Journal of Materials Science

, Volume 54, Issue 6, pp 4559–4572 | Cite as

Citric acid-modulated in situ synthesis of 3D hierarchical Bi@BiOCl microsphere photocatalysts with enhanced photocatalytic performance

  • Xiangde Su
  • Liqiong Hou
  • Le Xia
  • Xiang Yu
  • Jia Guo
  • Yi ZhuEmail author
  • Yuanming ZhangEmail author
Chemical routes to materials


3D hierarchical Bi@BiOCl microspheres were successfully synthesized by a facile solvothermal method using citric acid as a modulating agent and the growth process was revealed. The modulation of citric acid not only reduced the size of BiOCl nanosheets, finally transforming BiOCl microflowers into microspheres, but also induced the in situ reductive deposition of metallic Bi on the surface of the microspheres. Consequently, Bi@BiOCl microspheres showed larger specific surface areas and total pore volumes, higher absorptivity to the visible light and better charge transfer ability than BiOCl microflowers. As a result, Bi@BiOCl microspheres exhibited much better photocatalytic performance than BiOCl microflowers. Bi@BiOCl microspheres modulated by 2.8 g citric acid showed the highest photocatalytic activity, which was 4.4 and 2.5 times higher than BiOCl microflowers in degrading RhB under visible light and salicylic acid under UV light, respectively. This work may provide a new insight into simultaneous size control and in situ metal deposition for Bi-containing photocatalysts and other materials.



This work was supported by National Natural Science Foundation of China (21276104 and 21706091) and GuangDong Provincial Department of Science and Technology Application Research and Development Supporting Special Fund Project (2015B020235007).

Compliance with ethical standards

Conflict of interest

We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted.

Supplementary material

10853_2018_3176_MOESM1_ESM.docx (1 mb)
Supplementary material 1 (DOCX 1045 kb)


