CN110656364A - Method for preparing large-area bismuth vanadate film based on electrodeposition method - Google Patents
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Abstract
A method for preparing a large-area bismuth vanadate film based on an electrodeposition method belongs to the technical field of material preparation. Firstly, putting a conductive side of a working electrode and a counter electrode in a facing manner in an electrodeposition solution, and adjusting the distance and the angle of the working electrode; depositing a layer of bismuth vanadate precursor film on the working electrode through constant voltage deposition; then dripping a vanadium source solution on the precursor film, placing the precursor film on a heating device for thermal diffusion and solvent evaporation, and covering a thin layer of vanadium source on the precursor film; finally, annealing the film, and cleaning the film in an alkaline solution to obtain a large-area bismuth vanadate film. The preparation method is simple, and can overcome the problem that the large-area uniform bismuth vanadate film is difficult to obtain by an electrodeposition-annealing method. The large-area bismuth vanadate film is prepared into a photoelectrode and then used for photoelectrocatalysis, and the practical application of photoelectrocatalysis water decomposition is hopeful to be promoted.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a method for preparing a large-area bismuth vanadate film based on an electrodeposition method.
Background
Bismuth vanadate is an environment-friendly, non-toxic, easy-to-prepare and cheap material, and can be used as a coloring agent or a photoelectric catalyst. The bismuth vanadate has a proper energy band structure and is considered to beOne of the very efficient photoanodes is used to efficiently decompose water to produce oxygen by photoelectrocatalysis. Almost all high-efficiency bismuth vanadate photo-anodes have the area smaller than 1cm at present2(Catal.,2017,7, 7010013). In order to further push the bismuth vanadate photo-anode to application, the preparation area is larger than 8 multiplied by 8cm2The large-area bismuth vanadate photoelectrode has important practical significance. However, a few of the large-area bismuth vanadate films prepared by the drop coating (adv. Mater.,2018,1804033; Energy technol.,2018,6, 100-), the spin coating (appl. Catal. B: environ.,2016,190,66-74) and the electrodeposition (adv. Energy Mater.,2018,8,1801403) have poor uniformity, so that the performance of the large-area bismuth vanadate photo-anode is far lower than that of the small-area (A)<1cm2) Performance of the photo-anode.
The high-performance bismuth vanadate film can be obtained by adopting an electrodeposition-annealing method, and after a precursor film of the bismuth vanadate is obtained by the electrodeposition method, a vanadium source is added for annealing to obtain the bismuth vanadate film. However, the precursor film obtained by electrodeposition is greatly affected by the deposition voltage, and the precursor film can be obtained only in a small voltage range. As the area of the substrate increases, the current density distribution on the substrate is very uneven, and thus it is difficult to obtain a precursor thin film uniform over a large area using the electrodeposition method. Secondly, even if a large-area uniform precursor film is obtained, after the precursor film dropwise added with the vanadium source is directly annealed, the vanadium source flows and evaporates during the temperature rising process, so that some positions of the film have no vanadium source and some positions have excessive vanadium source. Therefore, it is difficult to obtain a large-area bismuth vanadate thin film, i.e., a large-area bismuth vanadate photoelectrode.
Disclosure of Invention
The invention aims to provide a method for preparing a large-area bismuth vanadate film based on an electrodeposition method, which not only has simple preparation method, but also can overcome the problem that the large-area uniform bismuth vanadate film is difficult to obtain by an electrodeposition-annealing method; the large-area bismuth vanadate thin film can be made into a photoelectrode and then can be catalyzed by photoelectricity.
