Construction of Z-scheme BiOI/g-C3N4 heterojunction with enhanced photocatalytic activity and stability under visible light

  • Yuzhen LiEmail author
  • Zhen Li
  • Lizhen Gao


BiOI/g-C3N4 binary catalysts with different loading ratios were prepared by a mild one-step stirring method. The optimum loading ratio of BiOI was selected by photocatalytic degradation of 20 mg/L methyl orange (MO) under visible light irradiation. The experimental results of photocatalytic degradation of MO indicated that the loading of BiOI improves the photocatalytic performance of g-C3N4. The structure and morphology of the catalyst were examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet–visible (UV–vis) diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL) and fourier transform infrared spectroscopy (FT-IR). The characterization results showed that BiOI and g-C3N4 were well complexed together, the Z-type heterojunction between them increased the utilization of visible light by g-C3N4 and reduced the recombination rate of photogenerated electron–hole pairs. In addition, the effects of catalyst loading, initial concentration of solution and initial pH on the photocatalytic degradation of MO by BiOI/g-C3N4 under visible light were explored. As a result, it was found that the optimum dosage of the binary catalyst was 1.25 g/L, and the photocatalytic efficiency against MO decreased as the initial concentration increased. In addition, the initial pH of the MO solution had a complicated effect on the photocatalytic efficiency of the binary catalyst, which was related to the existence form of MO in different environments. Finally, the main factors of photocatalytic degradation of MO were confirmed by free radical trapping experiments. Based on the results, the possible mechanism of photocatalytic degradation of MO by BiOI/g-C3N4 was inferred. Enhanced visible light photocatalytic activity was obtained due to light trapping of photogenerated carriers, high transfer efficiency, and enhanced separation efficiency by Z-type heterojunction.



The authors are grateful for financial support from the Shanxi Provincial Key Research and Development Plan (general) Social Development Project (201703D321009-5).


  1. 1.
    B. Ge, L. Han, X. Liang, F. Li, X. Pu, X. Zhu, Z. Zhang, X. Shao, C. Jin, W. Li, Fabrication of superhydrophobic Cu-BiOBr surface for oil/water separation and water soluble pollutants degradation. Appl. Surf. Sci. 462, 583–589 (2018)CrossRefGoogle Scholar
  2. 2.
    I. Morosanu, C. Teodosiu, A. Coroaba, C. Paduraru, Sequencing batch biosorption of micropollutants from aqueous effluents by rapeseed waste: experimental assessment and statistical modelling. J. Environ. Manage. 230, 110–118 (2019)CrossRefGoogle Scholar
  3. 3.
    V.K. Gupta, R. Jain, A. Mittal, T.A. Saleh, A. Nayak, S. Agarwal, S. Sikarwar, Photo-catalytic degradation of toxic dye amaranth on TiO2/UV in aqueous suspensions. Mater. Sci. Eng. C. 32, 12–17 (2012)CrossRefGoogle Scholar
  4. 4.
    M. Bilal, H.M.N. Iqbal, H. Hu, W. Wang, X. Zhang, Enhanced bio-catalytic performance and dye degradation potential of chitosan-encapsulated horseradish peroxidase in a packed bed reactor system. Sci. Total Environ. 575, 1352–1360 (2017)CrossRefGoogle Scholar
  5. 5.
    L. Liu, R. Wang, J. Yu, L. Hu, Z. Wang, Y. Fan, Adsorption of Reactive Blue 19 from aqueous solution by chitin nanofiber-/nanowhisker-based hydrogels. RSC Adv. 8, 15804–15812 (2018)CrossRefGoogle Scholar
  6. 6.
    A.A. Oladipo, A.O. Ifebajo, M. Gazi, Magnetic LDH-based CoO–NiFe2O4 catalyst with enhanced performance and recyclability for efficient decolorization of azo dye via Fenton-like reactions. Appl. Catal. B 243, 243–252 (2019)CrossRefGoogle Scholar
  7. 7.
    Y. Chen, W. Huang, D. He, S. Yue, H. Hong, Construction of heterostructured g-C3N4/Ag/TiO2 microspheres with enhanced photocatalysis performance under visible-light irradiation. ACS Appl. Mater. Interfaces 6, 14405–14414 (2014)CrossRefGoogle Scholar
  8. 8.
