Skip to main content

Significantly boosting the visible light activity of BiOCl by facile solvothermal doping with chromium


Due to the unique layered crystal structure, BiOCl is potential as a semiconductor photocatalyst but limited by the insufficient absorption of visible light. In this work, Cr-doped and oxygen vacancy contained BiOCl photocatalyst (Cr-BOC) with uniform diameter around 1 µm was successfully synthesized without changing the morphology via a facile solvothermal method in ethylene glycol solvent. The prepared Cr-BOC doped with 5% Cr exhibits more outstanding visible light photocatalytic performance than BiOCl, totally decomposes 99.2% rhodamine B (RhB) only within 4 min irradiation with a largest apparent rate constant (k) of 1.0112 min−1, which are much higher than that of pure BiOCl (64.4% and 0.2134 min−1). On the basis of a series of characterizations, it is concluded that the remarkable photocatalytic activity was attributed to the increased specific surface area of Cr-BOC (38.25 m2 g−1) compared with BiOCl (13.33 m2 g−1) and improved photoinduced carrier separation efficiency by the doping energy level after the introduction of Cr ions. Moreover, the active species trapping experiments indicate that all the hole, superoxide radical and hydroxyl radical participate in the photocatalytic process of RhB degradation. This work shows the great potential of Cr-BOC as a photocatalyst towards organic pollutant degradation.

Graphical abstract

Cr-doped BiOCl photocatalyst with abundant oxygen vacancies was successfully synthesized via a facile solvothermal method with outstanding photocatalytic performance to decompose 99.2% rhodamine B only within 4 min visible light irradiation.

Crystal model (a) and promoted mechanism (b) of Cr doped BiOCl.


  • Cr-BiOCl photocatalyst was successfully synthesized via a facile solvothermal method.

  • Cr-BiOCl shows enhanced photocatalytic activity in comparison with BiOCl, totally decomposes 99.2% rhodamine B within 4 min irradiation.

  • The remarkable photocatalytic activity of Cr-BiOCl is attributed to the increased specific surface area and charge separation efficiency.

This is a preview of subscription content, access via your institution.

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


  1. Yao L, Yang H, Chen Z, Qiu M, Hu B, Wang X (2021) Bismuth oxychloride-based materials for the removal of organic pollutants in wastewater. Chemosphere 273:128576

    Article  CAS  Google Scholar 

  2. Shen H, Fu F, Xue W, Yang X, Ajmal S, Zhen Y, Guo L, Wang D, Chi R (2021) In situ fabrication of Bi2MoO6/Bi2MoO6-x homojunction photocatalyst for simultaneous photocatalytic phenol degradation and Cr(VI) reduction. J Colloid Interface Sci 599:741–751

    Article  CAS  Google Scholar 

  3. Li J, Yu Y, Zhang L (2014) Bismuth oxyhalide nanomaterials: layered structures meet photocatalysis. Nanoscale 6:8473–8488

    Article  CAS  Google Scholar 

  4. Jiang J, Zhang L, Li H, He W, Yin JJ (2013) Self-doping and surface plasmon modification induced visible light photocatalysis of BiOCl. Nanoscale 5:10573–10581

    Article  CAS  Google Scholar 

  5. Di J, Xia J, Li H, Guo S, Dai S (2017) Bismuth oxyhalide layered materials for energy and environmental applications. Nano Energy 41:172–192

    Article  CAS  Google Scholar 

  6. Singh S, Sharma R, Khanuja M (2018) A review and recent developments on strategies to improve the photocatalytic elimination of organic dye pollutants by BiOX (X=Cl, Br, I, F) nanostructures. Korean J Chem Eng 35:1955–1968

    Article  CAS  Google Scholar 

  7. Zhang H, Liu L, Zhou Z (2012) Towards better photocatalysts: first-principles studies of the alloying effects on the photocatalytic activities of bismuth oxyhalides under visible light. Phys Chem Chem Phys 14:1286–1292

    Article  CAS  Google Scholar 

  8. Liu J, Wang H, Chang M-J, Li W-J, Zhu W-Y, Bai G, Yang L-Q, Du H-L, Luo Z-M, Shang T (2023) Efficient doping to synthesize high-performance Co/Fe-BiOCl photocatalyst assisted by the ion release from novel CoFe2O4 nanofiber reservoir. Colloids Surf, A 660:130903

