Skip to main content
Log in

Crystal-chemistry insight into the photocatalytic activity of BiOCl x Br1−x nanoplate solid solutions

  • Research Article
  • Published:
Frontiers of Materials Science Aims and scope Submit manuscript

Abstract

In this study, a facile alcoholysis method was developed to synthesize BiOCl x Br1−x nanoplates at room temperature and atmospheric pressure. In this route, strong acid or alkaline environment was absolutely avoided to realize the high exposure of {001} crystal facets. The regular changes in XRD peaks and cell parameters as a function of the Br content strongly declared that the obtained BiOCl x Br1−x products belonged to a group of solid solutions. The 2D nanosheets with in-plane wrinkles were clearly observed in TEM images. Interestingly, as the Br content increased, band gaps of BiOCl x Br1−x solid solutions gradually decreased. The photocatalytic degradation of RhB under simulated sunlight irradiation indicated that BiOCl0.5Br0.5 had the best photocatalytic activity. From the viewpoint of crystal chemistry, the photocatalytic activity of BiOCl x Br1−x solid solutions was closely related with the exposure amount of {001} facets, interlayer spacing of (001) plane and energy-level position of valence band.

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.

Similar content being viewed by others

References

  1. Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode. Nature, 1972, 238(5358): 37–38

    Article  Google Scholar 

  2. Daghrir R, Drogui P, Robert D. Modified TiO2 for environmental photocatalytic application: a review. Industrial & Engineering Chemistry Research, 2013, 52(10): 3581–3599

    Article  Google Scholar 

  3. Kuo Y L, Su T L, Kung F C, et al. A study of parameter setting and characterization of visible-light driven nitrogen-modified commercial TiO2 photocatalysts. Journal of Hazardous Materials, 2011, 190(1–3): 938–944

    Article  Google Scholar 

  4. Chen X, Liu L, Huang F. Black titanium dioxide (TiO2) nanomaterials. Chemical Society Reviews, 2015, 44(7): 1861–1885

    Article  Google Scholar 

  5. Kumar S G, Devi L G. Review on modified TiO2 photocatalysis under UV/visible light: selected results and related mechanisms on interfacial charge carrier transfer dynamics. The Journal of Physical Chemistry A, 2011, 115(46): 13211–13241

    Article  Google Scholar 

  6. Nowotny J, Alim M A, Bak T, et al. Defect chemistry and defect engineering of TiO2-based semiconductors for solar energy conversion. Chemical Society Reviews, 2015, 44(23): 8424–8442

    Article  Google Scholar 

  7. Schneider J, Matsuoka M, Takeuchi M, et al. Understanding TiO2 photocatalysis: mechanisms and materials. Chemical Reviews, 2014, 114(19): 9919–9986

    Article  Google Scholar 

  8. Kapilashrami M, Zhang Y, Liu Y S, et al. Probing the optical property and electronic structure of TiO2 nanomaterials for renewable energy applications. Chemical Reviews, 2014, 114(19): 9662–9707

    Article  Google Scholar 

  9. Meng X C, Zhang Z S. Bismuth-based photocatalytic semiconductors: introduction, challenges and possible approaches. Journal of Molecular Catalysis A: Chemical, 2016, 423: 533–549

    Article  Google Scholar 

  10. Bhachu D S, Moniz S J A, Sathasivam S, et al. Bismuth oxyhalides: synthesis, structure and photoelectrochemical activity. Chemical Science, 2016, 7(8): 4832–4841

    Article  Google Scholar 

  11. Li G, Qin F, Wang R, et al. BiOX (X = Cl, Br, I) nanostructures: mannitol-mediated microwave synthesis, visible light photocatalytic performance, and Cr(VI) removal capacity. Journal of Colloid and Interface Science, 2013, 409: 43–51

    Article  Google Scholar 

  12. Keramidas K G, Voutsas G P, Rentzeperis P I. The crystal structure of BiOCl. Zeitschrift fur Kristallographie, 1993, 205: 35–40

