CN107362814B - Preparation method and application of tungsten oxide/bismuth oxybromide composite material - Google Patents
Preparation method and application of tungsten oxide/bismuth oxybromide composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 13
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000005303 weighing Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000003115 biocidal effect Effects 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 abstract description 15
- 229960004989 tetracycline hydrochloride Drugs 0.000 abstract description 15
- 239000011941 photocatalyst Substances 0.000 abstract description 10
- 239000003242 anti bacterial agent Substances 0.000 abstract description 8
- 229940088710 antibiotic agent Drugs 0.000 abstract description 7
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 235000007164 Oryza sativa Nutrition 0.000 abstract 1
- 235000009566 rice Nutrition 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 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 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 4
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 4
- 229960002303 citric acid monohydrate Drugs 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—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
- C02F2101/38—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention belongs to sodiumThe field of rice materials, and relates to a preparation method of a tungsten oxide/bismuth oxybromide composite material. Weighing a certain amount of Bi24O31Br10Adding a certain amount of deionized water into the powder, and performing ultrasonic stirring to uniformly disperse the deionized water to obtain a suspension 1; then weighing a certain amount of WO3Adding a certain amount of deionized water into the powder, and performing ultrasonic stirring to uniformly disperse the deionized water to obtain a suspension 2; then mixing the two suspensions, and stirring for 8-12h to obtain a suspension 3; then transferring the obtained suspension 3 into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a drying oven, and carrying out hydrothermal reaction; after naturally cooling to room temperature, the yellow solid precipitate is centrifuged out, washed, dried and taken out, and then ground into powder by a grinding bowl for later use. The prepared composite photocatalyst can effectively catalyze and degrade the antibiotic tetracycline hydrochloride under the irradiation of visible light, and has potential application prospect in the wastewater treatment of antibiotics.
Description
Technical Field
The invention belongs to the field of nano materials, relates to a preparation method of a tungsten oxide/bismuth oxybromide composite material, and particularly relates to a composite material which is simple in preparation process, stable in product performance and good in performance of photocatalytic degradation of organic pollutants, and a preparation method and application thereof.
Background
Antibiotics are one of the most commonly used drugs for people, but improper treatment of wastewater containing antibiotics causes serious water pollution and harms human health. Tetracycline hydrochloride (TC) is one of the most widely used antibiotics, which helps people to fight bacterial infections. In recent years, the problem of treating TC in wastewater has been the focus of attention because TC is hardly degraded in the conventional biological treatment method, and it gradually accumulates in the ecological environment, destroys the ecosystem, causes proliferation of antibiotic resistance genes, and finally causes serious harm to human health. Therefore, how to effectively degrade TC is a problem that needs to be solved by researchers. In recent years, the application of photocatalytic technology to the decomposition of residual antibiotics in the environment has received much attention and research. The principle is that the photocatalyst is excited under the condition of illumination to generate active substances with strong oxidizing ability to decompose antibiotics. Therefore, photocatalytic decomposition of antibiotics is a green and efficient technical means.
Bismuth oxyhalide (BiOX, X ═ Cl, Br, I), a class of bismuth-based semiconductor materials, is a new class of semiconductor photocatalyst materials that has been developed in recent years. Due to the special layered structure, the suitable forbidden band width and the excellent photocatalytic activity, the photocatalyst has potential application prospects in various fields, and becomes one of hot spots for the research of material science and catalysis. However, the materials also have the disadvantages of low utilization rate of visible light, easy recombination of holes and electrons, too regular conduction band position and the like, so that the application of the materials in the fields of environment, energy and the like is limited. Therefore, it is an urgent problem to improve the separation efficiency of photo-generated charges by modifying the photo-generated charges to increase the utilization rate of visible light, and inhibiting the recombination of holes and electrons.
Two-dimensional nanomaterials are receiving increasing attention due to their excellent physicochemical properties, high specific surface area and unique electronic structure. Among the numerous two-dimensional nanomaterials, tungsten oxide (WO)3) As a typical n-type semiconductor material, the material has the characteristics of narrow band gap (2.4-2.8 eV), simple preparation process, stable photocatalytic performance, low price, no toxicity and the like, and is widely concerned in the field of photocatalysis. However, the simple tungsten oxide photocatalyst also has the defects of easy recombination of photon-generated carriers, low utilization rate of visible light and the like, so that the photocatalyst cannot be applied to actual life, and therefore, a plurality of methods for modifying the tungsten oxide semiconductor photocatalyst are sequentially generated, such as: constructing a heterojunction structure, changing the appearance, modifying the structure surface and the like; among these methods, the method of forming a heterostructure with another semiconductor is a simple and easy method, and can effectively improve the photocatalytic efficiency. The technology of this aspect has been reported in many documents at home and abroad (for example: WO)3/CdWO4(RSC Advances,2015,5(8):6019-6026.)，WO3/BiVO4(Nano letters,2014,14(2): 1099-1105), etc.).