The invention is realized by the following technical scheme:
a method for preparing a large-area bismuth vanadate film based on an electrodeposition method is characterized by comprising the following steps:
1) placing the conductive side of the working electrode and the surface of the counter electrode in opposite directions in an electrodeposition solution, and adjusting the distance and the angle between the working electrode and the counter electrode to ensure that the distance D between the counter electrode and the bottom end of the working electrode is 1cm, and the inclination angle theta of the working electrode relative to the counter electrode is 14-32 degrees; depositing a layer of bismuth vanadate precursor film on the working electrode by adopting constant voltage deposition; the voltage of the constant voltage deposition is-0.23 to-0.27V, and the time is 100 to 1000 s;
2) dissolving 0.4-0.8M vanadium oxide acetylacetonate in a dimethyl sulfoxide solvent to obtain a vanadium source solution;
3) dropwise adding a vanadium source solution on the precursor film, making the vanadium source solution overhead above a glass culture dish, and then placing the glass culture dish on a heating device for thermal diffusion and solvent evaporation, wherein the heating temperature is 100-180 ℃, and the heating time is 7-20 min;
4) after removing the excess solution, the working electrode is directly placed on a heating device for further evaporation and drying; annealing the film in a muffle furnace at 400-500 ℃, and cleaning in 0.1-1M sodium hydroxide solution to obtain the large-area bismuth vanadate film.
Preferably, the size of the counter electrode in step 1) is equal to or larger than the size of the working electrode.
The electrodeposition solution is prepared by the following method: dissolving 7.5mM bismuth nitrate and 0.4M sodium iodide in nitric acid solution with pH of 1.2 to obtain solution A, and dissolving 0.3M p-benzoquinone in anhydrous ethanol to obtain solution B; wherein the volume ratio of the solution A to the solution B is 20: and 9, mixing the solution A and the solution B, and stirring for 1-2 hours to obtain the electrodeposition solution.
Preferably, the method for dropwise adding the vanadium source solution onto the precursor film in the step 3) adopts a dropping coating method, a spin coating method, a spraying method, a soaking method or a pulling method; and 3) selecting a hot plate, an oven or a muffle furnace as the heating device in the steps 3) and 4).
The invention has the following advantages and prominent technical effects:
the invention has the following advantages and prominent technical effects: the method is simple to operate and is suitable for preparing the large-area bismuth vanadate film. Secondly, the invention overcomes the problem that the large-area uniform bismuth vanadate photoelectrode is difficult to obtain by an electrodeposition-annealing method. The precursor and the bismuth vanadate thin film prepared by the method have good macroscopic and microscopic uniformity, and after the precursor and the bismuth vanadate thin film are prepared into a photoelectrode, the performance of the large-area bismuth vanadate photoelectrode is similar to that of a small-area photoelectrode, so that the large-area bismuth vanadate photoelectrode prepared by the method is expected to promote the practical application of photoelectrocatalysis in water decomposition.
Drawings
FIG. 1 is a schematic view of an electrodeposition apparatus.
In the figure: 1-a pair of electrodes; 2-a working electrode; d is the distance between the bottom ends of the counter electrode and the working electrode, and theta is the inclination angle of the working electrode relative to the counter electrode.
FIG. 2 is a microscopic topography of the precursor film prepared by the present invention at a position 1cm from the bottom of the working electrode.
FIG. 3 is a microscopic topography of a precursor film prepared according to the present invention at a location 4cm from the bottom of the working electrode.
FIG. 4 is a microscopic topography of the precursor film prepared by the present invention at a position 7cm from the bottom of the working electrode.
