CN109289887B - Preparation method and application of nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst - Google Patents
Preparation method and application of nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 29
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 26
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 238000010992 reflux Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 22
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims abstract description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
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- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
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- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 229960004368 oxytetracycline hydrochloride Drugs 0.000 claims description 3
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 5
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- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
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- 239000000969 carrier Substances 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a preparation method of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst, which comprises the following steps: slowly dropping tetrabutyl titanate into the isopropanol solution, and uniformly stirring to obtain a dispersion liquid A; adding ammonium metavanadate into absolute ethyl alcohol, and uniformly stirring to obtain a dispersion liquid B; slowly dripping the dispersion liquid B into the dispersion liquid A, uniformly stirring, heating and refluxing, and naturally cooling to room temperature to obtain a product V-TiO2(ii) a Subjecting the V-TiO to2Calcining at high temperature in ammonia atmosphere to obtain nano-block N/V-TiO2A photocatalyst; mixing the above N/V-TiO2Dispersing the photocatalyst in absolute ethyl alcohol, adding bismuth nitrate pentahydrate, adding tantalum pentachloride after the bismuth nitrate pentahydrate is completely dissolved, adjusting the pH to 9-11, and performing hydrothermal synthesis to obtain Bi3TaO7/N/V‑TiO2A composite material. Co-doping of TiO by N, V in the present invention2And Bi3TaO7The synergistic effect generated by the coupling not only improves the service life of the photo-generated electrons and the holes, but also effectively improves the stability of the catalyst after the recombination.
Description
Technical Field
The invention belongs to the technical field of synthesis of nano materials, and particularly relates to a preparation method and application of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst.
Background
Titanium dioxide (TiO2) has been attracting high attention of both domestic and foreign scholars in many fields such as energy conversion, wastewater treatment, environmental purification, sensors, paints, cosmetics, catalysts, fillers, etc. because of its chemical inertness, good biocompatibility, strong oxidizing ability, and chemical corrosion resistance, and low price. Particularly, as an N-type semiconductor material with excellent performance, the material can fully utilize solar energy, is energy-saving and environment-friendly, and is a nano functional material with the widest application prospect at present. Although titanium dioxide is a latent photocatalyst, the wide band gap (anatase is about 3.2eV and rutile is about 3.0eV) enables TiO2 to be excited only by ultraviolet rays (lambda < 387nm) with a shorter wavelength of 5% of sunlight, and at the same time, electrons and holes generated by photoexcitation are extremely easily recombined, resulting in a low quantum yield of absorbed light, which greatly hinders the use of titanium dioxide as a photocatalyst.
In order to solve the problem, scientists at home and abroad carry out a great deal of research, and the currently applied method mainly comprises the following steps: coupling with narrow bandgap semiconductors, surface sensitization with dyes or metal compounds, and noble metal deposition, among others. The metal/non-metal ion doping is widely used as a simpler and more efficient method, but in the research process, it is found that the doping of the metal element has some limitations, for example, a doped sample often has thermal instability and is easy to become a carrier recombination center, and the like, and the problems can limit the large-scale application of doping modification. Therefore, in recent years, research on doping and modifying titanium dioxide by using non-metallic elements has become a hot spot in research in the field of photocatalysis. Up to now, non-metal ion doping has mainly focused on nitrogen, carbon, sulfur, boron, and halogen elements, etc.
The main principle of doping non-metallic elements refers to the replacement of nano TiO by non-metallic elements2O in (1)2-Or nonmetal elements are filled in crystal lattice gaps of TiO2 to change the chemical composition and structure of TiO2 and further change the optical properties of the TiO2, and the currently common preparation method mainly comprises the following steps: solution combustion method, hydrothermal method, sol-microwave hydrothermal method combined with ultrasonic technology and the like, wherein the C, N doped nano titanium dioxide prepared by the solution combustion method is mainly anatase type, the grain size is 9-15 nm, and the grain size is 30-180 nmThe method has longer process time and high manufacturing cost, the formed material is easy to agglomerate, the utilization efficiency is low, and the method is not beneficial to popularization and use in practical application; the N-doped TiO2 microspheres prepared by combining a sol-microwave hydrothermal method with an ultrasonic technology do not damage the appearance of the microspheres before and after hydrothermal reaction, but have obvious nanocrystalline assembly on the surface, and along with the increase of the addition of ammonia water, part of the sample surface has the phenomena of compact stacking and agglomeration of nanocrystalline grains, so that the photocatalytic efficiency is seriously influenced.
