electrochemical synthesis, quantum photocurrent yield, heterostructures

How to Cite

Smilyk , V., Fomanyuk, S., Kolbasov, G., & Rusetskyi, I. (2019). PHOTOELECTROCHEMICAL PROPERTIES OF FILMS BASED ON BISMUTH AND COPPER VANADATES. Ukrainian Chemistry Journal, 85(10), 83-90.


BiVO4, BiVO4 / WO3 and Cu3VO4 films were obtained by the method of electrochemical synthesis using interferometric control of the film thickness during their deposition; It is shown that films absorb light in the long-wave region of the solar spectrum. The materials obtained also have good adhesion with the optically transparent substrate SnO2. From the analysis of the photocurrent spectra, it was determined that the photoelectrochemical efficiency of BiVO4 crystalline films depends on the thickness of such films. BiVO4 films with a thickness of 80–150 nm showed high values of the quantum yield of the photocurrent as compared with films with a thickness of 0.5–1 μm. From XRD, it was established that after annealing at 500°C, the films BiVO4 and WO3 crystallize into the structure of monoclinic scheelite. It has been established that the WO3 layer in the BiVO4 / WO3 heterostructure increases its overall photoelectrochemical efficiency in the ultraviolet and near visible regions of the spectrum. It was established that, depending on the heat treatment conditions, the band gap of the obtained Cu3VO4 films is from 1.4 to 2.2 eV, which allows them to be used as photoanods for photoelectrochemical converters of solar energy. Due to the narrow width of the bandgap, Cu3VO4 can absorb visible light in almost the entire long-wave region. But the literature data on photoelectrochemical properties of Cu3VO4 and BiVO4 are limited, in this connection there is a need for the development of techniques for the synthesis of photosensitive films based on Cu3VO4 and BiVO4 and their photoelectrochemical characteristics. In this paper we investigate the photoelectrochemical characteristics of copper vapor and vanadium Cu3VO4 and BiVO4 bismuth which can absorb visible light in the long-wave region of the solar spectrum and work in pairs as a photo anode (BiVO4) and a photocathode of Cu3VO4 in a photoelectrochemical cell for the production of hydrogen and oxygen.


1. Huang Z.-F. Pan L., Zou J.-J. Nanostructured bismuth vanadate-based materials for solar-energy-driven water oxidation: a review on recent progress. Nanoscale. 2014. 6 (23): 14044.
2. Marchelek M., Diak M., Kozak M., Zaleska-Medynska A., Grabowska E. Some Unitary, Binary, and Ternary Non-TiO2 Photocatalysts. Intech. 2015. 55: 240.
3. Sahoo S., Brandon Z., Maggard P. A. Optical, electronic, and photoelectrochemical properties of the p-type Cu3-xVO4 semiconductor. Journal of Materials Chemistry A. 2016. 18: 1.
4. Yang Y., Xu D., Wu Q., Diao P. Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction. Scientific Reports. 2016. 6 (1): 10.
5. Cho S.K., Park H. S., Heung C. L., Ki M. N., Allen J. B. Metal Doping of BiVO4 by Composite Electrodeposition with Improved Photoelectrochemical Water Oxidation. Journal of Physical Chemistry C. 2013. 117: 23048.
6. Choi J., Sudhagar P., Kim J. H. WO3/W:BiVO4/BiVO4 graded photoabsorber electrode for enhanced photoelectrocatalytic solar light driven water oxidation. Physical Chemistry Chemical Physics. 2017. 6: 2.
7. Krasnov Yu.S., Kolbasov G.Ya. Electrochromism and reversible changes in the position of fundamental absorption edge in cathodically deposited amorphous WO3. Electrochim. Acta. 2004. 49: 2425.
8. Lerner L. S. Physics for Scientists and Engineers. 1996. 2: 971.
9. Baek J.H., Kim B.J., Han G.S., Hwang S.W., Kim D.R., Cho I.S., Jung H.S. BiVO4/WO3/SnO2 Double-Heterojunction Photoanode with Enhanced Charge Separation and Visible-Transparency for Bias-Free Solar Water-Splitting with a Perovskite Solar Cell. ACS Applied Materials & Interfaces. 2017. 9: 1479.
10. Pihosh Y., Turkevych I., Mawatari K. Photocatalytic generation of hydrogen by core-shell WO3/BiVO4 nanorods with ultimate water splitting efficiency. Scientific Reports. 2015. 5: 11141.
11. Povar I., Spinu O., Zinicovscaia I., Pintilie B., Ubaldini S. Revised Pourbaix diagrams for the vanadium – water system. Journal Electrochemistry Science. 2019. 9 (2): 78.
12. Ziwritsch M., Müller S., Hempel H. Direct Time-Resolved Observation of Carrier Trapping and Polaron Conductivity in BiVO4. ACS Energy Letters. 2016. 1 (5): 888.
13. Butler K. T., Dringoli B. J., Zhou L., Rao P. M., Walshe A., Titova L. V. Ultrafast carrier dynamics in BiVO4 thin film photoanode material: interplay between free carriers, trapped carriers and low-frequency lattice vibrations. Journal of Materials Chemistry A. 2016. 4: 18516.
14. Smilyk V.O., Fomanyuk S.S., Kolbasov G.Y. Electrodeposition, optical and photoelectrochemical properties of BiVO4 and BiVO4/WO3 films. Res. Chem. Intermed. – 2019.
15. Gurevich Yu.Y., Pleskov Yu.V. Photoelectrochemistry of semiconductors. (Moscow: Science, 1983).
16. Del E., Lino C., Carlos H. Vanadium: History, chemistry, interactions with α-amino acids and potential therapeutic applications. Coordination Chemistry Reviews. 2018. 372: 117.
17. Chen H.Y., Wu L., Ren C., Luo Q.Z. The effect and mechanism of bismuth doped lead oxide on the performance of lead-acid batteries. Journal of Power Sources. 2001. 95 (1): 108.
18. Griva Z.I., Kots V.A., Piasiro V.D. Reference Chemist. –L: Chemistry, 1964.


Download data is not yet available.