CN112044428A - VO (volatile organic compound)2Filled TiO2Nanotube composite and method of making the same - Google Patents
VO (volatile organic compound)2Filled TiO2Nanotube composite and method of making the same Download PDFInfo
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- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000002071 nanotube Substances 0.000 claims abstract description 55
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 239000010955 niobium Substances 0.000 claims abstract description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 16
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical class NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 238000009423 ventilation Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
- 230000007704 transition Effects 0.000 description 10
- 238000000137 annealing Methods 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
VO (volatile organic compound)2Filled TiO2Nanotube composite material and preparation method thereof, VO2Filled TiO2The nanotube composite material is VO with metal doping property2Filled TiO2A nanotube composite. Metals that can be doped include tungsten, molybdenum, niobium, ruthenium. The invention mainly prepares materials by an anodic oxidation method and a hydrothermal method, has simple operation and easy realization, and enables VO to be generated in the reaction process2Filled in TiO2VO prepared by utilizing characteristics in nanotube2Can be applied toPhotoelectric equipment, infrared detection, temperature control switches, intelligent glass materials and the like; also, TiO may be varied2The photocatalytic performance of the photocatalyst is improved, and the photocatalytic activity is improved.
Description
Technical Field
The invention belongs to the technical field of titanium dioxide nano material modification methods, and particularly relates to VO2Filled TiO2Nanotube composites and methods of making the same.
Background
TiO2As an important inorganic material, the material has excellent performances such as photosensitivity, catalysis, gas sensitivity, photoelectricity and the like, and attracts the attention of researchers in various fields. TiO 22The band gap energy between energy bands is larger, the utilization rate of sunlight is low, and photon-generated carriers are quickly compounded, so that the TiO needs to be improved by modification2Photocatalytic efficiency. TiO 22Nanotubes are one of the existing forms of titanium dioxide, and due to the characteristics of high specific surface area, high contact area, size dependent effect and the like, the nanotubes are increasingly seen in the field of vision in recent years. With TiO2In contrast to other existing forms, TiO2The nano-tube has a unique tubular array structure, so that the nano-tube has higher photocatalysis capability.
Vanadium dioxide is widely concerned about reversible transformation between semiconductor and metal insulator at about 68 ℃, and is VO2Phase change property researchers have also proposed many potential applications, such as infrared detection, temperature controlled switches, smart glass materials, and the like. But we know VO2The phase transition temperature of (1) is about 340K, but the temperature is much higher than the room temperature, and how to make VO2The phase transition temperature of (2) is reduced to room temperature or the desired temperature, which is a problem that scientists have been exploring and trying to solve. According to the solid stateTheory of phase change structure, energy level structure is VO2The phase transition temperature is a main influence factor, and the narrower the forbidden band width is, the lower the phase transition temperature is. There are many factors affecting the phase transition of vanadium dioxide, and the factors include stress strain, size effect, doping, substrate regulation and the like.
Disclosure of Invention
The invention aims to provide a VO2Filled TiO2Preparation method of nanotube composite material, VO prepared by adopting method of the invention2Filled TiO2Nanotube composite material with reduced VO2The phase transition temperature of the titanium dioxide is increased, and the TiO is improved2The photocatalytic performance of (a). Solves the problems of the titanium dioxide nano material photocatalysis performance and VO existing in the prior art2Too high phase transition temperature and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
VO (volatile organic compound)2Filled TiO2The nanotube composite material is VO with metal doping property2Filled TiO2A nanotube composite.
Metals that can be doped include tungsten, molybdenum, niobium, ruthenium.
