CN116273168B - Preparation method and application of zinc tungstate/zinc benzoate photocatalytic material - Google Patents
Preparation method and application of zinc tungstate/zinc benzoate photocatalytic material Download PDFInfo
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- CN116273168B CN116273168B CN202310192491.3A CN202310192491A CN116273168B CN 116273168 B CN116273168 B CN 116273168B CN 202310192491 A CN202310192491 A CN 202310192491A CN 116273168 B CN116273168 B CN 116273168B
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 94
- 239000011701 zinc Substances 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 66
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 33
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims abstract description 8
- 235000010234 sodium benzoate Nutrition 0.000 claims abstract description 8
- 239000004299 sodium benzoate Substances 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000010757 Reduction Activity Effects 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000011651 chromium Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 18
- 238000006722 reduction reaction Methods 0.000 description 16
- 239000002131 composite material Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- WZOZCAZYAWIWQO-UHFFFAOYSA-N [Ni].[Ni]=O Chemical compound [Ni].[Ni]=O WZOZCAZYAWIWQO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 230000001052 transient effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- 241001083492 Trapa Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 231100000590 oncogenic Toxicity 0.000 description 1
- 230000002246 oncogenic effect Effects 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention discloses a preparation method of a zinc tungstate/zinc benzoate photocatalytic material, which comprises the following steps: (1) Dissolving sodium benzoate and sodium tungstate dihydrate in deionized water, and dropwise adding zinc acetate dihydrate solution under stirring to obtain a white suspension; (2) Transferring the suspension into a sealed polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction to obtain the zinc tungstate/zinc benzoate photocatalytic material. The invention also discloses application of the zinc tungstate/zinc benzoate photocatalytic material prepared by the preparation method in photocatalytic reduction of hexavalent chromium. The zinc tungstate/zinc benzoate photocatalytic material provided by the invention has excellent photocatalytic hexavalent chromium reduction activity and cycle stability, and has a wide practical application prospect in the aspect of treating harmful heavy metal ion wastewater.
Description
Technical Field
The invention relates to the technical field of preparation of environmental photocatalytic materials, in particular to a preparation method and application of a zinc tungstate/zinc benzoate photocatalytic material.
Background
Currently, water resource shortage and pollution problems become one of the key factors restricting sustainable healthy development of human society. Soluble heavy metal ions in inorganic pollutants are a water pollution source which is common and has great harm at present, wherein hexavalent chromium Cr (VI) is commonly existing in industrial wastewater such as mining, leather, aviation, printing and dyeing, steelmaking and the like. Cr (VI) has oncogenic and teratogenic effects on the ecosystem food chain and is considered one of the most toxic pollutants. Cr (VI), if not properly treated, would seriously threaten our life health and sustainable development of the ecosystem. The water body polluted by heavy metal ions is reprocessed, harmful heavy metal ion components in the polluted water body are removed, so that the polluted water body becomes clean and safe water body, and the water resource recycling has important practical significance.
The photocatalysis method can reduce Cr (VI) with strong mobility and high toxicity into Cr (III) with easy sedimentation and low toxicity, has the advantages of cleanness, environmental protection, high operation feasibility, availability of solar energy and the like, and is one of novel chromium-containing wastewater treatment technologies with great research value and application prospect. The Chinese patent document with the application number of CN202111410160.X discloses a preparation method of a composite material of red phosphorus loaded with nitrogen carbide nanotubes and a method for treating Cr (VI) -containing wastewater, wherein melamine and urea are used as raw materials, and CN nanotubes are prepared through a calcination process; grinding and mixing the obtained CN nano tube and pretreated red phosphorus, sealing the tube and calcining under vacuum condition to prepare the red phosphorus loaded nitrogen carbide nano tube composite material. The composite material prepared by the method can show better Cr (VI) photocatalytic reduction activity by utilizing sunlight to a greater extent. In addition, chinese patent application No. CN201911299894.8 discloses a method for treating hexavalent chromium-containing wastewater by photocatalytic reduction of nickel oxide-nickel cobaltate-black titania composite, and the method uses a complex preparation method of calcination-hydrothermal-calcination steps to obtain a nickel oxide-nickel cobaltate-black titania composite photocatalytic material applicable to the treatment of hexavalent chromium-containing wastewater.
