CN110898822A - Preparation method of black titanium dioxide nanowire network photo-anode material - Google Patents
Preparation method of black titanium dioxide nanowire network photo-anode material Download PDFInfo
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000010405 anode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000010936 titanium Substances 0.000 claims abstract description 69
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 69
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000005530 etching Methods 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003832 thermite Substances 0.000 claims 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 abstract description 15
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010242 baoji Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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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
- 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
-
- B01J35/33—
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a preparation method of a black titanium dioxide nanowire network photo-anode material, and belongs to the field of material chemistry. The black titanium dioxide nanowire network photo-anode material takes a titanium sheet as a substrate, white titanium dioxide is obtained by etching and a hydrothermal method, and black titanium dioxide is prepared by a hydrogen high-temperature reduction process. The substrate used by the method is an industrial titanium sheet, the method is cheap and easy to obtain, the used equipment is cheap and stable in performance, the process method is simple, large-scale preparation is easy, the prepared black titanium dioxide nanowire network and the matrix are combined stably and uniformly, and the black titanium dioxide nanowire network has a strong absorption effect in a visible spectrum region compared with a white titanium dioxide coating. The degradation rate of reactive brilliant blue KN-R to refractory organic pollutants under visible light reaches 84.12 percent, and the catalytic efficiency under the same experimental conditions is 3.5 times that of white titanium dioxide used as an anode material.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a preparation method of a black titanium dioxide nanowire network photo-anode material.
Background
In recent years, with social development, environmental pollution is more serious, and particularly, pollution to water bodies damages the ecological environment and even influences the production and life of people. Therefore, people pay more and more attention to solving the problem of water pollution. The white titanium dioxide is an intrinsic semiconductor, the forbidden band width is 3.2eV, and the surface area is small. According to the principle of semiconductor photocatalysis, white titanium dioxide can only exert the photocatalysis characteristic by absorbing ultraviolet part in solar spectrum. However, the ultraviolet portion of sunlight is only below 5%, and thus the quantum yield of white titanium dioxide is low. Moreover, the titanium dioxide is generally degraded in the solution as suspended particles, which greatly affects the absorption of light and the depth of irradiation, and the suspended particles are easily coagulated in water and difficult to recover after reaction, which seriously affects the practical application of the black titanium dioxide.
The invention adopts solid titanium sheets, and the black titanium dioxide nanowire network material is generated after hydrothermal and hydrogen heating reduction, because TiO2With Ti3+The self-doping of oxygen vacancy not only has larger specific surface area, but also can obviously improve the separation efficiency of photo-generated electrons and holes, so that the photo-generated electrons and holes have excellent photo-catalytic activity. Therefore, the reduced titanium dioxide nanowire network material is considered to be a promising photoelectric anode material and can play a photoelectric synergistic role in a photoelectrochemical process.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a black titanium dioxide nanowire network photo-anode material.
In order to achieve the above object, the technical scheme of the present invention is a preparation method of a black titanium dioxide nanowire network photo-anode material, comprising the following steps:
s1: taking a titanium sheet as a substrate, and washing with deionized water for 3-6 times; placing the washed titanium sheet in an oxalic acid solution with the mass percent of 7-15%, etching for 1-3 hours at the temperature of 75-95 ℃, stirring once every 15-25 min, and washing for 3-6 times by deionized water after etching;
s2: carrying out ultrasonic treatment on the titanium sheet etched in the step S1 in an acetone solution for 15-45 min, carrying out ultrasonic treatment in an ethanol solution for 15-45 min and carrying out ultrasonic treatment in deionized water for 25-40 min, taking out the titanium sheet, and drying the titanium sheet at 50-70 ℃ for 7-9 h;
s3: soaking the titanium sheet dried in the step S2 in 50-70 mL of 3-6 mol/L sodium hydroxide solution, preserving the heat at 180-250 ℃ for 4-7 h, and cooling to room temperature after the heat preservation is finished;
s4: taking out the titanium sheet cooled in the step S3, soaking the titanium sheet in HCl solution with the concentration of 0.8-1.5 mol/L for 4-7 min, washing the titanium sheet with deionized water for 3-6 times after taking out, vacuum-drying the titanium sheet at 50-70 ℃ for 7-9 h, and cooling the titanium sheet to room temperature after drying to obtain white titanium dioxide;
s5: heating the white titanium dioxide dried in the step S4 to 430-480 ℃ at a heating rate of 1.5-3.0 ℃/min, and preserving heat for 1-4 h;
s6: introducing the white titanium dioxide obtained in the step S5 into H2And N2The mixed gas is heated to 520-570 ℃ at a heating rate of 1.5-3.0 ℃/min, the temperature is kept for 3-5 h, and after the temperature is kept, the mixed gas is cooled to room temperature to obtain black titanium dioxide.
