CN113234220A - Flower-shaped structure Fe for photodegradation of ciprofloxacin3O4/Bi2WO6Process for preparing catalyst - Google Patents
Flower-shaped structure Fe for photodegradation of ciprofloxacin3O4/Bi2WO6Process for preparing catalyst Download PDFInfo
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- CN113234220A CN113234220A CN202110544335.XA CN202110544335A CN113234220A CN 113234220 A CN113234220 A CN 113234220A CN 202110544335 A CN202110544335 A CN 202110544335A CN 113234220 A CN113234220 A CN 113234220A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000001782 photodegradation Methods 0.000 title abstract description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 145
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000000243 solution Substances 0.000 claims abstract description 55
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 53
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 53
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000001632 sodium acetate Substances 0.000 claims abstract description 11
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 claims abstract description 9
- 150000001621 bismuth Chemical class 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 125000004185 ester group Chemical group 0.000 claims abstract description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002505 iron Chemical class 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 229940106691 bisphenol a Drugs 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 49
- 230000015556 catabolic process Effects 0.000 abstract description 48
- 230000000694 effects Effects 0.000 abstract description 42
- 239000000203 mixture Substances 0.000 abstract description 32
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 238000005406 washing Methods 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000005286 illumination Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- GLCNFWQJPDOWAQ-UHFFFAOYSA-N 2-hydroxy-2-[4-[(2-methylpropan-2-yl)oxycarbonyl]phenyl]acetic acid Chemical compound CC(C)(C)OC(=O)C1=CC=C(C(O)C(O)=O)C=C1 GLCNFWQJPDOWAQ-UHFFFAOYSA-N 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 229940088710 antibiotic agent Drugs 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 150000002148 esters Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 239000013076 target substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 208000019206 urinary tract infection Diseases 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
- C08G65/3326—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic aromatic
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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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- B01J35/39—Photocatalytic properties
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- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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Abstract
The invention discloses flower-shaped structure Fe for photodegradation of ciprofloxacin3O4/Bi2WO6A method for preparing the catalyst; the preparation method comprises the following steps: mixing iron salt, sodium acetate and modified polyethylene glycol to form a mixed solution, transferring the mixed solution into a reaction kettle, heating for reaction, cooling, cleaning and drying to obtain Fe3O4A precursor; forming a suspension of a bismuth salt solution and a sodium tungstate solution, and adjusting the pH; mixing Fe3O4Ultrasonically dispersing the precursor, adding the precursor into the suspension, stirring,transferring the mixture into a reaction kettle, heating for reaction, cooling, cleaning and drying to obtain the catalyst. The modified polyethylene glycol contains phenyl and ester functional groups; the catalyst has a flower-like structure and a relatively good specific surface area, and has a high-efficiency visible light driven degradation effect on ciprofloxacin; meanwhile, the photocatalyst has better photocatalytic stability and better catalytic degradation effect on RhB.
Description
Technical Field
The invention belongs to the technical field of inorganic environment-friendly photocatalytic materials, and particularly relates to flower-shaped structure Fe for photodegradation of ciprofloxacin3O4/Bi2WO6A method for preparing the catalyst.
Background
In recent years, the problem of environmental pollution caused by antibiotics has attracted more and more attention. Compared with the traditional wastewater treatment technology, the semiconductor photocatalysis technology has the advantages of mild reaction conditions, high stability, low secondary pollution and the like, and is an extremely important way for relieving the problem of environmental pollution.
Ciprofloxacin is an artificially synthesized third-generation quinolone drug, is mainly used for treating various bacterial infections such as urinary tract infection, skin infection and the like, and is one of the most widely used quinolone antibiotics at present; most of them are not completely metabolized by humans and animals, and 30% to 90% of the intake is discharged as proto-drugs and metabolites out of the body and further flows to municipal sewage plants. The presence of these broad spectrum antibiotics in aqueous environments can have long term destructive effects on the ecosystem and induce bacterial resistance; damage to ecosystem: the antibiotics enter the water body environment, can inhibit growth and even kill a plurality of microorganisms which do not harm the ecological environment and human beings and animals originally, reduce species diversity and destroy the ecological balance of the original system.
In the prior art, for example, application publication No. CN 102125877A discloses a preparation method of a photocatalyst for selectively degrading ciprofloxacin; the preparation method comprises the following steps: hydrothermal synthesis of ZnS semiconductor material, ZnS surface modification, preparation of molecular imprinting polymer photocatalyst, and elution of template molecules in the imprinting polymer from the obtained solid powder substance. The photocatalytic degradation process of the prepared molecular imprinting polymer photocatalyst can effectively realize the purposes of selective recognition, adsorption and catalytic degradation of target pollutants, improves the efficiency of effective degradation of target substances, and has the advantage of strong selective treatment of antibiotic wastewater.
