CN110813306A - Zinc ferrite/bismuth tungstate composite catalyst, preparation method thereof and application thereof in waste gas treatment - Google Patents
Zinc ferrite/bismuth tungstate composite catalyst, preparation method thereof and application thereof in waste gas treatment Download PDFInfo
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- CN110813306A CN110813306A CN201911090474.9A CN201911090474A CN110813306A CN 110813306 A CN110813306 A CN 110813306A CN 201911090474 A CN201911090474 A CN 201911090474A CN 110813306 A CN110813306 A CN 110813306A
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- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 74
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 33
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 33
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002912 waste gas Substances 0.000 title abstract description 23
- 239000002121 nanofiber Substances 0.000 claims abstract description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 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 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 claims abstract description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 24
- 150000001621 bismuth Chemical class 0.000 claims description 13
- 150000003657 tungsten Chemical class 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000002114 nanocomposite Substances 0.000 abstract description 10
- 235000019441 ethanol Nutrition 0.000 abstract description 9
- 239000011941 photocatalyst Substances 0.000 abstract description 7
- 239000002135 nanosheet Substances 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000004083 survival effect Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
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- 239000004065 semiconductor Substances 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
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- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
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Abstract
The invention discloses a zinc ferrite/bismuth tungstate composite catalyst, a preparation method thereof and application thereof in waste gas treatment; with zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O) polyvinylpyrrolidone (PVP, K90) as raw material, N-Dimethylformamide (DMF) as solvent, electrostatic spinning and high-temperature calcining to prepare zinc ferrite (ZnF)e2O4) A nanofiber; with bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) and sodium tungstate dihydrate (Na)2WO6·2H2O) is a bismuth source and a tungsten source, and is dissolved in a mixed solvent of absolute ethyl alcohol (Ethanol) and Ethylene glycol (Ethylene glycol), and ZnFe is added2O4Adding the nano-fiber into the mixed solution, and preparing Bi through heating reaction2WO6The nanosheet grows on ZnFe2O4Nanofibers to obtain ZnFe2O4/Bi2WO6The nano composite material is a zinc ferrite/bismuth tungstate composite catalyst. ZnFe of the invention2O4/Bi2WO6The nano composite photocatalyst promotes Bi2WO6And ZnFe2O4The separation efficiency of the photo-generated carriers in the two materials effectively prolongs the survival life of the photo-generated charges and promotes the photocatalytic activity of the photo-generated charges.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to zinc ferrite/bismuth tungstate (ZnFe)2O4/Bi2WO6) A preparation method of the composite catalyst and application of the composite catalyst to the aspect of waste gas treatment.
Background
With the rapid development of social economy and industrialization, the pollution of industrial exhaust gas is increasingly serious, and great harm is brought to human beings, animals and plants. In addition, the exhaust gas causes environmental pollution such as acid rain, acid mist and photochemical smog. Therefore, the search for a cheap, efficient and energy-saving method for degrading and treating the waste gas has become a hot problem of environmental research. At present, the semiconductor photocatalysis technology has the advantages of no toxicity, high degradation efficiency, strong oxidation-reduction capability and the like, and is considered to be one of the most economic and effective methods for treating waste gas pollution. Among the many photocatalysts currently available, Bi2WO6Is an oxide semiconductor photocatalyst which has been widely studied, however, Bi2WO6Also have their own deficiencies such as the easy and rapid recombination of photogenerated electrons and holes upon illumination. Therefore, it is necessary to develop a new method for Bi2WO6Different modification modes are carried out, so that the photocatalytic activity is further improved.
Disclosure of Invention
The invention aims to provide a nano composite material ZnFe capable of responding to visible light2O4/Bi2WO6And a method for preparing the same andvisible light photocatalytic degradation of exhaust gas. Adding Bi2WO6The nanosheet photocatalyst is modified to ZnFe through solvothermal mode2O4On the nano-fiber to obtain ZnFe2O4/Bi2WO6The nano composite material is used for carrying out photocatalytic degradation on the waste gas so as to effectively treat the waste gas.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
the preparation method of the zinc ferrite/bismuth tungstate composite catalyst comprises the following steps of mixing ZnFe2O4Adding the nano-fiber into a solution containing bismuth salt and tungsten salt, and heating for reaction to obtain the zinc ferrite/bismuth tungstate composite catalyst.
