Investigation of post-annealing treatment effect on film properties of sputter-deposited BiVO4 nanoporous photocatalyst

Document Type : Research Paper


1 School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, Tehran, Iran; Institut FEMTO-ST, UMR 6174, CNRS, Univ. Bourgogne Franche-Comté, 15B, Avenue des Montboucons, 25030 Besançon, France.

2 School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, Tehran, Iran.

3 Institut FEMTO-ST, UMR 6174, CNRS, Univ. Bourgogne Franche-Comté, 15B, Avenue des Montboucons, 25030 Besançon, France.

4 School of Space Science and Physics, Shandong University, Weihai 264209, China.

5 Institut FEMTO-ST, UMR 6174, CNRS, Univ. Bourgogne Franche-Comté, 15B, Avenue des Montboucons, 25030 Besançon, France



Nanoporous BiVO4 thin films were deposited on fused silica substrate using reactive magnetron sputtering. The effect of annealing temperature on the microstructure, morphology and optical properties was evaluated. The samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), ultraviolet-visible spectroscopy (UV-Vis) and X-ray photoelectron spectroscopy (XPS). XPS demonstrated the Bi+3 and V+5 oxidation states, as well as the adsorbed and lattice oxygen on the film surface. The as-deposited films proved to be amorphous by the XRD results, while the pure monoclinic scheelite BiVO4 crystal structure was obtained after a post-annealing treatment at 300 and 450 ℃. FESEM images displayed a uniform surface with no grain boundaries for the as-deposited film, whereas nanopores with an average diameter of 20˗40 nm were observable in the film annealed at 450 ℃ as opposed to the film annealed at 300 ℃ with a dense and cracked surface. The association of nanoporosity with the efficiency of visible-light absorption was demonstrated by the UV-Vis spectrophotometry results with the narrowest bandgap (2.5 eV) concerning the film annealed at 450 ℃. The photocatalytic experiment under visible light showed an 80 % photodegradation of Rhodamine-B solution after 7 h, and the recycling experiment proved the stability of the thin films after three cycles. These results show the great potential of BiVO4 thin films deposited by reactive magnetron sputtering in photocatalytic wastewater treatment applications.  