    Google Scholar 

  13. Bannister F A, Hey M H. The crystal-structure of the bismuth oxyhalides. Mineralogical Magazine, 1935, 24(149): 49–58

    Article  Google Scholar 

  14. Li J, Yu Y, Zhang L. Bismuth oxyhalide nanomaterials: layered structures meet photocatalysis. Nanoscale, 2014, 6(15): 8473–8488

    Article  Google Scholar 

  15. Xu Z F, Hao W C, Zhang Q F, et al. Indirect-direct band transformation of few-layer BiOCl under biaxial strain. Journal of Physical Chemistry C, 2016, 120(16): 8589–8594

    Article  Google Scholar 

  16. Cheng H, Huang B, Dai Y. Engineering BiOX (X = Cl, Br, I) nanostructures for highly efficient photocatalytic applications. Nanoscale, 2014, 6(4): 2009–2026

    Article  Google Scholar 

  17. Yin S, Di J, Li M, et al. Ionic liquid-assisted synthesis and improved photocatalytic activity of p-n junction g-C3N4/BiOCl. Journal of Materials Science, 2016, 51(10): 4769–4777

    Article  Google Scholar 

  18. Tripathi G K, Kurchania R. Effect of doping on structural, optical and photocatalytic properties of bismuth oxychloride nanomaterials. Journal of Materials Science Materials in Electronics, 2016, 27(5): 5079–5088

    Article  Google Scholar 

  19. Keller E, Krämer V. A strong deviation from Vegard’s rule: X-ray powder investigations of the three quasi-binary phase systems BiOX–BiOY (X, Y = Cl, Br,I). Zeitschrift für Naturforschung B, 2014, 60(12): 1255–1263

    Google Scholar 

  20. Gnayem H, Sasson Y. Hierarchical nanostructured 3D flowerlike BiOClxBr1–x semiconductors with exceptional visible light photocatalytic activity. ACS Catalysis, 2013, 3(2): 186–191

    Article  Google Scholar 

  21. Mao X M, Fan C M. Rhodamine B from water. International Journal of Minerals Metallurgy and Materials, 2013, 20(11): 1089–1096

    Article  Google Scholar 

  22. Zhang X, Wang L W, Wang C Y, et al. Synthesis of BiOClxBr1–x nanoplate solid solutions as a robust photocatalyst with tunable band structure. Chemistry, 2015, 21(33): 11872–11877

    Article  Google Scholar 

  23. Du D D, Li W J, Chen S S, et al. Synergistic degradation of rhodamine B on BiOClxBr1–x sheets by combined photosensitization and photocatalysis under visible light irradiation. New Journal of Chemistry, 2015, 39(4): 3129–3136

    Article  Google Scholar 

  24. Li T B, Chen G, Zhou C, et al. New photocatalyst BiOCl/BiOI composites with highly enhanced visible light photocatalytic performances. Dalton Transactions, 2011, 40(25): 6751–6758

    Article  Google Scholar 

  25. Xiao X, Hao R, Liang M, et al. One-pot solvothermal synthesis of three-dimensional (3D) BiOI/BiOCl composites with enhanced visible-light photocatalytic activities for the degradation of bisphenol-A. Journal of Hazardous Materials, 2012, 233–234: 122–130

    Article  Google Scholar 

  26. Dong F, Sun Y, Fu M, et al. Room temperature synthesis and highly enhanced visible light photocatalytic activity of porous BiOI/BiOCl composites nanoplates microflowers. Journal of Hazardous Materials, 2012, 219–220: 26–34

    Article  Google Scholar 

  27. Sun L M, Xiang L, Zhao X, et al. Enhanced visible-light photocatalytic activity of BiOI/BiOCl heterojunctions: key role of crystal facet combination. ACS Catalysis, 2015, 5(6): 3540–3551

