CN108579723B - Vanadium-doped nano titanium dioxide photocatalyst and preparation method thereof - Google Patents
Vanadium-doped nano titanium dioxide photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 16
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002071 nanotube Substances 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 25
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical group [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000010453 quartz Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910000856 hastalloy Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002135 nanosheet Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 10
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910003699 H2Ti12O25 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZDNBCKZJXCUXCR-UHFFFAOYSA-L dihydroxy(oxo)titanium Chemical compound O[Ti](O)=O ZDNBCKZJXCUXCR-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 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
-
- 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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Abstract
The invention discloses a vanadium-doped nano titanium dioxide photocatalyst and a preparation method thereof, relating to the technical field of photocatalytic materials. The method comprises the following steps: mixing isopropyl titanate, a vanadium source and an organic solvent in a container to obtain a mixed solution; placing the container in a hydrothermal reaction kettle filled with absolute ethyl alcohol, and keeping the temperature at 290-300 ℃ for 4-6 h to obtain an initial product; and annealing the initial product at 580-620 ℃ in an inert atmosphere for 4-5 h to obtain black vanadium-doped titanium dioxide powder. V/TiO prepared by the invention2The nano particles are in a nano sheet shape with the length of about 200nm, are self-assembled into a nano tube shape, have large specific surface area and strong adsorption performance; the process flow is simple, and the experimental repeatability is good; the obtained nano particles have good application prospect in the field of photocatalysis.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a vanadium-doped nano titanium dioxide photocatalyst and a preparation method thereof.
Background
Nano TiO 22Due to excellent physical and chemical properties, the material has wide application in the fields of environmental engineering, energy conversion and the like. However, TiO2The performance of the material is also limited, and the most remarkable point is TiO2The most common anatase phase crystal of the photocatalyst has a band gap of 3.2eV, namely, the photocatalyst can only absorb light above an ultraviolet region (equal to or more than 387nm), and the utilization rate of sunlight is extremely low, so that a plurality of scholars are engaged in widening TiO for decades2Visible light response range.
In the energy band engineering of titanium dioxide, the simplest method to utilize is to treat TiO2Doping is performed to introduce an impurity level in the forbidden band. Wherein, vanadium ion (V)5+) Due to its doping to TiO2The most significant red shift of the absorption edge of (V) is of great concern5+The doping method of (2) is also various, such as a solid phase method, a sol-gel method, a hydrothermal method or an oil bath method.
All the methods have certain defects, and the vanadium-doped nano titanium dioxide photocatalyst with higher comprehensive performance cannot be obtained.
Disclosure of Invention
In view of this, the embodiment of the invention provides a vanadium-doped nano titanium dioxide photocatalyst and a preparation method thereof, and mainly aims to solve the problem of low comprehensive performance of a vanadium-doped nano titanium dioxide material.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
a preparation method of a vanadium-doped nano titanium dioxide photocatalyst comprises the following steps:
mixing isopropyl titanate, a vanadium source and an organic solvent in a container to obtain a mixed solution;
placing the container in a hydrothermal reaction kettle filled with absolute ethyl alcohol, and keeping the temperature at 290-300 ℃ for 4-6 h to obtain an initial product;
and annealing the initial product at 580-620 ℃ in an inert atmosphere for 4-5 h to obtain black vanadium-doped titanium dioxide powder.
Preferably, the container is a quartz cup, the reaction kettle is a hastelloy reaction kettle, and the annealing is performed in a tubular furnace;
preferably, the vanadium source is vanadyl acetylacetonate; the organic solvent is ethylene glycol; firstly, adding the ethylene glycol into the container, then adding the vanadyl acetylacetonate into the container, placing the container in a water bath at the temperature of 50 ℃, and stirring by adopting magnetic force until the vanadyl acetylacetonate is completely dissolved to form a precursor solution.