The photocatalytic material disclosed in the above patent document shows a certain hexavalent chromium photocatalytic reduction activity, but has the defects of low migration efficiency of a photocatalysed carrier of the photocatalytic material, poor photocatalytic cycle stability and the like, and obviously has the defects of complex preparation process, high energy consumption, high production cost and the like. The above problems greatly limit the practical application of these photocatalytic materials in the treatment of hexavalent chromium-containing wastewater by photocatalytic reduction. Therefore, development of a simple and economical method for preparing novel high-efficiency photocatalytic materials is needed to promote practical application of the photocatalytic technology in treatment of harmful heavy metal ion wastewater.
Disclosure of Invention
The invention aims to provide a zinc tungstate/zinc benzoate photocatalytic material and a preparation method thereof, and the material is applied to photocatalytic reduction treatment of hexavalent chromium-containing wastewater.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a zinc tungstate/zinc benzoate photocatalytic material comprises the following steps:
(1) Dissolving sodium benzoate and sodium tungstate dihydrate in deionized water to prepare a component A, and adding zinc acetate dihydrate solution into the component A under the stirring condition to obtain a white suspension;
(2) And (3) placing the white suspension in a polytetrafluoroethylene lining hydrothermal kettle, and performing hydrothermal reaction to obtain the zinc tungstate/zinc benzoate photocatalytic material.
The preparation principle of the zinc tungstate/zinc benzoate photocatalytic material provided by the invention is as follows: in a multi-ion reaction system, zinc ions react with tungstate ions to generate zinc tungstate nano-particles, and under a hydrothermal condition, the zinc tungstate particles self-assemble to form a zinc tungstate cubic block. And meanwhile, the generated zinc benzoate is anchored on the surface of the zinc tungstate cube, and finally the zinc tungstate/zinc benzoate composite photocatalytic material is obtained. The complexing energy of the zinc benzoate can provide a large number of adsorption active sites for the target removed Cr (VI); the generated zinc tungstate/zinc benzoate heterojunction can enhance the light absorption capacity and accelerate the separation and migration efficiency of photo-generated electrons, thereby obviously improving the photocatalytic Cr (VI) reduction performance.
According to the invention, the zinc tungstate/zinc benzoate photocatalytic material is obtained through a simple one-step hydrothermal reaction, and the organic/inorganic composite heterojunction is constructed, so that the visible light absorption capacity is enhanced, the separation and migration efficiency of photogenerated electrons are accelerated, and the efficient photocatalytic reduction of Cr (VI) in water environment is realized.
The sodium benzoate, sodium tungstate dihydrate and zinc acetate dihydrate are all analytical grades and require no further purification treatment.
Further, the zinc tungstate/zinc benzoate photocatalytic material is formed by in-situ compounding of zinc tungstate and zinc benzoate. Wherein the mole fraction of the zinc benzoate is 1-100%.
Further, the dosage of the zinc acetate dihydrate is 30-40 mg/mL; the dosage of the sodium tungstate dihydrate is 10-40 mg/mL; the dosage of the sodium benzoate is 10-40 mg/mL.
Further, the hydrothermal temperature is 160-200 ℃, and the reaction time is 32-40h.
Further, the zinc tungstate/zinc benzoate photocatalytic material can be used as a catalyst for photocatalytic reduction of hexavalent chromium heavy metal ions. The photocatalytic reduction performance of the photocatalytic material on hexavalent chromium is evaluated in an XPA photocatalytic reactor produced by Nanj xu river electric power plant, a 400W metal halogen lamp is selected as a light source, 30mg of the photocatalytic material and 50mL of potassium dichromate solution with the concentration of 20mg/L are placed in a quartz reaction tube, and the materials are stirred and dispersed for 1 hour in a dark environment before illumination, so that circulating cooling water is kept smooth in the whole experimental process. The potassium dichromate solution is sampled at certain intervals, and the change of absorbance is tested by a spectrophotometer, and the change of the concentration of the potassium dichromate solution is analyzed through the change of the absorption value of the optimal absorption wavelength of the potassium dichromate solution.