In addition, the novel Z-type photocatalyst can effectively promote the separation and transfer of electron holes, and is an effective way for further improving the photocatalytic performance and activity of the novel Z-type photocatalyst. By means of bismuth tantalate (Bi)3TaO7) Nano-point supported nitrogen (N) and vanadium (V) co-doped TiO2The nano-block for constructing the Z-type heterojunction photocatalytic system can effectively make up the defects of monomer substances and solve the problems. Therefore, the invention provides a preparation method of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate heterojunction photocatalyst, and aims to utilize Bi3TaO7With N/V-TiO2The synergistic effect generated by the combination of the two materials is used for enhancing the stability of the composite material and promoting the rapid separation of photo-generated electrons and holes, thereby inhibiting the combination of photo-generated carriers and improving the photocatalytic activity of the photo-generated carriers.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method and application of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst is characterized by comprising the following steps:
and step 3: slowly dripping the dispersion liquid B into the dispersion liquid A, uniformly stirring, heating and refluxing, naturally cooling to room temperature, centrifugally separating, and washing to obtain a product V-TiO2;
And 4, step 4: subjecting the V-TiO to2Calcining at high temperature in ammonia atmosphere to obtain nano-block N/V-TiO2A photocatalyst;
and 5: mixing the above N/V-TiO2Dispersing a photocatalyst in absolute ethyl alcohol, adding bismuth nitrate pentahydrate, adding tantalum pentachloride until the tantalum pentachloride is completely dissolved after the bismuth nitrate pentahydrate is completely dissolved, adjusting the pH value to 9-11, placing in an environment of 180-240 ℃, carrying out constant-temperature thermal reaction for 12-24 h, centrifuging, washing and drying to obtain Bi3TaO7/N/V-TiO2A composite material.
Preferably, in the step 3, the reflux temperature of the heating reflux treatment is 60-80 ℃, and the reflux time is 4-6 h.
Preferably, the high-temperature calcination method in the step 4 comprises the following steps: by reacting V-TiO2Placing the mixture in a tubular furnace in an ammonia atmosphere, heating to 500-800 ℃ at a heating rate of 3-5 ℃/min, keeping the temperature for 4-8 h, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the nano-bulk N/V-TiO2A photocatalyst; more preferably, the temperature is raised to 650 ℃ at the temperature raising rate of 4 ℃/min, and the temperature is kept for 6 h.
Preferably, in step 5, the bismuth nitrate, the tantalum pentachloride and the N/V-TiO are mixed2And the dosage ratio of the absolute ethyl alcohol is 0.1-0.3 g: 0.05-0.2 g: 0.2-0.4 g: 20-40 mL.
Preferably, in the step 5, the concentration of the NaOH solution is 0.5-1.0 mol/L; more preferably, the concentration of the NaOH solution is 1.0 mol/L.
Preferably, in the step 5, the washing means alternately washing with ultrapure water and absolute ethyl alcohol for 3 times, and the drying means drying for 5-10 hours in a vacuum drying environment at 50-60 ℃.
The invention also aims to provide application of the nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst in catalytic degradation of organic pollutants in water under irradiation of ultraviolet light or visible light.
The invention has the beneficial effects that:
(1) the nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction material prepared by the method disclosed by the invention is green and simple in preparation process, low in cost, environment-friendly and easy for large-scale industrial production, has excellent environmental stability and has potential application prospects in the aspects of solving solar energy conversion and environmental pollution.
(2) The nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction material improves the visible light absorption capacity, and effectively improves the utilization rate of a light source due to the suspension characteristic in the photocatalytic degradation process.