Preferably, the isopropyl titanate is dripped into the precursor solution and is magnetically stirred to form the mixed solution; the number ratio of vanadium atoms to titanium atoms in the mixed solution is 0.5: 100.
preferably, the constant temperature of the container in the reaction kettle is 290-295 ℃, and the constant temperature time is 4.5-5.5 h.
Preferably, after the initial product is naturally cooled to room temperature, the initial product is washed with alcohol and deionized water and then annealed.
Preferably, the initial product is annealed in a nitrogen atmosphere at a temperature of 590 ℃ to 610 ℃ for 4.5h to 5h to obtain black vanadium-doped titanium dioxide powder.
Preferably, the vanadium-doped titanium dioxide powder is in a nanosheet shape with the length of 200nm, and the nanoparticles are self-assembled into a nanotube shape to form the photocatalytic material of the vanadium-doped titanium dioxide nanotube.
On the other hand, the embodiment of the invention provides a vanadium-doped nano titanium dioxide photocatalyst, which is prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a steam thermal method to prepare isopropyl titanate and vanadyl acetylacetonate in a quartz cup with glycol as a solvent in a high-temperature and high-pressure environment and then carry out subsequent annealing to obtain V/TiO2And (3) nano materials. V/TiO prepared by the invention2The nano particles are in a nano sheet shape with the length of about 200nm, are self-assembled into a nano tube shape, have large specific surface area and strong adsorption performance; the process flow is simple, and the experimental repeatability is good; the obtained nano particles have good application prospect in the field of photocatalysis.
Drawings
FIG. 1 is a schematic view of a steam thermal reaction apparatus provided in example 1 of the present invention;
FIG. 2 shows V/HTO and V/TiO provided in example 1 of the present invention2(ii) an X-ray diffraction pattern of (a) a steam-thermal V/HTO, and (b) an annealed V/TiO2An X-ray diffraction pattern of the sample, (c) standard PDF card of anatase (PDF No. 75-1537);
FIG. 3 is an SEM image of a VAT sample prepared by a steam thermal method according to example 1 of the present invention, wherein (a) is a TEM image of a hollow V/HTO sphere, and the insert is a TEM image of a single hollow V/HTO sphere, and (b) is a SEM image of a hollow V/HTO sphere, and the insert is a SEM image of a single hollow V/HTO sphere;
FIG. 4 shows the annealed V/TiO material provided in example 1 of the present invention2Electron microscope pictures of samples, (a) V/TiO prepared by annealing2Transmission electron microscope picture of tube, (b) V/TiO prepared by annealing2Scanning electron microscope picture of tube, inset is single TiO2Scanning electron microscope pictures of the tube with high resolution;
FIG. 5 shows V/TiO provided in example 1 of the present invention2X-ray photoelectron spectrum picture of tube, (a) is V/TiO2The X-ray photoelectron spectrum of the tube, and (b) is the spectrum of the V element.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, technical solutions, features and effects according to the present invention will be given with preferred embodiments. The particular features, structures, or characteristics may be combined in any suitable manner in the embodiments or embodiments described below.
Example 1
(1) Into a quartz cell, 90mL of Ethylene Glycol (EG) was added as a solvent, and 19mg of vanadyl acetylacetonate (VO (acac)2) was added, and the mixture was subjected to water bath at 50 ℃ and magnetic stirring for 10min to VO (acac)2Completely dissolving to obtain a precursor solution;
(2) measuring 4mL isopropyl titanate (TIP, atomic ratio: V/Ti is 0.5%) by a pipettor, slowly dropping into a quartz cup, and continuously magnetically stirring for 5min to obtain a mixed solution;
(3) injecting 200mL of absolute ethyl alcohol into a 1000mL Hastelloy reaction kettle, then placing a quartz cup into the kettle, heating to 290 ℃, keeping the temperature for 5 hours, and obtaining an initial product;
(4) after the reaction is finished, naturally cooling the kettle body to room temperature, taking out a sample, repeatedly washing the sample with alcohol and deionized water for a plurality of times, and drying the sample;
(5) placing the obtained powder in a tube furnace, N2Annealing at 600 ℃ for 4h in the atmosphere to obtain black V-doped TiO2And (3) powder.