VO (volatile organic compound)2Filled TiO2A method for preparing a nanotube composite, comprising the method steps of:
1) polishing a pure titanium sheet and then cleaning;
2) preparing electrolyte, taking the titanium sheet treated in the step 1) as an anode and graphite as a cathode, and electrolyzing by adopting a direct current stabilized voltage power supply, wherein the voltage is adjusted to 15-25V, and the electrolysis time is 5-25 min to obtain TiO2A nanotube;
3) oxalic acid or NaHSO with the mass concentration of not less than 99.5 percent3Or phenethylamines with V2O5Weighing according to the molar ratio of (1-3) to (1-2);
4) oxalic acid or NaHSO weighed in the step 3)3Or dissolving phenylethylamine in deionized water to prepare a solution with the concentration of 0.6-0.8 mol/L;
5) adding weighed V into the prepared solution in the step 4)2O5Mixing the powder for 25-35 min by means of a magnetic stirrer;
6) placing the solution prepared in the step 5) into a polytetrafluoroethylene reaction kettle, and then placing the TiO prepared in the step 2)2Placing the nanotube into a polytetrafluoroethylene lining, and preserving heat for 18-36 hours at the temperature of 150-200 ℃;
7) after the reaction kettle is cooled to room temperature, putting the powder obtained in the step 6) into a constant-temperature ventilation drying oven at the temperature of 50-80 ℃ for drying for 6-8 h to obtain VO2Filled in TiO2A composite of nanotubes;
8) VO is introduced into a reactor2Filled in TiO2Placing the composite material of the nanotube in a vacuum tube furnace, carrying out heat treatment at 400-600 ℃, and keeping the temperature for 0.5-2 h to obtain novel VO2Filled in TiO2Composite material within the nanotube.
The electrolyte in the step 2) is 0.5-0.8 wt% HF aqueous solution or 0.5-1.0 mol/L NH4F aqueous solution or 0.5 to 0.8 wt% NH4And mixing the glycerol solution of F for 25-35 min by means of a magnetic stirrer.
The voltage in the step 2) is adjusted to 20V.
In the step 5), one or more metal ions of tungsten, molybdenum, niobium and ruthenium are doped by a hydrothermal method.
The invention prepares TiO by an anodic oxidation method2Nanotubes, followed by hydrothermal synthesis of VO2Grown on TiO2In the nano tube, obtain VO2Filled in TiO2Composite material within the nanotube. VO (vacuum vapor volume)2Filled in TiO2The composite material in the nano tube can be respectively annealed at 450 deg.C, 500 deg.C, 550 deg.C and 600 deg.C so as to regulate the ratio of anatase type and rutile type, and the TiO can be annealed at 450 deg.C2The rutile phase is an anatase phase, the mass fraction of the rutile phase after annealing at 500 ℃ is less than 0.48 percent, the mass fraction of the rutile phase after annealing at 550 ℃ is 1.86-2.30 percent, and the mass fraction of the rutile phase after annealing at 600 ℃ is 6.35-8.5 percent.
Compared with the prior art, the invention has the beneficial effects that:
the invention mainly prepares materials by an anodic oxidation method and a hydrothermal method, has simple operation and easy realization, and enables VO to be generated in the reaction process2Filled in TiO2In the nano tube, VO can be regulated and controlled by regulating the tube diameter of the titanium dioxide nano tube and by the size effect2Diameter of the particles, change VO2Phase transition temperature of, TiO2Nanotube wall and VO2Interfacial effect of surface and VO2The phase change can change TiO2The photocatalytic performance widens the light absorption range, enhances the effective separation of the material on photon-generated carriers, and improves the photocatalytic activity. The photocatalytic composite material prepared by the method can be widely applied to organic pollution in waste water and air, and is safe and environment-friendly.
In addition, VO of the present invention may be used2Filled TiO2The specific metal ions are doped in the nanotube composite material, so that VO can be generated2Lower phase transition temperature of and also lower TiO2The forbidden band width widens the light absorption range and improves the photocatalysis efficiency.
Detailed Description
The present invention will be described in detail below, but the scope of the present invention is not limited to the following embodiments.