(3)0D/3D Bi3TaO7nanodot/N/V-TiO2The nano-bulk composite material can be used as a visible light photocatalyst with excellent performance. N, V Co-doping with TiO2On the basis of Bi3TaO7The synergistic effect generated by coupling is beneficial to prolonging the service life of photo-generated electrons and holes, promoting the transmission of photo-generated charges and effectively improving the stability of the catalyst after recombination. Thus, Bi3TaO7nanodot/N/V-TiO2The nano-block composite material remarkably improves the degradation effect of the catalyst on organic dye, and has wide prospect in the field of actual application of photocatalysis.
Drawings
FIG. 1 shows Bi obtained in this example3TaO7/N/V-TiO2An X-ray diffraction pattern (XRD) of the heterojunction material;
FIG. 2 shows Bi of this example3TaO7/N/V-TiO2Atomic force microscope and transmission electron microscope images of heterojunction materials, wherein (A) is N/V-TiO2The atomic force microscope of (B) is N/V-TiO2The thickness of (a); (C) the figure is N/V-TiO2A transmission electron microscope; the (D, E) diagram is Bi3TaO7/N/V-TiO2Transmission electron microscope, the picture (F) is Bi3TaO7/N/V-TiO2Diffraction pattern of transmission electron microscopy.
FIG. 3 is a UV-VIS absorption spectrum of the prepared heterojunction material;
FIG. 4 shows a binary composite photocatalyst Bi3TaO7/N/V-TiO2Photocurrent (a) and impedance diagram (b);
FIG. 5 is a graph showing the effect of photocatalytic degradation and cycling stability of the prepared sample on oxytetracycline hydrochloride at a concentration of 20mg/L under irradiation of visible light.
Detailed Description
The following is a detailed description of the embodiments of the present invention, which is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1
A preparation method of nitrogen and vanadium co-doped titanium dioxide comprises the following steps:
1. slowly dripping 0.25mL of tetrabutyl titanate into 10mL of isopropanol, and fully stirring and uniformly mixing to obtain a dispersion liquid A;
2. dispersing 0.5g of ammonium metavanadate in a mixed solution of 70mL of absolute ethyl alcohol and 0.15mL of ultrapure water, and performing ultrasonic dispersion for 0.5h to obtain a dispersion liquid B;
3. slowly dropping the dispersion liquid A into the dispersion liquid B, refluxing for 5h at 80 ℃, and obtaining a product V-TiO2Washed with alcohol for 3 times and dried under vacuum. Subsequently, the ground V-TiO is subjected to2Putting the mixture into a ceramic crucible, putting the ceramic crucible into a tubular furnace, heating the mixture to 600 ℃ in an ammonia atmosphere, calcining the mixture for 4 hours, and cooling the calcined mixture to room temperature after the calcination is finished to obtain nano blocky N/V-TiO2A photocatalyst.
The N/V-TiO is added2The X-ray diffraction pattern of the photocatalyst, as shown in FIG. 1, can be found in comparison with the finding of TiO2,N/V-TiO2The peak positions of (A) and (B) are significantly shifted, which indicates that N/V-TiO2The N and V elements in the composite material have been successfully doped and are free of other impurities.
The N/V-TiO is added2The photocatalyst is subjected to atomic force microscope and transmission electron microscope, as shown in FIG. 2, wherein (A) is N/V-TiO2The atomic force microscope of (B) is N/V-TiO2The thickness of (A) is shown in the figure, and N/V-TiO is shown in the figure2Is about 9 nm; (C) the figure is N/V-TiO2The transmission electron microscope has a nano-bulk structure, uniform dispersion and good permeability.
Example 2
A preparation method of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst comprises the following steps:
and step 3: slowly dripping the dispersion liquid B into the dispersion liquid A, uniformly stirring, heating and refluxing, naturally cooling to room temperature, centrifugally separating, and washing to obtain a product V-TiO2The reflux temperature of the heating reflux treatment is 70 ℃, and the reflux time is 5 hours;
and 4, step 4: step V-TiO2Placing in a tubular furnace in ammonia atmosphere, heating to 650 deg.C at a heating rate of 3 deg.C/min, maintaining for 6h, and cooling to room temperature at a cooling rate of 5 deg.C/min to obtain nanometer block-shaped N/V-TiO2A photocatalyst;
and 5: mixing the above 0.3g N/V-TiO2Dispersing a photocatalyst in 30mL of absolute ethyl alcohol, adding 0.2g of bismuth nitrate pentahydrate, adding 0.1g of tantalum pentachloride after the bismuth nitrate pentahydrate is completely dissolved, adjusting the pH to 10 by using a sodium hydroxide solution with the concentration of 1.0mol/L, placing in an environment at 200 ℃, carrying out constant-temperature thermal reaction for 16h, centrifuging, alternately washing with deionized water and absolute ethyl alcohol for three times, and drying to obtain Bi3TaO7Bi with the mass fraction of 10%3TaO7/N/V-TiO2Composite materials, i.e. 10% Bi3TaO7/N/V-TiO2。
Mixing the 10% Bi3TaO7/N/V-TiO2Subjecting the composite material to X-ray diffraction pattern, as shown in FIG. 1, Bi3TaO7/N/V-TiO2Bi exists in the X-ray diffraction pattern of the composite material3TaO7Has a diffraction peak of N/V-TiO2Showing a diffraction peak of Bi3TaO7/N/V-TiO2The successful preparation.
Mixing the 10% Bi3TaO7/N/V-TiO2The composite material was subjected to an atomic force microscope and a transmission electron microscope, and as shown in FIG. 2(D, E), Bi was observed3TaO7Is uniformly distributed in the N/V-TiO2The agglomeration phenomenon is avoided on the surface of the nano block; FIG. 2(F) is a view showing Bi3TaO7/N/V-TiO2The diffraction pattern of a transmission electron microscope shows that Bi3TaO7/N/V-TiO2High purity and good crystallinity.
Adding the Bi3TaO7/N/V-TiO2The composite material was tested for UV-visible absorption spectrum, as shown in FIG. 3, compared to pure Bi3TaO7And N/V-TiO2,Bi3TaO7/N/V-TiO2The visible light absorption of the composite material is obviously enhanced.
Mixing the 10% Bi3TaO7/N/V-TiO2The composite material is subjected to photocurrent and impedance tests, and the test results in fig. 4 show that the photocurrent is in the order from high to low: i isBi3TaO7/N/V-TiO2>IN/V-TiO2>IBi3TaO7>ITiO2The impedance is completely opposite to the photocurrent sequence, and the result shows that the binary composite material Bi3TaO7/N/V-TiO2The method has the best photoproduction electron hole separation efficiency, the best electron service life and better photocatalytic degradation efficiency.
Mixing the 10% Bi3TaO7/N/V-TiO2Composite material and Bi3TaO7And N/V-TiO2The photocatalytic degradation experiments are respectively carried out, the photocatalytic degradation and the circulation stability effects of each sample on the oxytetracycline hydrochloride with the concentration of 20mg/L under the irradiation of visible light are shown in figure 5, and the results show that 10% Bi3TaO7/N/V-TiO2Has good recycling performance and optimal photocatalytic degradation efficiency, and the result is consistent with the photochemical test result shown in figure 4.
Example 3
A preparation method of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst comprises the following steps:
and step 3: slowly dripping the dispersion liquid B into the dispersion liquid A, uniformly stirring, heating and refluxing, naturally cooling to room temperature, centrifugally separating, and washing to obtain a product V-TiO2The reflux temperature of the heating reflux treatment is 60 ℃, and the reflux time is 6 hours;
and 4, step 4: step V-TiO2Placing in a tubular furnace in ammonia atmosphere, heating to 800 deg.C at a heating rate of 5 deg.C/min, maintaining for 4h, and cooling to room temperature at a cooling rate of 5 deg.C/min to obtain nanometer block N/V-TiO2A photocatalyst;
and 5: mixing the above N/V-TiO2Dispersing a photocatalyst in 20mL of absolute ethyl alcohol, adding 0.3g of bismuth nitrate pentahydrate, adding 0.2g of tantalum pentachloride after the bismuth nitrate pentahydrate is completely dissolved, adjusting the pH value to 9, placing in an environment at 180 ℃, carrying out constant-temperature thermal reaction for 12h, centrifuging, alternately washing with deionized water and absolute ethyl alcohol for three times, and drying to obtain Bi3TaO7Bi with the mass fraction of 20%3TaO7/N/V-TiO2Composite materials, i.e. 20% Bi3TaO7/N/V-TiO2。
As shown in FIG. 5(a), 20% Bi obtained in this example3TaO7/N/V-TiO2The composite material had high degradation efficiency, and as shown in FIG. 5(b), the 20% Bi3TaO7/N/V-TiO2Has good photocatalytic stability, and is an ideal photocatalyst form.
Example 4
A preparation method of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst comprises the following steps:
and step 3: slowly dripping the dispersion liquid B into the dispersion liquid A, uniformly stirring, heating and refluxing, naturally cooling to room temperature, centrifugally separating, and washing to obtain a product V-TiO2The reflux temperature of the heating reflux treatment is 80 ℃, and the reflux time is 4 hours;
and 4, step 4: step V-TiO2Placing in a tubular furnace in ammonia atmosphere, heating to 500 deg.C at a heating rate of 3 deg.C/min, maintaining for 4h, and cooling to room temperature at a cooling rate of 5 deg.C/min to obtain nanometer block-shaped N/V-TiO2A photocatalyst;
and 5: mixing the above 0.3g N/V-TiO2Dispersing a photocatalyst in 30mL of absolute ethyl alcohol, adding 0.2g of bismuth nitrate pentahydrate, adding 0.1g of tantalum pentachloride after the bismuth nitrate pentahydrate is completely dissolved, adjusting the pH value to 9, placing in an environment at 180 ℃, carrying out constant-temperature thermal reaction for 12h, centrifuging, alternately washing with deionized water and absolute ethyl alcohol for three times, and drying to obtain Bi3TaO7Bi with the mass fraction of 15 percent3TaO7/N/V-TiO2Composite materials, i.e. 15% Bi3TaO7/N/V-TiO2。
As shown in FIG. 5(a), 15% Bi obtained in this example3TaO7/N/V-TiO2The composite material has high degradation efficiency and is an ideal photocatalyst form.
Example 5
A preparation method of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst comprises the following steps:
and step 3: slowly dropping the dispersion liquid BUniformly stirring the dispersion liquid A, heating and refluxing the dispersion liquid A, naturally cooling the dispersion liquid A to room temperature, centrifugally separating the dispersion liquid A, and washing the dispersion liquid A to obtain a product V-TiO2The reflux temperature of the heating reflux treatment is 80 ℃, and the reflux time is 4 hours;
As shown in FIG. 5(a), 5% Bi obtained in this example3TaO7/N/V-TiO2The composite material has high degradation efficiency and is an ideal photocatalyst form.
Comparative example 1
A preparation method of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate photocatalyst comprises the following steps:
and step 3: slowly dripping the dispersion liquid B into the dispersion liquid A, uniformly stirring, heating and refluxing, naturally cooling to room temperature, centrifugally separating, and washing to obtain a product V-TiO2The reflux temperature of the heating reflux treatment is 80 ℃, and the reflux time is 4 hours;
and 4, step 4: step V-TiO2Placing in a tubular furnace in ammonia atmosphere, heating to 500 deg.C at a heating rate of 3 deg.C/min, maintaining for 4h, and cooling to room temperature at a cooling rate of 5 deg.C/min to obtain nanometer block-shaped N/V-TiO2A photocatalyst;
and 5: adding 0.2g of bismuth nitrate pentahydrate into 40mL of absolute ethyl alcohol, adding 0.1g of tantalum pentachloride into the absolute ethyl alcohol until the bismuth nitrate pentahydrate is completely dissolved, adjusting the pH value to 9 by using a sodium hydroxide solution, placing the solution in an environment at 180 ℃, carrying out constant-temperature thermal reaction for 12 hours, centrifuging, alternately washing the solution with deionized water and absolute ethyl alcohol for three times, and drying to obtain Bi3TaO7A photocatalyst.