Example 2
(1) Into a quartz cell, 90mL of Ethylene Glycol (EG) was added as a solvent, and 19mg of vanadyl acetylacetonate (VO (acac)2) was added, and the mixture was subjected to water bath at 50 ℃ and magnetic stirring for 10min to VO (acac)2Completely dissolving to obtain a precursor solution;
(2) measuring 4mL isopropyl titanate (TIP, atomic ratio: V/Ti is 0.5%) by a pipettor, slowly dropping into a quartz cup, and continuously magnetically stirring for 5min to obtain a mixed solution;
(3) injecting 200mL of isopropanol into a 1000mL Hastelloy reaction kettle, then placing a quartz cup into the kettle, heating to 295 ℃, and keeping the temperature for 4.5 hours to obtain an initial product;
(4) after the reaction is finished, naturally cooling the kettle body to room temperature, taking out a sample, repeatedly washing the sample with alcohol and deionized water for a plurality of times, and drying the sample;
(5) placing the obtained powder in a tube furnace, N2Annealing at 610 ℃ for 3.5h in the atmosphere to obtain black V-doped TiO2And (3) powder.
Example 3
(1) Into a quartz cell, 90mL of Ethylene Glycol (EG) was added as a solvent, and 19mg of vanadyl acetylacetonate (VO (acac)2) was added, and the mixture was subjected to water bath at 50 ℃ and magnetic stirring for 10min to VO (acac)2Completely dissolving to obtain a precursor solution;
(2) measuring 4mL isopropyl titanate (TIP, atomic ratio: V/Ti is 0.5%) by a pipettor, slowly dropping into a quartz cup, and continuously magnetically stirring for 5min to obtain a mixed solution;
(3) injecting 200mL of methanol into a 1000mL Hastelloy reaction kettle, then placing a quartz cup into the kettle, heating to 300 ℃, and keeping the temperature for 4.2 hours to obtain an initial product;
(4) after the reaction is finished, naturally cooling the kettle body to room temperature, taking out a sample, repeatedly washing the sample with alcohol and deionized water for a plurality of times, and drying the sample;
(5) placing the obtained powder in a tube furnace, N2Annealing at 595 ℃ for 4.5h in the atmosphere to obtain black V-doped TiO2And (3) powder.
According to the invention, water is slowly generated through alcohol etherification reaction to supply water for the hydrolysis of isopropyl titanate, and the product, namely the hollow sphere prepared in the step (3), of the titanyl hydroxide self-assembly is annealed at the high temperature of 600 ℃, so that the titanyl hydroxide is converted into pure black anatase phase TiO2The hollow spheres collapse and break into nanotubes.
Selection of doping sources of the invention: in order to obtain the hollow nanosphere structure, the precursor solution of the steam thermal reaction needs to contain no water, so the V-doped primary reagent needs to be an organic vanadium source which does not contain bound water and can be dissolved in alcohol, and the vanadium source selected by the invention is vanadyl acetylacetonate.
The selection of the steam thermal reaction temperature of the invention is as follows: the decomposition temperature of the vanadyl acetylacetonate is 290 ℃, and the vanadyl acetylacetonate can not be decomposed below the decomposition temperature, so that the doping failure is caused; the reaction temperature is higher than 300 ℃, and the product of the steam thermal reaction is TiO mixed by anatase phase and rutile phase2Pure phase anatase TiO is not available2Thus, a suitable reaction temperature should be between 290 ℃ and 300 ℃.
Selection of the steam thermal reaction solvent of the invention: at the determined reaction temperature, the critical temperature of the dispersion solvent in the quartz cup must be higher than the reaction temperature, otherwise the dispersion solvent cannot be used as a solvent in a liquid state, and the dispersion solvent selected in the invention is preferably glycol; the reaction solvent in the reaction kettle can be selected from solvents with etherification temperature lower than the condition, such as isopropanol, ethanol, methanol and the like, and the preferred reaction solvent in the invention is ethanol.