Disclosure of Invention
The invention aims to provide Fe with a flower-like structure3O4/Bi2WO6The catalyst has a better specific surface area, and has a certain absorption and degradation effect on the ciprofloxacin under the condition of no illumination; under the illumination condition, the ciprofloxacin degradation agent has a high-efficiency visible light driven degradation effect on ciprofloxacin; meanwhile, the photocatalyst has better photocatalytic stability and better catalytic degradation effect on RhB.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a modified polyethylene glycol containing phenyl and ester functional groups.
Preferably, the modified polyethylene glycol is 4- (carboxy-hydroxy-methyl) -benzoic acid tert-butyl ester modified polyethylene glycol.
The invention adopts 4- (carboxyl-hydroxyl-methyl) -tert-butyl benzoate containing phenyl and ester groups to modify polyethylene glycol, and the modified polyethylene glycol is used as a surfactant in the preparation process of a catalyst to obtain Fe with a flower-like structure3O4/Bi2WO6The composite catalyst has uniform grain size distribution and large specific surface area, and further has efficient visible light driven catalysis; the reason may be that the modified polyethylene glycol as a surfactant, which contains more active functional groups or better internal structure, is used for preparing Fe3O4In the case of precursors, Fe may be caused3O4Has better surface tension and excellent dispersibility, so that the material can be mixed with Bi2WO6Uniformly combined to form Fe with flower-shaped structure3O4/Bi2WO6A composite catalyst; the catalyst has better grain size and specific surface area, so that the catalyst can be used in the absence of lightThe catalyst also has degradation effect on ciprofloxacin, has efficient visible light driven catalytic degradation effect on ciprofloxacin under the condition of illumination, and has excellent photocatalytic stability, namely, the catalyst still has good catalytic degradation performance after being recycled for multiple times.
The invention also discloses a surfactant which comprises modified polyethylene glycol.
The invention also discloses the application of the surfactant in preparing the photocatalyst.
Preferably, the surfactant is used for preparing Fe with flower-like structure3O4/Bi2WO6Use in catalysts.
The invention also discloses flower-shaped structure Fe3O4/Bi2WO6A method for preparing the catalyst.
The technical scheme adopted by the invention for realizing the purpose is as follows:
flower-shaped structure Fe3O4/Bi2WO6The preparation method of the catalyst comprises the following steps:
(1)Fe3O4preparing a precursor:
dissolving ferric salt in ethylene glycol to form clear liquid, and then adding sodium acetate and modified polyethylene glycol into the clear liquid to stir to form mixed liquid; placing the mixed solution in a reaction kettle, heating to 180-230 ℃, reacting for 5-10 h, cooling to room temperature, cleaning and drying to obtain Fe3O4A precursor;
(2)Fe3O4/Bi2WO6preparation of the catalyst:
dissolving bismuth salt to form a solution, dissolving sodium tungstate in deionized water, dropwise adding the bismuth salt solution to form a suspension, and adding a sodium hydroxide solution to adjust the pH; mixing the above Fe3O4Placing the precursor in deionized water for ultrasonic dispersion, adding the precursor into the suspension, stirring for 25-50 min, transferring into a reaction kettle, heating to 150-180 ℃, reacting for 4-7 h, cooling to room temperature, cleaning and drying to obtain flower-shaped structure Fe3O4/Bi2WO6A catalyst.
Preferably, in the step (1), the iron salt is 1.15-1.85 parts, the ethylene glycol is 25-45 parts, the sodium acetate is 3-4.5 parts, and the modified polyethylene glycol is 0.5-1.5 parts by weight.
Preferably, 0.25 to 0.75 part by weight of bismuth salt, 0.1 to 0.25 part by weight of sodium tungstate, and Fe3O4The precursor is 0.025-0.045 parts.
Preferably, the pH value in the step (2) is adjusted to 3.0-3.5.
The invention also discloses flower-shaped structure Fe3O4/Bi2WO6The application of the catalyst in degrading ciprofloxacin by light.
The invention also discloses application of bisphenol-A polyoxyethylene ether in improving Fe content3O4/Bi2WO6Use of a catalyst for catalytic stability.
According to the invention, 4- (carboxyl-hydroxyl-methyl) -tert-butyl benzoate containing phenyl and ester groups is adopted to modify polyethylene glycol, and the modified polyethylene glycol is used as a surfactant in the preparation process of a catalyst, so that Fe with a flower-like structure is obtained3O4/Bi2WO6The composite catalyst has the following beneficial effects: the catalyst has good grain size and specific surface area, so that the catalyst has degradation effect on ciprofloxacin under the condition of no illumination, has efficient catalytic degradation effect on ciprofloxacin under the condition of illumination, and has excellent photocatalytic stability, namely, the catalyst still has good catalytic degradation performance after being recycled for multiple times; in addition, the addition of bisphenol-A polyoxyethylene ether further improves Fe3O4/Bi2WO6The catalyst has high catalytic stability and excellent degradation performance on RhB. Thus, the present invention is a Fe having a flower-like structure3O4/Bi2WO6The catalyst has a better specific surface area, and has a certain absorption and degradation effect on the ciprofloxacin under the condition of no illumination; under the illumination condition, the ciprofloxacin degradation agent has a high-efficiency visible light driven degradation effect on ciprofloxacin; simultaneously has better photocatalytic stability and good stabilityRhB also has better catalytic degradation effect.