    M. Xu, L. Han, S. Dong, Facile fabrication of highly efficient g-C3N4/Ag2O heterostructured photocatalysts with enhanced visible-light photocatalytic activity. ACS Appl. Mater. Interfaces 5, 12533–12540 (2013)CrossRefGoogle Scholar
  9. 9.
    A. Fujishima, K. Honda, Electrochemical photolysis of water at a semiconductor electrode. Nature 238, 37–38 (1972)CrossRefGoogle Scholar
  10. 10.
    W. Liang, G. Tang, H. Zhang, C. Li, H. Li, H. Tang, Core–shell structured AgBr incorporated g-C3N4 nanocomposites with enhanced photocatalytic activity and stability. Mater. Technol. 32, 675–685 (2017)CrossRefGoogle Scholar
  11. 11.
    C. Chang, L. Zhu, S. Wang, X. Chu, L. Yue, Novel mesoporous graphite carbon nitride/bioi heterojunction for enhancing photocatalytic performance under visible-light irradiation. ACS Appl. Mater. Interfaces 6, 5083–5093 (2014)CrossRefGoogle Scholar
  12. 12.
    X. Guo, X. Li, L. Qin, S.-Z. Kang, G. Li, A highly active nano-micro hybrid derived from Cu-bridged TiO2/porphyrin for enhanced photocatalytic hydrogen production. Appl. Catal. B 243, 1–9 (2019)CrossRefGoogle Scholar
  13. 13.
    X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J.M. Carlsson, K. Domen, M. Antonietti, A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat. Mater. 8, 76–80 (2009)CrossRefGoogle Scholar
  14. 14.
    B.V. Lotsch, M. Döblinger, J. Sehnert, L. Seyfarth, J. Senker, O. Oeckler, W. Schnick, Unmasking melon by a complementary approach employing electron diffraction, solid-state NMR spectroscopy, and theoretical calculations-structural characterization of a carbon nitride polymer. Chem. Eur. J. 13, 4969–4980 (2007)CrossRefGoogle Scholar
  15. 15.
    Y. Wang, X. Wang, M. Antonietti, Polymeric graphitic carbon nitride as a heterogeneous organocatalyst: from photochemistry to multipurpose catalysis to sustainable chemistry. Angew. Chem. Int. Ed. 43, 68–89 (2012)CrossRefGoogle Scholar
  16. 16.
    P. Murugesan, S. Narayanan, M. Manickam, Experimental studies on photocatalytic reduction of CO2 using AgBr decorated g-C3N4 composite in TEA mediated system. J CO2 Util. 22, 250–261 (2017)CrossRefGoogle Scholar
  17. 17.
    H. Wang, Y. Xu, L. Jing, S. Huang, Y. Zhao, M. He, H. Xu, H. Li, Novel magnetic BaFe12O19/g-C3N4 composites with enhanced thermocatalytic and photo-Fenton activity under visible-light. J. Alloys Compd. 710, 510–518 (2017)CrossRefGoogle Scholar
  18. 18.
    S.B. Kokane, R. Sasikala, D.M. Phase, S.D. Sartale, In2S3 nanoparticles dispersed on g-C3N4 nanosheets: role of heterojunctions in photoinduced charge transfer and photoelectrochemical and photocatalytic performance. J. Mater. Sci. 52, 1–14 (2017)CrossRefGoogle Scholar
  19. 19.
    R. Sun, Q. Shi, M. Zhang, L. Xie, J. Chen, X. Yang, M. Chen, W. Zhao, Enhanced photocatalytic oxidation of toluene with a coral-like direct Z-scheme BiVO4/g-C3N4 photocatalyst. J. Alloys Compd. 714, 619–626 (2017)CrossRefGoogle Scholar
  20. 20.
    X. Chen, D.H. Kuo, Y.X. Hou, Enhancing the photodegradation of charged pollutants under visible light in Ag2O/g-C3N4 catalyst by Coulombic interaction. J. Mater. Sci. 52, 5147–5154 (2017)CrossRefGoogle Scholar
  21. 21.