  1. 1.
    Cheng HF, Huang BB, Dai Y (2014) Engineering BiOX (X = Cl, Br, I) nanostructures for highly efficient photocatalytic applications. Nanoscale 6(4):2009–2026CrossRefGoogle Scholar
  2. 2.
    Li X, Yu JG, Jaroniec M (2016) Hierarchical photocatalysts. Chem Soc Rev 45(9):2603–2636CrossRefGoogle Scholar
  3. 3.
    Yu CL, Zhou WQ, Liu H, Liu Y, Dionysiou DD (2016) Design and fabrication of microsphere photocatalysts for environmental purification and energy conversion. Chem Eng J 287:117–129CrossRefGoogle Scholar
  4. 4.
    Li J, Yu Y, Zhang LZ (2014) Bismuth oxyhalide nanomaterials: layered structures meet photocatalysis. Nanoscale 6(15):8473–8488. CrossRefGoogle Scholar
  5. 5.
    Ye LQ, Su YR, Jin XL, Xie HQ, Zhang C (2014) Recent advances in BiOX (X = Cl, Br and I) photocatalysts: synthesis, modification, facet effects and mechanisms. Environ Sci-Nano 1(2):90–112. CrossRefGoogle Scholar
  6. 6.
    He RA, Cao SW, Yu JG (2016) Recent advances in morphology control and surface modification of Bi-based photocatalysts. Acta Phys Chim Sin 32(12):2841–2870Google Scholar
  7. 7.
    Song JM, Mao CJ, Niu HL, Shen YH, Zhang SY (2010) Hierarchical structured bismuth oxychlorides: self-assembly from nanoplates to nanoflowers via a solvothermal route and their photocatalytic properties. CrystEngComm 12(11):3875–3881. CrossRefGoogle Scholar
  8. 8.
    Li K, Liang YJ, Yang J, Gao Q, Zhu YL, Liu SQ, Xu R, Wu XY (2017) Controllable synthesis of 001 facet dependent foursquare BiOCl nanosheets: a high efficiency photocatalyst for degradation of methyl orange. J Alloys Compd 695:238–249CrossRefGoogle Scholar
  9. 9.
    Xu YQ, Hu XL, Zhu HK, Zhang JB (2016) Insights into BiOCl with tunable nanostructures and their photocatalytic and electrochemical activities. J Mater Sci 51(9):4342–4348. CrossRefGoogle Scholar
  10. 10.
    Kang SH, Pawar RC, Pyo YJ, Khare V, Lee CS (2015) Size-controlled BiOCl-RGO composites having enhanced photodegradative properties. J Exp Nanosci 11(4):259–275CrossRefGoogle Scholar
  11. 11.
    Ding LY, Wei RJ, Chen H, Hu JC, Li JL (2015) Controllable synthesis of highly active BiOCl hierarchical microsphere self-assembled by nanosheets with tunable thickness. Appl Catal B-Environ 172–173:91–99Google Scholar
  12. 12.
    Xu Y, Xu SC, Wang S, Zhang YX, Li GH (2014) Citric acid modulated electrochemical synthesis and photocatalytic behavior of BiOCl nanoplates with exposed 001 facets. Dalton Trans 43(2):479–485CrossRefGoogle Scholar
  13. 13.
    Zhao S, Zhang YW, Zhou YM, Fang JS, Wang YY, Zhang C, Chen WX (2018) Fabrication of sandwich-structured g-C3N4/Au/BiOCl Z-scheme photocatalyst with enhanced photocatalytic performance under visible light irradiation. J Mater Sci 53(8):6008–6020. CrossRefGoogle Scholar
  14. 14.
    Huang YK, Kang SF, Yang Y, Qin HF, Ni ZJ, Yang SJ, Li X (2016) Facile synthesis of Bi/Bi2WO6 nanocomposite with enhanced photocatalytic activity under visible light. Appl Catal B-Environ 196:89–99CrossRefGoogle Scholar
  15. 15.
    Lu SY, Yu YN, Bao SJ, Liao SH (2015) In situ synthesis and excellent photocatalytic activity of tiny Bi decorated bismuth tungstate nanorods. RSC Adv 5(104):85500–85505CrossRefGoogle Scholar
  16. 16.
    Hu Y, Cao YT, Wang PX et al (2012) A new perspective for effect of Bi on the photocatalytic activity of Bi-doped TiO2. Appl Catal B-Environ 125:294–303CrossRefGoogle Scholar
  17. 17.
    Chen Y, Chen DL, Chen JF, Lu QJ, Zhang M, Liu BT, Wang QY, Wang ZF (2015) Facile synthesis of Bi nanoparticle modified TiO2 with enhanced visible light photocatalytic activity. J Alloy Compd 651:114–120CrossRefGoogle Scholar
  18. 18.
    Dong F, Zhao ZW, Sun YJ, Zhang YX, Yan S, Wu ZB (2015) An advanced semimetal-organic Bi spheres-g-C3N4 Nanohybrid with SPR-enhanced visible-light photocatalytic performance for NO purification. Environ Sci Technol 49(20):12432–12440CrossRefGoogle Scholar
  19. 19.
    Wang ZY, Yan S, Sun YJ, Xiong T, Dong F, Zhang W (2017) Bi metal sphere/graphene oxide nanohybrids with enhanced direct plasmonic photocatalysis. Appl Catal B-Environ 214(148):148–157CrossRefGoogle Scholar
  20. 20.
    Wang B, Feng WH, Zhang LL, Zhang Y, Huang XY, Fang ZB, Liu P (2017) In situ construction of a novel Bi/CdS nanocomposite with enhanced visible light photocatalytic performance. Appl Catal B-Environ 206:510–519CrossRefGoogle Scholar
  21. 21.
    Wang DH, Gao GQ, Zhang YW, Zhou LS, Xu AW, Chen W (2012) Nanosheet-constructed porous BiOCl with dominant 001 facets for superior photosensitized degradation. Nanoscale 4(24):7780–7785CrossRefGoogle Scholar