Drawings
FIG. 1 is an infrared spectrum of polyethylene glycol before and after modification in example 2;
FIG. 2 shows Fe in example 43O4/Bi2WO6SEM image of catalyst;
FIG. 3 is Fe3O4/Bi2WO6The specific surface area of the catalyst;
FIG. 4 is Fe3O4/Bi2WO6The degradation effect of the catalyst on the ciprofloxacin under the dark condition;
FIG. 5 is Fe3O4/Bi2WO6The degradation effect of the catalyst on the ciprofloxacin under the visible light condition;
FIG. 6 is Fe3O4/Bi2WO6Degradation effect of the catalyst after recycling;
FIG. 7 is Fe3O4/Bi2WO6The catalytic degradation effect of the catalyst on RhB under the dark condition;
FIG. 8 is Fe3O4/Bi2WO6The catalytic degradation effect of the catalyst on RhB under visible light conditions.
Detailed Description
The experimental methods described in the following examples of the present invention are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In some embodiments of the present invention, the modified polyethylene glycol is prepared by the following steps:
dissolving 1.5-2.5 parts by weight of polyethylene glycol (with the molecular weight of 900-1100, purchased from Jiangsu Jiafeng chemical Co., Ltd.) in 75-85 parts by weight of dichloromethane solution, then adding 0.8-2.2 parts by weight of 4- (carboxyl-hydroxy-methyl) -tert-butyl benzoate, 1.2-2.0 parts by weight of DCC and 0.01-0.08 part by weight of DMAP into the polyethylene glycol solution, magnetically stirring at room temperature for 20-24 h, filtering, distilling under reduced pressure to remove the solution, dissolving the sample after removing the solution with 45-55 parts by weight of isopropanol, standing at 3-5 ℃ overnight, carrying out suction filtration under reduced pressure to obtain a solid, washing with ice isopropanol and ethyl ether, and carrying out vacuum drying to obtain the modified polyethylene glycol with the yield of 78.2-86.7%.
In some embodiments of the invention, the flower-like structure is Fe3O4/Bi2WO6The preparation method of the catalyst comprises the following steps:
(1)Fe3O4preparing a precursor:
weighing 1.15-1.85 parts by weight of FeCl3·6H2Dissolving O in 25-45 parts by weight of glycol solution to form clear liquid, and then adding 3-4.5 parts by weight of sodium acetate and 0.5-1.5 parts by weight of modified polyethylene glycol into the clear liquid to stir to form mixed liquid; placing the mixture into a reaction kettle, heating the mixture to 180-230 ℃, reacting the mixture for 5-10 hours, cooling the mixture to room temperature, respectively washing the mixture for 3-5 times by using deionized water and ethanol, and drying the mixture for 18-24 hours at 40-50 ℃ to obtain Fe3O4And (3) precursor.
(2)Fe3O4/Bi2WO6Preparation of the catalyst:
weighing 0.25-0.75 weight part of Bi (NO)3)3·5H2Dissolving O in 2.5-3.5 parts by weight of nitric acid solution, and adding 0.1-0.25 part by weight of NaWO4·2H2Dissolving O in 2-4 parts by weight of deionized water, and then dropwise adding the Bi (NO)3)3The solution forms a suspension, and sodium hydroxide solution is added to adjust the pH value to 3.0-3.5; 0.025 to 0.045 parts by weight of the Fe3O4Placing the precursor into 10-20 parts by weight of deionized water for ultrasonic dispersion, adding the precursor into the suspension, stirring for 25-50 min, transferring into a reaction kettle, heating to 150-180 ℃, reacting for 4-7 h, cooling to room temperature, respectively washing with deionized water and ethanol for 3-5 times, placing at 40-50 ℃ for drying for 18-24 h to obtain flower-shaped structure Fe3O4/Bi2WO6A catalyst.
To further increase Fe3O4/Bi2WO6Catalytic stabilization of catalystsMeanwhile, the catalyst has better catalytic degradation effect on rhodamine B, and the adopted preferable measures further comprise:
in step (2) Fe3O4/Bi2WO6bisphenol-A polyoxyethylene ether is added in the preparation of the catalyst; the suspension formed by bisphenol-A polyoxyethylene ether, bismuth salt and sodium tungstate may have excellent dispersibility and uniformity, thereby possibly improving Bi2WO6Grain size and surface tension of, then with Fe3O4The precursors are compounded to form Fe with flower-shaped structure3O4/Bi2WO6Compounding catalysts to improve Fe3O4/Bi2WO6The grain size and the specific surface area of the catalyst further improve the photocatalytic stability of the catalyst, and simultaneously the catalyst has better catalytic degradation effect on rhodamine B.