    Article  CAS  Google Scholar 

  9. Wang L, Lv D, Dong F, Wu X, Cheng N, Scott J, Xu X, Hao W, Du Y (2019) Boosting visible-light-driven photo-oxidation of BiOCl by promoted charge separation via vacancy engineering. ACS Sustain Chem Eng 7:3010–3017

    Article  CAS  Google Scholar 

  10. Li H, Li J, Ai Z, Jia F, Zhang L (2018) Oxygen vacancy-mediated photocatalysis of BiOCl: reactivity, selectivity, and perspectives. Angew Chem Int Ed 57:122–138

    Article  CAS  Google Scholar 

  11. Tian J, Chen Z, Deng X, Sun Q, Sun Z, Li W (2018) Improving visible light driving degradation of norfloxacin over core-shell hierarchical BiOCl microspherical photocatalyst by synergistic effect of oxygen vacancy and nanostructure. Appl Surf Sci 453:373–382

    Article  CAS  Google Scholar 

  12. Zhao H, Liu X, Dong Y, Xia Y, Wang H (2019) A special synthesis of BiOCl photocatalyst for efficient pollutants removal: new insight into the band structure regulation and molecular oxygen activation. Appl Catal, B 256:117872

    Article  CAS  Google Scholar 

  13. Song Z, Dong X, Fang J, Xiong C, Wang N, Tang X (2019) Improved photocatalytic degradation of perfluorooctanoic acid on oxygen vacancies-tunable bismuth oxychloride nanosheets prepared by a facile hydrolysis. J Hazard Mater 377:371–380

    Article  CAS  Google Scholar 

  14. Zhong X, Zhang KX, Wu D, Ye XY, Huang W, Zhou BX (2020) Enhanced photocatalytic degradation of levofloxacin by Fe-doped BiOCl nanosheets under LED light irradiation. Chem Eng J 383:123148

    Article  CAS  Google Scholar 

  15. Tian F, Li G, Zhao H, Chen F, Li M, Liu Y, Chen R (2019) Residual Fe enhances the activity of BiOCl hierarchical nanostructure for hydrogen peroxide activation. J Catal 370:265–273

    Article  CAS  Google Scholar 

  16. Yu H, Ge D, Liu Y, Lu Y, Wang X, Huo M, Qin W (2020) One-pot synthesis of BiOCl microflowers co-modified with Mn and oxygen vacancies for enhanced photocatalytic degradation of tetracycline under visible light. Sep Purif Technol 251:117414

    Article  CAS  Google Scholar 

  17. Cao J, Li J, Chu W, Cen W (2020) Facile synthesis of Mn-doped BiOCl for metronidazole photodegradation: Optimization, degradation pathway, and mechanism. Chem Eng J 400:125813

    Article  CAS  Google Scholar 

  18. Li WT, Huang WZ, Zhou H, Yin HY, Zheng YF, Song XC (2015) Synthesis of Zn2+ doped BiOCl hierarchical nanostructures and their exceptional visible light photocatalytic properties. J Alloy Compd 638:148–154

    Article  CAS  Google Scholar 

  19. Wang CY, Zhang YJ, Wang WK, Pei DN, Huang GX, Chen JJ, Zhang X, Yu HQ (2018) Enhanced photocatalytic degradation of bisphenol A by Co-doped BiOCl nanosheets under visible light irradiation. Appl Catal, B 221:320–328

    Article  CAS  Google Scholar 

  20. Liu J, Wang H, Chang M, Sun M, Zhang C, Yang L, Du H, Luo Z (2022) Facile synthesis of BiOCl with extremely superior visible light photocatalytic activity synergistically enhanced by Co doping and oxygen vacancies. Sep Purif Technol 301:121953

    Article  CAS  Google Scholar 

  21. Di J, Xia J, Yin S, Xu H, Xu L, Xu Y, He M, Li H (2014) One-pot solvothermal synthesis of Cu-modified BiOCl via a Cu-containing ionic liquid and its visible-light photocatalytic properties. RSC Adv 4:14281

    Article  CAS  Google Scholar 

  22. Gao M, Zhang D, Pu X, Li H, Li W, Shao X, Lv D, Zhang B, Dou J (2016) Combustion synthesis of Fe-doped BiOCl with high visible-light photocatalytic activities. Sep Purif Technol 162:114–119