    Y. Yuan, G.F. Huang, W.Y. Hu, D.N. Xiong, B.X. Zhou, S. Chang, W.Q. Huang, Construction of g-C3N4/CeO2/ZnO ternary photocatalysts with enhanced photocatalytic performance. J. Phys. Chem. Solids 106, 1–9 (2017)CrossRefGoogle Scholar
  22. 22.
    J. Chen, X. Xiao, Y. Wang, Z. Ye, Fabrication of hierarchical sheet-on-sheet WO3/g-C3N4 composites with enhanced photocatalytic activity. J. Alloys Compd. 777, 325–334 (2019)CrossRefGoogle Scholar
  23. 23.
    W. Chen, Z.-C. He, G.-B. Huang, C.-L. Wu, W.-F. Chen, X.-H. Liu, Direct Z-scheme 2D/2D MnIn2S4/g-C3N4 architectures with highly efficient photocatalytic activities towards treatment of pharmaceutical wastewater and hydrogen evolution. Chem. Eng. J. 359, 244–253 (2019)CrossRefGoogle Scholar
  24. 24.
    Q. Wang, K. Wang, L. Zhang, H. Wang, W. Wang, Photocatalytic reduction of CO2 to methane over PtOx-loaded ultrathin Bi2WO6 nanosheets. Appl. Surf. Sci. 470, 832–839 (2019)CrossRefGoogle Scholar
  25. 25.
    X. Shi, P. Wang, W. Li, Y. Bai, H. Xie, Y. Zhou, L. Ye, Change in photocatalytic NO removal mechanisms of ultrathin BiOBr/BiOI via NO3 adsorption. Appl. Catal. B 243, 322–329 (2019)CrossRefGoogle Scholar
  26. 26.
    H. Li, Y. Chen, W. Zhou, H. Gao, G. Tian, Tuning in BiVO4/Bi4V2O10 porous heterophase nanospheres for synergistic photocatalytic degradation of organic pollutants. Appl. Surf. Sci. 470, 631–638 (2019)CrossRefGoogle Scholar
  27. 27.
    L.S. Zhang, H.L. Wang, Z.G. Chen, P.K. Wong, J.S. Liu, Bi2WO6 micro/nano-structures: synthesis, modifications and visible-light-driven photocatalytic applications. Appl. Catal. B. 106, 1–13 (2011)Google Scholar
  28. 28.
    Y. Zhang, J. Lu, M.R. Hoffmann, Q. Wang, Y. Cong, Q. Wang, H. Jin, Synthesis of g-C3N4/Bi2O3/TiO2 composite nanotubes: enhanced activity under visible light irradiation and improved photoelectrochemical activity. RSC Adv. 5, 48983–48991 (2015)CrossRefGoogle Scholar
  29. 29.
    G. Zhu, M. Hojamberdiev, S. Zhang, S.T.U. Din, W. Yang, Enhancing visible-light-induced photocatalytic activity of BiOI microspheres for NO removal by synchronous coupling with Bi metal and graphene. Appl. Surf. Sci. 467–468, 968–978 (2019)CrossRefGoogle Scholar
  30. 30.
    J. Zhong, J. Li, X. Liu, Q. Wang, H. Yang, W. Hu, C. Cheng, J. Song, M. Li, T. Jin, Enhanced photo-induced charge separation and solar-driven photocatalytic activity of g-C3N4 decorated by SO4 2−. Mater. Sci. Semicond. Process. 40, 508–515 (2015)CrossRefGoogle Scholar
  31. 31.
    K. Dai, L. Lu, C. Liang, G. Zhu, Q. Liu, L. Geng, J. He, A high efficient graphitic-C3N4/BiOI/graphene oxide ternary nanocomposite heterostructured photocatalyst with graphene oxide as electron transport buffer material. Dalton Trans. 44, 7903–7910 (2015)CrossRefGoogle Scholar
  32. 32.
    Z. Jiang, X. Liang, Y. Liu, T. Jing, Z. Wang, X. Zhang, X. Qin, Y. Dai, B. Huang, Enhancing visible light photocatalytic degradation performance and bactericidal activity of BiOI via ultrathin-layer structure. Appl. Catal. B 211, 252–257 (2017)CrossRefGoogle Scholar
  33. 33.