Preferably, the weight portion of the bisphenol-A polyoxyethylene ether is 0.05-0.1.
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1
The preparation method of the modified polyethylene glycol comprises the following steps:
dissolving 1.75 parts by weight of polyethylene glycol (molecular weight is 1000) in 75 parts by weight of dichloromethane solution, then adding 1.5 parts by weight of 4- (carboxyl-hydroxy-methyl) -benzoic acid tert-butyl ester, 1.65 parts by weight of DCC and 0.04 part by weight of DMAP into the polyethylene glycol solution, magnetically stirring at room temperature for reaction for 20 hours, filtering, distilling under reduced pressure to remove the solution, dissolving a sample after removing the solution with 50 parts by weight of isopropanol, standing overnight at 3 ℃, carrying out suction filtration under reduced pressure to obtain a solid, washing with ice isopropanol and ice ethyl ether, and carrying out vacuum drying to obtain modified polyethylene glycol with the yield of 79.6%.
Example 2
The preparation method of the modified polyethylene glycol comprises the following steps:
dissolving 2.2 parts by weight of polyethylene glycol (molecular weight is 1000) in 80 parts by weight of dichloromethane solution, then adding 1.9 parts by weight of 4- (carboxyl-hydroxy-methyl) -benzoic acid tert-butyl ester, 1.7 parts by weight of DCC and 0.03 part by weight of DMAP into the polyethylene glycol solution, magnetically stirring at room temperature for 24 hours, filtering, distilling under reduced pressure to remove the solvent, dissolving the sample after removing the solution with 55 parts by weight of isopropanol, standing at 4 ℃ overnight, carrying out suction filtration under reduced pressure to obtain a solid, washing with ice isopropanol and ice ethyl ether, and carrying out vacuum drying to obtain modified polyethylene glycol with the yield of 83.4%.
Example 3
Flower-shaped structure Fe3O4/Bi2WO6The preparation method of the catalyst comprises the following steps:
(1)Fe3O4preparing a precursor:
1.35 parts by weight of FeCl are weighed3·6H2Dissolving O in 30 parts by weight of glycol solution to form clear solution, and then adding 3.5 parts by weight of sodium acetate and 0.7 part by weight of the modified polyethylene glycol in the embodiment 1 into the clear solution to stir to form mixed solution; placing the mixture into a reaction kettle, heating the mixture to 180 ℃, reacting for 6h, cooling the mixture to room temperature, respectively washing the mixture for 5 times by using deionized water and ethanol, and drying the mixture for 20h at 45 ℃ to obtain Fe3O4And (3) precursor.
(2)Fe3O4/Bi2WO6Preparation of the catalyst:
0.65 part by weight of Bi (NO) was weighed3)3·5H2O was dissolved in 2.5 parts by weight of a nitric acid solution, and 0.15 part by weight of NaWO was added4·2H2O was dissolved in 3 parts by weight of deionized water, and the above Bi (NO) was added dropwise thereto3)3The solution formed a suspension, then 10% sodium hydroxide solution was added to adjust the pH to 3.2; 0.025 parts by weight of the above Fe3O4Placing the precursor in 10 parts by weight of deionized water for ultrasonic dispersion, adding the precursor into the suspension, stirring for 30min, transferring the suspension into a reaction kettle, heating to 150 ℃ for reaction for 4h, cooling to room temperature, respectively washing with deionized water and ethanol for 5 times, placing at 45 ℃ for drying for 18h to obtain flower-like structure Fe3O4/Bi2WO6A catalyst.
Example 4
Flower-shaped structure Fe3O4/Bi2WO6The preparation method of the catalyst is the same as the embodiment 3 except that the steps are as follows:
(1)Fe3O4preparing a precursor:
1.35 parts by weight of FeCl are weighed3·6H2Dissolving O in 30 parts by weight of glycol solution to form clear solution, and then adding 3.5 parts by weight of sodium acetate and 0.7 part by weight of the modified polyethylene glycol in the embodiment 2 into the clear solution to stir to form mixed solution; placing the mixture into a reaction kettle, heating the mixture to 180 ℃, reacting for 6h, cooling the mixture to room temperature, respectively washing the mixture for 5 times by using deionized water and ethanol, and drying the mixture for 20h at 45 ℃ to obtain Fe3O4And (3) precursor.