  1. Tayebi M, Lee B-K. Recent advances in BiVO4 semiconductor materials for hydrogen production using photoelectrochemical water splitting. Renewable and Sustainable Energy Reviews. 2019;111:332-43.
  2. Peral J, Ollis D. Heterogeneous photocatalytic oxidation of gas-phase organics for air purification: Acetone, 1-butanol, butyraldehyde, formaldehyde, and m-xylene oxidation. Journal of Catalysis. 1992;136(2):554-65.
  3. Behjati S, Sheibani S, Herritsch J, Gottfried JM. Photodegradation of dyes in batch and continuous reactors by Cu2O-CuO nano-photocatalyst on Cu foils prepared by chemical-thermal oxidation. Materials Research Bulletin. 2020;130:110920.
  4. Razi R, Sheibani S. Photocatalytic activity enhancement by composition control of mechano-thermally synthesized BiVO4-Cu2O nanocomposite. Ceramics International. 2021;47(21):29795-806.
  5. Yu C, Dong S, Zhao J, Han X, Wang J, Sun J. Preparation and characterization of sphere-shaped BiVO 4 /reduced graphene oxide photocatalyst for an augmented natural sunlight photocatalytic activity. Journal of Alloys and Compounds. 2016;677:219-27.
  6. Holkar CR, Jadhav AJ, Pinjari DV, Mahamuni NM, Pandit AB. A critical review on textile wastewater treatments: Possible approaches. Journal of Environmental Management. 2016;182:351-66.
  7. Chahkandi M, Zargazi M. New water based EPD thin BiVO4 film: Effective photocatalytic degradation of Amoxicillin antibiotic. Journal of Hazardous Materials. 2020;389:121850.
  8. Zhang X, Zhang Y, Quan X, Chen S. Preparation of Ag doped BiVO4 film and its enhanced photoelectrocatalytic (PEC) ability of phenol degradation under visible light. Journal of Hazardous Materials. 2009;167(1-3):911-4.
  9. Montakhab E, Rashchi F, Sheibani S. Effect of cathode size on the morphology of the anodized TiO2 nanotube photocatalyst. Journal of Ultrafine Grained and Nanostructured Materials. 2021 Jun 20;54(1):85-92.
  10. Fatolah M, Khayati GR. Facile decoration of CdS nanoparticles on TiO2: robust photocatalytic activity under LED illumination. Zeitschrift für Naturforschung B. 2021;0(0).
  11. Paul KK, Giri PK. Plasmonic Metal and Semiconductor Nanoparticle Decorated TiO2-Based Photocatalysts for Solar Light Driven Photocatalysis. Encyclopedia of Interfacial Chemistry: Elsevier; 2018. p. 786-94.
  12. Meng X, Zhang Z. Bismuth-based photocatalytic semiconductors: Introduction, challenges and possible approaches. Journal of Molecular Catalysis A: Chemical. 2016;423:533-49.
  13. Gao X, Wang Z, Zhai X, Fu F, Li W. The synthesize of lanthanide doped BiVO4 and its enhanced photocatalytic activity. Journal of Molecular Liquids. 2015;211:25-30.
  14. Sharma R, Uma, Singh S, Verma A, Khanuja M. Visible light induced bactericidal and photocatalytic activity of hydrothermally synthesized BiVO 4 nano-octahedrals. Journal of Photochemistry and Photobiology B: Biology. 2016;162:266-72.
  15. Wang M, Yang G-j, You M-y, Xie Y-h, Wang Y-z, Han J, et al. Effects of Ni doping contents on photocatalytic activity of B-BiVO 4 synthesized through sol-gel and impregnation two-step method. Transactions of Nonferrous Metals Society of China. 2017;27(9):2022-30.
  16. Yu J, Zhang Y, Kudo A. Synthesis and photocatalytic performances of BiVO4 by ammonia co-precipitation process. Journal of Solid State Chemistry. 2009;182(2):223-8.
  17. Samsudin MFR, Sufian S, Hameed BH. Epigrammatic progress and perspective on the photocatalytic properties of BiVO4-based photocatalyst in photocatalytic water treatment technology: A review. Journal of Molecular Liquids. 2018;268:438-59.
  18. Lu F, Chen K, Feng Q, Cai H, Ma D, Wang D, et al. Insight into the enhanced magnetic separation and photocatalytic activity of Sn-doped TiO2 core-shell photocatalyst. Journal of Environmental Chemical Engineering. 2021;9(5):105840.
  19. Sarkar S, Das NS, Chattopadhyay KK. Optical constants, dispersion energy parameters and dielectric properties of ultra-smooth nanocrystalline BiVO4 thin films prepared by rf-magnetron sputtering. Solid State Sciences. 2014;33:58-66.
  20. Ma C, Lee J, Kim Y, Cheol Seo W, Jung H, Yang W. Rational design of α-Fe2O3 nanocubes supported BiVO4 Z-scheme photocatalyst for photocatalytic degradation of antibiotic under visible light. Journal of Colloid and Interface Science. 2021;581:514-22.
  21. Bakhtiarnia S, Sheibani S, Aubry E, Sun H, Briois P, Arab Pour Yazdi M. One-step preparation of Ag-incorporated BiVO4 thin films: plasmon-heterostructure effect in photocatalytic activity enhancement. Applied Surface Science. 2022;580:152253.
  22. Ullah H, Tahir AA, Mallick TK. Structural and electronic properties of oxygen defective and Se-doped p-type BiVO4(001) thin film for the applications of photocatalysis. Applied Catalysis B: Environmental. 2018;224:895-903.
  23. Bakhtiarnia S, Sheibani S, Billard A, Sun H, Aubry E, Yazdi MAP. Enhanced photocatalytic activity of sputter-deposited nanoporous BiVO4 thin films by controlling film thickness. Journal of Alloys and Compounds. 2021;879:160463.
  24. Dong Q, Yang F, Liang F, Zhang Y, Xia D, Zhao W, et al. Silver particle on BiVO4 nanosheet plasmonic photocatalyst with enhanced photocatalytic oxidation activity of sulfadiazine. Journal of Molecular Liquids. 2021;331:115751.
  25. Kumar KV, Porkodi K, Rocha F. Langmuir–Hinshelwood kinetics – A theoretical study. Catalysis Communications. 2008;9(1):82-4.
  26. Gao L, Long X, Wei S, Wang C, Wang T, Li F, et al. Facile growth of AgVO3 nanoparticles on Mo-doped BiVO4 film for enhanced photoelectrochemical water oxidation. Chemical Engineering Journal. 2019;378:122193.
  27. Li M, Xu G, Guan Z, Wang Y, Yu H, Yu Y. Synthesis of Ag/BiVO4/rGO composite with enhanced photocatalytic degradation of triclosan. Science of The Total Environment. 2019;664:230-9.
  28. Geng Y, Zhang P, Li N, Sun Z. Synthesis of Co doped BiVO 4 with enhanced visible-light photocatalytic activities. Journal of Alloys and Compounds. 2015;651:744-8.
  29. Sinclair DC, Watson CJ, Howie RA, Skakle JMS, Coats AM, Kirk CA, et al. NaBi3V2O10: a new oxide ion conductor. Journal of Materials Chemistry. 1998;8(2):281-2.
  30. Miyaji T, Nitta N. Nanoporous Structure Formation on the Surface of InSb by Ion Beam Irradiation. Nanomaterials (Basel). 2017;7(8):204.
  31. Cook GO, Sorensen CD. Overview of transient liquid phase and partial transient liquid phase bonding. Journal of Materials Science. 2011;46(16):5305-23.
  32. Kim D, Chang J-h, Park J, Pak JJ. Formation and behavior of Kirkendall voids within intermetallic layers of solder joints. Journal of Materials Science: Materials in Electronics. 2011;22(7):703-16.
  33. Walsh A, Yan Y, Huda MN, Al-Jassim MM, Wei S-H. Band Edge Electronic Structure of BiVO4: Elucidating the Role of the Bi s and V d Orbitals. Chemistry of Materials. 2009;21(3):547-51.