CN112452322A - Preparation method of high-performance photo-anode BiVO4 thin film catalyst - Google Patents
Preparation method of high-performance photo-anode BiVO4 thin film catalyst Download PDFInfo
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- CN112452322A CN112452322A CN202011231979.5A CN202011231979A CN112452322A CN 112452322 A CN112452322 A CN 112452322A CN 202011231979 A CN202011231979 A CN 202011231979A CN 112452322 A CN112452322 A CN 112452322A
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- 229910002915 BiVO4 Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010409 thin film Substances 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 143
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 43
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 43
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000151 deposition Methods 0.000 claims abstract description 30
- 238000004140 cleaning Methods 0.000 claims abstract description 28
- 230000008021 deposition Effects 0.000 claims abstract description 27
- 239000010408 film Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910052786 argon Inorganic materials 0.000 claims abstract description 16
- 238000004544 sputter deposition Methods 0.000 claims abstract description 15
- 239000013077 target material Substances 0.000 claims abstract description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000000137 annealing Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000000861 blow drying Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 239000011521 glass Substances 0.000 description 12
- 238000010849 ion bombardment Methods 0.000 description 11
- 238000011068 loading method Methods 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000003247 decreasing effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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Abstract
The invention relates to a preparation method of a high-performance photoanode BiVO4 thin film catalyst, which comprises the following steps: s1, cleaning a substrate and drying; s2, placing the substrate in a deposition chamber, and then depositing a bismuth vanadate film on the surface of the substrate by adopting a direct-current magnetron sputtering method, wherein the target material is a bismuth vanadate ceramic target, the included angle between the target material and the substrate is 60-90 degrees during sputtering, the sputtering gas is argon and oxygen, the total pressure is 0.5-2.5 Pa, the oxygen partial pressure is 5-20%, the distance between the target material and the substrate is 7-20 cm, and the initial substrate temperature is room temperature. According to the invention, based on the adjustable angle between the target and the substrate in the magnetron sputtering bismuth vanadate process, the preparation process is optimized, and the bismuth vanadate film with a loose structure can be prepared at a special angle, so that the effective contact area with a liquid phase can be increased, the separation of photo-generated electron-hole pairs is promoted, and the photoelectrocatalysis performance of the bismuth vanadate film is improved.
Description
Technical Field
The invention relates to the technical field of functional materials, and particularly relates to a preparation method of a high-performance photoanode BiVO4 thin-film catalyst.
Background
Solar energy is a new renewable clean energy, and has become one of the first-choice alternative energy sources for solving the problems of energy shortage, environmental pollution and the like, but how to efficiently utilize solar energy becomes the key point and the difficulty of the current research.
As early as 1972, Fjulshima and Honda report that a titanium dioxide film can decompose water into hydrogen and oxygen under the condition of illumination so as to realize the conversion of solar energy into chemical energy for the first time, and therefore, a photocatalytic technology enters the visual field of people and attracts extensive attention, thereby becoming one of the current research hotspots. The photocatalytic oxidation technology can effectively utilize clean and renewable solar energy to decompose water to produce hydrogen and oxygen and degrade organic pollutants in water and atmosphere, can effectively reduce energy consumption, and reduces the possibility of byproducts and secondary pollution. It can not only relieve the problem of energy shortage, but also effectively treat environmental pollution, and is a high-efficiency oxidation technology with development prospect.
BiVO4 is an environment-friendly light yellow pigment with bright color, and in recent years, due to the characteristics of wide sources of constituent elements, good chemical and thermal stability and the like, particularly, due to the characteristics of narrow forbidden band width and proper valence band position, the BiVO4 shows excellent photocatalytic explanation of organic pollutants and photocatalytic water splitting activity, thereby attracting wide attention of people. BiVO4 mainly has three crystal phase structures, namely monoclinic scheelite type, tetragonal scheelite type and tetragonal zircon type, and the three crystal phases can be mutually converted under a certain temperature condition. Among them, the monoclinic scheelite-type BiVO4 structure is the most thermodynamically stable crystal phase structure, and exhibits the best photocatalytic activity in the aspects of degrading organic pollutants by visible light and producing oxygen by photolyzing water to produce hydrogen, and the like, thereby obtaining extensive research.
