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KR-102963907-B1 - PREPARATION METHOD OF LARGE-AREA BIVO4 AND BIVO4 PHOTOCATALYST MANUFACTURED THEREOF

KR102963907B1KR 102963907 B1KR102963907 B1KR 102963907B1KR-102963907-B1

Abstract

The present invention relates to a method for producing large-area bismuth vanadate and a bismuth vanadate photocatalyst produced thereby. The present invention enables the production of bismuth vanadate ( BiVO₄ ), which could not be produced in large areas in the past, in large areas.

Inventors

  • 백상철
  • 손유현
  • 장지현
  • 강지훈

Assignees

  • 에쓰대시오일 주식회사
  • 울산과학기술원

Dates

Publication Date
20260512
Application Date
20241014

Claims (20)

  1. (a) a step of attaching a masking film to a substrate to divide the substrate into multiple regions having a width of 0.2 to 3 cm and an aspect ratio of 3:1 or greater; (b) a step of electrodepositing a bismuth precursor on the substrate; (c) a step of applying a mixed solution containing a solvent and a vanadic acid precursor onto a substrate on which the bismuth precursor is deposited; (d) a step of performing a first heat treatment on a substrate coated with the above-mentioned mixed solution; and (e) a step of removing the masking film from the first heat-treated substrate and then performing a second heat treatment to produce bismuth vanadate; a method for producing bismuth vanadate comprising.
  2. A method for manufacturing bismuth vanadate according to claim 1, wherein the substrate comprises one or more of FTO, ZnO, ITO, AZO, GZO, IZO, and IGZO.
  3. In paragraph 1, The above masking film is a method for manufacturing bismuth vanadate comprising one or more of polyimide, glass fiber, and carbon.
  4. A method for manufacturing bismuth vanadate according to claim 1, wherein the width of the masking film is 0.2 to 0.7 cm.
  5. A method for producing bismuth vanadate according to claim 1, wherein the bismuth precursor comprises bismuth oxyiodide (BiOI).
  6. A method for producing bismuth vanadate according to claim 1, wherein the electro-deposition is performed at a voltage of -1 to -0.05 V.
  7. A method for producing bismuth vanadate according to claim 1, wherein the electro-deposition is performed for 0.1 to 5 minutes.
  8. A method for manufacturing bismuth vanadate according to claim 1, wherein the bismuth precursor is electrodeposited to a thickness of 0.5 to 10 μm.
  9. A method for producing bismuth vanadate according to claim 1, wherein the solvent comprises one or more of dimethyl sulfoxide (DMSO), water, alcohol, ethylene glycol, and methylene iodide.
  10. A method for preparing bismuth vanadate according to claim 1, wherein the vanadate precursor comprises one or more of vanadyl acetylacetonate, vanadium pentoxide, vanadium trioxide, and ammonium metavanadate ( NH₄VO₃ ).
  11. A method for producing bismuth vanadate according to claim 1, wherein the concentration of the vanadic acid precursor in the mixed solution is 0.05 to 3 M.
  12. In paragraph 1, The above first heat treatment is performed by raising the temperature to the first heat treatment temperature at a first heating rate, and A method for manufacturing bismuth vanadate, wherein the first heating rate is 0.05 to 0.1 ℃/min.
  13. In paragraph 1, The above first heat treatment is performed by raising the temperature to the first heat treatment temperature at a first heating rate, and A method for manufacturing bismuth vanadate, wherein the first heat treatment temperature is 35 to 100 ℃.
  14. A method for manufacturing bismuth vanadate according to claim 1, wherein the second heat treatment is performed at 300 to 600 ℃.
  15. A method for producing bismuth vanadate according to claim 1, wherein the second heat treatment is performed for 0.8 to 3.5 hours.
  16. A method for manufacturing bismuth vanadate according to claim 1, further comprising the step of etching the bismuth vanadate after step (e).
  17. In paragraph 1, Each of the above plurality of regions has a width of 0.8 to 2 cm and an aspect ratio of 3.1 : 1 to 25 : 1, and The above masking film comprises polyimide, and The above solvent is dimethyl sulfoxide (DMSO), and A method for preparing bismuth vanadate, wherein the concentration of the vanadic acid precursor in the above mixed solution is 0.3 to 0.7 M.
  18. In paragraph 1, The width of the masking film is 0.4 to 0.5 cm, and The above bismuth precursor is bismuth oxyiodide (BiOI), and The above electrodeposition is performed at a voltage of -0.4 to -0.08 V for 0.3 to 2 minutes to form the bismuth precursor to a thickness of 2 to 4 μm, and The above vanadium acid precursor is vanadyl acetylacetonate, and A method for manufacturing bismuth vanadate in which the above vanadate precursor is applied to a thickness of 2 to 4 μm.
  19. Bismuth vanadate produced according to any one of claims 1 to 18.
  20. A photocatalyst for water splitting comprising bismuth vanadate of claim 19.