Step 6: 0.27g of nano-bulk N/V-TiO is weighed2Photocatalyst and 0.03gBi3TaO7The photocatalyst is physically mixed uniformly to obtain the physically mixed Bi3TaO7/N/V-TiO2I.e., B/NVTi-PM.
As shown in FIG. 5(a), the B/NVTi-PM composite material obtained in this example has a significantly reduced photocatalytic effect compared to the composite materials described in examples 2-5 above.
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 considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A preparation method of a nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst is characterized by comprising the following steps:
step 1, slowly dropping tetrabutyl titanate into an isopropanol solution, and uniformly stirring to obtain a dispersion liquid A, wherein the volume of the tetrabutyl titanate is 0.1-0.3 mL, and the volume of the isopropanol solution is 5-20 mL;
step 2, adding ammonium metavanadate into absolute ethyl alcohol, and uniformly stirring to obtain a dispersion liquid B, wherein the mass of the ammonium metavanadate is 0.2-0.6 g, and the volume of the absolute ethyl alcohol is 50-80 mL;
and step 3: slowly dripping the dispersion liquid B into the dispersion liquid A, uniformly stirring, heating and refluxing, naturally cooling to room temperature, centrifugally separating, and washing to obtain a product V-TiO2;
And 4, step 4: subjecting the V-TiO to2Calcining at high temperature in ammonia atmosphere to obtain nano-block N/V-TiO2A photocatalyst;
and 5: mixing the above N/V-TiO2Dispersing a photocatalyst in absolute ethyl alcohol, adding bismuth nitrate pentahydrate, adding tantalum pentachloride until the tantalum pentachloride is completely dissolved after the bismuth nitrate pentahydrate is completely dissolved, adjusting the pH to 9-11 by using NaOH solution, placing the solution in an environment of 180-240 ℃, carrying out constant-temperature thermal reaction for 12-24 h, centrifuging, washing and drying to obtain Bi3TaO7/N/V-TiO2A composite material.
2. The preparation method of the nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst according to claim 1, wherein the preparation method comprises the following steps: in the step 3, the reflux temperature of the heating reflux treatment is 60-80 ℃, and the reflux time is 4-6 h.
3. The preparation method of the nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst according to claim 1, wherein the specific high-temperature calcination method in the step 4 comprises the following steps: by reacting V-TiO2Placing the mixture in a tubular furnace in an ammonia atmosphere, heating to 500-800 ℃ at a heating rate of 3-5 ℃/min, keeping the temperature for 4-8 h, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the nano-bulk N/V-TiO2A photocatalyst.
4. The preparation method of the nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst according to claim 1, wherein the preparation method comprises the following steps: in step 5, the bismuth nitrate, the tantalum pentachloride and the N/V-TiO are added2And the dosage ratio of the absolute ethyl alcohol is 0.1-0.3 g: 0.05-0.2 g: 0.2-0.4 g: 20-40 mL.
5. The preparation method of the nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst according to claim 1, wherein the preparation method comprises the following steps: in the step 5, the washing means alternately washing with ultrapure water and absolute ethyl alcohol for 3 times, and the drying means drying for 5-10 hours in a vacuum drying environment at 50-60 ℃.
6. The preparation method of the nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst according to claim 1, wherein the preparation method comprises the following steps: in the step 5, the concentration of the NaOH solution is 0.5-1.0 mol/L.
7. The application of the nitrogen and vanadium co-doped titanium dioxide/bismuth tantalate Z-type heterojunction photocatalyst prepared according to the method in any one of claims 1 to 5 in catalytic degradation of oxytetracycline hydrochloride in water under irradiation of visible light.
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