The energy gap Eg of monoclinic scheelite-type BiVO4 is equal to 2.4eV, the valence band position fully meets the requirement of oxidizing water, and the conduction band position is almost consistent with the hydrogen reduction potential, which means that the energy consumption of hydrogen production of BiVO4 is less than that of other visible light semiconductors In the complete Photoelectrochemistry (PEC) water decomposition process, and meanwhile, theoretical calculation shows that the effective mass of photogenerated electrons and holes In BiVO4 is less than that of other traditional oxide semiconductors, such as TiO2 and In2O3, and is more favorable for the separation and transmission of photogenerated carriers.
However, the practical photoelectric conversion efficiency of BiVO4 photocatalytic material is still far lower than its theoretical value due to some problems existing in itself, so that the practical application is limited, and there are several problems: (1) the charge transfer, especially the electron transfer rate, in BiVO4 material is slow, resulting in about 60% -80% recombination of the generated charge carriers before reaching the surface of the material; (2) the rate of kinetics of oxygen evolution from this reaction is very slow compared to the oxidation reaction of sulfites. Therefore, how to further optimize the preparation method of the bismuth vanadate thin film is necessary. Meanwhile, in the prior art, magnetron sputtering is adopted to obtain a compact film under a common condition, the angle between a target and a substrate in the conventional magnetron sputtering equipment is fixed to be 37 degrees, the angle can balance deposition efficiency and film compactness, the smaller the angle is, the shorter the film movement distance is, the higher the bombardment energy is, the more compact the film is correspondingly, but the smaller the angle is, the different target heads can influence each other, and meanwhile, the sputtering process is reflected insufficiently, so that the film composition is easy to be uneven. Therefore, a preparation method of a high-performance photo-anode BiVO4 thin film catalyst is provided.
Disclosure of Invention
The bismuth vanadate film prepared based on the method has good separation and transport capacity of photon-generated carriers, has a large effective contact area range with a liquid phase, and is widely applied to the fields of photocatalysis, electrocatalysis, photoelectrocatalysis and the like. Compared with a widely used solution method, the method has high efficiency and simple preparation process, can be prepared at room temperature, and the obtained film has a loose porous structure, so that the interface resistance of the film is effectively reduced, and the problems in the background art can be effectively solved.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a high-performance photoanode BiVO4 thin film catalyst comprises the following steps:
s1, cleaning the substrate and drying;
s2, placing a substrate in a deposition chamber, and then depositing a bismuth vanadate film on the surface of the substrate by adopting a direct-current magnetron sputtering method, wherein a target material is a bismuth vanadate ceramic target, an included angle between the target material and the substrate is 60-90 degrees during sputtering, sputtering gases are argon and oxygen, the total pressure is 0.5-2.5 Pa, the oxygen partial pressure is 5-20%, the distance between the target material and the substrate is 7-20 cm, the initial substrate temperature is room temperature, the substrate is heated in the sputtering process, the heating temperature range is 350-500 ℃, the power of a direct-current power supply applied to the target material is 50-500W or the power density is 0.6-6.4W/cm 2, and the deposition time is 5-60 min;
s3, after S2, lowering the temperature to room temperature, taking out the sample, sending the sample into a muffle furnace for heat treatment, and after the annealing is finished, lowering the temperature of the sample to room temperature to prepare BiVO4A film.
Further, the initial background vacuum of the deposition chamber in S2 is less than 10-4 Pa。
Preferably, the substrate in S1 is a transparent conductive electrode FTO, ITO, AZO, ATO, or a porous electrode nickel foam or a metal nanowire electrode Cu, Au, Ag, and Al.
Preferably, the method for cleaning the substrate in S1 is to sequentially perform ultrasonic cleaning for 30min by using acetone and absolute ethyl alcohol respectively; the drying method is compressed air blow drying.
Further, in the step S4, the heat treatment temperature is 500 ℃, the temperature rising speed is 1-10 ℃/min, and the heat preservation time is 60-480 min.
Compared with the prior art, the invention has the following beneficial effects:
the magnetron sputtering process has mild conditions, simple process and short period, can be continuously prepared and is not limited by the size, the texture and the shape of a substrate;
secondly, by controlling the included angle between the target material and the substrate, the bismuth vanadate film with a special loose structure can be prepared, so that the contact area with a liquid phase is improved, the interface resistance is reduced, and the separation of photon-generated carriers is promoted;
according to the invention, based on the adjustable angle between the target and the substrate in the magnetron sputtering bismuth vanadate process, the preparation process is optimized, and the bismuth vanadate film with a loose structure can be prepared at a special angle, so that the effective contact area with a liquid phase can be increased, the separation of photo-generated electron-hole pairs is promoted, and the photoelectrocatalysis performance of the bismuth vanadate film is improved.