Description

Preparation Method of Large-Area Bismuth Vanadate and Bismuth Vanadate Photocatalyst Manufactured Thereof The present invention relates to a method for producing large-area bismuth vanadate and a bismuth vanadate photocatalyst produced thereby. Research aimed at replacing existing fossil fuel sources, such as petroleum and coal, continues to be recognized for its importance in developing sustainable and eco-friendly energy sources. Among various energy sources, hydrogen energy is gaining attention as a future alternative energy source due to its abundance and the advantage of being able to store large quantities for long periods. There are various methods for producing hydrogen energy, and among them, the photoelectrochemical (PEC) water splitting method is attracting attention as an eco-friendly way to produce hydrogen gas by replacing the electrical energy used in conventional water electrolysis with solar energy. In particular, metal oxides are widely used as photoelectrodes in the photoelectrochemical water splitting method due to their advantages, such as low cost, an appropriate bandgap, and stability in the reaction. Among metal oxides used as photoelectrodes, bismuth vanadate ( BiVO₄ ) is a suitable candidate for commercialization because it is easy to produce in large quantities, but there was a limitation in that it could not be fabricated on a large area due to the difficulty of uniform coating. FIG. 1 is a schematic diagram showing the process of a method for manufacturing bismuth vanadate according to one embodiment of the present invention. Figure 2 is a photographic image and schematic diagram showing the aspect ratio of a vanadium-coated bismuth oxyiodide (BiOI) electrode. Figure 3 is a photographic image showing the process of manufacturing a vanadium-coated bismuth oxyiodide (BiOI) electrode in Example 1 of the present invention. Figure 4 shows a photographic image of a vanadium-coated bismuth oxyiodide (BiOI) electrode prepared in Comparative Example 1 of the present invention. Figure 5 shows a photographic image of a vanadium-coated bismuth oxyiodide (BiOI) electrode prepared in Comparative Example 2 of the present invention. Figure 6 shows a photographic image of a vanadium-coated bismuth oxyiodide (BiOI) electrode prepared in Comparative Example 2 of the present invention. Figure 7 shows a photographic image of a bismuth vanadate ( V₂O₅ / BiVO₄ ) electrode with an excess amount of vanadium oxide deposited , prepared in Comparative Example 2 of the present invention. Figure 8 shows a photographic image of a bismuth vanadate ( V₂O₅ / BiVO₄ ) electrode with an excess amount of vanadium oxide deposited , prepared in Comparative Example 3 of the present invention. Figure 9 shows photographic images of a vanadium-coated bismuth oxyiodide (BiOI) electrode and a bismuth vanadate electrode prepared in Example 1 of the present invention. The advantages and features of the present invention and the methods for achieving them will become clear by referring to the embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below but may be implemented in various different forms. These embodiments are provided merely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims. In describing the present invention, detailed descriptions of related prior art are omitted if it is determined that such detailed descriptions may unnecessarily obscure the essence of the invention. Where terms such as “comprising,” “having,” or “consisting of” are used in this specification, other parts may be added unless “only” is used. Furthermore, terms such as “comprising” or “having” are intended to specify the existence of features, numbers, steps, components, or combinations thereof described in the specification, and should not be understood as excluding the existence or addition of one or more other features, numbers, steps, components, or combinations thereof. Additionally, when a component is expressed in the singular, it includes cases where it is included in the plural unless specifically stated otherwise. Conventionally, when coating a vanadic acid precursor to manufacture bismuth vanadate, there was a limitation in that the vanadic acid precursor solution could not be coated uniformly, making it impossible to manufacture over a large area. Accordingly, in the present invention, a substrate is divided into multiple regions with a width of 0.2 to 3 cm and an aspect ratio of 3:1 or more using a masking film, and bismuth vanadate is manufactured in the multiple regions, thereby improving the phenomenon where the vanadic acid precursor solution aggregates and is coated unevenly, making it possible to manufacture bismuth vanadate over a large area of 20 cm² or more without