    M. Pirhashemi, A. Habibi-Yangjeh, Simple and large scale one-pot method for preparation of AgBr–ZnO nanocomposites as highly efficient visible light photocatalyst. Appl. Surf. Sci. 283, 1080–1088 (2013)CrossRefGoogle Scholar
  34. 34.
    S.C. Yan, Z.S. Li, Z.G. Zou, Photodegradation of rhodamine B and methyl orange over boron-doped g-C3N4 under visible light irradiation. Langmuir 26, 3894–3901 (2010)CrossRefGoogle Scholar
  35. 35.
    L. Ye, J. Liu, Z. Jiang, T. Peng, L. Zan, Facets coupling of BiOBr-g-C3N4 composite photocatalyst for enhanced visible-light-driven photocatalytic activity. Appl. Catal. B 142, 1–7 (2013)Google Scholar
  36. 36.
    J.C. Wang, H.C. Yao, Z.Y. Fan, L. Zhang, J.S. Wang, S.Q. Zang, Z.J. Li, Indirect Z-Scheme BiOI/g-C3N4 photocatalysts with enhanced photoreduction CO2 activity under visible light irradiation. ACS Appl. Mater. Interfaces 8, 3765–3775 (2016)CrossRefGoogle Scholar
  37. 37.
    Z. You, C. Wu, Q. Shen, Y. Yu, H. Chen, Y. Su, H. Wang, C. Wu, F. Zhang, H. Yang, A novel efficient g-C3N4@BiOI p-n heterojunction photocatalyst constructed through the assembly of g-C3N4 nanoparticles. Dalton Trans. 47, 7353–7361 (2018)CrossRefGoogle Scholar
  38. 38.
    S. Ning, H. Lin, Y. Tong, X. Zhang, Q. Lin, Y. Zhang, J. Long, X. Wang, Dual couples Bi metal depositing and Ag@AgI islanding on BiOI 3D architectures for synergistic bactericidal mechanism of E. coli under visible light. Appl Catal B. 204, 1–10 (2017)CrossRefGoogle Scholar
  39. 39.
    X. Zhou, C. Shao, X. Li, X. Wang, X. Guo, Y. Liu, Three dimensional hierarchical heterostructures of g-C3N4 nanosheets/TiO2 nanofibers: controllable growth via gas-solid reaction and enhanced photocatalytic activity under visible light. J. Hazard. Mater. 344, 113–122 (2017)CrossRefGoogle Scholar
  40. 40.
    J. Cao, B. Xu, H. Lin, B. Luo, S. Chen, Novel heterostructured Bi2S3/BiOI photocatalyst: facile preparation, characterization and visible light photocatalytic performance. Dalton Trans. 41, 11482–11490 (2012)CrossRefGoogle Scholar
  41. 41.
    J. Deli, C. Linlin, Z. Jianjun, C. Min, S. Weidong, X. Jimin, Novel p-n heterojunction photocatalyst constructed by porous graphite-like C3N4 and nanostructured BiOI: facile synthesis and enhanced photocatalytic activity. Dalton Trans. 42, 15726–15734 (2013)CrossRefGoogle Scholar
  42. 42.
    J. Oh, J.M. Lee, Y. Yoo, J. Kim, S.J. Hwang, S. Park, New insight of the photocatalytic behaviors of graphitic carbon nitrides for hydrogen evolution and their associations with grain size, porosity, and photophysical properties. Appl. Catal. B 218, 349–358 (2017)CrossRefGoogle Scholar
  43. 43.
    R. Hao, X. Xiao, X. Zuo, J. Nan, W. Zhang, Efficient adsorption and visible-light photocatalytic degradation of tetracycline hydrochloride using mesoporous BiOI microspheres. J. Hazard. Mater. 209–210, 137–145 (2012)CrossRefGoogle Scholar
  44. 44.
    X. Zhang, L. Zhang, T. Xie, D. Wang, Low-temperature synthesis and high visible-light-induced photocatalytic activity of BiOI/TiO2 heterostructures. J. Phys. Chem. C 113, 7371–7378 (2009)CrossRefGoogle Scholar
  45. 45.