The invention also discloses a method for treating the waste gas by photocatalysis, which comprises the following steps: ZnFe is mixed with water2O4Adding the nano-fiber into a solution containing bismuth salt and tungsten salt, and heating for reaction to obtain a zinc ferrite/bismuth tungstate composite catalyst; then the gas containing the waste gas passes through a zinc ferrite/bismuth tungstate composite catalyst to be irradiated by light, so as to realize the photocatalytic treatment of the waste gas.
In the invention, a solution containing zinc salt and iron salt is used as a spinning solution, and ZnFe is prepared by spinning and calcining2O4And (3) nano fibers. Preferably, the spinning solution consists of zinc salt, iron salt, an adhesive and a solvent; preferably, the spinning is electrospinning.
In the technical scheme, the using amount ratio of the zinc salt, the ferric salt and the adhesive is (0.5-5) mmol, (1-5) mmol and (1-10) g; the voltage of electrostatic spinning is 10-20 kV, and the injection speed is 0.15-0.25 mm/min; the calcining temperature is 500-800 ℃, and the time is 1-3 h.
In the technical scheme, the mass ratio of the bismuth salt to the tungsten salt is (100-500) to (10-100); the heating reaction temperature is 30-200 ℃, and the time is 12-48 h.
In the technical scheme, bismuth salt, tungsten salt and ZnFe2O4The mass ratio of the nano fibers is 6: 2: 0.6-1.5.
In the invention, zinc salt is zinc nitrate hexahydrate, ferric salt is ferric nitrate nonahydrate, adhesive is polyvinylpyrrolidone, and solvent is N, N-dimethylformamide; the bismuth salt is bismuth nitrate pentahydrate, and the tungsten salt is sodium tungstate dihydrate; in the solution containing bismuth salt and tungsten salt, the solvent is a mixed solvent of absolute ethyl alcohol (Ethanol) and Ethylene glycol (Ethylene glycol).
The preparation method of the zinc ferrite/bismuth tungstate composite catalyst comprises the following steps:
(1) with zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O) polyvinylpyrrolidone (PVP, K90) as raw material, N-Dimethylformamide (DMF) as solvent, electrostatic spinning and high-temperature calcining to prepare zinc ferrite (ZnFe)2O4) A nanofiber;
(2) with bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) and sodium tungstate dihydrate (Na)2WO6·2H2O) is a bismuth source and a tungsten source, and is dissolved in a mixed solvent of absolute ethyl alcohol (Ethanol) and Ethylene glycol (Ethylene glycol), and ZnFe is added2O4Adding the nano-fiber into the mixed solution, and preparing Bi through heating reaction2WO6The nanosheet grows on ZnFe2O4Nanofibers to obtain ZnFe2O4/Bi2WO6The nano composite material is a zinc ferrite/bismuth tungstate composite catalyst.
The invention discloses a method for treating waste gas by photocatalysis, which comprises the following steps:
(1) with zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O) polyvinylpyrrolidone (PVP, K90) as raw material, N-Dimethylformamide (DMF) as solvent, electrostatic spinning and high-temperature calcining to prepare zinc ferrite (ZnFe)2O4) A nanofiber;
(2) with bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) and sodium tungstate dihydrate (Na)2WO6·2H2O) is a bismuth source and a tungsten source, and is dissolved in a mixed solvent of absolute ethyl alcohol (Ethanol) and Ethylene glycol (Ethylene glycol), and ZnFe is added2O4Adding the nano-fiber into the mixed solution, and preparing Bi through heating reaction2WO6The nanosheet grows on ZnFe2O4Nanofibers to obtain ZnFe2O4/Bi2WO6The nano composite material is a zinc ferrite/bismuth tungstate composite catalyst;
(3) and (3) allowing the gas containing the waste gas to flow through the zinc ferrite/bismuth tungstate composite catalyst, and illuminating to realize the photocatalytic treatment of the waste gas.
The invention also discloses the application of the zinc ferrite/bismuth tungstate composite catalyst in waste gas treatment.
In the invention, the waste gas is nitric oxide, and the light irradiation is visible light irradiation.