    Article  CAS  Google Scholar 

  23. Nguyen SN, Truong TK, You SJ, Wang YF, Cao TM, Pham VV (2019) Investigation on photocatalytic removal of NO under visible light over Cr-doped ZnO nanoparticles. ACS Omega 4:12853–12859

    Article  CAS  Google Scholar 

  24. Gomez-Polo C, Larumbe S, Gil A, Muñoz D, Fernández LR, Barquín LF, García-Prieto A, Fdez-Gubieda ML, Muela A (2021) Improved photocatalytic and antibacterial performance of Cr doped TiO2 nanoparticles. Surf Interfaces 22:100867

  25. Zhang L, Liang C, Guo H, Niu CG, Zhao XF, Wen XJ, Zeng GM (2019) Construction of a high-performance photocatalytic fuel cell (PFC) based on plasmonic silver modified Cr-BiOCl nanosheets for simultaneous electricity production and pollutant removal. Nanoscale 11:6662–6676

    Article  CAS  Google Scholar 

  26. Ye L, Deng K, Xu F, Tian L, Peng T, Zan L (2012) Increasing visible-light absorption for photocatalysis with black BiOCl. Phys Chem Chem Phys 14:82–85

    Article  CAS  Google Scholar 

  27. Zhu J, Deng Z, Chen F, Zhang J, Chen H, Anpo M, Huang J, Zhang L (2006) Hydrothermal doping method for preparation of Cr3+-TiO2 photocatalysts with concentration gradient distribution of Cr3+. Appl Catal, B 62:329–335

    Article  CAS  Google Scholar 

  28. Ashiri R, Nemati A, Ghamsari MS, Aadelkhani H (2009) Characterization of optical properties of amorphous BaTiO3 nanothin films. J Non-Cryst Solids 355:2480–2484

    Article  CAS  Google Scholar 

  29. ASHIRI R (2014) Analysis and characterization of relationships between the processing and optical responses of amorphous BaTiO3 nanothin films obtained by an improved wet chemical process. Metall Mater Trans B 45:1472–1483

    Article  CAS  Google Scholar 

  30. Liu S, Zhou X, Wei C, Hu Y (2022) Spatial directional separation and synergetic treatment of Cr(VI) and Rhodamine B mixed pollutants on three-layered Pd@MIL-101/P25 photocatalyst. Sci Total Environ 842:156836

    Article  CAS  Google Scholar 

  31. Xie F, Mao X, Fan C, Wang Y (2014) Facile preparation of Sn-doped BiOCl photocatalyst with enhanced photocatalytic activity for benzoic acid and rhodamine B degradation. Mater Sci Semicond Process 27:380–389

    Article  CAS  Google Scholar 

  32. Zhang X, Wei J, Li R, Zhang C, Zhang H, Han P, Fan C (2017) DFT+U predictions: structural stability, electronic and optical properties, oxidation activity of BiOCl photocatalysts with 3d transition metals doping. J Mater Sci 53:4494–4506

    Article  Google Scholar 

  33. Ma ZP, Zhang L, Ma X, Shi FN (2022) A dual strategy for synthesizing crystal plane/defect co-modified BiOCl microsphere and photodegradation mechanism insights. J Colloid Interface Sci 617:73–83

    Article  CAS  Google Scholar 

  34. Cui J, Tao S, Yang X, Yu X, Sun S, Yang Q, Wei W, Liang S (2021) Facile construction of nickel-doped hierarchical BiOCl architectures for enhanced visible-light-driven photocatalytic activities. Mater Res Bull 138:111208

    Article  CAS  Google Scholar 

Download references


This work was supported by the Science and Technology Department of Shaanxi Province (2021JM-386, 2022JM-072), Science and Technology Department of Yulin (CXY-2022-156), Provincial Joint Fund of Shaanxi (2021JLM-28) and National Natural Science Foundation of China (52172099).

Author information

Authors and Affiliations


Corresponding authors

Correspondence to Jun Liu or Meng-Jie Chang.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

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

Liu, J., Wang, H., Du, HL. et al. Significantly boosting the visible light activity of BiOCl by facile solvothermal doping with chromium. J Sol-Gel Sci Technol 105, 793–803 (2023).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: