CN108355633B - Preparation method of visible light response nitrogen-doped nano titanium dioxide photocatalyst - Google Patents
Preparation method of visible light response nitrogen-doped nano titanium dioxide photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000004298 light response Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 230000001276 controlling effect Effects 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 12
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000008280 blood Substances 0.000 claims abstract description 8
- 210000004369 blood Anatomy 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 71
- 239000004408 titanium dioxide Substances 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 4
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 abstract description 9
- 230000031700 light absorption Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 29
- 230000007547 defect Effects 0.000 description 11
- 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 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910003081 TiO2−x Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003608 titanium Chemical class 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
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- 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
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- 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
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- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a preparation method of a visible light response nitrogen-doped nano titanium dioxide photocatalyst, which comprises the steps of adding ascorbic acid and urea into deionized water, and stirring to obtain a transparent solution; then adding a trivalent titanium solution and a sodium hydroxide solution, adjusting the pH value to 1.5-5, and continuously stirring to obtain a brown or blood red solution; transferring the solution into a hydrothermal kettle, and reacting at the temperature of 180 ℃ to obtain a brown-yellow primary product; washing the brown yellow primary product until the pH value is 7, and drying the product overnight to obtain a black product which is ground into brown powder; and placing the brown powder in a tubular furnace under the protection of inert gas, regulating the vacuum degree to-0.03 to-0.08 atm by controlling a vacuum pump, calcining at the constant temperature of 400-500 ℃ for 2-4 hours, and cooling to room temperature to obtain the visible-light response nitrogen-doped nano titanium dioxide material. The invention enhances the light absorption capacity of the photocatalyst in ultraviolet, visible and near infrared.
Description
Technical Field
The invention belongs to the field of materials science, relates to a titanium dioxide photocatalytic material, and particularly relates to a preparation method of a visible light response nitrogen-doped nano titanium dioxide photocatalyst.
Background
Nano titanium dioxide (TiO)2) The photocatalyst has the advantages of no toxicity, low cost, high chemical stability and the like, and can efficiently and safely decompose organic pollutants such as formaldehyde, rhodamine B and the like and decompose water to prepare hydrogen under the excitation of light. However, the problems of low quantum efficiency and high photo-generated carrier recombination of untreated white titanium dioxide under full spectrum severely limit the application of the untreated white titanium dioxide in the field of photocatalysisThe practical application of (1).
In recent years, researchers at home and abroad successfully improve the full-spectrum absorption performance of the titanium dioxide material by means of metal/nonmetal doping, heterojunction construction, photosensitizer sensitization and the like. In addition, by itself Ti3+Or introduction of oxygen deficiency (Vo) to produce reduced titanium dioxide (TiO) of different colors2-x) The photocatalytic capacity of the material can also be improved (Science 2011,331,746). The study shows that Ti3+Distribution and concentration of/Vo defects on modified TiO2-xThe light absorption and carrier separation efficiency of (2) have important effects, and these defects can be in TiO2A local state is introduced into the forbidden band, so that the band gap width is reduced, and the visible light absorption capacity of the material is improved. However, Ti introduced in excess3+the/Vo defect forms a new recombination center of a photon-generated carrier, and the defect is concentrated on TiO on the surface of the sample2-xThe material has the defects of poor stability and the like in air. On the other hand, nitrogen is easy to dope and introduce into the structure of titanium dioxide due to the similar radius of nitrogen and oxygen atoms. Nitrogen doping can improve TiO by reducing the forbidden band width of the photocatalyst2The light absorption capacity of the photocatalytic material and the ability to stabilize Ti3+Vo defects increase the stability of reduced titania (Energy environ. sci.2014,7,967). In summary, the stable and efficient reduced TiO is prepared by combining the defect self-doping and nitrogen doping processes2Has important function for improving the activity of the photocatalyst.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method of a visible light response nitrogen-doped nano titanium dioxide photocatalyst, and the preparation method of the visible light response nitrogen-doped nano titanium dioxide photocatalyst aims to solve the technical problems of low visible light catalytic activity and low stability of a titanium dioxide photocatalytic material in the prior art.
The invention provides a preparation method of a visible light response nitrogen-doped nano titanium dioxide photocatalyst, which comprises the following steps:
1) adding ascorbic acid and urea into deionized water, wherein the material ratio of the ascorbic acid to the urea to the deionized water is (0.5-1 g): 5-50 mg: 35-50 mL, and stirring to obtain a transparent solution;
2) adding a trivalent titanium solution into the solution obtained in the step 1), wherein the mass volume ratio of trivalent titanium to the transparent solution is 2-10 g: 20-100 ml, the trivalent titanium compound is titanium trichloride and titanium oxychloride, then adding a sodium hydroxide solution, the concentration of the sodium hydroxide solution is 0.2-1.5 mo/L, adjusting the pH value to 1.5-5, and continuously stirring for 0.5-2 hours at the rotating speed of 250-1000 r/min to obtain a brown or blood red solution;
3) transferring the solution obtained in the step 2) into a hydrothermal kettle, and reacting for 8-12 hours at the temperature of 180 ℃ to obtain a brown-yellow primary product;
4) washing the brown yellow primary product obtained in the step 3) by deionized water and ethanol until the pH value is 7, and drying overnight to obtain a black product which is carefully ground into brown powder;
5) placing the brown powder obtained in the step 4) in a tubular furnace under the protection of inert atmosphere, adjusting the vacuum degree to-0.03 to-0.08 atm by controlling a vacuum pump, calcining at the constant temperature of 400 to 500 ℃ for 2 to 4 hours, and cooling to room temperature to obtain the visible light response nitrogen-doped nano titanium dioxide material.
Further, placing the brown powder in the step 4) in a tubular furnace under the protection of inert gas (nitrogen or argon), calcining at the constant temperature of 400-500 ℃ for 2 hours while regulating the vacuum degree to-0.03-0.08 atm by controlling a vacuum pump, and cooling to room temperature to obtain gray powder.
Further, placing the brown powder in the step 4) in a tubular furnace under the protection of inert gas (nitrogen or argon), calcining at the constant temperature of 400-500 ℃ for 2 hours while regulating the vacuum degree to-0.03-0.08 atm by controlling a vacuum pump, and cooling to room temperature to obtain light yellow powder.
Further, the stirring speed in the step 1) is 250-1000 r/min.
Further, the inert atmosphere is nitrogen or argon.
The invention also provides application of the visible light response nitrogen-doped nano titanium dioxide catalyst, and the material is used for purifying air and water sources, self-cleaning, water decomposition by sunlight or water decomposition by solar photoelectrocatalysis.
The invention takes trivalent titanium salt as raw material, ascorbic acid as reducing agent and urea as nitrogen source, and combines hydrothermal method and high-temperature roasting treatment to prepare the nitrogen-doped nano titanium dioxide photocatalyst. By introducing oxygen defects and nitrogen elements into the titanium dioxide photocatalyst, the light absorption performance of the titanium dioxide material in ultraviolet, visible and near infrared regions is adjusted, and the light absorption capacity of the titanium dioxide material in a full spectrum is enhanced. Meanwhile, the product performance and color are controlled by controlling the mixing and stirring speed of the precursor and the high-temperature roasting vacuum degree, and the crystallinity and defect concentration of the nano titanium dioxide are adjusted, so that the photocatalytic activity of the nano titanium dioxide is improved. The preparation process is mild and is more moderate than the traditional hydrogen or sodium borohydride nano TiO2The modification method is safer, and the product properties can be adjusted through different vacuum degrees in the roasting process.
Compared with the prior art, the invention has remarkable technical progress. The invention enhances the light absorption capacity of the photocatalyst in ultraviolet, visible and near infrared by introducing oxygen defects and nitrogen elements into the titanium dioxide photocatalyst. The method combines a hydrothermal method and high-temperature roasting treatment, can accurately regulate and control the color, the crystallinity and the defect concentration of the titanium dioxide, and meets different use environments.
Drawings
FIG. 1 is a photographic image of a black, gray, and pale yellow nano-titania photocatalyst of the present invention, wherein a is a black sample, b is a gray sample, and c is a pale yellow sample.
FIG. 2 is a graph showing the ultraviolet-visible solid diffuse reflection absorption spectrum of a pale yellow titanium dioxide powder prepared in example 1.
Fig. 3 is an XRD pattern of light yellow titanium dioxide powder prepared in example 1.
FIG. 4 is a scanning electron micrograph and an elemental analysis chart of a pale yellow titanium dioxide powder prepared in example 1.
FIG. 5 is a transmission electron micrograph of a pale yellow titanium dioxide powder prepared in example 1.
FIG. 6 is a graph comparing the effect of light yellow titanium dioxide prepared in examples 1 and 2 on the degradation of RhB by black titanium dioxide type P25.
Detailed Description
The present invention is described in basic terms by the following examples, it should be noted that the examples are only for illustrative purposes and should not be construed as limiting the scope of the invention, and that those skilled in the art can make insubstantial modifications and adaptations of the invention based on the teachings of the invention described above.
Example 1
a. Adding 0.5g of ascorbic acid and 40mg of urea into 35mL of deionized water to obtain a transparent solution;
b. adding 1.5mL of trivalent titanium solution into the solution obtained in the step a, adding 1mol/L of sodium hydroxide solution, adjusting the pH value to 4, and continuously stirring at the rotating speed of 500r/min to obtain a blood red solution;
c. transferring the solution in the step b into a hydrothermal kettle, and reacting for 8 hours at the temperature of 180 ℃ to obtain a brown yellow primary product;
d. washing the brown yellow primary product in the step c for 3-5 times by using deionized water and ethanol until the pH value is 7, drying overnight to obtain a black product, and carefully grinding the black product to obtain brown powder;
e. and d, placing the brown powder in the step d into a tubular furnace under the protection of inert gas, controlling a vacuum pump to adjust the vacuum degree to-0.08 atm, calcining at the constant temperature of 450 ℃ for 4 hours, and cooling to room temperature to obtain the light yellow titanium dioxide photocatalyst.
Example 2
a. Adding 0.5g of ascorbic acid and 150mg of urea into 35mL of deionized water to obtain a transparent solution;
b. adding 1.5mL of trivalent titanium solution into the solution obtained in the step a, adding 1mol/L of sodium hydroxide solution, adjusting the pH value to 4, and continuously stirring at the rotating speed of 500r/min to obtain a blood red solution;
c. transferring the solution in the step b into a hydrothermal kettle, and reacting for 8 hours at the temperature of 180 ℃ to obtain a brown yellow primary product;
d. washing the brown yellow primary product in the step c for 3-5 times by using deionized water and ethanol until the pH value is 7, drying overnight to obtain a black product, and carefully grinding the black product to obtain brown powder;
e. and d, placing the brown powder in the step d into a tubular furnace under the protection of inert gas, controlling a vacuum pump to adjust the vacuum degree to-0.08 atm, calcining at the constant temperature of 450 ℃ for 4 hours, and cooling to room temperature to obtain the light yellow titanium dioxide photocatalyst.
Example 3
a. Adding 0.5g of ascorbic acid and 120mg of urea into 35mL of deionized water to obtain a transparent solution;
b. adding 1.5mL of trivalent titanium solution into the solution obtained in the step a, adding 1mol/L of sodium hydroxide solution, adjusting the pH value to 4, and continuously stirring at the rotating speed of 750r/min to obtain a blood red solution;
c. transferring the solution in the step b into a hydrothermal kettle, and reacting for 8 hours at the temperature of 180 ℃ to obtain a brown yellow primary product;
d. washing the brown yellow primary product in the step c for 3-5 times by using deionized water and ethanol until the pH value is 7, and drying the product overnight to obtain a brown yellow product which is carefully ground into brown powder;
e. and d, placing the brown powder in the step d into a tube furnace under the protection of inert gas, controlling a vacuum pump to adjust the vacuum degree to-0.07 atm, calcining at the constant temperature of 450 ℃ for 4 hours, and cooling to room temperature to obtain the light yellow titanium dioxide photocatalyst.
Example 4
a. Adding 0.5g of ascorbic acid and 20mg of urea into 35mL of deionized water to obtain a transparent solution;
b. adding 1.5mL of trivalent titanium solution into the solution obtained in the step a, adding 1mol/L of sodium hydroxide solution, adjusting the pH value to 4, and continuously stirring at a rotating speed of 250r/min to obtain a brown solution;
c. transferring the solution in the step b into a hydrothermal kettle, and reacting for 12 hours at the temperature of 180 ℃ to obtain a brown yellow primary product;
d. washing the brown yellow primary product in the step c for 3-5 times by using deionized water and ethanol until the pH value is 7, and drying the product overnight to obtain a brown yellow product which is carefully ground into brown powder;
e. and d, placing the brown powder in the step d into a tube furnace under the protection of inert gas, controlling a vacuum pump to adjust the vacuum degree to-0.07 atm, calcining at the constant temperature of 450 ℃ for 4 hours, and cooling to room temperature to obtain the light yellow titanium dioxide photocatalyst.
Example 5
a. Adding 0.5g of ascorbic acid and 120mg of urea into 35mL of deionized water to obtain a transparent solution;
b. adding 1.5mL of trivalent titanium solution into the solution obtained in the step a, adding 1mol/L of sodium hydroxide solution, adjusting the pH value to 4, and continuously stirring at the rotating speed of 500r/min to obtain a blood red solution;
c. transferring the solution in the step b into a hydrothermal kettle, and reacting for 8 hours at the temperature of 180 ℃ to obtain a brown yellow primary product;
d. washing the brown yellow primary product in the step c for 3-5 times by using deionized water and ethanol until the pH value is 7, drying overnight to obtain a black product, and carefully grinding the black product to obtain brown powder;
e. and d, placing the brown powder in the step d into a tubular furnace under the protection of inert gas, controlling a vacuum pump to adjust the vacuum degree to-0.03 atm, calcining at the constant temperature of 450 ℃ for 4 hours, and cooling to room temperature to obtain the gray titanium dioxide photocatalyst.
Example 6
a. Adding 0.5g of ascorbic acid and 20mg of urea into deionized water to obtain a transparent solution;
b. adding 1.5mL of trivalent titanium solution into the solution obtained in the step a, adding 1mol/L of sodium hydroxide solution, adjusting the pH value to 4, and continuously stirring at the rotating speed of 750r/min to obtain a blood red solution;
c. transferring the solution in the step b into a hydrothermal kettle, and reacting for 12 hours at the temperature of 180 ℃ to obtain a brown yellow primary product;
d. washing the brown yellow primary product in the step c for 3-5 times by using deionized water and ethanol until the pH value is 7, drying overnight to obtain a black product, and carefully grinding the black product to obtain brown powder;
e. and d, placing the brown powder in the step d into a tubular furnace under the protection of inert gas, calcining at the constant temperature of 450 ℃ for 4 hours while regulating the normal pressure state by controlling a vacuum pump, and cooling to room temperature to obtain the black titanium dioxide photocatalyst.
Application example 1 catalytic Properties of light-yellow titanium dioxide powder prepared according to the invention
10mg of sample 1 in example 1 and 100mL of 20ppm rhodamine B solution are taken and placed in a beaker, wrapped by tinfoil paper, stirred overnight in the dark, the stirred solution is transferred into a reaction vessel, a mercury lamp light source provided with a visible light filter (lambda is more than 420nm) is turned on to irradiate the reaction solution, about 1.5mL of the solution is taken at intervals and placed in a centrifuge tube, the centrifuge tube is centrifuged at 9000rpm for 3min, the supernatant is taken, and the content of rhodamine B in the supernatant is detected by an ultraviolet-visible spectrophotometer. The degradation curve of the test sample 1 to rhodamine B in the figure 6 is obtained.
Application example 2 catalytic Properties of light-yellow titanium dioxide powder prepared according to the invention
10mg of sample 2 in example 2 and 100mL of 20ppm rhodamine B solution are taken and placed in a beaker, wrapped by tinfoil paper, stirred overnight in the dark, the stirred solution is transferred into a reaction vessel, a mercury lamp light source with a visible light filter (lambda is more than 420nm) is turned on to illuminate the reaction solution, about 1.5mL of the solution is taken at intervals and placed in a centrifuge tube, the centrifuge tube is centrifuged at 9000rpm for 3min, the supernatant is taken, and the content of rhodamine B in the supernatant is detected by an ultraviolet-visible spectrophotometer. The degradation curve of the test sample 2 for rhodamine B in FIG. 6 is obtained.
Claims (4)
1. A preparation method of a visible light response nitrogen-doped nano titanium dioxide photocatalyst is characterized by comprising the following steps:
1) adding ascorbic acid and urea into deionized water, wherein the material ratio of the ascorbic acid to the urea to the deionized water is (0.5-1 g): (5-50 mg): (35-50 mL), and stirring to obtain a transparent solution;
2) adding a trivalent titanium solution into the solution obtained in the step 1), wherein the mass volume ratio of trivalent titanium to the transparent solution is (2-10 g) - (20-100 ml), the trivalent titanium compound is titanium trichloride and titanium oxychloride, then adding a sodium hydroxide solution, the concentration of the sodium hydroxide solution is 0.2-1.5 mo/L, adjusting the pH value to 1.5-5, and continuously stirring for 0.5-2 hours at the rotating speed of 250-1000 r/min to obtain a brown or blood red solution;
3) transferring the solution obtained in the step 2) into a hydrothermal kettle, and reacting for 8-12 hours at the temperature of 180 ℃ to obtain a brown-yellow primary product;
4) washing the brown yellow primary product obtained in the step 3) by deionized water and ethanol until the pH value is 7, and drying overnight to obtain a black product which is carefully ground into brown powder;
5) placing the brown powder obtained in the step 4) in a tubular furnace under the protection of inert atmosphere, adjusting the vacuum degree to-0.03 to-0.08 atm by controlling a vacuum pump, calcining at the constant temperature of 400 to 500 ℃ for 2 to 4 hours, and cooling to room temperature to obtain the visible light response nitrogen-doped nano titanium dioxide material.
2. The preparation method of the visible-light-responsive nitrogen-doped nano titanium dioxide photocatalyst according to claim 1, which is characterized in that: the stirring speed in the step 1) is 250-1000 r/min.
3. The preparation method of the visible-light-responsive nitrogen-doped nano titanium dioxide photocatalyst according to claim 1, which is characterized in that: the inert atmosphere is nitrogen or argon, and titanium dioxide powder with different colors and performances is prepared by regulating and controlling the roasting vacuum degree.
4. The use of the titanium dioxide obtained by the preparation method of the visible light response nitrogen-doped nano titanium dioxide photocatalyst in claim 1 is characterized in that: the material is used for purifying air and water sources, self-cleaning, decomposing water by sunlight or decomposing water by solar photoelectrocatalysis.
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