Skip to main content
Log in

Improving the visible-light photocatalytic activity of Bi2O4 by the combination of the p–n junction and oxygen vacancy strategy for the degradation of organic pollutants

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

Abstract

Constructing p–n heterojunction has been recognized as an effective solution to facilitate the separation of photogenerated carriers through the internal electric field. The introduction of oxygen vacancies (OVs) on the surface of photocatalyst can produce an intermediate band (IB) below the conduction band (CB) of photocatalyst and act as electron trap centers. The catalytic activity of photocatalyst can be improved by adopting p–n heterojunction or OVs strategy, respectively. In this paper, a novel high-performance BiOCl-OVs/Bi2O4 p–n heterostructure, combining the advantages of the above two strategies, was successfully synthesized via a facile mechanical stirring method. The structure, morphology, and photoelectrochemical properties of the samples were studied in detail. The obtained BiOCl-OVs/Bi2O4 catalysts show enhanced visible-light photocatalytic activity compared with pure Bi2O4. The apparent rate constant of the optimal BiOCl-OVs/Bi2O4-2/5 sample is 1.66 and 2.71 times higher than that of Bi2O4 for the degradation of methyl orange (MO) and bisphenol A (BPA), respectively. The improved photocatalytic performance of BiOCl-OVs/Bi2O4 catalyst is mainly attributed to the combined p–n heterojunction effect and OVs formed on the surface of BiOCl. Finally, a probable photocatalytic reaction mechanism was proposed.

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

Access this article

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
Fig. 11

Similar content being viewed by others

References

  1. Y. Wang, C. Liu, J. Tang, Z. Zhang, X. Cao, M. Fang, Y. Xu, W. Zhu, Z. Wu, C. Li, Boron-doped graphene/ZnO nanoflower heterojunction composite with superior photocatalytic activity. J. Inorg. Organomet. Polym Mater. 28, 1520–1527 (2018)

    Article  CAS  Google Scholar 

  2. Z. Abbasi, A. Farrokhnia, E.I. Garcia-Lopez, M. ZargarShoushtari, E. Aghaie, Synthesis of ZnO–Ag2CO3–Fe3O4@rGO core–shell structure: magnetically separable photocatalyst for degradation of MB using the Box–Behnken design. J. Mater. Sci. 31, 19554 (2020)

    Google Scholar 

  3. M. Salah, W. Zayani, B. Bouricha, S. Azizi, A. Alatrache, M. Amlouk, J. Lamloumi, Vibrational study of Li-doped ZnO sprayed thin films along with sensors under ethanol vapor and photocatalytic applications. J. Mater. Sci. 31, 18883–18902 (2020)

    Google Scholar 

  4. H. Sudrajat, P. Sujaridworakun, Low-temperature synthesis of δ-Bi2O3 hierarchical nanostructures composed of ultrathin nanosheets for efficient photocatalysis. Mater. Des. 130, 501–511 (2017)

    Article  CAS  Google Scholar 

  5. W. Xu, J. Fang, X. Zhu, Z. Fang, C. Cen, Fabricaion of improved novel p–n junction BiOI/Bi2Sn2O7 nanocomposite for visible light driven photocatalysis. Mater. Res. Bull. 72, 229–234 (2015)

    Article  CAS  Google Scholar 

  6. X. Wu, J.N. Hart, X. Wen, L. Wang, Y. Du, S.X. Dou, Y.H. Ng, R. Amal, J. Scott, Improving the photo-oxidative performance of Bi2MoO6 by harnessing the synergy between spatial charge separation and rational co-catalyst deposition. ACS Appl. Mater. Interfaces 10, 9342–9352 (2018)

    Article  CAS  Google Scholar 

  7. M. Mao, F. Chen, C. Zheng, J. Ning, Y. Zhong, Y. Hu, Facile synthesis of porous Bi2O3-BiVO4 p–n heterojunction composite microrods with highly efficient photocatalytic degradation of phenol. J. Alloy. Compd. 688, 1080–1087 (2016)

    Article  CAS  Google Scholar 

  8. F. Bessoussa, J.B. Naceur, L. Samet, R. Chtourou, Controlled hydrothermal synthesis and solar light photocatalysis properties of branched Bi2S3/TiO2 nano-heterostructure. J. Mater. Sci. 6, 125029 (2020)

    Google Scholar 

  9. C. Zhang, Y. Ma, C. Li, F. Qin, C. Hu, Q. Hu, S. Duo, Spatially confined growth of Bi2O4 into hierarchical TiO2 spheres for improved visible light photocatalytic activity. J. Mater. Sci. 55, 3181–3194 (2019)