Detailed Description
The invention provides a method for preparing a large-area bismuth vanadate film based on an electrodeposition method, which specifically comprises the following steps:
1) dissolving 7.5mM bismuth nitrate and 0.4M sodium iodide in nitric acid solution with pH of 1.2 to obtain solution A, and dissolving 0.3M p-benzoquinone in anhydrous ethanol to obtain solution B; wherein the volume ratio of the solution A to the solution B is 20: 9, mixing the solution A and the solution B, and stirring for 1-2 hours to obtain an electrodeposition solution;
2) placing the conductive side of the working electrode and the surface of the counter electrode in opposite directions, placing the working electrode and the counter electrode in an electrodeposition solution, and adjusting the distance and the angle between the working electrode and the counter electrode, wherein the distance D between the counter electrode and the bottom end of the working electrode is 1cm, and the inclination angle theta of the working electrode relative to the counter electrode is 14-32 degrees; depositing a layer of bismuth vanadate precursor film on the working electrode by constant voltage deposition, wherein the voltage of the constant voltage deposition is-0.23 to-0.27V, and the time is 100 to 1000 s; the size of the counter electrode is larger than or equal to that of the working electrode;
3) dissolving 0.4-0.8M vanadium oxide acetylacetonate in a dimethyl sulfoxide solvent to obtain a vanadium source solution;
4) and dropwise adding a vanadium source solution on the precursor film, erecting the vanadium source solution above a glass culture dish, and then placing the glass culture dish on a heating device for thermal diffusion and solvent evaporation, wherein the heating temperature is 100-180 ℃, and the heating time is 7-20 min. The method for dropwise adding the vanadium source solution on the precursor film adopts a dripping method, a spin-coating method, a spraying method, a soaking method or a pulling method; the heating device is a hot plate, an oven or a muffle furnace;
5) after removing the excess solution, the working electrode is directly placed on a heating device for further evaporation and drying; annealing the film in a muffle furnace at 400-500 ℃, and cleaning in 0.1-1M sodium hydroxide solution to obtain the large-area bismuth vanadate film. The heating device is a hot plate, an oven or a muffle furnace.
The preparation method and the practical effect of the invention are further explained in the following by combining the drawings and the specific embodiments, so that the purpose and the technical scheme of the invention are more clearly understood. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1:
1) the fluorine-doped tin oxide conductive glass (FTO) is ultrasonically cleaned in deionized water, acetone and isopropanol for 15min respectively, and then stored in an isopropanol solution for later use.
2) A solution A was prepared by dissolving 7.5mM bismuth nitrate and 0.4M sodium iodide in 100mL of nitric acid having a pH of 1.2, a solution B was prepared by dissolving 0.3M p-benzoquinone in 45mL of anhydrous ethanol, and the solutions A and B were mixed and stirred for 1 hour.
3) Placing the three electrodes in a container containing the solution prepared in 2), and placing a reference electrode (silver/silver chloride) and a counter electrode (9X 9 cm)2Platinum mesh) was placed vertically, and the working electrode (9X 10cm) was placed2FTO) was placed in parallel with the conductive face of the electrode facing the counter electrode at a distance of 1cm, and then the top end of the FTO was turned outward (offset) with the bottom end of the FTO held stationaryThe direction of the counter electrode) is rotated by 14 deg..
4) Electrode wires of the electrochemical workstation are respectively connected to the top ends of the three electrodes in 3), wherein the top end of the FTO is clamped by a commercial stainless steel plate clamp (with the length of 10cm) and then is connected with the electrode wires.
5) And depositing for 400s under a voltage of-0.25V relative to the reference electrode in a standing state to obtain a uniform precursor film of bismuth vanadate, which is shown in FIGS. 2 to 4.
6) 0.6M vanadium oxide acetylacetonate was dissolved in dimethyl sulfoxide as a vanadium source solution for subsequent use.
7) Placing the precursor film obtained in the step 5) on a glass support table of a heated hot plate (180 ℃), dropwise adding 1.5mL of vanadium source prepared in the step 6) on the film, absorbing the residual vanadium source by using filter paper after 7min of thermal diffusion, directly placing the residual vanadium source on the hot plate (180 ℃) for rapid evaporation, and covering a layer of thin vanadium source on the surface of the precursor film.
8) And (3) placing the film obtained in the step 7) in a muffle furnace, raising the temperature to 450 ℃ at the speed of 5 ℃/min, annealing for 1h, then cleaning the film in 0.5M sodium hydroxide solution for 15min, and washing the film with deionized water to obtain the bismuth vanadate film after blow-drying.