    Article  Google Scholar 

  28. Yang C Y, Li F, Zhang M, et al. Preparation and first-principles study for electronic structures of BiOI/BiOCl composites with highly improved photocatalytic and adsorption performances. Journal of Molecular Catalysis A: Chemical, 2016, 423: 1–11

    Article  Google Scholar 

  29. Jia Z F, Wang F M, Xin F, et al. Simple solvothermal routes to synthesize 3D BiOBrxI1–x microspheres and their visible-lightinduced photocatalytic properties. Industrial & Engineering Chemistry Research, 2011, 50(11): 6688–6694

    Article  Google Scholar 

  30. Lin L, Huang M H, Long L P, et al. Fabrication of a threedimensional BiOBr/BiOI photocatalyst with enhanced visible light photocatalytic performance. Ceramics International, 2014, 40(8): 11493–11501

    Article  Google Scholar 

  31. Zheng C, Cao C, Ali Z. In situ formed Bi/BiOBrxI1–x heterojunction of hierarchical microspheres for efficient visiblelight photocatalytic activity. Physical Chemistry Chemical Physics, 2015, 17(20): 13347–13354

    Article  Google Scholar 

  32. Zhang X, Wang C Y, Wang L W, et al. Fabrication of BiOBrxI1–x photocatalysts with tunable visible light catalytic activity by modulating band structures. Scientific Reports, 2016, 6: 22800

    Article  Google Scholar 

  33. Ou M Y, Dong F, Zhang W, et al. Efficient visible light photocatalytic oxidation of NO in air with band-gap tailored (BiO)2CO3–BiOI solid solutions. Chemical Engineering Journal, 2014, 255: 650–658

    Article  Google Scholar 

  34. Ding J, Dai Z, Qin F, et al. Z-scheme BiO1–xBr/Bi2O2CO3 photocatalyst with rich oxygen vacancy as electron mediator for highly efficient degradation of antibiotics. Applied Catalysis B: Environmental, 2017, 205: 281–291

    Article  Google Scholar 

  35. Tian F, Xiong J Y, Zhao H P, et al. Mannitol-assisted solvothermal synthesis of BiOCl hierarchical nanostructures and their mixed organic dye adsorption capacities. CrystEngComm, 2014, 16(20): 4298–4305

    Article  Google Scholar 

  36. Tian F, Zhang Y F, Li G F, et al. Thickness-tunable solvothermal synthesis of BiOCl nanosheets and their photosensitization catalytic performance. New Journal of Chemistry, 2015, 39(2): 1274–1280

    Article  Google Scholar 

  37. Li G F, Qin F, Yang H, et al. Facile microwave synthesis of 3D flowerlike BiOBr nanostructures and their excellent CrVI removal capacity. European Journal of Inorganic Chemistry, 2012, (15): 2508–2513

    Article  Google Scholar 

  38. Cui P Z, Wang J L, Wang Z M, et al. Bismuth oxychloride hollow microspheres with high visible light photocatalytic activity. Nano Research, 2016, 9(3): 593–601

    Article  Google Scholar 

  39. Xiong J Y, Cheng G, Qin F, et al. Tunable BiOCl hierarchical nanostructures for high-efficient photocatalysis under visible light irradiation. Chemical Engineering Journal, 2013, 220: 228–236

    Article  Google Scholar 

  40. Chen H B, Yu X, Zhu Y, et al. Controlled synthesis of {001} facets-dominated dye-sensitized BiOCl with high photocatalytic efficiency under visible-light irradiation. Journal of Nanoparticle Research, 2016, 18(8): 225

    Article  Google Scholar 

  41. Li J, Zhang L, Li Y, et al. Synthesis and internal electric field dependent photoreactivity of Bi3O4Cl single-crystalline nanosheets with high {001} facet exposure percentages. Nanoscale, 2014, 6(1): 167–171

    Article  Google Scholar 

  42. Lei Y Q, Wang G H, Song S Y, et al. Synthesis, characterization and assembly of BiOCl nanostructure and their photocatalytic properties. CrystEngComm, 2009, 11(9): 1857–1862