Example 1:
VO (volatile organic compound)2Filled TiO2A method for preparing a nanotube composite, comprising the method steps of:
1) polishing pure titanium sheets, and then respectively putting the polished pure titanium sheets in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20 min;
2) 0.5 wt% NH is prepared4Mixing the glycerol solution of F for 30min by means of a magnetic stirrer;
3) taking the titanium sheet treated in the step 1) as an anode, graphite as a cathode, taking the solution treated in the step 2) as an electrolyte, adjusting the voltage to 20V by adopting a direct current stabilized voltage power supply, and electrolyzing for 25min to obtain TiO2A nanotube;
4) oxalic acid with the concentration of 99.5 percent is mixed with V2O5Weighing according to the molar ratio of 2: 1;
5) dissolving the oxalic acid weighed in the step 4) in deionized water to prepare an oxalic acid solution with the concentration of 0.8 mol/L;
6) v added into the prepared oxalic acid solution in the step 5)2O5Mixing the powder with magnetic stirrer for 30 min;
7) placing the solution prepared in the step 6) into a polytetrafluoroethylene reaction kettle, and then placing the TiO prepared in the step 3)2Placing the nano tube into a polytetrafluoroethylene lining, and keeping the temperature for 36 hours at 190 ℃;
8) after the reaction kettle is cooled to room temperature, the powder obtained in the step 7) is put in a constant temperature ventilation drying oven at 80 ℃ for drying for 6 hours to obtain VO2Filled in TiO2A composite of nanotubes;
9) VO is introduced into a reactor2Filled in TiO2Placing the nanotube composite material in a vacuum tube furnace, and performing heat treatment at 450 ℃, 500 ℃, 550 ℃ and 600 ℃ respectively for 2 h;
TiO after annealing at 450 DEG C2The rutile phase is an anatase phase, the mass fraction of the rutile phase after annealing at 500 ℃ is 0.42 percent, the mass fraction of the rutile phase after annealing at 550 ℃ is 2.30 percent, and the mass fraction of the rutile phase after annealing at 600 ℃ is 6.35 percent. The composite material prepared at the annealing temperature of 450 ℃, 500 ℃, 550 ℃ and 600 ℃ is subjected to catalytic performance evaluation, and the degradation rates of rhodamine B within 60min can be respectively measured to be 64%, 53%, 67% and 43%. In conclusion, the annealing temperature of 550 ℃ has the best photocatalysis performance.
Example 2: this example is at VO2Filled TiO2In the preparation process of the nanotube composite material, the doped metal tungsten is prepared by a hydrothermal method.
VO (volatile organic compound)2Filled TiO2A method for preparing a nanotube composite, comprising the method steps of:
1) polishing pure titanium sheets, and then respectively putting the polished pure titanium sheets in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20 min;
2) preparing 0.5 wt% HF aqueous solution, and mixing for 30min by means of a magnetic stirrer;
3) taking the titanium sheet treated in the step 1) as an anode and graphite asTaking the mixed solution treated in the step 2) as an electrolyte, regulating the voltage to 25V by adopting a direct current stabilized voltage power supply, and electrolyzing for 15min to obtain TiO, wherein the electrolyte is used as a cathode2A nanotube;
4) oxalic acid, V, with a concentration of 99.5%2O5Weighing according to a molar ratio of 3: 1;
5) dissolving the oxalic acid weighed in the step 4) in deionized water to prepare an oxalic acid solution with the concentration of 0.8 mol/L;
6) adding V into the prepared oxalic acid solution in the step 5)2O5Heating the powder in a constant-temperature water bath kettle at 60 ℃ for 30min, mixing by a magnetic stirrer, adding a proper amount of sodium tungstate, and stirring for dissolving;
7) adding 10mL of urea with the concentration of 10mol/L as a precipitator, placing the solution prepared in the step 6) into a polytetrafluoroethylene reaction kettle, and then placing the TiO prepared in the step 3) into the reaction kettle2Placing the nano tube into a polytetrafluoroethylene lining, and preserving heat for 72 hours at 190 ℃;
8) after the reaction kettle is cooled to room temperature, the sample prepared in the step 7) is placed in a constant temperature ventilation drying oven at 80 ℃ for drying for 6 hours to obtain VO doped with tungsten2Filled in TiO2A composite of nanotubes;
9) VO to be doped with tungsten2Filled in TiO2The nano tube is placed in a vacuum tube furnace and is subjected to heat treatment at 450 ℃, and the heat preservation time is 2 hours.