The zinc tungstate/zinc benzoate photocatalytic material obtained by the preparation method uses ZnWO 4 /Zn(Bro) 2 Representation, wherein Zn (Bro) 2 Nanoparticle anchoring dispersion in ZnWO 4 Surface of cubic block, loaded with Zn (Bro) 2 The nano particles can provide a large number of adsorption active sites for the target removed Cr (VI); znWO produced 4 /Zn(Bro) 2 Heterojunction can enhance light absorption capacity and accelerate separation and migration efficiency of photo-generated electrons, thus ZnWO 4 /Zn(Bro) 2 Exhibits excellent photocatalytic chromium removal activity.
The invention has the following positive effects:
(1) The zinc tungstate/zinc benzoate photocatalytic material provided by the invention is prepared by adopting a simple one-step hydrothermal method to perform in-situ Zn (Bro) 2 Nanoparticle anchoring dispersion in ZnWO 4 The surface of the cubic block develops a preparation method suitable for the organic/inorganic composite material, and is hopeful to be popularized to a series based on zinc ferrite, zinc vanadate and the likeAnd (3) column composite materials.
(2) The zinc tungstate/zinc benzoate photocatalytic material provided by the invention is loaded with Zn (Bro) 2 The nano particles can provide a large number of adsorption active sites for hexavalent chromium as a target remover; znWO produced 4 /Zn(Bro) 2 The heterojunction can enhance the visible light absorption capacity and accelerate the separation and migration efficiency of photo-generated electrons, thereby obviously improving the photocatalytic chromium removal performance.
(3) The zinc tungstate/zinc benzoate photocatalytic material provided by the invention is ZnWO 4 /Zn(Bro) 2 The composite photocatalytic material has excellent photocatalytic reduction activity on Cr (VI), the photocatalytic reduction efficiency on 20mg/L of Cr (VI) in 30min is about 96%, and the photocatalytic reduction efficiency on hexavalent chromium is still as high as 92% after five cycles. The zinc tungstate/zinc benzoate photocatalytic material provided by the invention has excellent photocatalytic chromium removal application potential.
Drawings
FIG. 1 shows ZnWO prepared in example 1, comparative example 1 and comparative example 2 4 /Zn(Bro) 2 、ZnWO 4 And Zn (Bro) 2 XRD spectrum of the photocatalytic material.
FIG. 2 shows ZnWO prepared in example 1 4 /Zn(Bro) 2 TEM photograph (a-C), STEM photograph (d) and EDS element imaging photograph of the composite photocatalytic material, (e) C, (f) Zn, (g) W, (h) O.
FIG. 3 shows ZnWO prepared in example 1, comparative example 1 and comparative example 2 4 /Zn(Bro) 2 、ZnWO 4 And Zn (Bro) 2 Ultraviolet-visible diffuse reflectance spectrum (a) and corresponding band gap diagram (b) of the photocatalytic material.
FIG. 4 shows ZnWO prepared in example 1, comparative example 1 and comparative example 2 4 /Zn(Bro) 2 、ZnWO 4 And Zn (Bro) 2 Transient photocurrent density map of photocatalytic material.
FIG. 5 shows ZnWO prepared in example 1, comparative example 1 and comparative example 2 4 /Zn(Bro) 2 、ZnWO 4 And Zn (Bro) 2 Photocatalytic material versus Cr (VI) reduction.
FIG. 6 shows the ZnWO obtained in example 1 4 /Zn(Bro) 2 Cyclic stability bar graph of photocatalytic reduction of Cr (VI) by composite photocatalytic material.
Detailed Description
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention.
Example 1
(1) 1.44g of sodium benzoate and 1.65g of sodium tungstate dihydrate are dissolved and dispersed in 50mL of deionized water to obtain solution A; 2.195g of zinc acetate dihydrate is dissolved in 25mL of deionized water to obtain a solution B, and the solution B is dropwise added to the solution A under the stirring condition to obtain a white uniform suspension;
(2) Placing the suspension in a polytetrafluoroethylene lining hydrothermal kettle to react for 32 hours at 180 ℃ to obtain zinc tungstate/zinc benzoate (ZnWO) 4 /Zn(Bro) 2 ) Photocatalytic material.