    K. Santosh, T. Surendar, B. Arabinda, K. Bharat, S. Vishnu, Synthesis of novel and stable g-C3N4/N-doped SrTiO3 hybrid nanocomposites with improved photocurrent and photocatalytic activity under visible light irradiation. Dalton Trans. 43, 16105–16114 (2014)CrossRefGoogle Scholar
  46. 46.
    Z. Xiu, H. Bo, Y. Wu, X. Hao, Graphite-like C3N4 modified Ag3PO4 nanoparticles with highly enhanced photocatalytic activities under visible light irradiation. Appl. Surf. Sci. 289, 394–399 (2014)CrossRefGoogle Scholar
  47. 47.
    S. Wan, M. Ou, W. Cai, S. Zhang, Q. Zhong, Preparation, characterization, and mechanistic analysis of BiVO4/CaIn2S4 hybrids that photocatalyze NO removal under visible light. J. Phys. Chem. Solids 122, 239–245 (2018)CrossRefGoogle Scholar
  48. 48.
    Q. Xiang, J. Yu, M. Jaroniec, Preparation and enhanced visible-light photocatalytic H2-production activity of graphene/C3N4 composites. J. Phys. Chem. C 115, 7355–7363 (2011)CrossRefGoogle Scholar
  49. 49.
    Y. Zhang, J. Wu, Y. Deng, Y. Xin, H. Liu, D. Ma, N. Bao, Synthesis and visible-light photocatalytic property of Ag/GO/g-C3N4 ternary composite. J. Mater. Sci. Eng. B 221, 1–9 (2017)CrossRefGoogle Scholar
  50. 50.
    S.C. Yan, Z.S. Li, Z.G. Zou, Photodegradation performance of g-C3N4 fabricated by directly heating melamine. Langmuir 25, 10397–10401 (2009)CrossRefGoogle Scholar
  51. 51.
    J. Di, J. Xia, S. Yin, H. Xu, L. Xu, Y. Xu, M. He, H. Li, Preparation of sphere-like g-C3N4/BiOI photocatalysts via a reactable ionic liquid for visible-light-driven photocatalytic degradation of pollutants. J. Mater. Chem. A 2, 5340–5351 (2014)CrossRefGoogle Scholar
  52. 52.
    V. Vaiano, M. Matarangolo, J.J. Murcia, H. Rojas, J.A. Navío, M.C. Hidalgo, Enhanced photocatalytic removal of phenol from aqueous solutions using ZnO modified with Ag. Appl. Catal. B 225, 197–206 (2018)CrossRefGoogle Scholar
  53. 53.
    J. Zhang, Q. Zhou, L. Ou, Kinetic, isotherm, and thermodynamic studies of the adsorption of methyl orange from aqueous solution by chitosan/alumina composite. J. Chem. Eng. Data 57, 412–419 (2012)CrossRefGoogle Scholar
  54. 54.
    C. Cai, H. Zhang, X. Zhong, L. Hou, Ultrasound enhanced heterogeneous activation of peroxymonosulfate by a bimetallic Fe-Co/SBA-15 catalyst for the degradation of Orange II in water. J. Hazard. Mater. 283, 70–79 (2015)CrossRefGoogle Scholar
  55. 55.
    M. Karimi-Shamsabadi, M. Behpour, A.K. Babaheidari, Z. Saberi, Efficiently enhancing photocatalytic activity of NiO-ZnO doped onto nanozeoliteX by synergistic effects of p-n heterojunction, supporting and zeolite nanoparticles in photodegradation of Eriochrome Black T and Methyl Orange. J. Photochem. Photobiol. A 346, 133–143 (2017)CrossRefGoogle Scholar
  56. 56.
    A. Nezamzadeh-Ejhieh, M. Karimi-Shamsabadi, Decolorization of a binary azo dyes mixture using CuO incorporated nanozeolite-X as a heterogeneous catalyst and solar irradiation. Chem. Eng. J. 228, 631–641 (2013)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Environmental Science and EngineeringTaiyuan University of TechnologyTaiyuanChina
  2. 2.China Institute for Radiation ProtectionTaiyuanChina
  3. 3.School of Mechanical EngineeringUniversity of Western AustraliaPerthAustralia

Personalised recommendations