    Article  CAS  Google Scholar 

  10. X. Li, C. Zhang, C. Hu, L. Xu, Q. Hu, S. Duo, W. Li, Y. Kang, Synthesis of Bi2O4@TiO2 heterojunction with enhanced visible light photocatalytic activity. J. Clust. Sci. 28, 2409–2418 (2017)

    Article  CAS  Google Scholar 

  11. Y. Ma, C. Zhang, C. Li, F. Qin, L. Wei, C. Hu, Q. Hu, S. Duo, Nanoscaled Bi2O4 confined in firework-shaped TiO2 microspheres with enhanced visible light photocatalytic performance. Colloids Surf. A 580, 123757 (2019)

    Article  CAS  Google Scholar 

  12. J. Li, Y. Li, G. Zhang, H. Huang, X. Wu, One-dimensional/two-dimensional core–shell-structured Bi2O4/BiO2–x heterojunction for highly efficient broad spectrum light-driven photocatalysis: faster interfacial charge transfer and enhanced molecular oxygen activation mechanism. ACS Appl. Mater. Interfaces 11, 7112–7122 (2019)

    Article  CAS  Google Scholar 

  13. J. Zhao, Z. Zhao, N. Li, J. Nan, R. Yu, J. Du, Visible-light-driven photocatalytic degradation of ciprofloxacin by a ternary Mn2O3/Mn3O4/MnO2 valence state heterojunction. Chem. Eng. J. 353, 805–813 (2018)

    Article  CAS  Google Scholar 

  14. W. Wang, J. Wang, Z. Wang, X. Wei, L. Liu, Q. Ren, W. Gao, Y. Liang, H. Shi, p–n junction CuO/BiVO4 heterogeneous nanostructures: synthesis and highly efficient visible-light photocatalytic performance. Dalton Trans. 43, 6735–6743 (2014)

    Article  CAS  Google Scholar 

  15. H. Lin, H. Ye, B. Xu, J. Cao, S. Chen, Ag3PO4 quantum dot sensitized BiPO4: a novel p–n junction Ag3PO4/BiPO4 with enhanced visible-light photocatalytic activity. Catal. Commun. 37, 55–59 (2013)

    Article  CAS  Google Scholar 

  16. C. Li, Y. Ma, S. Zheng, C. Hu, F. Qin, L. Wei, C. Zhang, S. Duo, Q. Hu, Acid etching followed by hydrothermal preparation of nanosized Bi2O4/Bi2O3 p–n junction as highly efficient visible-light photocatalyst for organic pollutants removal. J. Colloid Interface Sci. 576, 291–301 (2020)

    Article  CAS  Google Scholar 

  17. C. Li, Y. Ma, S. Zheng, C. Hu, F. Qin, L. Wei, C. Zhang, S. Duo, Q. Hu, One-pot synthesis of Bi2O3/Bi2O4 pn heterojunction for highly efficient photocatalytic removal of organic pollutants under visible light irradiation. J. Phys. Chem. Solids 140, 109376 (2020)

    Article  CAS  Google Scholar 

  18. J. Wang, Z. Zhang, X. Wang, Y. Shen, Y. Guo, P.K. Wong, R. Bai, Synthesis of novel p–n heterojunction m-Bi2O4/BiOCl nanocomposite with excellent photocatalytic activity through ion-etching method. Chin. J. Catal. 39, 1792–1803 (2018)

    Article  CAS  Google Scholar 

  19. X. Wang, Q. Ni, D. Zeng, G. Liao, Y. Wen, B. Shan, C. Xie, BiOCl/TiO2 heterojunction network with high energy facet exposed for highly efficient photocatalytic degradation of benzene. Appl. Surf. Sci. 396, 590–598 (2017)

    Article  CAS  Google Scholar 

  20. Q. Wang, W. Wang, L. Zhong, D. Liu, X. Cao, F. Cui, Oxygen vacancy-rich 2D/2D BiOCl-g-C3N4 ultrathin heterostructure nanosheets for enhanced visible-light-driven photocatalytic activity in environmental remediation. Appl. Catal. B 220, 290–302 (2018)

    Article  CAS  Google Scholar 

  21. W. Yang, B. Ma, W. Wang, Y. Wen, D. Zeng, B. Shan, Enhanced photosensitized activity of a BiOCl–Bi2WO6 heterojunction by effective interfacial charge transfer. Phys. Chem. Chem. Phys. 15, 19387–19394 (2013)