To date, hydrothermal preparation of tungsten oxide/bismuth oxybromide has not been found (WO)3/Bi24O31Br10) Composite semiconductor material, Bi used therefor24O31Br10The nanometer material has stable chemical and physical properties, cheap and easily obtained raw materials, no toxicity, and the preparation of WO by taking the nanometer material as a carrier3/Bi24O31Br10The reaction process of the composite semiconductor material is simple, and the obtained composite material has good photocatalytic degradation performance and recyclable stability performance on the antibiotic tetracycline hydrochloride (TC), and has potential application prospects in antibiotic wastewater treatment.
Disclosure of Invention
The invention is directed to a monomer Bi24O31Br10Has the problems of low utilization rate of visible light and easy recombination of holes and electrons, and provides a simple WO3/Bi24O31Br10A preparation method of a composite photocatalytic material. The preparation method synthesizes WO by a simple and feasible hydrothermal method3/Bi24O31Br10The photocatalyst prepared from the composite material has better visible light catalysis efficiency.
The invention is realized by the following steps:
(1) preparation of Bi24O31Br10Semiconductor material: weighing a certain amount of bismuth nitrate pentahydrate in a beaker, adding ethylene glycol into the beaker, and carrying out ultrasonic treatment and stirring to fully dissolve the bismuth nitrate pentahydrate; weighing a certain amount of ammonium bromide in another beaker, adding deionized water into the beaker, and stirring the beaker to dissolve the ammonium bromide; mixing the two solutions, and stirring to obtain a white suspension; then adding ethanolamine, and continuing stirring; then transferring the obtained suspension into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a drying oven, and carrying out hydrothermal reaction; naturally cooling to room temperature, centrifuging to obtain solid, washing, drying, taking out, grinding to powder by grinding bowl for later use to obtain Bi24O31Br10A sample; specific references may be made to: applied Catalysis B: Environmental,2017,205: 615-.
The mass ratio of the raw material bismuth nitrate pentahydrate to the ammonium bromide is 4.95: 1.
The volume ratio of the ethylene glycol, the deionized water and the ethanolamine is 8.3:20.8: 1.
The temperature of the hydrothermal reaction is 140-200 ℃, and the reaction time is 8-15 h.
(2) Preparation of WO3Semiconductor material: weighing a certain amount of twoAdding a certain amount of deionized water into a beaker, stirring until the sodium tungstate hydrate and citric acid monohydrate are completely dissolved, then dropwise adding a hydrochloric acid solution into the beaker to adjust the pH value of the solution to 1, continuously stirring until a light yellow suspension is obtained, then transferring the obtained suspension into a reaction kettle with a polytetrafluoroethylene lining, and putting the reaction kettle into a drying oven for hydrothermal reaction; naturally cooling to room temperature, centrifuging to obtain yellowish precursor, washing, oven drying, taking out, grinding to powder with a grinding bowl, transferring into a semi-closed crucible, transferring into a temperature programmed tube furnace, calcining, naturally cooling to room temperature, taking out, and reserving to obtain WO3A sample; specific references may be made to: chemical engineering journal,2016,300:280-290.
The mass ratio of the sodium tungstate dihydrate to the citric acid monohydrate is 5: 3.
The concentration of the hydrochloric acid solution is 6mol L-1。
The temperature of the hydrothermal reaction is 100-150 ℃, and the reaction time is 8-15 h.
The calcination temperature for calcining the light yellow precursor is 400-600 ℃, the heating rate is 3-8 ℃/min, and the calcination time is 1-5 h.
(3) Preparation of WO3/Bi24O31Br10Composite semiconductor material: weighing a certain amount of Bi24O31Br10Adding a certain amount of deionized water into the powder, and performing ultrasonic stirring to uniformly disperse the deionized water to obtain a suspension 1; then weighing a certain amount of WO3Adding a certain amount of deionized water into the powder, and performing ultrasonic stirring to uniformly disperse the deionized water to obtain a suspension 2; then mixing the two suspensions, and stirring for 8-12h to obtain a suspension 3; then transferring the obtained suspension 3 into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a drying oven, and carrying out hydrothermal reaction; naturally cooling to room temperature, centrifuging to obtain yellow solid precipitate, washing, oven drying, taking out, grinding into powder with a grinding bowl to obtain WO3/Bi24O31Br10And (3) sampling.
The temperature of the hydrothermal reaction is 140 ℃ and 180 ℃, and the reaction time is 8-15 h.
Said WO3/Bi24O31Br10In composite materials WO3The composite mass ratio of (A) to (B) is 5-30%; preferably 10%.