Comparative example 1
(1) 3.299g of sodium tungstate dihydrate is dissolved and dispersed in 50mL of deionized water to obtain a solution A; 2.195g of zinc acetate dihydrate is dissolved in 25mL of deionized water to obtain a solution B, and the solution B is dropwise added to the solution A under the stirring condition to obtain a white uniform suspension;
(2) Transferring the suspension into a sealed polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 180 ℃ for 36h, naturally cooling to room temperature, washing and drying to obtain a zinc tungstate photocatalytic material, namely ZnWO 4 。
Comparative example 2
(1) 2.882g of sodium benzoate was dissolved and dispersed in 50mL of deionized water to give solution A; 2.195g of zinc acetate dihydrate is dissolved in 25mL of deionized water to obtain a solution B, and the solution B is dropwise added to the solution A under the stirring condition to obtain a white uniform suspension;
(2) Transferring the suspension into a sealed polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 180 ℃ for 36h, naturally cooling to room temperature, washing and drying to obtain a zinc benzoate photocatalytic material, and marking as Zn (Bro) 2 。
Characterization of materials
FIG. 1 shows ZnWO prepared in example 1, comparative example 1 and comparative example 2 4 /Zn(Bro) 2 、ZnWO 4 And Zn (Bro) 2 XRD spectrum of the photocatalytic material. ZnWO (zinc-oxygen) preparation method 4 The photocatalytic material detects characteristic diffraction peaks at diffraction angles 2θ=18.9°,23.8 °,24.5 °,30.4 °,30.7 °,36.4 °,38.3 °,41.3 °,51.7 °,53.6 °,61.7 ° and 64.7 °, corresponding to monoclinic ZnWO, respectively 4 (100), (01-1), (110), (11-1), (111), (002), (200), (121), (130), (20-2), (11-3) and (13-2) crystal planes (JCPSDSNo. 96-210-1675). Zn (Bro) 2 The characteristic peak of the photocatalytic material is mainly distributed at a low diffraction angle of 40 degrees or less. ZnWO prepared in example 1 4 /Zn(Bro) 2 ZnWO is obviously detected by the photocatalytic material 4 And Zn (Bro) 2 Is shown to successfully prepare ZnWO by a simple one-step hydrothermal reaction 4 /Zn(Bro) 2 A composite material.
FIGS. 2 (a) and (b) show the preparation of ZnWO for example 1 4 /Zn(Bro) 2 TEM photographs of photocatalytic materials. It was found that the irregular nanoparticles were dispersed on the surface of the cubic block with sharp water chestnut. FIG. 2c is ZnWO 4 /Zn(Bro) 2 The HRTEM photo of the photocatalytic material can clearly see the lattice stripes of the cubic block, and the lattice spacing of 0.47nm corresponds to monoclinic ZnWO 4 The (100) crystal plane of (d). FIG. 2 (d-h) shows ZnWO 4 /Zn(Bro) 2 STEM photo and image graph of distribution of C, zn, W and O elements in the photocatalytic material, wherein the Zn and O elements are clearly imaged and uniformly distributed on the whole, and the W element is mainly distributed in the cubic block, further explaining that the composition of the cubic block is ZnWO 4 . In addition, a large number of C and O elements are distributed imagewise at the periphery of the cubic block, illustrating Zn (Bro) 2 Nanoparticle anchoring dispersion in ZnWO 4 The surface of the cubic block.