Drawings
FIG. 1 is a schematic diagram of a magnetron sputtering technique;
FIG. 2 is a scanning electron photograph of a bismuth vanadate thin film obtained by magnetron sputtering deposition when the included angle between a target and a substrate is 90 degrees;
FIG. 3 is a photo current curve of bismuth vanadate films prepared at different angles between the target and the substrate in neutral electrolyte.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
The equipment used in the following embodiments is a three-target co-sputtering film coating machine with model number of MSP-3200, which is assembled by Wennake technologies of Beijing, Chuangshi, and comprises a deposition chamber, a sample chamber, a plurality of target heads, a tray, a direct current power supply and a series of vacuum pumps, and the equipment is arranged in a room with constant temperature of 22 ℃, so the initial substrate temperature related to the following embodiments is 22 ℃ without repeated limitation; the purity of the high purity argon and the high purity oxygen referred to below was 99.99%.
Example 1
Ultrasonic cleaning of substrate (FTO glass), ultrasonic cleaning of substrate with acetone and absolute ethanol respectively for 30 minutes, respectivelySequentially fixed on a substrate plate, placed in a sample introduction chamber, and then opened to load the sample into a vacuum degree (background vacuum degree) of 10－4 Pa or less. By modifying the position of a sputtering target head, an included angle between the normal of the bismuth vanadate target and the normal of a substrate is 90 degrees (as shown in figure 1), high-purity argon and oxygen are introduced, the flow is 60sccm and 3.5sccm, the pressure is 0.6 Pa, the distance between the target and the substrate is 8cm, the initial chamber temperature is heated to 500 ℃, a direct-current power supply (the electric power is 200W) is started, and the pure bismuth vanadate target is sputtered for 10 min. After deposition is completed, the sample is removed after the substrate temperature has decreased back to room temperature due to the increased temperature of the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The heating speed is 1 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out.
Example 2
Ultrasonically cleaning a substrate (FTO glass), respectively ultrasonically cleaning the substrate with acetone and absolute ethyl alcohol for 30 minutes, sequentially fixing the substrate on a substrate plate, placing the substrate plate into a sample introduction chamber, opening a gate, and loading the substrate plate until the vacuum degree (background vacuum degree) reaches 10－4 Pa or less. The included angle between the normal of the bismuth vanadate target and the normal of the substrate is 90 degrees, high-purity argon and oxygen are introduced, the flow is 60sccm and 3.5sccm, the pressure is 0.6 Pa, the distance between the target and the substrate is 8cm, the initial chamber temperature is heated to 500 ℃, a direct current power supply (the electric power is 200W) is started, and the pure bismuth vanadate target is sputtered for 30 min. After the deposition is finished, the substrate is taken out after the temperature of the substrate is reduced to the room temperature due to the temperature rise caused by the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The heating speed is 1 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out. The microstructure of the surface of the material is tested by a field emission scanning electron microscope, as shown in figure 2, the material has an obvious loose structure and is convenient for the penetration of liquid, and the photoelectrocatalysis performance of the material is as shown in figure 3, so that the material has the best photoelectrocatalysis performance.
Example 3
Ultrasonically cleaning the substrate (ITO glass), respectivelyUltrasonically cleaning the substrate with acetone and anhydrous ethanol for 30min, fixing the substrate on a substrate plate, placing the substrate plate into a sample chamber, opening a gate, and loading until the vacuum degree (background vacuum degree) reaches 10－4 Pa or less. The included angle between the normal of the bismuth vanadate target and the normal of the substrate is 90 degrees, pure argon and oxygen are introduced, the flow is 60sccm and 10sccm respectively, the pressure is 0.6 Pa, the distance between the target and the substrate is 8cm, the initial chamber is heated to 500 ℃, a direct current power supply (the electric power is 200W) is started, the pure bismuth vanadate target is sputtered, and the deposition time is 10 min. After the deposition is finished, the substrate is taken out after the temperature of the substrate is reduced to the room temperature due to the temperature rise caused by the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The heating speed is 1 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out.