And (3) analyzing the morphology and structure of the product by using an X-ray diffractometer (XRD) and a Transmission Electron Microscope (TEM), performing a photocatalytic degradation experiment by using an antibiotic tetracycline hydrochloride (TC) solution as a target dye, and measuring absorbance by using an ultraviolet-visible spectrophotometer to evaluate the photocatalytic activity of the product.
The invention has the characteristics that:
the invention successfully prepares high-efficiency WO for the first time by adopting a simple and feasible hydrothermal method3/Bi24O31Br10The preparation process of the heterojunction composite photocatalyst has the advantages of simple process, low cost, short period, environmental friendliness and the like. WO prepared3/Bi24O31Br10The composite material can effectively improve the separation efficiency of the photo-generated electron-hole pairs, further improve the performance of the photo-catalytic degradation of pollutants, and meanwhile, the composite photocatalyst has good recyclable stability and has potential application prospects in the field of antibiotic wastewater treatment.
Drawings
FIG. 1 shows the prepared monomer WO3、Bi24O31Br10And WO3/Bi24O31Br10XRD diffraction pattern of the composite material. It can be seen from the figure that WO is followed3Increase in content of WO3/Bi24O31Br10In composite materials WO3The characteristic diffraction peak of the composite material is more and more obvious, and only WO is contained in the composite material3And Bi24O31Br10The diffraction peak of (A) shows that the prepared sample has high purity and no impurities.
FIG. 2 shows the monomer WO prepared3、Bi24O31Br10And WO3/Bi24O31Br10Transmission electron micrograph of composite sample, (a) monomer WO3Transmission electron microscopy images of; (b) monomer Bi24O31Br10Transmission electron microscopy images of; (c) 10% -WO3/Bi24O31Br10Transmission electron microscopy images of; (d) 10% -WO3/Bi24O31Br10High resolution electron microscopy images of; WO can be seen in FIG. 2c3The nano material is successfully loaded on Bi24O31Br10On the surface of the nanomaterial; WO is evident from the high resolution photograph of FIG. 2d3And Bi24O31Br10The lattice fringes of (2).
FIG. 3 shows different WO3Time-degradation efficiency relation graph of TC solution photocatalytic degradation of composite material with content, and prepared WO3/Bi24O31Br10The composite material has excellent photocatalytic activity, especially 10% -WO3/Bi24O31Br10The degradation efficiency of the sample on the TC solution after 60min of photocatalytic reaction reaches 80 percent.
Detailed Description
Example 1 Bi24O31Br10Preparation of
Weighing 0.97g of bismuth nitrate pentahydrate in a beaker, adding 10mL of ethylene glycol, and carrying out ultrasonic treatment and stirring for 30min to fully dissolve the bismuth nitrate pentahydrate; weighing 0.196g of ammonium bromide in another beaker, adding 25mL of deionized water, and stirring for 20min to dissolve; mixing the two solutions, and stirring for 20min to obtain white suspension; then adding 1.2mL of ethanolamine, and continuing stirring for 20 min; then transferring the obtained suspension into a 50mL reaction kettle with a polytetrafluoroethylene lining, and putting the reaction kettle into an oven to react for 12 hours at 160 ℃; naturally cooling to room temperature, centrifuging to obtain solid, washing with deionized water and anhydrous ethanol for 3 times, centrifuging, and drying at 60 deg.C. Taking out, grinding to powder by grinding bowl for standby.
Example 2 WO3Preparation of
Weighing 0.5g of sodium tungstate dihydrate and 0.3g of citric acid monohydrate in a beaker, adding 30mL of deionized water, stirring for 20min until the sodium tungstate dihydrate and the citric acid monohydrate are completely dissolved, and dropwise adding 6mol L of the deionized water-1Adjusting pH of the solution to 1 with hydrochloric acid solution, stirring for 1 hr to obtain yellow suspension, and mixing the obtained suspensionTransferring the mixture into a 50mL reaction kettle, and putting the reaction kettle into an oven for hydrothermal reaction at 120 ℃ for 12 hours; after naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3 times respectively, centrifugally separating, and drying at 60 ℃. Taking out, grinding to powder by a grinding bowl, transferring into a semi-closed crucible, and transferring into a temperature programmed tube furnace for calcining for 2h at 500 ℃.
Example 35% -WO3/Bi24O31Br10Preparation of composite materials
0.0053g of WO is weighed3And 0.1g Bi24O31Br10Dissolving the powder in 20mL and 60mL of deionized water respectively, and then carrying out ultrasonic treatment and stirring in an ultrasonic cleaning machine for 30min to uniformly disperse the powder respectively; then adding WO3Suspension 2 and Bi24O31Br10Mixing the suspension 1, stirring for 12h, finally transferring the obtained suspension 3 into a 100mL reaction kettle, and putting the reaction kettle into an oven for hydrothermal reaction at 160 ℃ for 12 h; after naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3 times respectively, centrifugally separating, and drying at 60 ℃.