Example 5
Flower-shaped structure Fe3O4/Bi2WO6The preparation method of the catalyst is the same as the embodiment 4 except that the steps are as follows:
(1)Fe3O4preparing a precursor:
1.75 parts by weight of FeCl are weighed3·6H2Dissolving O in 45 parts by weight of glycol solution to form clear solution, and then adding 4.5 parts by weight of sodium acetate and 1.2 parts by weight of the modified polyethylene glycol in the example 2 into the clear solution to stir to form mixed solution; placing the mixture into a reaction kettle, heating the mixture to 210 ℃, reacting for 8 hours, cooling the mixture to room temperature, respectively washing the mixture with deionized water and ethanol for 5 times, and drying the mixture at 50 ℃ for 20 hours to obtain Fe3O4And (3) precursor.
Example 6
Flower-shaped structure Fe3O4/Bi2WO6The preparation method of the catalyst is the same as the embodiment 4 except that the steps are as follows:
(2)Fe3O4/Bi2WO6preparation of the catalyst:
0.35 part by weight of Bi (NO) was weighed3)3·5H2Dissolving O in 3.0 parts by weight of nitreIn the acid solution, 0.25 part by weight of NaWO was added4·2H2O was dissolved in 4 parts by weight of deionized water, and the above-mentioned Bi (NO) was added dropwise thereto3)3The solution formed a suspension, then 10% sodium hydroxide solution was added to adjust the pH to 3.5; 0.04 part by weight of the above Fe3O4Placing the precursor in 15 parts by weight of deionized water for ultrasonic dispersion, adding the precursor into the suspension, stirring for 50min, transferring into a reaction kettle, heating to 180 ℃ for reaction for 6h, cooling to room temperature, respectively washing with deionized water and ethanol for 5 times, placing at 50 ℃ for drying for 24h to obtain flower-like structure Fe3O4/Bi2WO6A catalyst.
Example 7
Flower-shaped structure Fe3O4/Bi2WO6The preparation method of the catalyst is the same as the embodiment 4 except that the steps are as follows:
(2)Fe3O4/Bi2WO6preparation of the catalyst:
0.35 part by weight of Bi (NO) was weighed3)3·5H2O was dissolved in 3.0 parts by weight of a nitric acid solution, and 0.25 part by weight of NaWO was added4·2H2O was dissolved in 4 parts by weight of deionized water, and the above-mentioned Bi (NO) was added dropwise thereto3)3The solution forms a suspension, then 0.05 weight part of bisphenol-A polyoxyethylene ether is added, and 10 percent sodium hydroxide solution is added to adjust the pH value to 3.5; 0.04 part by weight of the above Fe3O4Placing the precursor in 15 parts by weight of deionized water for ultrasonic dispersion, adding the precursor into the suspension, stirring for 50min, transferring into a reaction kettle, heating to 180 ℃ for reaction for 6h, cooling to room temperature, respectively washing with deionized water and ethanol for 5 times, placing at 50 ℃ for drying for 24h to obtain flower-like structure Fe3O4/Bi2WO6A catalyst.
Example 8
Flower-shaped structure Fe3O4/Bi2WO6The preparation method of the catalyst is the same as the embodiment 4 except that the steps are as follows:
(2)Fe3O4/Bi2WO6preparation of the catalyst:
0.35 part by weight of Bi (NO) was weighed3)3·5H2O was dissolved in 3.0 parts by weight of a nitric acid solution, and 0.25 part by weight of NaWO was added4·2H2O was dissolved in 4 parts by weight of deionized water, and the above-mentioned Bi (NO) was added dropwise thereto3)3The solution forms a suspension, then 0.1 weight part of bisphenol-A polyoxyethylene ether is added, and 10 percent sodium hydroxide solution is added to adjust the pH value to 3.5; 0.04 part by weight of the above Fe3O4Placing the precursor in 15 parts by weight of deionized water for ultrasonic dispersion, adding the precursor into the suspension, stirring for 50min, transferring into a reaction kettle, heating to 180 ℃ for reaction for 6h, cooling to room temperature, respectively washing with deionized water and ethanol for 5 times, placing at 50 ℃ for drying for 24h to obtain flower-like structure Fe3O4/Bi2WO6A catalyst.
Comparative example 1
Flower-shaped structure Fe3O4/Bi2WO6The preparation method of the catalyst is the same as the embodiment 4 except that the steps are as follows:
(1)Fe3O4preparing a precursor:
1.35 parts by weight of FeCl are weighed3·6H2Dissolving O in 30 parts by weight of glycol solution to form clear solution, and then adding 3.5 parts by weight of sodium acetate and 0.7 part by weight of polyethylene glycol (molecular weight 1000) into the clear solution to stir to form mixed solution; placing the mixture into a reaction kettle, heating the mixture to 180 ℃, reacting for 6h, cooling the mixture to room temperature, respectively washing the mixture for 5 times by using deionized water and ethanol, and drying the mixture for 20h at 45 ℃ to obtain Fe3O4And (3) precursor.