Example 4
Ultrasonically cleaning substrate (ATO glass), respectively ultrasonically cleaning the substrate with acetone and anhydrous ethanol for 30min, sequentially fixing on a substrate plate, placing into a sample chamber, opening a gate, and loading until vacuum degree (background vacuum degree) reaches 10－4 Pa or less. The included angle between the normal of the bismuth vanadate target and the normal of the substrate is 90 degrees, high-purity argon and oxygen are introduced, the flow is 60sccm and 3.5sccm, the pressure is 0.6 Pa, the distance between the target and the substrate is 8cm, the initial chamber temperature is heated to 350 ℃, a direct current power supply (the electric power is 200W) is started, and the pure bismuth vanadate target is sputtered for 10 min. And after the deposition is finished, the temperature of the substrate is reduced to the room temperature, and the substrate is taken out. The sample was then fed into a muffle furnace and heat treated. The heating speed is 1 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out.
Example 5
Ultrasonically cleaning a substrate (FTO glass), respectively ultrasonically cleaning the substrate with acetone and absolute ethyl alcohol for 30 minutes, sequentially fixing the substrate on a substrate plate, placing the substrate plate into a sample introduction chamber, opening a gate, and loading the substrate plate until the vacuum degree (background vacuum degree) reaches 10－4 Deposition chamber below PaIn (1). The included angle between the normal of the bismuth vanadate target and the normal of the substrate is 45 degrees, high-purity argon and oxygen are introduced, the flow is 60sccm and 3.5sccm, the pressure is 0.6 Pa, the distance between the target and the substrate is 8cm, the initial chamber temperature is kept at room temperature, a direct current power supply (the electric power is 200W) is started, the pure bismuth vanadate target is sputtered, the deposition time is 10 min, and the substrate is kept at room temperature. After deposition is completed, the sample is removed after the substrate temperature has decreased back to room temperature due to the increased temperature of the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The heating speed is 1 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out.
Example 6
Ultrasonically cleaning a substrate (FTO glass), respectively ultrasonically cleaning the substrate with acetone and absolute ethyl alcohol for 30 minutes, sequentially fixing the substrate on a substrate plate, placing the substrate plate into a sample introduction chamber, opening a gate, and loading the substrate plate until the vacuum degree (background vacuum degree) reaches 10－4 Pa or less. The included angle between the normal of the bismuth vanadate target and the normal of the substrate is 60 degrees, high-purity argon and oxygen are introduced, the flow is 60sccm and 5sccm, the pressure is 0.6 Pa, the distance between the target and the substrate is 8cm, the initial chamber temperature is heated to 500 ℃, a direct current power supply (the electric power is 200W) is started, and the pure bismuth vanadate target is sputtered for 10 min. After deposition is completed, the sample is removed after the substrate temperature has decreased back to room temperature due to the increased temperature of the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The heating speed is 1 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out.
Example 7
Ultrasonically cleaning a substrate (FTO glass), respectively ultrasonically cleaning the substrate with acetone and absolute ethyl alcohol for 30 minutes, sequentially fixing the substrate on a substrate plate, placing the substrate plate into a sample introduction chamber, opening a gate, and loading the substrate plate until the vacuum degree (background vacuum degree) reaches 10－4 Pa or less. The included angle between the normal of the bismuth vanadate target and the normal of the substrate is 90 degrees, high-purity argon and oxygen are introduced, the flow is 60sccm and 5sccm, the pressure is 0.6 Pa, the distance between the target and the substrate is 8cm, and the method is startedThe temperature of the chamber is heated to 500 ℃, a direct current power supply (the electric power is 200W) is started, and the pure bismuth vanadate target is sputtered for 10 min. Sputtering bismuth vanadate ceramic target material. After deposition is completed, the sample is removed after the substrate temperature has decreased back to room temperature due to the increased temperature of the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The temperature rise speed is 5 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out.