The visible light responding nano composite material ZnFe of the invention2O4/Bi2WO6The preparation method of (a) can be carried out as follows:
1.ZnFe2O4preparation of nanofibers
First, Zn (NO) is added3)2·6H2O and Fe (NO)3)3·9H2O is dissolved in DMF solution. After stirring at room temperature for several hours, PVP was added to the solution and the mixture was continuously magnetically stirred for several hours to give a reddish-brown homogeneous precursor solution. The precursor solution was then transferred to a plastic syringe fitted with a steel needle for electrospinning. Finally, calcining the obtained nano-fiber in the air to obtain ZnFe2O4And (3) nano fibers.
2. ZnFe2O4/Bi2WO6Preparation of composite materials
First, bismuth nitrate pentahydrate and sodium tungstate dihydrate were ultrasonically dissolved in ethylene glycol. Then, ethanol was slowly added to the mixed solvent. Then preparing ZnFe2O4The nano-fiber is added and mixed evenly under the stirring condition. Finally transferring the obtained solution into a reaction kettle for heating reaction, and centrifugally washing a solid productObtaining ZnFe2O4/Bi2WO6A composite material.
3. Photocatalytic degradation of exhaust gas
The operation of photocatalytic degradation of heavy metal wastewater is specifically as follows, ZnFe is researched under the same concentration2O4、Bi2WO6And a series of ZnFe2O4/Bi2WO6(100 mg) degradation effect on exhaust gas.
The scheme has the advantages that:
1. the invention adopts easy-to-operate electrostatic spinning and solvothermal method to prepare ZnFe2O4/Bi2WO6The composite photocatalyst has simple preparation process and low cost of raw materials, is beneficial to reducing the preparation cost and is easy to realize large-scale production.
2. ZnFe of the invention2O4/Bi2WO6The nano composite photocatalyst promotes Bi2WO6And ZnFe2O4The separation efficiency of the photo-generated carriers in the two materials effectively prolongs the survival life of the photo-generated charges and promotes the photocatalytic activity of the photo-generated charges.
3. ZnFe obtained by the invention2O4/Bi2WO6The nano composite material can improve the absorption and utilization of visible light and can effectively carry out photocatalytic degradation on waste gas.
Drawings
FIG. 1 is ZnFe2O4Scanning Electron Micrographs (SEM) of nanofibers;
FIG. 2 is ZnFe2O4Transmission Electron Microscopy (TEM) of nanofibers;
FIG. 3 is ZnFe2O4/Bi2WO6Scanning Electron Micrographs (SEM) of the composite;
FIG. 4 shows flower-like Bi2WO6Scanning Electron Micrographs (SEM) of the material;
FIG. 5 is ZnFe2O4、Bi2WO6And ZnFe2O4/Bi2WO6A catalytic effect graph of the complex;
FIG. 6 is ZnFe2O4/Bi2WO6Cyclic degradation profile of composite material.
Detailed Description
The preparation method of the zinc ferrite/bismuth tungstate composite catalyst comprises the following steps of mixing ZnFe2O4Adding the nano-fiber into a solution containing bismuth salt and tungsten salt, and heating for reaction to obtain the zinc ferrite/bismuth tungstate composite catalyst.
The present invention will be further described with reference to the following examples.
Example one
ZnFe2O4Preparing the nano-fibers: first, 1 mmol of Zn (NO)3)2·6H2O and 2 mmol of Fe (NO)3)3·9H2Dissolving O in 10 mL of DMF solution, stirring at room temperature for 1 hour, adding 2 g of PVP, and continuously magnetically stirring for 12 hours to obtain a brownish red uniform precursor solution which is spinning solution; then, the spinning solution was transferred into a 5 mL plastic syringe equipped with a steel needle having a diameter of 0.5 mm to carry out electrostatic spinning (voltage: 15 kV, injection rate: 0.2 mm min)-1) Obtaining the nano fiber; finally, the obtained nano-fiber is calcined in the air at 600 ℃ for 2 hours, and the heating rate is 1 ℃ for min-1(room temperature to 600 ℃ C.) to obtain ZnFe2O4And (3) nano fibers.