Comparative example 2
Flower-shaped structure Fe3O4/Bi2WO6The preparation method of the catalyst is the same as the example 7 in other steps, and is different from the example 7 in that:
(1)Fe3O4preparing a precursor:
weighing 1.35 weight portionsQuantitative part of FeCl3·6H2Dissolving O in 30 parts by weight of glycol solution to form clear solution, and then adding 3.5 parts by weight of sodium acetate and 0.7 part by weight of polyethylene glycol (molecular weight 1000) into the clear solution to stir to form mixed solution; placing the mixture into a reaction kettle, heating the mixture to 180 ℃, reacting for 6h, cooling the mixture to room temperature, respectively washing the mixture for 5 times by using deionized water and ethanol, and drying the mixture for 20h at 45 ℃ to obtain Fe3O4And (3) precursor.
Test example 1
1. Determination of polyethylene glycol infrared spectrum before and after modification
Adopting a 5700 Fourier-infrared spectrometer of Nicolet company and a potassium bromide tabletting method, wherein the scanning interval is 400-4000 cm-1。
FIG. 1 is an infrared spectrum of polyethylene glycol before and after modification in example 2. As can be seen from FIG. 1, in polyethylene glycol, at 2988cm-1The characteristic peak appearing nearby is its surface-CH2The stretching vibration of (2); at 1102cm-1Stretching vibration with a characteristic peak of-C-O appears nearby; in the modified polyethylene glycol, the concentration is 3607cm-1The characteristic peak appearing nearby is stretching vibration of-OH in 4- (carboxyl-hydroxyl-methyl) -tert-butyl benzoate; at 3094cm-1The characteristic peak appearing nearby is the stretching vibration of a benzene ring; at 1760cm-1The characteristic peak appearing nearby is the stretching vibration of an ester group connected with a benzene ring; at 1733cm-1The characteristic peak appeared nearby is the stretching vibration of the ester group formed by 4- (carboxyl-hydroxyl-methyl) -tert-butyl benzoate and polyethylene glycol; from this, it is known that modified polyethylene glycol is obtained by modifying polyethylene glycol with 4- (carboxy-hydroxy-methyl) -benzoic acid tert-butyl ester.
2.Fe3O4/Bi2WO6Determination of catalyst surface morphology
The surface morphology of the obtained sample was observed with a cold field emission scanning electron microscope (acceleration voltage 50kV) of JSM-6701F, Japan Electron Ltd.
FIG. 2 shows Fe in example 43O4/Bi2WO6SEM image of catalyst. As can be seen from FIG. 2, Fe3O4/Bi2WO6The catalyst has an irregular flower-like structure similar to the shape of a petal of a flower, Fe3O4Nanoparticles are attached to Bi2WO6The surface has good dispersivity, the grain size is relatively uniform, and no obvious agglomeration phenomenon occurs.
3.Fe3O4/Bi2WO6Determination of the specific surface area of the catalyst
Using ASAP2460 type N2Adsorption isothermometers (BET, gmimer instruments ltd, usa); the specific method comprises the following steps: 0.1g of the dry powder was weighed into a Pitot tube, pretreated at 150 ℃ for 2 hours, placed into a Dewar flask filled with liquid nitrogen, and analyzed by starting the software.
FIG. 3 is Fe3O4/Bi2WO6Specific surface area of the catalyst. As can be seen from FIG. 3, Fe in examples 3 to 63O4/Bi2WO6The specific surface area of the catalyst is higher than 175cm2(iv)/g, comparative example 4 to comparative example 1, example 4 having a higher specific surface area than comparative example 1, which illustrates the modification of polyethylene glycol with tert-butyl 4- (carboxy-hydroxy-methyl) -benzoate as Fe preparation3O4Surfactant of precursor, and Bi2WO6Compounding to obtain Fe3O4/Bi2WO6Catalyst, raising Fe3O4/Bi2WO6The specific surface area of the catalyst; comparative example 4 with examples 7-8, comparative example 1 with comparative example 2, Fe in examples 7-83O4/Bi2WO6The specific surface area of the catalyst is not obviously different from that of example 4, and the specific surface area of comparative example 2 is not obviously different from that of comparative example 1, which shows that Fe is prepared3O4/Bi2WO6bisphenol-A polyoxyethylene ether is added in the process of the catalyst, and the P-Fe3O4/Bi2WO6The specific surface area of the catalyst is not greatly affected.