Example 8
Ultrasonically cleaning a substrate (FTO glass), respectively ultrasonically cleaning the substrate with acetone and absolute ethyl alcohol for 30 minutes, sequentially fixing the substrate on a substrate plate, placing the substrate plate into a sample introduction chamber, opening a gate, and loading the substrate plate until the vacuum degree (background vacuum degree) reaches 10－4 Pa or less. The included angle between the normal of the bismuth vanadate target and the normal of the substrate is 90 degrees, high-purity argon and oxygen are introduced, the flow is 60sccm and 15sccm, the pressure is 0.6 Pa, the distance between the target and the substrate is 8cm, the initial chamber temperature is heated to 500 ℃, a direct current power supply (the electric power is 200W) is started, and the pure bismuth vanadate target is sputtered for 10 min. Sputtering bismuth vanadate ceramic target material, keeping the substrate at room temperature. After deposition is completed, the sample is removed after the substrate temperature has decreased back to room temperature due to the increased temperature of the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The heating speed is 1 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 240 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out.
Example 9
Ultrasonically cleaning a substrate (FTO glass), respectively ultrasonically cleaning the substrate with acetone and absolute ethyl alcohol for 30 minutes, sequentially fixing the substrate on a substrate plate, placing the substrate plate into a sample introduction chamber, opening a gate, and loading the substrate plate until the vacuum degree (background vacuum degree) reaches 10－4 Pa or less. The included angle between the normal of the bismuth vanadate target and the normal of the substrate is 90 degrees, high-purity argon and oxygen are introduced, the flow is 60sccm and 3.5sccm, the pressure is 2 Pa, the distance between the target and the substrate is 8cm, the initial chamber temperature is heated to 500 ℃, a direct current power supply (the electric power is 200W) is started, and the pure bismuth vanadate target is sputtered for 30 min.After deposition is completed, the sample is removed after the substrate temperature has decreased back to room temperature due to the increased temperature of the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The heating speed is 1 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out.
Example 10
Ultrasonically cleaning a substrate (FTO glass), respectively ultrasonically cleaning the substrate with acetone and absolute ethyl alcohol for 30 minutes, sequentially fixing the substrate on a substrate plate, placing the substrate plate into a sample introduction chamber, opening a gate, and loading the substrate plate until the vacuum degree (background vacuum degree) reaches 10－4 Pa or less. The included angle between the normal of the bismuth vanadate target and the normal of the substrate is 90 degrees, high-purity argon and oxygen are introduced, the flow is 60sccm and 3.5sccm, the pressure is 2 Pa, the distance between the target and the substrate is 8cm, the initial chamber temperature is heated to 400 ℃, a direct current power supply (the electric power is 200W) is started, and the pure bismuth vanadate target is sputtered for 30 min. After deposition is completed, the sample is removed after the substrate temperature has decreased back to room temperature due to the increased temperature of the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The heating speed is 1 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out.
Example 11
Ultrasonically cleaning a substrate (FTO glass), respectively ultrasonically cleaning the substrate with acetone and absolute ethyl alcohol for 30 minutes, sequentially fixing the substrate on a substrate plate, placing the substrate plate into a sample introduction chamber, opening a gate, and loading the substrate plate until the vacuum degree (background vacuum degree) reaches 10－4 Pa or less. The included angle between the normal of the bismuth vanadate target and the normal of the substrate is 90 degrees, high-purity argon and oxygen are introduced, the flow is 60sccm and 3.5sccm, the pressure is 0.5 Pa, the distance between the target and the substrate is 8cm, the initial chamber temperature is heated to 500 ℃, a direct current power supply (the electric power is 200W) is started, and the pure bismuth vanadate target is sputtered for 30 min. After the deposition is finished, the substrate is taken out after the temperature of the substrate is reduced to the room temperature due to the temperature rise caused by the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The heating rate is 1 ℃/min, the annealing temperature is 500 ℃, and the temperature is keptThe temperature is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out.
Comparative example 1
Ultrasonically cleaning a substrate (FTO glass), respectively ultrasonically cleaning the substrate with acetone and absolute ethyl alcohol for 30 minutes, sequentially fixing the substrate on a substrate plate, placing the substrate plate into a sample introduction chamber, opening a gate, and loading the substrate plate until the vacuum degree (background vacuum degree) reaches 10－4 Pa or less. Introducing pure argon gas with the flow of 60sccm and the pressure of 0.6 Pa, keeping the distance between the target and the substrate at 8cm, starting a direct-current power supply (with the electric power of 200W) under the condition that the initial chamber temperature is kept at room temperature, sputtering the pure bismuth vanadate target, wherein the deposition time is 10 min, and keeping the substrate at room temperature. After deposition is completed, the sample is removed after the substrate temperature has decreased back to room temperature due to the increased temperature of the ion bombardment. The sample was then fed into a muffle furnace and heat treated. The heating speed is 1 ℃/min, the annealing temperature is 500 ℃, and the heat preservation time is 120 min. After the annealing is completed, the temperature of the sample is cooled back to the room temperature, and the sample is taken out. The photoelectrocatalysis performance of the film prepared without modification is shown in figure 3, and the photoelectricity value of the film is far smaller than the value of the sputtering included angle of 90 degrees in the example 2.