In order to observe the morphology of the material, a scanning electron microscope and a transmission electron microscope are used to characterize the product prepared in this example, and fig. 1 shows ZnFe prepared in this example2O4Scanning electron micrographs of nanofibers, (a) and (b) represent the ZnFe prepared in this example2O4And (3) nano fibers. FIG. 2 shows ZnFe prepared in this example2O4Transmission Electron microscopy of nanofibers, (a) and (b) shows the ZnFe prepared in this example2O4And (3) nano fibers.
Example two
ZnFe2O4/Bi2WO6Preparing a composite material: first, 240 mg of Bi (NO)3)3·5H2O and 80 mg of Na2MoO4·2H2Dissolving O in 5 mL of ethylene glycol by ultrasonic; then, 30 mL of ethanol is slowly added into the mixed solvent; then adding the prepared ZnFe under the stirring condition2O4Mixing the nano-fibers (example one), transferring the mixture into a reaction kettle, heating the mixture to 160 ℃ and reacting the mixture for 24 hours; then naturally cooling to room temperature, repeatedly washing the obtained solid product with deionized water and ethanol for 3 times, and then drying in a 60 ℃ oven to obtain ZnFe2O4/Bi2WO6(simply labeled as ZFO/BWO) composite material, which is a zinc ferrite/bismuth tungstate composite catalyst. According to the addition of ZnFe2O4The quality is different, so that ZnFe can be obtained2O4ZnFe with different contents2O4/Bi2WO6The composite material comprises 15% ZFO/BWO, 20% ZFO/BWO and 30% ZFO/BWO, wherein 20% ZFO/BWO represents ZnFe2O4The addition of the nano-fiber is 40 mg, and the pure flower-shaped Bi2WO6The material yield is 160 mg, ZnFe2O4In ZnFe2O4/Bi2WO6The mass fraction in the composite material is 20%.
In order to observe the morphology of the composite material, a scanning electron microscope is used to characterize the product prepared in this example, and fig. 3 shows the visible light response ZnFe prepared in this example2O4/Bi2WO6Scanning electron micrographs of the composite catalyst, (a) and (b) represent ZnFe prepared in this example2O4/Bi2WO6And (3) compounding a catalyst.
EXAMPLE III
Flower-like Bi2WO6Preparation of the material: first, 240 mg of Bi (NO)3)3·5H2O and 80 mg of Na2MoO4·2H2O was dissolved in 5 mL of ethylene glycol with sonication. Then, 30 mL of ethanol was slowly added to the above mixed solvent. Finally, transferring the obtained solution into a reaction kettle, heating to 160 ℃ and reacting for 24 hours. When the belt system is naturally cooled to room temperature, the obtained solid product is sequentially deionizedRepeatedly washing with water and ethanol for 3 times, and oven drying at 60 deg.C to obtain flower-like Bi2WO6Material, yield 160 mg.
In order to observe the morphology of the material, the product prepared in this example was characterized by scanning electron microscopy, and fig. 4 shows the flower-like Bi prepared in this example2WO6Scanning Electron micrograph of catalyst, (a) shows flower-like Bi prepared in this example2WO6A catalyst.
Based on the above, it can be seen from FIGS. 1 (a-b) and 2 (a-b) that ZnFe is produced2O4The nanofiber is in a one-dimensional fibrous shape, the diameter of the nanofiber is 100-200 nm, and the length of the nanofiber is several micrometers; bi is found in FIGS. 3 (a) and (b)2WO6The nano-sheet is uniformly loaded on ZnFe2O4On the nano-fiber; FIG. 4 (a) shows Bi in the form of flower ball2WO6Is composed of a large amount of Bi2WO6The nano sheets are combined.
Example four
The method for treating the waste gas through photocatalysis comprises the following specific steps: 100mg of the catalyst to be detected is flatly laid on a wood board in a closed cylindrical detection chamber with the volume of 2.26L, and a 300W xenon lamp is vertically placed above the wood board. The gas flow concentration was controlled to 600 ppb by mixing the air in the compressed bottle with nitric oxide and was passed through the reaction chamber at a flow rate of 1.2L/min. When the catalyst reached the adsorption-desorption equilibrium (about 0.5 h), the xenon lamp was turned on and the catalyst was in the NO statexThe photocatalytic measurement was started on the analyzer. The measurement time is 30 min, the sampling time interval is 1 min, and 30 groups of data are obtained in total.