4.Fe3O4/Bi2WO6Determination of ciprofloxacin photocatalytic activity by using catalyst
The method adopts a photocatalytic reaction device to carry out photocatalytic degradation on ciprofloxacin, the light source is a long-arc xenon lamp, and the working parameters are as follows: the power is 500W, the working current is 3A, the working voltage is 100V, the diameter is 24mm, and the length of the light-emitting body is 190 mm; the specific test method comprises the following steps: weighing 0.15g of sample, adding the sample into 100mL of CIP (ciprofloxacin) solution with the concentration of 12mg/L, carrying out dark ultrasound for 30min, then carrying out dark treatment and stirring for 30min to ensure that the catalyst sample and the reaction solution reach adsorption-desorption balance, and taking a small amount of liquid and marking every 20min in the period; turning on a light source, starting timing after the radiation of the light source is stable (5min, taking a small amount of liquid and marking every 30min, irradiating for 90 min), centrifuging the sample at 10000r/min, taking out supernatant, testing absorbance (lambda is 272nm) in an ultraviolet-visible spectrophotometer, measuring the degradation activity of the photocatalyst according to the change of CIP absorbance at different stages, and taking a test group without the catalyst as a blank group.
FIGS. 4 and 5 show Fe3O4/Bi2WO6The degradation effect of the catalyst on the ciprofloxacin in dark and visible light conditions. As can be seen from FIGS. 4 and 5, the degradation effect of the blank group hardly changed with time in the dark, whereas the degradation effect of examples 3 to 8 on ciprofloxacin was not less than 58%, probably because of Fe3O4/Bi2WO6The catalyst has excellent specific surface area and can absorb and degrade the ciprofloxacin; under the irradiation of visible light, the photodegradation effect of the blank group is still not obviously changed along with the increase of time, and the photodegradation effect of the blank group is almost 0; the degradation effect of the example 3-8 on the ciprofloxacin is higher than 99% when the illumination time is 90min, the degradation effect of the example 4 on the ciprofloxacin is higher than that of the comparative example 1 in the comparative example 4 and the comparative example 1 under the dark and the visible light conditions, which shows that the polyethylene glycol is modified by the 4- (carboxyl-hydroxyl-methyl) -tert-butyl benzoate, and the modified polyethylene glycol is used for preparing Fe3O4Surfactant of precursor, and Bi2WO6Compounding to obtain Fe3O4/Bi2WO6Catalyst, raising Fe3O4/Bi2WO6Photocatalytic effect of catalystFruit, so that the degradation effect of the fruit can reach more than 99 percent within 90 min; comparing example 4 with example 7, and comparing example 1 with comparing example 2, the degradation effect of example 4 on ciprofloxacin was not significantly different from example 7, and the degradation effect of comparing example 1 on ciprofloxacin was not significantly different from comparing example 2, which indicates that Fe is being produced3O4/Bi2WO6bisphenol-A polyoxyethylene ether is added in the process of the catalyst, so that the degradation effect of the catalyst on degrading ciprofloxacin is not obviously influenced.
5.Fe3O4/Bi2WO6Determination of the photocatalytic stability of the catalyst
Testing the photocatalytic stability of the sample by the degradation performance of the catalyst after recycling; and (3) centrifugally collecting the sample after the completion of the photodegradation reaction, washing the sample with ethanol and water for multiple times respectively, and drying the sample at 85 ℃ for 12 hours. Weighing the sample, adding the sample into ciprofloxacin standard solution according to the same proportion for photocatalytic degradation test, and performing a cycle experiment according to the same steps after degradation. And (3) carrying out 5 times of cyclic photodegradation tests to determine the degradation rate of the sample by ensuring that the adding ratio of the sample to the ciprofloxacin, the concentration of the ciprofloxacin and the illumination conditions are the same as those in the initial test in each cyclic experiment.
FIG. 6 is Fe3O4/Bi2WO6The degradation effect of the catalyst after recycling. As can be seen from FIG. 6, after 5 cycles of photodegradation tests, Fe was found in examples 3-63O4/Bi2WO6The photodegradation effect of the catalyst is still higher than 91.5%, the photodegradation effect of comparative example 4 and comparative example 1 is higher than that of comparative example 1, which shows that 4- (carboxyl-hydroxyl-methyl) -tert-butyl benzoate is adopted to modify polyethylene glycol to prepare Fe3O4Surfactant of precursor, and Bi2WO6Compounding to obtain Fe3O4/Bi2WO6Catalyst, raising Fe3O4/Bi2WO6The catalyst has good photocatalytic degradation effect after 5 times of recycling due to the photocatalytic stability; the photodegradation effects of examples 7-8 were greater than 93%, forFe in comparative example 4 and examples 7-8, comparative example 1 and comparative example 2, and examples 7-83O4/Bi2WO6The photodegradation effect of the catalyst was higher than that of example 4, and that of comparative example 2 was higher than that of comparative example 1, indicating that Fe was being produced3O4/Bi2WO6bisphenol-A polyoxyethylene ether is added in the process of the catalyst, so that Fe is increased3O4/Bi2WO6Catalytic stability of the catalyst.