  22. 22.
    Shi S, Gondal MA, Rashid SG et al (2014) Synthesis of g-C3N4/BiOClxBr1−x hybrid photocatalysts and the photoactivity enhancement driven by visible light. Colloids Surf A Physicochem Eng Asp 461:202–211CrossRefGoogle Scholar
  23. 23.
    Oliveira RC, Hammer P, Guibal E, Taulemesse JM, Garcia O Jr (2014) Characterization of metal-biomass interactions in the lanthanum (III) biosorption on Sargassum sp. using SEM/EDX, FTIR, and XPS: preliminary studies. Chem Eng J 239:381–391CrossRefGoogle Scholar
  24. 24.
    Gao XY, Zhang XC, Wang YW, Peng SQ, Yue B, Fan CM (2015) Rapid synthesis of hierarchical BiOCl microspheres for efficient photocatalytic degradation of carbamazepine under simulated solar irradiation. Chem Eng J 263:419–426CrossRefGoogle Scholar
  25. 25.
    Zhao QH, Liu XY, Xing YX, Liu ZL, Du CF (2016) Synthesizing Bi2O3/BiOCl heterojunctions by partial conversion of BiOCl. J Mater Sci 52(4):2117–2130. CrossRefGoogle Scholar
  26. 26.
    Yu SX, Zhang YH, Li M, Du X, Huang HW (2017) Non-noble metal Bi deposition by utilizing Bi2WO6 as the self-sacrificing template for enhancing visible light photocatalytic activity. Appl Surf Sci 391:491–498CrossRefGoogle Scholar
  27. 27.
    Liu H, Su Y, Chen Z, Jin ZT, Wang Y (2014) Graphene sheets grafted three-dimensional BiOBr 0.2I0.8 microspheres with excellent photocatalytic activity under visible light. J Hazard Mater 266:75–83CrossRefGoogle Scholar
  28. 28.
    Yu HG, Cao C, Wang XF, Yu JG (2017) Ag-modified BiOCl single-crystal nanosheets: dependence of photocatalytic performance on the region-selective deposition of Ag nanoparticles. J Phys Chem C 121(24):13191–13201CrossRefGoogle Scholar
  29. 29.
    Tang GG, Dong JZ, Wu KQ, Liang W, Zhou DY, Ma SB, Tang H, Li CS (2016) Novel 3D flowerlike BiOCl0.7Br 0.3 microspheres coupled with graphene sheets with enhanced visible-light photocatalytic activity for the degradation of rhodamine B. Ceram Int 42(5):5607–5616CrossRefGoogle Scholar
  30. 30.
    Wang QZ, He JJ, Shi YB, Zhang SL, Niu TJ, She HD, Bi YP (2017) Designing non-noble/semiconductor Bi/BiVO4 photoelectrode for the enhanced photoelectrochemical performance. Chem Eng J 326:411–418CrossRefGoogle Scholar
  31. 31.
    Cui PZ, Wang JL, Wang ZM, Chen J, Xing XR, Wang LZ, Yu RB (2016) Bismuth oxychloride hollow microspheres with high visible light photocatalytic activity. Nano Res 9(3):593–601CrossRefGoogle Scholar
  32. 32.
    Wei XX, Chen CM, Guo SQ et al (2014) Advanced visible-light-driven photocatalyst BiOBr–TiO2-graphene composite with graphene as a nano-filler. J Mater Chem A 2(13):4667–4675. CrossRefGoogle Scholar
  33. 33.
    Liu D, Cai WB, Wang YG, Zhu YF (2018) Constructing a novel Bi2SiO5/BiPO4 heterostructure with extended light response range and enhanced photocatalytic performance. Appl Catal B-Environ 236:205–211CrossRefGoogle Scholar
  34. 34.
    Su XD, Yang JJ, Yu X, Zhu Y, Zhang YM (2018) In situ grown hierarchical 50% BiOCl/BiOI hollow flowerlike microspheres on reduced graphene oxide nanosheets for enhanced visible-light photocatalytic degradation of rhodamine B. Appl Surf Sci 433:502–512CrossRefGoogle Scholar
  35. 35.
    Liu Y, Yuan XZ, Wang H et al (2015) Solvothermal synthesis of graphene/BiOCl0.75Br0.25 microspheres with excellent visible-light photocatalytic activity. RSC Adv 5(42):33696–33704CrossRefGoogle Scholar
  36. 36.
    Zhang YH, Zhang N, Tang ZR, Xu YJ (2012) Graphene transforms wide band gap ZnS to a visible light photocatalyst. The new role of graphene as a macromolecular photosensitizer. ACS Nano 6(11):9777–9789CrossRefGoogle Scholar
  37. 37.
    Weng SX, Chen BB, Xie LY, Zheng ZY, Liu P (2013) Facile in situ synthesis of a Bi/BiOCl nanocomposite with high photocatalytic activity. J Mater Chem A 1(9):3068–3075. CrossRefGoogle Scholar
  38. 38.
    Yu Y, Cao CY, Liu H, Li P, Wei FF, Jiang Y, Song WG (2014) A Bi/BiOCl heterojunction photocatalyst with enhanced electron–hole separation and excellent visible light photodegrading activity. J Mater Chem A 2(6):1677–1681CrossRefGoogle Scholar
  39. 39.
    Zhang FN, Zhao Y, Li YW, Wu GJ, Zhao JZ (2017) CTAB induced hierarchical bismuth microspheres for visible-light photocatalytic study. J Colloid Interf Sci 505:519–527CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of ChemistryJinan UniversityGuangzhouPeople’s Republic of China
  2. 2.Analytical and Testing CenterJinan UniversityGuangzhouPeople’s Republic of China
  3. 3.Department of EcologyJinan UniversityGuangzhouPeople’s Republic of China

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