FIG. 5 is ZnFe2O4、Bi2WO6And ZnFe2O4/Bi2WO6Effect chart of treating exhaust gas, and ZnFe is found by effect chart 52O4/Bi2WO6The catalytic efficiency of the catalyst to waste gas is obviously better than that of ZnFe2O4(25%) and Bi2WO6(29%). And by regulating the ZnFe addition2O4The content of (a) can achieve a degradation effect of up to 53%. Description of ZnFe2O4/Bi2WO6The compound has higher catalytic degradation activity on nitric oxide.
FIG. 6 is ZnFe2O4/Bi2WO6The cycle effect of (20% ZFO/BWO) on the waste gas degradation is shown in the figure, and the degradation effect is only reduced by 6% after 5 cycles, and the good degradation effect is still shown. Therefore, the catalyst can be repeatedly used and has good stability.
The composite catalyst in the prior art is adopted for carrying out parallel test comparison: CN108273515A embodiment I discloses a zinc ferrite doped bismuth tungstate photocatalyst, which basically achieves degradation balance after 45 minutes by adopting the same photocatalysis waste gas treatment test method, and the final degradation efficiency is 33% in 60 minutes; the appearance of the composite material has great influence on the performance.
Through the analysis, the ZnFe is successfully prepared by electrostatic spinning and solvothermal method which are simple and easy to operate2O4/Bi2WO6A nanocomposite material. The composite material disclosed by the invention has stronger visible light catalytic degradation on waste gas. In addition, the invention has the advantages of simple manufacturing process, economy, environmental protection and the like, and the preparation cost is low, so the invention has good application prospect in waste gas treatment.
Claims (10)
1. The zinc ferrite/bismuth tungstate composite catalyst is characterized in that the preparation method of the zinc ferrite/bismuth tungstate composite catalyst comprises the following steps of mixing ZnFe2O4Adding the nano-fiber into a solution containing bismuth salt and tungsten salt, and heating for reaction to obtain the zinc ferrite/bismuth tungstate composite catalyst.
2. The zinc ferrite/bismuth tungstate composite catalyst as claimed in claim 1, wherein the ZnFe is prepared by spinning and calcining a solution containing zinc salt and iron salt as a spinning solution2O4And (3) nano fibers.
3. The zinc ferrite/bismuth tungstate composite catalyst as claimed in claim 2, wherein the spinning solution is composed of zinc salt, iron salt, binder and solvent; the spinning is electrostatic spinning; the calcining temperature is 500-800 ℃, and the time is 1-3 h.
4. The zinc ferrite/bismuth tungstate composite catalyst as claimed in claim 2, wherein the ratio of the zinc salt to the iron salt to the binder is (0.5-5) mmol to (1-10) g; the voltage of electrostatic spinning is 10-20 kV, and the injection speed is 0.15-0.25 mm/min; the zinc salt is zinc nitrate hexahydrate, the ferric salt is ferric nitrate nonahydrate, and the adhesive is polyvinylpyrrolidone.
5. The zinc ferrite/bismuth tungstate composite catalyst as claimed in claim 1, wherein the mass ratio of the bismuth salt to the tungsten salt is (100-500) to (10-100); the heating reaction temperature is 30-200 ℃, and the time is 12-48 h.
6. The zinc ferrite/bismuth tungstate composite catalyst as claimed in claim 1, wherein the bismuth salt, the tungsten salt, and the ZnFe salt are used as the catalyst2O4The mass ratio of the nano fibers is 6: 2: 0.6-1.5.
7. The zinc ferrite/bismuth tungstate composite catalyst as claimed in claim 1, wherein the bismuth salt is bismuth nitrate pentahydrate, and the tungsten salt is sodium tungstate dihydrate; in the solution containing bismuth salt and tungsten salt, the solvent is a mixed solvent of absolute ethyl alcohol and glycol.
8. The use of the zinc ferrite/bismuth tungstate composite catalyst as set forth in claim 1 for the treatment of exhaust gas.
9. Use according to claim 8, wherein the exhaust gas is a nitride.
10. The preparation method of the zinc ferrite/bismuth tungstate composite catalyst is characterized by comprising the following steps of mixing ZnFe2O4The nano-fiber is added with a solution containing bismuth salt and tungsten saltIn the solution, heating and reacting to obtain the zinc ferrite/bismuth tungstate composite catalyst.
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