    Article  CAS  Google Scholar 

  22. D. Chen, M. Zhang, Q. Lu, J. Chen, B. Liu, Z. Wang, Facile synthesis of Bi/BiOCl composite with selective photocatalytic properties. J. Alloy. Compd. 646, 647–654 (2015)

    Article  CAS  Google Scholar 

  23. F.-T. Li, Y.-L. Li, M.-J. Chai, B. Li, Y.-J. Hao, X.-J. Wang, R.-H. Liu, One-step construction of 001 facet-exposed BiOCl hybridized with Al2O3 for enhanced molecular oxygen activation. Catal. Sci. Technol. 6, 7985–7995 (2016)

    Article  CAS  Google Scholar 

  24. H. Li, L. Zhang, Oxygen vacancy induced selective silver deposition on the 001 facets of BiOCl single-crystalline nanosheets for enhanced Cr(VI) and sodium pentachlorophenate removal under visible light. Nanoscale 6, 7805–7810 (2014)

    Article  CAS  Google Scholar 

  25. H. Li, H. Shang, X. Cao, Z. Yang, Z. Ai, L. Zhang, Oxygen vacancies mediated complete visible light NO oxidation via side-on bridging superoxide radicals. Environ. Sci. Technol. 52, 8659–8665 (2018)

    Article  CAS  Google Scholar 

  26. Y. Guo, J. Li, J. Sun, Oxygen vacancy-assistant enhancement of photoluminescence performance of Eu3+ and La3+-codoped BiOCl ultrathin nanosheets. J. Lumin. 208, 267–272 (2019)

    Article  CAS  Google Scholar 

  27. W. He, Y. Wang, C. Fan, Y. Wang, X. Zhang, J. Liu, R. Li, Enhanced charge separation and increased oxygen vacancies of h-BN/OV-BiOCl for improved visible-light photocatalytic performance. RSC Adv. 9, 14286–14295 (2019)

    Article  CAS  Google Scholar 

  28. J. Wang, K. Chen, Y. Shen, X. Wang, Y. Guo, X. Zhou, R. Bai, Enhanced photocatalytic degradation for organic pollutants by a novel m-Bi2O4/Bi2O2CO3 photocatalyst under visible light. Res. Chem. Intermed. 44, 3061–3079 (2018)

    Article  CAS  Google Scholar 

  29. L. Sun, L. Xiang, X. Zhao, C.-J. Jia, J. Yang, Z. Jin, X. Cheng, W. Fan, Enhanced visible-light photocatalytic activity of BiOI/BiOCl heterojunctions: key role of crystal facet combination. ACS Catal. 5, 3540–3551 (2015)

    Article  CAS  Google Scholar 

  30. P. Zhang, Y. Qiu, S. Yang, Y. Jiao, C. Ji, Y. Li, B. Chen, H. Fan, Oxygen-deficient bismuth oxychloride nanosheets: Superior photocatalytic performance. Mater. Res. Bull. 96, 478–484 (2017)

    Article  CAS  Google Scholar 

  31. H. Yu, D. Ge, Y. Wang, S. Zhu, X. Wang, M. Huo, Y. Lu, Facile synthesis of Bi-modified Nb-doped oxygen defective BiOCl microflowers with enhanced visible-light-driven photocatalytic performance. J. Alloy. Compd. 786, 155–162 (2019)

    Article  CAS  Google Scholar 

  32. X. Zeng, X. Gong, Y. Wan, R. He, Z. Xu, Formation of oxygen vacancies on the 010 facets of BiOCl and visible light activity for degradation of ciprofloxacin. Chem. Res. Chin. Univ. 34, 711–718 (2018)

    Article  CAS  Google Scholar 

  33. Y. Jia, S. Li, H. Ma, J. Gao, G. Zhu, F. Zhang, J.Y. Park, S. Cha, J.-S. Bae, C. Liu, Oxygen vacancy rich Bi2O4-Bi4O7-BiO2-x composites for UV–Vis–NIR activated high efficient photocatalytic degradation of bisphenol A. J. Hazard. Mater. 382, 121121 (2020)

    Article  CAS  Google Scholar 

  34. N. Mohaghegh, M. Tasviri, E. Rahimi, M.R. Gholami, A novel p–n junction Ag3PO4/BiPO4-based stabilized Pickering emulsion for highly efficient photocatalysis. RSC Adv. 5, 12944–12955 (2015)

    Article  CAS  Google Scholar 

  35. D. Cui, L. Wang, K. Xu, L. Ren, L. Wang, Y. Yu, Y. Du, W. Hao, Band-gap engineering of BiOCl with oxygen vacancies for efficient photooxidation properties under visible-light irradiation. J. Mater. Chem. A 6, 2193–2199 (2018)

    Article  CAS  Google Scholar 

  36. X. Li, F. Chen, C. Lian, S. Zheng, Q. Hu, S. Duo, W. Li, C. Hu, Au/TiO2/graphene composite with enhanced photocatalytic activity under both UV and visible light irradiation. J. Clust. Sci. 27, 1877–1892 (2016)

    Article  CAS  Google Scholar 

  37. X. Li, S. Zheng, C. Zhang, C. Hu, F. Chen, Y. Sun, S. Duo, R. Zhang, Q. Hu, W. Li, Y. Kang, Synergistic promotion of photocatalytic performance by core@shell structured TiO2/Au@rGO ternary photocatalyst. Mol. Catal. 438, 55–65 (2017)

    Article  CAS  Google Scholar 

  38. W. Wang, X. Chen, G. Liu, Z. Shen, D. Xia, P.K. Wong, J.C. Yu, Monoclinic dibismuth tetraoxide: a new visible-light-driven photocatalyst for environmental remediation. Appl. Catal. B 176–177, 444–453 (2015)

    Article  CAS  Google Scholar 

  39. F. Duo, Y. Wang, X. Mao, X. Zhang, Y. Wang, C. Fan, A BiPO4/BiOCl heterojunction photocatalyst with enhanced electron-hole separation and excellent photocatalytic performance. Appl. Surf. Sci. 340, 35–42 (2015)

    Article  CAS  Google Scholar 

  40. Z. Cui, H. Song, S. Ge, W. He, Y. Liu, Fabrication of BiOCl/BiOBr hybrid nanosheets with enhanced superoxide radical dominating visible light driven photocatalytic activity. Appl. Surf. Sci. 467–468, 505–513 (2019)

    Article  CAS  Google Scholar 

  41. H. Li, J. Shi, K. Zhao, L. Zhang, Sustainable molecular oxygen activation with oxygen vacancies on the 001 facets of BiOCl nanosheets under solar light. Nanoscale 6, 14168–14173 (2014)

    Article  CAS  Google Scholar 

  42. L. Ji, H. Wang, R. Yu, Heterogeneous photocatalysts BiOX/NaBiO3 (X = Cl, Br, I): Photo-generated charge carriers transfer property and enhanced photocatalytic activity. Chem. Phys. 478, 14–22 (2016)

    Article  CAS  Google Scholar 

  43. S. Li, J. Chen, Y. Liu, K. Xu, J. Liu, In situ anion exchange strategy to construct flower-like BiOCl/BiOCOOH p–n heterojunctions for efficiently photocatalytic removal of aqueous toxic pollutants under solar irradiation. J. Alloy. Compd. 781, 582–588 (2019)

    Article  CAS  Google Scholar 

  44. Y. Xiang, P. Ju, Y. Wang, Y. Sun, D. Zhang, J. Yu, Chemical etching preparation of the Bi2WO6/BiOI p–n heterojunction with enhanced photocatalytic antifouling activity under visible light irradiation. Chem. Eng. J. 288, 264–275 (2016)

    Article  CAS  Google Scholar 

  45. Z. He, Y. Shi, C. Gao, L. Wen, J. Chen, S. Song, BiOCl/BiVO4 p–n heterojunction with enhanced photocatalytic activity under visible-light irradiation. J. Phys. Chem. C 118, 389–398 (2013)

    Article  CAS  Google Scholar 

  46. J. Tian, T. Yan, Z. Qiao, L. Wang, W. Li, J. You, B. Huang, Anion-exchange synthesis of Ag2S/Ag3PO4 core/shell composites with enhanced visible and NIR light photocatalytic performance and the photocatalytic mechanisms. Appl. Catal. B 209, 566–578 (2017)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors are thankful to the National Natural Science Foundation of China (Grant No. 21663012) and Natural Science Foundation of Jiangxi province (Grant No. 20181BAB203009).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Changyuan Hu.

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

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, C., Zhang, C., Zheng, S. et al. Improving the visible-light photocatalytic activity of Bi2O4 by the combination of the p–n junction and oxygen vacancy strategy for the degradation of organic pollutants. J Mater Sci: Mater Electron 32, 10398–10411 (2021). https://doi.org/10.1007/s10854-021-05696-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10854-021-05696-x

Navigation