. 13

    Lu Z, Yu Z, Dong J, Song M, Liu Y, Liu X, Huo P (2018) Facile microwave synthesis of a Z-scheme imprinted ZnFe2O4/Ag/PEDOT with the specific recognition ability towards improving photocatalytic activity and selectivity for tetracycline. Chem Eng J 337:228–241

  14. 14

    Zhu Z, Huo P, Lu Z, Yan Y, Liu Z, Shi W (2018) Fabrication of magnetically recoverable photocatalysts using g-C3N4 for effective separation of charge carriers through like-Z-scheme mechanism with Fe3O4 mediator. Chem Eng J 331:615–625

  15. 15

    Wang B, Cai H, Shen S (2019) Single metal atom photocatalysis. Small Methods 3:447–454

  16. 16

    Zhao D, Dong C, Wang B, Chen C, Shen S (2019) Synergy of dopants and defects in graphitic carbon nitride with exceptionally modulated band structures for efficient photocatalytic oxygen evolution. Adv Mater 31:545–553

  17. 17

    Liu K, Zhang Z, Shan C, Feng Z, Li J, Song C (2016) A flexible and superhydrophobic upconversion-luminescence membrane as an ultrasensitive fluorescence sensor for single droplet detection. Light Sci Appl 5:e16136–e16142

  18. 18

    Che H, Che G, Zhou P, Liu C, Dong H, Li C, Song N, Li C (2020) Nitrogen doped carbon ribbons modified g-C3N4 for markedly enhanced photocatalytic H2-production in visible to near-infrared region. Chem Eng J 382:122870–122878

  19. 19

    Wang K, Zhang G, Li J, Li Y, Wu X (2017) 0D/2D Z-scheme heterojunctions of bismuth tantalate quantum dots/ultrathin g-C3N4 nanosheets for highly efficient visible light photocatalytic degradation of antibiotics. ACS Appl Mater Interfaces 9:43704–43715

  20. 20

    Zhao D, Wang M, Kong T, Shang Y, Du X, Guo L, Shen S (2019) Electronic pump boosting photocatalytic hydrogen evolution over graphitic carbon nitride. Mater Today Chem 11:296–302

  21. 21

    Tong Z, Yang D, Xiao T, Tian Y, Jiang Z (2015) Biomimetic fabrication of g-C3N4/TiO2 nanosheets with enhanced photocatalytic activity toward organic pollutant degradation. Chem Eng J 260:117–125

  22. 22

    Li M, Zhang L, Wu M, Du Y, Wang M, Zhang L, Kong Q, Shi J (2016) Mesostructured CeO2/g-C3N4 nanocomposites: remarkably enhanced photocatalytic activity for CO2 reduction by mutual component activations. Nano Energy 19:145–155

  23. 23

    Jiang F, Yan T, Chen H, Sun A, Xu C, Wang X (2014) A g-C3N4–CdS composite catalyst with high visible-light-driven catalytic activity and photostability for methylene blue degradation. Appl Surf Sci 295:164–172

  24. 24

    Shao Z, Zeng T, He Y, Zhang D, Pu X (2019) A novel magnetically separable CoFe2O4/Cd0.9Zn0.1S photocatalyst with remarkably enhanced H2 evolution activity under visible light irradiation. Chem Eng J 359:485–495

  25. 25

    Popat Y, Orlandi M, Patel N, Edla R, Gupta S, Yadav M, Pillai S, Patel M, Miotello A (2019) Pulsed laser deposition of CoFe2O4/CoO hierarchical-type nanostructured heterojuction forming a Z-scheme for efficient spatial separation of photoinduced electron-hole pairs and highly active surface area. Appl Surf Sci 489:584–594

  26. 26

    Bian W, Yang Z, Strasser P, Yang R (2014) A CoFe2O4/graphene nanohybrid as an efficient bi-functional electrocatalyst for oxygen reduction and oxygen evolution. J Power Sources 250:196–203

  27. 27

    Zhu Y, DiMarco C, Maturavongsadit P, Yu N (2018) Optical conductivity-based ultrasensitive mid-infrared biosensing on a hybrid metasurface. Light Sci Appl 7:67–78

  28. 28

    Jing H, Huang J, Li N, Li L, Zhang J (2019) Fabrication of magnetically recyclable ZrO2–TiO2/CoFe2O4 hollow core/shell photocatalysts: improving photocatalytic efficiency under sunlight irradiation. Korean J Chem Eng 36:605–612

  29. 29

    Gan L, Xu L, Qian K (2016) Preparation of core-shell structured CoFe2O4 incorporated Ag3PO4 nanocomposites for photocatalytic degradation of organic dyes. Mater Des 109:354–360

  30. 30

    Li M, Song C, Wu Y, Wang M, Pan Z, Sun Y, Meng L, Han S, Xu L, Gan L (2019) Novel Z-scheme visible-light photocatalyst based on CoFe2O4/BiOBr/Graphene composites for organic dye degradation and Cr(VI) reduction. Appl Surf Sci 478:744–753

  31. 31

    Ferdosi E, Bahiraei H, Ghanbari D (2019) Investigation the photocatalytic activity of CoFe2O4/ZnO and CoFe2O4/ZnO/Ag nanocomposites for purification of dye pollutants. Sep Purif Technol 211:35–39

  32. 32

    Chang C, Chu K, Wei Y (2016) CoFe2O4@ZnS core–shell spheres as magnetically recyclable photocatalysts for hydrogen production. J Taiwan Inst Chem E 66:386–393

  33. 33

    Li J, Ma Y, Ye Z, Zhou M, Wang HQ, Ma C, Huo P, Yan Y (2017) Fast electron transfer and enhanced visible light photocatalytic activity using multi-dimensional components of carbon quantum dots@3D daisy-like In2S3/single-wall carbon nanotubes. Appl Catal B Environ 204:224–238

  34. 34

    Zheng J, Zhu Z, Gao G, Liu Z, Yan Y (2019) Construction of spindle structured CeO2 modified with rod-like attapulgite as a high-performance photocatalyst for CO2 reduction. Catal Sci Technol 9:3788–7799

  35. 35

    Maguid E, Yulevich I, Yannai M, Kleiner V, Hasman E (2017) Multifunctional interleaved geometric-phase dielectric metasurfaces. Light Sci Appl 6:e17027–e17032

  36. 36

    Qi H, Wang H, Jiang W (2019) Preparation and photocatalytic activity of Ag-modified GO-TiO2 mesocrystals under visible light irradiation. Appl Surf Sci 480:105–114

  37. 37

    Xing W, Ni L, Huo P, Lu X, Luo Y, Yan Y (2012) Preparation high photocatalytic activity of CdS/halloysite nanotubes (HNTs) nanocomposites with hydrothermal method. Appl Surf Sci 259:698–704

  38. 38

    Jiang L, Huang YP, Liu TX (2015) Enhanced visible-light photocatalytic performance of electrospun carbon-doped TiO2/halloysite nanotube hybrid nanofibers. J Colloid Interface Sci 439:62–68

  39. 39

    Sangmanee M, Maensiri S (2009) Nanostructures and magnetic properties of cobalt ferrite (CoFe2O4) fabricated by electro spinning. Appl Phys A 97:167–177

  40. 40

    Pincella F, Isozaki K, Miki K (2014) A visible light-driven plasmonic photocatalyst. Light Sci Appl 3:e133–e139

  41. 41

    Senapati K, Borgohain C, Sarma K, Phukan P (2011) Photocatalytic degradation of methylene blue in water using CoFe2O4–Cr2O3–SiO2 fluorescent magnetic nanocomposite. J Mol Catal A: Chem 346:111–116

  42. 42

    Ye Z, Li J, Zhou M, Wang H, Huo P (2016) Well-dispersed nebula-like ZnO/CeO2@HNTs heterostructure for efficient photocatalytic degradation of tetracycline. Chem Eng J 15:917–933

  43. 43

    Chen X, Zhang J, Fu X, Antonietti M, Wang X (2009) Fe–g-C3N4-catalyzed oxidation of benzene to phenol using hydrogen peroxide and visible light. J Am Chem Soc 131:11658–11659

  44. 44

    Zhao Z, Li K, Muhmood T, Xia M, Wang F (2018) Facile approach to synthesis the curly leaf-like nano-sheets of g-C3N4 with enhanced photocatalytic ability. Mater Res Express 5:132–139

  45. 45

    Zhu Z, Tang T, Fan W, Liu Z, Huo P, Yan Y (2019) Insight into the effect of Co-doped to the photocatalytic performance and electronic structure of g-C3N4 by first principle. Appl Catal B Environ 241:319–328

  46. 46

    Chen J, Dong C, Zhao D, Huang Y, Wang X, Samad L, Dang L, Shearer M, Shen S, Guo L (2017) Molecular design of polymer heterojunctions for efficient solar-hydrogen conversion. Adv Mater 29(21):1606198–1606208

  47. 47

    Ma XC, Dai Y, Yu L, Huang B (2016) Energy transfer in plasmonic photocatalytic composites. Light Sci Appl 5:e16017–e16029

  48. 48

    Ma X, Lv Y, Xu J, Liu Y, Zhang R, Zhu Y (2012) A strategy of enhancing the photoactivity of g-C3N4 via doping of nonmetal elements: a first-principles study. J Phys Chem C 116:23485–23493

  49. 49

    Zhang G, Zhang M, Ye X, Qiu X, Lin S, Wang X (2014) Iodine modified carbon nitride semiconductors as visible light photocatalysts for hydrogen evolution. Adv Mater 26:805–809

  50. 50

    Shi L, Liang L, Ma J, Wang F, Sun J (2014) Remarkably enhanced photocatalytic activity of ordered mesoporous carbon/g-C3N4 composite photocatalysts under visible light. Dalton Trans 43:7236–7244

  51. 51

    Sugioka K, Cheng Y (2014) Ultrafast lasers-reliable tools for advanced materials processing. Light Sci Appl 3:e149–e158

  52. 52

    Bai X, Wang L, Wang Y, Yao W, Zhu Y (2014) Enhanced oxidation ability of g-C3N4 photocatalyst via C60 modification. Appl Catal B Environ 152:262–270

  53. 53

    Ge L, Han C, Liu J, Li Y (2011) Enhanced visible light photocatalytic activity of novel polymeric g-C3N4 loaded with Ag nanoparticles. Appl Catal A Gen 409:215–222

  54. 54

    Chen J, Zhao D, Diao Z, Wang M, Shen S (2016) Ferrites boosting photocatalytic hydrogen evolution over graphitic carbon nitride a case study of (Co, Ni)Fe2O4 modification. Sci Bull 61(4):292–301

  55. 55

    Shi L, Liang L, Ma J, Wang F, Sun J (2014) Enhanced photocatalytic activity over the Ag2O–g-C3N4 composite under visible light. Catal Sci Technol 4:758–765

  56. 56

    Shi L, Wang F, Zhang J, Sun J (2016) Onion-like carbon modified porous graphitic carbon nitride with excellent photocatalytic activities under visible light. Ceram Int 42:18116–18123

  57. 57

    Bonefacino J, Tam H, Glen T, Cheng X, Pun C, Wang J (2018) Ultra-fast polymer optical fibre Bragg grating inscription for medical devices. Light Sci Appl 7:17161–17171

  58. 58

    Lu Z, Chen F, He M, Song M, Lan J, Li F, Xiao P (2014) Microwave synthesis of a novel magnetic imprinted TiO2 photocatalyst with excellent transparency for selective photodegradation of enrofloxacin hydrochloride residues solution. Chem Eng J 249:15–26

  59. 59

    He F, Lu Z, Song M, Liu X, Tang H, Huo P, Fan W, Dong H, Wu X, Song H (2019) Selective reduction of Cu2+ with simultaneous degradation of tetracycline by the dual channels ion imprinted POPD-CoFe2O4 heterojunction photocatalyst. Chem Eng J 360:750–761

  60. 60

    Zhu Z, Yu Y, Dong H, Li C, Huo P (2017) Intercalation effect of ATP in g-C3N4 modified with Fe3O4-QDs to enhance photocatalytic activity for removing 2-mercaptobenzothiazole under visible light. ACS Sustain Chem Eng 5:10614–10623

  61. 61

    Li L, Lin H, Qiao S, Huang YZ, Li JY, Michon J (2018) Monolithically integrated stretchable photonics. Light Sci Appl 7:17138–17146

  62. 62

    Che H, Liu H, Che G, Dong H, Liu C, Li C (2019) Control of energy band, layer structure and vacancy defect of graphitic carbon nitride by intercalated hydrogen bond effect of NO3 toward improving photocatalytic performance. Chem Eng J 357:209–6219

  63. 63

    Kumar S, Kumar A, Kumar A, Balaji R, Krishnan V (2018) Highly efficient visible light active 2D-2D nanocomposites of N-ZnO–g-C3N4 for photocatalytic degradation of diverse industrial pollutants. Chemistryselect 3:1919–1932

  64. 64

    Lin X, Liu C, Wang J, Yang S, Shi J, Hong Y (2019) Graphitic carbon nitride quantum dots and nitrogen-doped carbon quantum dots co-decorated with BiVO4 microspheres: a ternary heterostructure photocatalyst for water purification. Sep Purif Technol 226:117–127

  65. 65

    Zhao M, Liao H, Molokeev M (2019) Emerging ultra-narrow-band cyan-emitting phosphor for white LEDs with enhanced color rendition. Light Sci Appl 8:38

  66. 66

    Zhu Z, Ma C, Yu K, Lu Z, Liu Z, Huo P, Xu T, Yan Y (2020) Synthesis Ce-doped biomass carbon-based g-C3N4 via plant growing guide and temperature-programmed technique for degrading 2-Mercaptobenzothiazole. Appl Catal B: Environ. https://doi.org/10.1016/j.apcatb.2019.118432

Download references

Acknowledgements

This work is financially supported by the National Natural Science Foundation of China (Nos. U1662125, 21908080, 21871124), the Natural Science Foundation of Jiangsu Province (Nos. BK20190862, BK20181231 and BK20180884), and China Postdoctoral Science Foundation-funded project (Nos. 2016M590418).

Author information

Correspondence to Xu Tang or Pengwei Huo.

Ethics declarations

Conflict of interest

All the authors declare that they have no conflict of interest.

Additional information

Publisher's Note

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

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhu, Z., Ma, C., Yu, K. et al. Fabrication of CoFe2O4-modified and HNTs-supported g-C3N4 heterojunction photocatalysts for enhancing MBT degradation activity under visible light. J Mater Sci 55, 4358–4371 (2020) doi:10.1007/s10853-019-04170-8

Download citation