FIG. 3 shows ZnWO prepared in example 1, comparative example 1 and comparative example 2 4 /Zn(Bro) 2 、ZnWO 4 And Zn (Bro) 2 Ultraviolet-visible diffuse reflection spectrum of photocatalytic material, and the result shows that ZnWO 4 /Zn(Bro) 2 Photocatalytic materials are compared to pure ZnWO 4 And Zn (Bro) 2 The photocatalytic material has a stronger light absorbing capacity. According to the Tauc conversion,obtaining ZnWO 4 、Zn(Bro) 2 And ZnWO 4 /Zn(Bro) 2 Band gap (E) of photocatalytic material g ) 3.86eV, 4.25eV and 3.78eV, respectively (FIG. 3 b), indicating the introduction of Zn (Bro) 2 Contributing to the reduction of ZnWO 4 The band gap of the photocatalytic material improves the visible light response capability. This helps to increase its photocatalytic reduction activity towards Cr (VI).
FIG. 4 shows ZnWO prepared in example 1, comparative example 1 and comparative example 2 4 /Zn(Bro) 2 、ZnWO 4 And Zn (Bro) 2 Transient photocurrent density map of photocatalytic material. ZnWO under the same conditions 4 /Zn(Bro) 2 The photocurrent density of the photocatalytic material is obviously higher than that of ZnWO 4 And Zn (Bro) 2 Indicating ZnWO 4 /Zn(Bro) 2 The photocatalytic material has faster electron transfer efficiency and lower photo-generated electron hole recombination probability, which can effectively increase the activity of photo-generated electrons (active species playing a main role in photocatalytic chromium removal) in a reaction system, thereby improving the photocatalytic reduction efficiency of Cr (VI).
Performance testing
FIG. 5 shows ZnWO prepared in example 1, comparative example 1 and comparative example 2 4 /Zn(Bro) 2 、ZnWO 4 And Zn (Bro) 2 Photocatalytic material versus Cr (VI) reduction. As a result of the test, it was found that ZnWO 4 And Zn (Bro) 2 The photocatalytic material has no significant photocatalytic reduction activity for Cr (VI). ZnWO (zinc-oxygen) preparation method 4 /Zn(Bro) 2 The photocatalytic material has excellent photocatalytic reduction activity on Cr (VI), and ZnWO after 30min of illumination 4 /Zn(Bro) 2 The catalytic reduction rate of Cr (VI) is as high as 96%. FIG. 6 shows the ZnWO obtained in example 1 4 /Zn(Bro) 2 Cyclic stability bar graph of photocatalytic reduction of Cr (VI) by composite photocatalytic material. ZnWO (zinc-oxygen) preparation method 4 /Zn(Bro) 2 The photocatalytic reduction efficiency of the composite photocatalytic material on Cr (VI) after 5 times of cyclic catalysis is still up to 92%, which shows that ZnWO 4 /Zn(Bro) 2 The composite photocatalytic material has excellent photocatalytic cycle stability for reducing Cr (VI).
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (3)
1. The preparation method of the zinc tungstate/zinc benzoate photocatalytic material is characterized by comprising the following steps of:
(1) Dissolving sodium benzoate and sodium tungstate dihydrate in deionized water to obtain a solution A, adding zinc acetate dihydrate solution into the component A under stirring to obtain a white suspension, wherein the dosage of the sodium tungstate dihydrate is 10-40 mg/mL, the dosage of the zinc acetate dihydrate is 30-40 mg/m, and the dosage of the sodium benzoate is 10-40 mg/mL;
(2) And (3) placing the white suspension in a polytetrafluoroethylene lining hydrothermal kettle, and performing hydrothermal reaction to obtain the zinc tungstate/zinc benzoate photocatalytic material, wherein the hydrothermal temperature is 160-200 ℃ and the reaction time is 32-40h, and the zinc benzoate is anchored on the surface of a zinc tungstate cube.
2. The zinc tungstate/zinc benzoate photocatalytic material obtained by the preparation method according to claim 1.
3. Use of the zinc tungstate/zinc benzoate photocatalytic material according to claim 2 as a catalyst in photocatalytic reduction of hexavalent chromium reactions.
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| CN113559936A (en) * | 2021-07-30 | 2021-10-29 | 陕西科技大学 | Defective UiO-66 photocatalytic material and preparation method and application thereof |
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| Title |
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| Controllable construction of ZnWO4 nanostructure with enhanced performance for photosensitized Cr(VI) reduction;Hongbo He etal.;《 Applied Surface Science》;第490卷;460-468 * |
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