Example 410% -WO3/Bi24O31Br10Preparation of composite materials
Weighing 0.0111g of WO3And 0.1g Bi24O31Br10Dissolving the powder in 20mL and 60mL of deionized water respectively, and then carrying out ultrasonic treatment and stirring in an ultrasonic cleaning machine for 30min to uniformly disperse the powder respectively; then adding WO3Suspension 2 and Bi24O31Br10Mixing the suspension 1, stirring for 12h, finally transferring the obtained suspension 3 into a 100mL reaction kettle, and putting the reaction kettle into an oven for hydrothermal reaction at 160 ℃ for 12 h; after naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3 times respectively, centrifugally separating, and drying at 60 ℃.
Example 520% -WO3/Bi24O31Br10Preparation of composite materials
0.025g of WO was weighed3And 0.1g Bi24O31Br10Dissolving the powder in 20mL and 60mL of deionized water respectively, and ultrasonically stirring in an ultrasonic cleaning machine for 30minSo that the mixture is dispersed uniformly; then adding WO3Suspension 2 and Bi24O31Br10Mixing the suspension 1, stirring for 12h, finally transferring the obtained suspension 3 into a 100mL reaction kettle, and putting the reaction kettle into an oven for hydrothermal reaction at 160 ℃ for 12 h; after naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3 times respectively, centrifugally separating, and drying at 60 ℃.
Example 630% -WO3/Bi24O31Br10Preparation of composite materials
Weighing 0.0429g WO3And 0.1g Bi24O31Br10Dissolving the powder in 20mL and 60mL of deionized water respectively, and then carrying out ultrasonic treatment and stirring in an ultrasonic cleaning machine for 30min to uniformly disperse the powder respectively; then adding WO3Suspension 2 and Bi24O31Br10Mixing the suspension 1, stirring for 12h, finally transferring the obtained suspension 3 into a 100mL reaction kettle, and putting the reaction kettle into an oven for hydrothermal reaction at 160 ℃ for 12 h; after naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3 times respectively, centrifugally separating, and drying at 60 ℃.
Example 7WO3/Bi24O31Br10Photocatalytic activity test of composite material
(1) Preparing a tetracycline hydrochloride (TC) solution with the concentration of 35mg/L, and placing the prepared solution in a dark place.
(2) Weighing 0.04g of each sample, placing the sample in a photocatalytic reactor, adding 40mL of the target degradation liquid prepared in the step (1), stirring the sample material by magnetic force for 60min, turning on a circulating water source and a light source after the sample material is uniformly dispersed, and carrying out a photocatalytic degradation experiment.
(3) Absorbing the photocatalytic degradation liquid in a reactor of 3-5mL every 10min, and centrifuging the photocatalytic degradation liquid for measuring the ultraviolet-visible absorbance.
(4) WO prepared as can be seen in FIG. 33/Bi24O31Br10The composite material has excellent photocatalytic activity, especially 10% -WO3/Bi24O31Br10The degradation efficiency of the composite material to the TC solution reaches 80 percent after 60min of photocatalytic reaction.
Claims (5)
1. The preparation method of the tungsten oxide/bismuth oxybromide composite material is characterized by comprising the following steps of: weighing a certain amount of Bi24O31Br10Adding a certain amount of deionized water into the powder, and performing ultrasonic stirring to uniformly disperse the deionized water to obtain a suspension 1; then weighing a certain amount of WO3Adding a certain amount of deionized water into the powder, and performing ultrasonic stirring to uniformly disperse the deionized water to obtain a suspension 2; then mixing the two suspensions, and stirring for 8-12h to obtain a suspension 3; then transferring the obtained suspension 3 into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a drying oven, and carrying out hydrothermal reaction; naturally cooling to room temperature, centrifuging to obtain yellow solid precipitate, washing, oven drying, taking out, grinding into powder with mortar to obtain WO3/Bi24O31Br10And (3) sampling.
2. The method for preparing the tungsten oxide/bismuth oxybromide composite material as claimed in claim 1, wherein the hydrothermal reaction temperature is 140-180 ℃ and the reaction time is 8-15 h.
3. The method of claim 1, wherein the tungsten oxide/bismuth oxybromide composite material comprises WO3The composite mass ratio of (A) to (B) is 5-30%.
4. The method of claim 3, wherein the tungsten oxide/bismuth oxybromide composite material comprises WO3The composite mass ratio of (2) is 10%.
5. Use of a tungsten oxide/bismuth oxybromide composite material prepared according to the method of claim 1 in the treatment of antibiotic wastewater.
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