    Article  Google Scholar 

  43. Liu Y, Son W J, Lu J, et al. Composition dependence of the photocatalytic activities of BiOCl1–xBrx solid solutions under visible light. Chemistry, 2011, 17(34): 9342–9349

    Article  Google Scholar 

  44. Li H, Shi J, Zhao K, et al. Sustainable molecular oxygen activation with oxygen vacancies on the 001 facets of BiOCl nanosheets under solar light. Nanoscale, 2014, 6(23): 14168–14173

    Article  Google Scholar 

  45. Feng H, Xu Z, Wang L, et al. Modulation of photocatalytic properties by strain in 2D BiOBr nanosheets. ACS Applied Materials & Interfaces, 2015, 7(50): 27592–27596

    Article  Google Scholar 

  46. Xu H Y, Wu L C, Jin L G, et al. Combination mechanism and enhanced visible-light photocatalytic activity and stability of CdS/ g-C3N4 heterojunctions. Journal of Materials Science and Technology, 2017, 33(1): 30–38

    Article  Google Scholar 

  47. Li J, Li H, Zhan G, et al. Solar water splitting and nitrogen fixation with layered bismuth oxyhalides. Accounts of Chemical Research, 2017, 50(1): 112–121

    Article  Google Scholar 

  48. Xiong J Y, Cheng G, Li G F, et al. Well-crystallized square-like 2D BiOCl nanoplates: mannitol-assisted hydrothermal synthesis and improved visible-light-driven photocatalytic performance. RSC Advances, 2011, 1(8): 1542–1553

    Article  Google Scholar 

  49. Jiang J, Zhao K, Xiao X, et al. Synthesis and facet-dependent photoreactivity of BiOCl single-crystalline nanosheets. Journal of the American Chemical Society, 2012, 134(10): 4473–4476

    Article  Google Scholar 

  50. Zhao J L, Lv X W, Wang X X, et al. Fabrication of BiOX (X = Cl, Br, and I) nanosheeted films by anodization and their photocatalytic properties. Materials Letters, 2015, 158: 40–44

    Article  Google Scholar 

  51. Jia M, Hu X, Wang S, et al. Photocatalytic properties of hierarchical BiOXs obtained via an ethanol-assisted solvothermal process. Journal of Environmental Sciences, 2015, 35(9): 172–180

    Article  Google Scholar 

  52. Zhang Y Y, Sun X G, Yang G Z, et al. Preparation and characterization of bifunctional BiOClxIy solid solutions with excellent adsorption and photocatalytic abilities for removal of organic dyes. Materials Science in Semiconductor Processing, 2016, 41: 193–199

    Article  Google Scholar 

  53. Zhang W D, Zhang Q, Dong F. Visible-light photocatalytic removal of NO in air over BiOX (X = Cl, Br, I) single-crystal nanoplates prepared at room temperature. Industrial & Engineering Chemistry Research, 2013, 52(20): 6740–6746

    Article  Google Scholar 

  54. Shang J, Hao W C, Lv X J, et al. Bismuth oxybromide with reasonable photocatalytic reduction activity under visible light. ACS Catalysis, 2014, 4(3): 954–961

    Article  Google Scholar 

  55. Tian F, Zhao H P, Dai Z, et al. Mediation of valence band maximum of BiOI by Cl incorporation for improved oxidation power in photocatalysis. Industrial & Engineering Chemistry Research, 2016, 55(17): 4969–4978

    Article  Google Scholar 

Download references

Acknowledgements

We express our great appreciation for the financial support of the Program for New Century Excellent Talents in Heilongjiang Provincial Universities (1253-NCET-010).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Huan-Yan Xu.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Xu, HY., Han, X., Tan, Q. et al. Crystal-chemistry insight into the photocatalytic activity of BiOCl x Br1−x nanoplate solid solutions. Front. Mater. Sci. 11, 120–129 (2017). https://doi.org/10.1007/s11706-017-0379-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11706-017-0379-7

Keywords

Navigation