In step S1, the substrate is a titanium sheet, but not limited to a titanium sheet, and specifically includes a nickel foil, a zinc sheet, and a tin sheet.
In the step S1, the purity of the titanium sheet is 99.5-99.9%, the size of the titanium sheet is 60 x 5-80 x 80mm, and the thickness of the titanium sheet is 0.5-2 mm.
In step S1, the titanium sheet substrate is rectangular, but is not limited to rectangular, and specifically includes square, triangle, and circle.
Wherein, in step S6, H2And N2The volume ratio of the mixed gas is 0.5-1.2: 10.
The process of preparing the white titanium dioxide in steps S1 to S4 is a hydrothermal method, but is not limited to the hydrothermal method, and specifically includes an electrodeposition method, a vapor deposition method, and a coating method.
The process for preparing the black titanium dioxide in steps S5 to S6 is a hydrogen heating reduction method, but is not limited to the hydrogen heating reduction method, and specifically includes an aluminothermic reduction method and a plasma hydrogenation method.
The preparation method of the black titanium dioxide nanowire network photo-anode material has the beneficial effects that the black titanium dioxide nanowire network photo-anode material is prepared by taking a titanium sheet as a substrate through a hydrothermal method and a hydrogen heating reduction process, the material is good in catalytic effect, and valence band electrons can be excited to a conduction band under the irradiation of light to form electrons and holes and O adsorbed on the surface of the electrons and the holes2And H2The O interacts to generate free radicals with strong oxidative decomposition capacity, the free radicals are used as electrode materials to play a role of photoelectric synergy in the photoelectrochemical process, the free radicals have organic dye pollutant degradation capacity in sewage treatment, the degradation rate of the active brilliant blue KN-R of the organic pollutants difficult to degrade reaches 84.12%, and the catalytic efficiency is 3.5 times that of white titanium dioxide used as an anode material under the same experimental conditions.
Drawings
FIG. 1 is a macroscopic view of the surface of a titanium sheet after etching;
FIG. 2 is a macroscopic view of the surface of a white titanium dioxide sheet;
FIG. 3 is a macroscopic view of the surface of a black titanium dioxide plate;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the surface of the etched titanium plate;
FIG. 5 is a Scanning Electron Microscope (SEM) image of the surface of a white titanium dioxide sheet;
FIG. 6 is a Scanning Electron Microscope (SEM) image of the surface of a black titanium dioxide plate;
FIG. 7 is a graph of the ultraviolet-visible Diffuse Reflection (DRS) effect of the prepared black titanium dioxide nanowire network material;
FIG. 8 is an X-ray diffraction (XRD) effect diagram of the prepared black titanium dioxide nanowire network material;
FIG. 9 is a diagram showing the effect of the prepared black titanium dioxide nanowire network material as an anode material on degrading active brilliant blue KN-R.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
In order to make the objects, schemes, procedures and advantages of the present invention more clear, the present invention is further described in detail with reference to the embodiments, it should be noted that the specific embodiments are only used for explaining the present invention and not for limiting the present invention. For example, the processes for preparing white titanium dioxide also include electrodeposition, vapor deposition, and coating, and the processes for preparing black titanium dioxide also include aluminothermic reduction and plasma hydrogenation.
In the following examples, unless otherwise specified, the experimental methods used were all conventional methods, the titanium sheets used in the present invention were purchased from titanium processing factory of Baoji, and the reagents used were purchased from chemical reagents of Kemiou, Tianjin, Inc.
Example 1
A preparation method of a black titanium dioxide nanowire network photo-anode material comprises the following steps:
s1: cutting a titanium sheet with the purity of 99.7 percent and the thickness of 1mm into a rectangle with the size of 70 multiplied by 10mm as a substrate by using an aviation shear, and washing the substrate for 5 times by using deionized water; and placing the washed titanium sheet in 10 mass percent oxalic acid solution, etching for 2 hours at 80 ℃, stirring once every 20 minutes, and washing for 5 times by deionized water after etching. FIG. 1 is a macroscopic view of the surface of the etched titanium plate, and FIG. 4 is a Scanning Electron Microscope (SEM) view of the surface of the etched titanium plate;
s2: carrying out ultrasonic treatment on the titanium sheet etched in the step S1 in an acetone solution for 30min, an ethanol solution for 30min and deionized water for 30min, taking out, and drying in a 60 ℃ oven for 8 h;
s3: adding 60mL of sodium hydroxide solution with the concentration of 5mol/L into a stainless steel autoclave with the volume of 80mL, soaking the titanium sheet dried in the step S2 into the solution, placing the autoclave in an oven, preserving heat at 200 ℃ for 6h, taking out the autoclave after heat preservation is finished, and cooling the autoclave to room temperature;
s4: and (4) taking out the titanium sheet cooled in the step S3, soaking the titanium sheet in HCl solution with the concentration of 1.0mol/L for 5min, washing the titanium sheet with deionized water for 5 times after the titanium sheet is taken out, drying the titanium sheet in a vacuum drying oven at the temperature of 60 ℃ for 8h, and cooling the titanium sheet to room temperature after the drying is finished to obtain white titanium dioxide. FIG. 2 is a macroscopic view of the surface of a white titanium dioxide plate, and FIG. 5 is a Scanning Electron Microscope (SEM) view of the surface of the white titanium dioxide plate;
s5: placing the white titanium dioxide dried in the step S4 in a muffle furnace, heating to 450 ℃ at a heating rate of 2.0 ℃/min, and preserving heat for 2 h;
s6: putting the white titanium dioxide obtained in the step S5 into a tube furnace, and introducing H2And N2Heating the mixed gas with the volume ratio of 1:10 to 550 ℃ at the heating rate of 2.0 ℃/min, preserving the heat for 4h, and cooling to room temperature after the heat preservation is finished to obtain the black titanium dioxide. Fig. 3 is a macroscopic view of the surface of the black titanium dioxide plate, and fig. 6 is a Scanning Electron Microscope (SEM) view of the surface of the black titanium dioxide plate.
Example 2
A preparation method of a black titanium dioxide nanowire network photo-anode material comprises the following steps:
s1: cutting a titanium sheet with the purity of 99.7 percent and the thickness of 1.5mm into a square with the size of 80 multiplied by 80mm as a substrate by using an aviation shear, and washing with deionized water for 4 times; placing the washed titanium sheet in an oxalic acid solution with the mass percentage of 12%, etching for 3 hours at the temperature of 75 ℃, stirring once every 25 minutes, and washing for 4 times by deionized water after etching;
s2: carrying out ultrasonic treatment on the titanium sheet etched in the step S1 in an acetone solution for 20min, an ethanol solution for 20min and deionized water for 25min, taking out, and drying in a 50 ℃ drying oven for 9 h;
s3: adding 60mL of sodium hydroxide solution with the concentration of 4mol/L into a stainless steel autoclave with the volume of 80mL, soaking the titanium sheet dried in the step S2 into the solution, placing the autoclave in an oven, preserving the heat at 180 ℃ for 7h, taking out the autoclave after the heat preservation is finished, and cooling the autoclave to room temperature;
s4: taking out the titanium sheet cooled in the step S3, soaking the titanium sheet in HCl solution with the concentration of 0.8mol/L for 7min, washing the titanium sheet with deionized water for 4 times after taking out, drying the titanium sheet in a vacuum drying oven at 50 ℃ for 9h, and cooling the titanium sheet to room temperature after drying to obtain white titanium dioxide;
s5: placing the white titanium dioxide dried in the step S4 in a muffle furnace, heating to 430 ℃ at a heating rate of 2.0 ℃/min, and preserving heat for 4 h;
s6: putting the white titanium dioxide obtained in the step S5 into a tube furnace, and introducing H2And N2Heating the mixed gas with the volume ratio of 0.7:10 to 570 ℃ at the heating rate of 2.0 ℃/min, preserving the heat for 3h, and cooling to room temperature after the heat preservation is finished to obtain the black titanium dioxide.
Example 3
A preparation method of a black titanium dioxide nanowire network photo-anode material comprises the following steps:
s1: cutting a titanium sheet with the purity of 99.7 percent and the thickness of 0.8mm into a round shape with the diameter of 60mm by using an aviation shear to be used as a substrate, and washing for 6 times by using deionized water; placing the washed titanium sheet in 8% oxalic acid solution by mass, etching for 1.5h at 90 ℃, stirring once every 15min, and washing for 6 times by deionized water after etching;
s2: carrying out ultrasonic treatment on the titanium sheet etched in the step S1 in an acetone solution for 35min, an ethanol solution for 35min and deionized water for 35min, taking out, and drying in a 70 ℃ drying oven for 7 h;
s3: adding 60mL of sodium hydroxide solution with the concentration of 6mol/L into a stainless steel autoclave with the volume of 80mL, soaking the titanium sheet dried in the step S2 into the solution, placing the autoclave in an oven, preserving the heat at 220 ℃ for 5 hours, taking out the autoclave after the heat preservation is finished, and cooling the autoclave to room temperature;
s4: taking out the titanium sheet cooled in the step S3, soaking the titanium sheet in 1.2mol/L HCl solution for 4min, washing the titanium sheet with deionized water for 6 times after taking out, drying the titanium sheet in a vacuum drying oven at 70 ℃ for 7h, and cooling the titanium sheet to room temperature after drying to obtain white titanium dioxide;
s5: placing the white titanium dioxide dried in the step S4 in a muffle furnace, heating to 480 ℃ at a heating rate of 2.0 ℃/min, and preserving heat for 1.5 h;
s6: putting the white titanium dioxide obtained in the step S5 into a tube furnace, and introducing H2And N2Heating the mixed gas with the volume ratio of 1.2:10 to 520 ℃ at the heating rate of 2.0 ℃/min, preserving the heat for 5h, and cooling to room temperature after the heat preservation is finished to obtain the black titanium dioxide.
Example 4
Ultraviolet-visible diffuse emission (DRS) experiments of the black titanium dioxide nanowire network photoanode material prepared in example 1:
starting a computer and a spectrophotometer, starting test software to preheat for 20min, then setting basic parameters, placing a barium sulfate sample in a large sample tank to start measuring a base line, and starting measuring the absorbance of the sample in a wavelength range of 200-800 nm. The samples were tested using a Cary100/UV1007M122 spectrophotometer (VARIAN, USA).
As shown in fig. 7, the ultraviolet-visible diffuse emission (DRS) experimental results showed that the prepared black titanium dioxide has higher absorption capacity than the white titanium dioxide in the ultraviolet and visible spectral regions.
Example 5
Surface Scanning Electron Microscope (SEM) observation of the black titanium dioxide nanowire network photoanode material prepared in example 2:
the black titanium dioxide nanowire network photoanode material prepared in example 2 was cut into squares of 5 × 5mm, square samples were attached to a test tray with a conductive tape, a layer of gold was sprayed, the square samples were placed in a test cell, and then vacuum was applied to start the test. The surface of the black titanium dioxide nanowire network photo-anode material is observed by using a Hitachi-1510 scanning electron microscope (Hitachi, Japan).
As shown in the attached figure 6, the observation result of a Scanning Electron Microscope (SEM) shows that the surface of the prepared black titanium dioxide nanowire network photo-anode material is full of spider-web nanowires.
Example 6
X-ray diffraction (XRD) experiments for the black titanium dioxide nanowire network photo-anode material prepared in example 3:
the black titanium dioxide nanowire network photo-anode material prepared in example 3 is cut into a circle with a proper radius of 5mm, the test surface of the round sample is polished to be flat and smooth by using sand paper, and the processed round sample is adhered to the rectangular holes of the aluminum sample rack by using paraffin to ensure that the surface of the sample is flush with the surface of the aluminum sample rack. The phase of the black titanium dioxide nanowire network photoanode material is measured and analyzed by an XRD-6100X-ray diffractometer (SHIMADZU, Japan).
As shown in fig. 8, the X-ray diffraction (XRD) results showed that the black titanium dioxide material was mainly classified into anatase titanium dioxide and titanium.
Example 7
Experiment of black titanium dioxide nanowire network photo-anode material prepared in example 1 as anode material to degrade active brilliant blue KN-R:
the experimental device, namely the photocatalytic activity testing device, is composed of a light source, a magnetic stirrer, a photocatalytic reactor and a photocatalytic adjustable direct current stabilized power supply. The light source is a 175W xenon lamp, and is inserted into the photocatalytic reactor to ensure that light rays can directly irradiate on the working electrode; the magnetic stirrer is used for ensuring that the dye concentration is kept in a relatively uniform state; the photocatalytic reactor is a quartz backflow cooling sleeve, and the quartz material is adopted to ensure that ultraviolet light can effectively pass through the sleeve. And during the whole reaction period, continuously introducing condensed water into the sleeve to ensure that the temperature of the whole reaction system is within a certain range.
250mL of reactive brilliant blue KN-R solution with the concentration of 60mg/L is prepared, and 3.55g of anhydrous sodium sulfate (Na) is added into the solution2SO4) And as a supporting electrolyte, pouring the prepared reactive brilliant blue KN-R solution into a photocatalytic reactor to serve as a simulated dye. The black titanium dioxide nanowire network photo-anode material prepared in the example 1 is used as a reaction anode, an etched titanium sheet is used as a reaction cathode, the titanium sheet is inserted into a reactor and placed in parallel, and then the reactor is opened to be cooledCondensing water and a stirrer, and taking 3mL of reactor liquid as a No. 1 sample by using a 5mL pipette after the solution is completely mixed. The dark reaction is carried out for 30min without turning on the light source, so that the dye and the catalyst reach an adsorption-desorption equilibrium state. After the dark reaction was completed, 3mL of the reactor liquid was taken as sample # 2 by using a 5mL pipette. And turning on a light source to start the photoelectrocatalysis reaction, wherein the light reaction lasts for 180 min. During the whole photoreaction process, 3mL of reactor liquid was taken out by a 5mL pipette at 20min intervals, and the reactor liquid was sequentially sequenced into a 3# sample and a 4# sample, … … 11# sample.
After the experiment, the absorbance of all samples at 592nm was measured with a UV759 ultraviolet spectrophotometer (Shanghai apparatus electric analyzer Co., Ltd.), and the degradation rate of reactive brilliant blue KN-R was calculated according to formula 1, and the experimental results are shown in FIG. 5.
D＝(A0-At)/A0100% of formula 1
In the formula:
d-degradation rate,%;
A0-initial absorbance of reactive brilliant blue KN-R solution;
Atthe absorbance of the reactive brilliant blue KN-R at the time of degradation t.
The black titanium dioxide nanowire network photo-anode material is used as an anode material, and after the dark reaction stage is finished, the result shows that the active brilliant blue KN-R has no catalytic degradation effect. In the photoreaction stage, the photocatalytic time is prolonged at any time, the degradation efficiency of the reactive brilliant blue KN-R is gradually improved, and after the reaction is finished, the degradation rate of the reactive brilliant blue KN-R reaches 84.12 percent. This is because under light irradiation, the valence band electrons of black titanium dioxide can be excited to the conduction band to form electrons and holes, together with O adsorbed on the surface thereof2And H2And (4) generating free radicals with strong oxidative decomposition capacity by the interaction of O, and efficiently catalyzing and degrading the active brilliant blue KN-R by using the free radicals as electrode materials.
As shown in the attached FIG. 9, a photocatalytic activity testing device was used to perform a control experiment on the degradation of active Brilliant blue KN-R by using white titanium dioxide as an anode material. The capability of the black titanium dioxide nanowire network photo-anode material for catalyzing and degrading the reactive brilliant blue KN-R is improved by 3.5 times compared with the capability of taking white titanium dioxide as an anode material under the same condition.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (7)
1. A preparation method of a black titanium dioxide nanowire network photo-anode material is characterized by comprising the following steps:
s1: washing a titanium sheet serving as a substrate with deionized water for 3-6 times, then placing the titanium sheet in an oxalic acid solution with the mass percentage of 7-15%, etching for 1-3 hours at the temperature of 75-95 ℃, stirring once every 15-25 min, and washing with deionized water for 3-6 times after etching;
s2: carrying out ultrasonic treatment on the titanium sheet etched in the step S1 in an acetone solution for 15-45 min, carrying out ultrasonic treatment in an ethanol solution for 15-45 min and carrying out ultrasonic treatment in deionized water for 25-40 min, taking out, and drying at 50-70 ℃ for 7-9 h;
s3: soaking the titanium sheet dried in the step S2 in 50-70 mL of 3-6 mol/L sodium hydroxide solution, preserving the heat at 180-250 ℃ for 4-7 h, and cooling to room temperature after the heat preservation;
s4: taking out the titanium sheet cooled in the step S3, soaking the titanium sheet in HCl solution with the concentration of 0.8-1.5 mol/L for 4-7 min, washing the titanium sheet with deionized water for 3-6 times after taking out, vacuum-drying the titanium sheet at 50-70 ℃ for 7-9 h, and cooling the titanium sheet to room temperature after drying to obtain white titanium dioxide;
s5: heating the white titanium dioxide dried in the step S4 to 430-480 ℃ at a heating rate of 1.5-3.0 ℃/min, preserving heat for 1-4H, introducing a mixed gas of H2 and N2, heating to 520-570 ℃ at a heating rate of 1.5-3.0 ℃/min, preserving heat for 3-5H, and cooling to room temperature to obtain black titanium dioxide.
2. The method as claimed in claim 1, wherein the substrate in step S1 further comprises nickel foil, zinc foil, and tin foil.
3. The method as claimed in claim 1, wherein the titanium sheet in step S1 has a purity of 99.5-99.9%, a size of 60 x 5-80 x 80mm, and a thickness of 0.5-2 mm.
4. The method as claimed in claim 1, wherein the titanium substrate in step S1 is rectangular, but not limited to rectangular, and specifically includes square, triangle, and circle.
5. The method as claimed in claim 1, wherein the H in step S5 is H2And N2The volume ratio of the mixed gas is 0.5-1.2: 10.
6. The method for preparing a black titanium dioxide nanowire network photoanode material as claimed in claim 1, wherein the process of preparing white titanium dioxide in steps S1-S4 further comprises electrodeposition, vapor deposition, and coating.
7. The method for preparing a black titanium dioxide nanowire network photoanode material as claimed in claim 1, wherein the process of preparing black titanium dioxide in step S5 further comprises thermite reduction and plasma hydrogenation.
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