6.Fe3O4/Bi2WO6Determination of catalytic activity of catalyst on rhodamine B
The test method of this test was the same as "test example 1: fe3O4/Bi2WO6Measurement of photocatalytic Activity of ciprofloxacin Using catalyst, 100mL of a 12mg/L CIP (ciprofloxacin) solution was replaced with 100mL of a 2.0X 10 solution-5Rhodamine B solution (RhB).
FIGS. 7 and 8 are Fe3O4/Bi2WO6The catalytic degradation effect of the catalyst on RhB in dark and visible light conditions. As can be seen from FIGS. 7 and 8, the degradation efficiency of the blank group hardly changed with time in the dark, while Fe in example 43O4/Bi2WO6The photocatalytic degradation efficiency of the catalyst on RhB is higher than 38%, and Fe is adopted in examples 7-83O4/Bi2WO6The degradation efficiency of the catalyst on RhB is not lower than 55%; under the illumination condition, the degradation efficiency of the blank group still has no obvious change along with the change of time; when the solution is irradiated for 90min, the photocatalytic degradation efficiency of example 4 is not lower than 95%, the degradation efficiency of examples 7-8 is higher than 99%, the degradation efficiency of comparative example 4 and comparative example 1, and the degradation efficiency of example 4 to RhB under dark and light conditions is not obviously different from that of comparative example 1, which shows that the polyethylene glycol is modified by 4- (carboxyl-hydroxyl-methyl) -tert-butyl benzoate, and the modified polyethylene glycol is used for preparing Fe3O4Surfactant of precursor, and Bi2WO6Compounding to obtain Fe3O4/Bi2WO6Catalyst having no effect on the photocatalytic degradation effect of RhBLarge; comparing example 4 with examples 7-8, and comparative example 1 with comparative example 2, examples 7-8 showed higher RhB degradation efficiency than example 4, and comparative example 2 showed higher RhB degradation efficiency than comparative example 1, indicating that Fe was being produced3O4/Bi2WO6bisphenol-A polyoxyethylene ether is added in the process of the catalyst, so that Fe is increased3O4/Bi2WO6The catalyst has a photocatalytic degradation effect on RhB.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A modified polyethylene glycol is characterized in that: the modified polyethylene glycol contains phenyl and ester functional groups.
2. The modified polyethylene glycol according to claim 1, wherein: the modified polyethylene glycol is 4- (carboxyl-hydroxyl-methyl) -tert-butyl benzoate modified polyethylene glycol.
3. A surfactant comprising the modified polyethylene glycol of claim 1.
4. Use of the surfactant of claim 3 in the preparation of a photocatalyst.
5. Use of the surfactant according to claim 4 in the preparation of a photocatalyst, characterized in that: the surfactant is used for preparing Fe with a flower-like structure3O4/Bi2WO6Use in catalysts.
6. Flower-shaped structure Fe3O4/Bi2WO6The preparation method of the catalyst comprises the following steps:
(1)Fe3O4preparing a precursor:
dissolving iron salt in ethylene glycol to form clear liquid, then adding sodium acetate and the modified polyethylene glycol of claim 1 into the clear liquid, and stirring to form mixed liquid; placing the mixed solution in a reaction kettle, heating to 180-230 ℃, reacting for 5-10 h, cooling to room temperature, cleaning and drying to obtain Fe3O4A precursor;
(2)Fe3O4/Bi2WO6preparation of the catalyst:
dissolving bismuth salt to form a solution, dissolving sodium tungstate in deionized water, dropwise adding the bismuth salt solution to the solution to form a suspension, and adding a sodium hydroxide solution to adjust the pH; subjecting said Fe to3O4Placing the precursor in deionized water for ultrasonic dispersion, adding the precursor into the suspension, stirring for 25-50 min, transferring into a reaction kettle, heating to 150-180 ℃, reacting for 4-7 h, cooling to room temperature, cleaning and drying to obtain flower-shaped structure Fe3O4/Bi2WO6A catalyst.
7. Flower-like structure Fe according to claim 63O4/Bi2WO6The preparation method of the catalyst is characterized by comprising the following steps: in the step (1), by weight, the iron salt is 1.15-1.85 parts, the ethylene glycol is 25-45 parts, the sodium acetate is 3-4.5 parts, and the modified polyethylene glycol is 0.5-1.5 parts.
8. Flower-like structure Fe according to claim 63O4/Bi2WO6The preparation method of the catalyst is characterized by comprising the following steps: in the step (1), 0.25-0.75 parts by weight of bismuth salt, 0.1-0.25 parts by weight of sodium tungstate, and Fe3O4The precursor is 0.025-0.045 parts.
9. Flower-like structure Fe as claimed in claim 63O4/Bi2WO6The application of the catalyst in degrading ciprofloxacin by light.
10. Use of bisphenol-A polyoxyethylene ether in improving Fe3O4/Bi2WO6Use of a catalyst for catalytic stability.
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