Other examples, with the same operations, were prepared as follows:
| examples | 1 | 2 | 3 | 4 | 5 |
| Working electrode inclination angle theta (degree) | 14 | 20 | 25 | 30 | 32 |
| Voltage value of constant voltage deposition V (V) | -0.25 | -0.23 | -0.27 | -0.27 | -0.25 |
| Time of constant voltage deposition t(s) | 300s | 300s | 100s | 400s | 1000s |
| Concentration of vanadium oxide acetylacetonate C (M) | 0.5 | 0.6 | 0.4 | 0.6 | 0.8 |
| Thermal diffusion temperature T (. degree. C.) of vanadium source | 150 | 180 | 100 | 180 | 180 |
| Thermal diffusion time t (min) of vanadium source | 12 | 7 | 20 | 7 | 7 |
| Annealing temperature T (. degree. C.) | 450 | 430 | 400 | 450 | 500 |
| Concentration of sodium hydroxide C (M) | 0.4 | 0.5 | 0.1 | 0.5 | 1 |
Claims (5)
1. A method for preparing a large-area bismuth vanadate film based on an electrodeposition method is characterized by comprising the following steps:
1) placing the conductive side of the working electrode and the surface of the counter electrode in opposite directions in an electrodeposition solution, and adjusting the distance and the angle between the working electrode and the counter electrode to ensure that the distance D between the counter electrode and the bottom end of the working electrode is 1cm, and the inclination angle theta of the working electrode relative to the counter electrode is 14-32 degrees; depositing a layer of bismuth vanadate precursor film on the working electrode by adopting constant voltage deposition; the voltage of the constant voltage deposition is-0.23 to-0.27V, and the time is 100 to 1000 s;
2) dissolving 0.4-0.8M vanadium oxide acetylacetonate in a dimethyl sulfoxide solvent to obtain a vanadium source solution;
3) dropwise adding a vanadium source solution on the precursor film, making the vanadium source solution overhead above a glass culture dish, and then placing the glass culture dish on a heating device for thermal diffusion and solvent evaporation, wherein the heating temperature is 100-180 ℃, and the heating time is 7-20 min;
4) after removing the excess solution, directly placing the working electrode on a heating device, and further evaporating and drying; annealing the film in a muffle furnace at 400-500 ℃, and then cleaning the film in 0.1-1M sodium hydroxide solution to obtain the large-area bismuth vanadate film.
2. The method of claim 1, wherein the counter electrode in step 1) has a size equal to or greater than the size of the working electrode.
3. The method of claim 1, wherein the bath is prepared by:
dissolving 7.5mM bismuth nitrate and 0.4M sodium iodide in nitric acid solution with pH of 1.2 to obtain solution A, and dissolving 0.3M p-benzoquinone in anhydrous ethanol to obtain solution B; wherein the volume ratio of the solution A to the solution B is 20: and 9, mixing the solution A and the solution B, and stirring for 1-2 hours to obtain the electrodeposition solution.
4. A method according to any one of claims 1 to 3, wherein the method for dripping the vanadium source solution on the precursor film in the step 3) adopts a dripping method, a spin coating method, a spray coating method, a soaking method or a pulling method.
5. A method according to any one of claims 1 to 3, wherein the heating means in steps 3) and 4) is a hot plate, oven or muffle.
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Cited By (3)
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| CN113373470A (en) * | 2021-05-31 | 2021-09-10 | 深圳先进技术研究院 | Bismuth vanadate photo-anode, preparation method thereof and photoelectrochemical device |
| CN114438546A (en) * | 2021-12-20 | 2022-05-06 | 苏州大学 | Multifunctional amorphous film photoelectrode and preparation method thereof |
| CN115261869A (en) * | 2022-08-03 | 2022-11-01 | 中国石油大学(北京) | Preparation method and application of bismuth vanadate-based photoproduction cathode protection coating |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113373470A (en) * | 2021-05-31 | 2021-09-10 | 深圳先进技术研究院 | Bismuth vanadate photo-anode, preparation method thereof and photoelectrochemical device |
| CN114438546A (en) * | 2021-12-20 | 2022-05-06 | 苏州大学 | Multifunctional amorphous film photoelectrode and preparation method thereof |
| CN114438546B (en) * | 2021-12-20 | 2023-01-06 | 苏州大学 | Multifunctional amorphous film photoelectrode and preparation method thereof |
| CN115261869A (en) * | 2022-08-03 | 2022-11-01 | 中国石油大学(北京) | Preparation method and application of bismuth vanadate-based photoproduction cathode protection coating |
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