Comparative example 2
Bismuth vanadate and citric acid are mixed according to a molar ratio of 1:1 and Bi (NO)3)3·5H2Preparing 10ml of 0.012mol aqueous solution by using O and citric acid as raw materials, uniformly stirring, and adding ethanolamine until the solution is clear and transparent. At the same time, 0.012molNH was weighed4VO3And 0.216mol of citric acid were added to 10ml of boiling water, and stirred until completely dissolved. 10ml of the solution prepared in the first step was slowly added dropwise to the solution prepared in the second step, and stirring was continued for 5 hours while maintaining the boiling state. Respectively cleaning the FTO substrate by using deionized water, acetone and ethanol, drying by using nitrogen, then exposing by using ultraviolet light for 20min, then spin-coating the BiVO4 sol obtained by the reaction on the surface of the FTO substrate at the rotating speed of 2000rpm, and then 200oC hold 6min after repeating spin coating 5 times in this manner, the final sample was placed 500 in a muffle furnaceoC, heat treatment is carried out for 1 h. After the temperature had dropped to room temperature, samples were taken and tested for photocurrent, which was much less than the 90 ° sputtering angle in example 2, as shown in fig. 3.
In conclusion, the angle between the target head and the substrate is adjusted, namely the angle of the sputtered particles bombarding the substrate is adjusted, the angle is improved by modifying equipment, so that the particle deposition distance is increased, and the prepared film is looser; in the process of photoelectrocatalysis, liquid can be immersed into the gaps of the film, so that the migration distance of carriers is shortened, and the performance of photoelectrocatalysis is improved finally.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A preparation method of a high-performance photoanode BiVO4 thin film catalyst is characterized by comprising the following steps:
s1, cleaning the substrate and drying;
s2, placing a substrate in a deposition chamber, and then depositing a bismuth vanadate film on the surface of the substrate by adopting a direct-current magnetron sputtering method, wherein a target material is a bismuth vanadate ceramic target, an included angle between the target material and the substrate is 60-90 degrees during sputtering, sputtering gases are argon and oxygen, the total pressure is 0.5-2.5 Pa, the oxygen partial pressure is 5-20%, the distance between the target material and the substrate is 7-20 cm, the initial substrate temperature is room temperature, the substrate is heated in the sputtering process, the heating temperature range is 350-500 ℃, the power of a direct-current power supply applied to the target material is 50-500W or the power density is 0.6-6.4W/cm 2, and the deposition time is 5-60 min;
s3, after S2, lowering the temperature to room temperature, taking out the sample, sending the sample into a muffle furnace for heat treatment, and after the annealing is finished, lowering the temperature of the sample to room temperature to prepare BiVO4A film.
2. Root of herbaceous plantThe method for preparing a high-performance photoanode BiVO4 thin film catalyst as claimed in claim 1, wherein the initial background vacuum degree of the deposition chamber in S2 is less than 10-4 Pa。
3. The preparation method of the high-performance photoanode BiVO4 thin film catalyst according to claim 1, wherein the substrate in S1 is a transparent conductive electrode FTO, ITO, AZO, ATO, or porous electrode nickel foam or metal nanowire electrode Cu, Au, Ag, or Al.
4. The method for preparing the high-performance photoanode BiVO4 thin film catalyst according to claim 1, wherein the method for cleaning the substrate in S1 comprises sequentially performing ultrasonic cleaning with acetone and absolute ethyl alcohol for at least 30 min; the drying method is compressed air blow drying.
5. The preparation method of the high-performance photoanode BiVO4 thin film catalyst according to claim 1, wherein the heat treatment temperature in S3 is 500 ℃, the temperature rise rate is 1-10 ℃/min, and the heat preservation time is 60-480 min.
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