Firstly, preparing titanium dioxide nanotubes from titanium sheets by an anodic oxidation method, and then preparing VO doped with tungsten by a hydrothermal method2. VO to be doped with tungsten2Filled in TiO2In nanotubes, TiO2Nanotube and VO2Heterojunction can be formed at the interface to improve TiO2The photocatalytic performance of the nanotube promotes the separation of photogenerated electrons and photogenerated holes. VO in titanium dioxide nanotube after doping tungsten2The phase transition temperature is reduced to about 32 ℃, and TiO is reduced due to ion doping2The forbidden band width of the TiO is increased2The light absorption range of the method improves the photocatalytic performance, and the rate of degrading rhodamine B is obviously improved by evaluating the catalytic performance.
Claims (6)
1. VO (volatile organic compound)2Filled TiO2The nanotube composite material is characterized in that the material is VO with metal doping property2Filled TiO2A nanotube composite.
2. VO according to claim 12Filled TiO2The nanotube composite material is characterized in that the metal capable of being doped comprises tungsten, molybdenum, niobium and ruthenium.
3. The VO of claim 12Filled TiO2The preparation method of the nanotube composite material is characterized by comprising the following steps:
1) polishing a pure titanium sheet and then cleaning;
2) preparing electrolyte, taking the titanium sheet treated in the step 1) as an anode and graphite as a cathode, and electrolyzing by adopting a direct current stabilized voltage power supply, wherein the voltage is adjusted to 15-25V, and the electrolysis time is 5-25 min to obtain TiO2A nanotube;
3) oxalic acid or NaHSO with the mass concentration of not less than 99.5 percent3Or phenethylamines with V2O5Weighing according to the molar ratio of (1-3) to (1-2);
4) oxalic acid or NaHSO weighed in the step 3)3Or dissolving phenylethylamine in deionized water to prepare a solution with the concentration of 0.6-0.8 mol/L;
5) adding weighed V into the prepared solution in the step 4)2O5Mixing the powder for 25-35 min by means of a magnetic stirrer;
6) placing the solution prepared in the step 5) into a polytetrafluoroethylene reaction kettle, and then placing the TiO prepared in the step 2)2Placing the nanotube into a polytetrafluoroethylene lining, and preserving heat for 18-36 hours at the temperature of 150-200 ℃;
7) after the reaction kettle is cooled to room temperature, putting the powder obtained in the step 6) into a constant-temperature ventilation drying oven at the temperature of 50-80 ℃ for drying for 6-8 h to obtain VO2Filled in TiO2A composite of nanotubes;
8) VO is introduced into a reactor2Filled in TiO2Placing the nanotube composite material in a vacuum tube furnace, carrying out heat treatment at 450-600 ℃, and keeping the temperature for 0.5-2 h to obtain novel VO2Filled in TiO2Composite material within the nanotube.
4. VO according to claim 32Filled TiO2The preparation method of the nanotube composite material is characterized in that the electrolyte in the step 2) adopts 0.5-0.8 wt% of HF aqueous solution or 0.5-1.0 mol/L NH4F aqueous solution or 0.5 to 0.8 wt% NH4And mixing the glycerol solution of F for 25-35 min by means of a magnetic stirrer.
5. VO according to claim 32Filled TiO2The preparation method of the nanotube composite material is characterized in that the voltage in the step 2) is adjusted to be 20V.
6. VO according to claim 32Filled TiO2The preparation method of the nanotube composite material is characterized in that one or more metal ions of tungsten, molybdenum, niobium and ruthenium are doped in the step 5) by a hydrothermal method.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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