The key steps of the invention are as follows:
1. the reaction takes place in supercritical state of ethanol, the critical temperature of the dispersion solution is higher than the reaction temperature, the alcohol etherification reaction produces water, and then the water reacts with TIP to produce H2Ti12O25Hollow spheres;
2. the temperature of the hollow sphere in the subsequent annealing process is too low to remove H2Ti12O25Conversion of TiO2In addition, the hollow ball can not be converted into a tube, the annealing temperature is too high, and the tubular structure collapses and agglomerates;
3. the invention selects vanadyl acetylacetonate (VO (acac)2) As a doping source, VO (acac)2Can be dissolved in organic solvent and decomposed at 290 deg.C.
As shown in figures 1-5, the invention adopts a steam thermal method to prepare isopropyl titanate and vanadyl acetylacetonate in a quartz cup with glycol as a solvent in a high-temperature and high-pressure environment and then carry out subsequent annealing to obtain V/TiO2And (3) nano materials. V/TiO prepared by the invention2The nano particles are in a nano sheet shape with the length of about 200nm, are self-assembled into a nano tube shape, have large specific surface area and strong adsorption performance.
The embodiments of the present invention are not exhaustive, and those skilled in the art can select them from the prior art.
The above disclosure is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and shall be covered by the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the above claims.
Claims (9)
1. The preparation method of the vanadium-doped nano titanium dioxide photocatalyst is characterized by comprising the following steps of:
mixing isopropyl titanate, a vanadium source and an organic solvent in a container to obtain a mixed solution; the vanadium source is vanadyl acetylacetonate; the organic solvent is ethylene glycol;
placing the container in a hydrothermal reaction kettle filled with absolute ethyl alcohol, and keeping the temperature at 290-300 ℃ for 4-6 h to obtain an initial product;
and annealing the initial product at 580-620 ℃ in an inert atmosphere for 4-5 h to obtain black vanadium-doped titanium dioxide powder.
2. The method for preparing the vanadium-doped nano titanium dioxide photocatalyst according to claim 1, wherein the container is a quartz cup, the reaction kettle is a hastelloy reaction kettle, and the annealing is performed in a tube furnace.
3. The method for preparing the vanadium-doped nano titanium dioxide photocatalyst according to claim 1, wherein the ethylene glycol is added into the container, the vanadyl acetylacetonate is added into the container, the container is placed in a water bath at the temperature of 50 ℃ and is stirred by magnetic force until the vanadyl acetylacetonate is completely dissolved to form a precursor solution.
4. The method for preparing the vanadium-doped nano titanium dioxide photocatalyst according to claim 3, wherein the isopropyl titanate is dropwise added into the precursor solution and magnetically stirred to form the mixed solution; the number ratio of vanadium atoms to titanium atoms in the mixed solution is 0.5: 100.
5. the method for preparing the vanadium-doped nano titanium dioxide photocatalyst according to claim 4, wherein the constant temperature of the container in the reaction kettle is 290-295 ℃, and the constant temperature time is 4.5-5 h.
6. The method of claim 1, wherein the initial product is naturally cooled to room temperature, and then is cleaned with alcohol and deionized water and then annealed.
7. The method of claim 1, wherein the initial product is annealed in a nitrogen atmosphere at a temperature of 590 ℃ to 610 ℃ for 3.5h to 4.5h to obtain black vanadium-doped titanium dioxide powder.
8. The method of claim 1, wherein the vanadium-doped titanium dioxide powder is in the form of nanoplatelets having a length of 200nm, and the nanoparticles are self-assembled in the form of nanotubes to form the photocatalytic material of the vanadium-doped titanium dioxide nanotubes.
9. A vanadium doped nano titania photocatalyst, characterized in that it is prepared by the method of any one of claims 1 to 8.
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