CN111167466A - Z-type catalyst CdWO with dual-response activity4/ZnFe2O4And preparation method and application thereof - Google Patents
Z-type catalyst CdWO with dual-response activity4/ZnFe2O4And preparation method and application thereof Download PDFInfo
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- CN111167466A CN111167466A CN202010093054.2A CN202010093054A CN111167466A CN 111167466 A CN111167466 A CN 111167466A CN 202010093054 A CN202010093054 A CN 202010093054A CN 111167466 A CN111167466 A CN 111167466A
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- 230000009977 dual effect Effects 0.000 title claims abstract description 17
- 230000004044 response Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 73
- 230000015556 catabolic process Effects 0.000 claims abstract description 40
- 238000006731 degradation reaction Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 230000003115 biocidal effect Effects 0.000 claims abstract description 9
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 8
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 7
- 230000002195 synergetic effect Effects 0.000 claims abstract description 4
- 239000004098 Tetracycline Substances 0.000 claims description 34
- 229960002180 tetracycline Drugs 0.000 claims description 34
- 229930101283 tetracycline Natural products 0.000 claims description 33
- 235000019364 tetracycline Nutrition 0.000 claims description 33
- 150000003522 tetracyclines Chemical class 0.000 claims description 33
- 230000000694 effects Effects 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
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- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
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- 238000001354 calcination Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 3
- 229960001180 norfloxacin Drugs 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 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 description 2
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 claims description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound 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
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 claims 2
- 150000003456 sulfonamides Chemical class 0.000 claims 1
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract 2
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 8
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- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
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- 230000002349 favourable effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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- B01J35/39—
-
- 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
- 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
-
- 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
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- 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
Abstract
The invention relates to a Z-type catalyst CdWO with dual-response activity4/ZnFe2O4And a preparation method and application thereof. The invention adopts an isoelectric point method and a high-temperature calcination method to obtain CdWO4/ZnFe2O4The nano particle catalyst is combined with the synergistic effect of ultraviolet light and microwave to degrade antibiotics. The method for treating the antibiotic wastewater has the advantages of high degradation efficiency, high speed, low cost, no secondary pollution and the like, and is suitable for large-scale treatment of the antibiotic wastewaterCan realize the rapid and thorough degradation of the antibiotic wastewater in a short time.
Description
Technical Field
The invention belongs to the field of catalytic degradation, and particularly relates to a method for preparing a Z-type catalyst CdWO by adopting an isoelectric point method and a high-temperature calcination method4/ZnFe2O4And application thereof in catalytic degradation of antibiotics in water under ultraviolet light-microwave.
Background
antibiotics are secondary metabolites with anti-pathogens or other activities generated by microorganisms (including bacteria, molds and other microorganisms) or higher animals and plants in the life process, and are chemical substances with functions of interfering development of other living cells.
Cadmium tungstate (CdWO)4) Has good physical and chemical stability, and is widely applied to medical X-ray detectors. CdWO4Is a broadband semiconductor (3.74eV), is favorable for the separation of electron-hole pairs, has higher photocatalytic activity, and has optical, structural and thermal stability, CdWO4Is considered to be a good photocatalyst. However, broad band CdWO4Only ultraviolet light can be absorbed, and if another semiconductor can be formed into a Z-type system, the photoresponse range can be widened.
Zinc ferrite (ZnFe)2O4) Has good visible light response and excellent photochemical stability, is a narrow-band semiconductor (1.92eV), and can be used as a photocatalyst. Furthermore, ZnFe2O4As the magnetic material, it has outstanding magnetic properties and can strongly absorb microwaves under microwave irradiation, and therefore, it can be used as a microwave catalyst.
Disclosure of Invention
The invention aims to provide a catalyst with ultraviolet-microwave dual-response activity, which makes full use of microwave and ultraviolet light energy and reduces the recombination of electron-hole pairs, thereby improving the catalytic activity of the catalyst.
The invention also aims to utilize the Z-type catalyst with dual-response activity to catalyze and degrade antibiotics in water under the irradiation of ultraviolet light-microwave.
The technical scheme adopted by the invention is as follows: z-type catalyst CdWO with dual-response activity4/ZnFe2O4The Z-type catalyst CdWO4/ZnFe2O4From CdWO4And ZnFe2O4Prepared according to the particle ratio of CdWO4:ZnFe2O4＝1:(4～12)。
Z-type catalyst CdWO with dual-response activity4/ZnFe2O4The preparation method comprises the following steps: in terms of particle ratio, CdWO4:ZnFe2O4Taking CdWO (4-12) ═ 14And ZnFe2O4Dissolving the powder in deionized water, ultrasonically dispersing for 30min, adjusting pH to 7.5 with NaOH or HCl, stirring and mixing uniformly, centrifuging, collecting precipitate, drying the precipitate at 100 deg.C, grinding, calcining at 600 deg.C for 2-3h, and grinding again to obtain the target product Z-type catalyst CdWO4/ZnFe2O4。
Further, the preparation method is the CdWO4The preparation method comprises the following steps: dropwise adding a sodium tungstate dihydrate aqueous solution into a cadmium nitrate tetrahydrate aqueous solution, magnetically stirring for 30min, pouring the mixed solution into a polytetrafluoroethylene reaction tank, and transferring the reaction tank into a microwave hydrothermal synthesizer to react for 30min at 1.5MPa and 210 ℃; washing the obtained product with deionized water, drying at 90 deg.C, calcining at 600 deg.C for 1-2h, and grinding to obtain CdWO4And (3) nanoparticles.
Further, the above preparation method, the ZnFe2O4The preparation method comprises the following steps: in terms of mole ratio, Fe3 +:Zn2+Weighing ferric nitrate nonahydrate and zinc chloride, adding deionized water to dissolve, magnetically stirring for 10min, dropwise adding NaOH to adjust the pH value of the solution to 10-13 under the condition of continuously stirring at 500rmp of the obtained mixed solution, continuously stirring for 15min, pouring the obtained mixed solution into a polytetrafluoroethylene reaction tank, transferring the mixed solution into a microwave hydrothermal synthesizer, reacting for 30min at 1.5MP and 210 ℃, washing the obtained product to be neutral by using the deionized water, drying at the constant temperature of 105 ℃, calcining for 1-2h at 600 ℃, and grinding to obtain ZnFe2O4And (3) nanoparticles.
The Z-type catalyst CdWO with dual-response activity4/ZnFe2O4The application of the catalytic degradation of the antibiotics in water under the synergistic action of ultraviolet light and microwave.
Further, the method is as follows: adding the above into solution containing antibioticsThe Z-type catalyst CdWO with dual response activity4/ZnFe2O4And performing catalytic degradation for 5-35min under the microwave power of 100-400W and the ultraviolet light power of 200W.
Further, the initial concentration of the antibiotic is 10.0-30.0 mg/L.
Further, Z-type catalyst CdWO with dual response activity4/ZnFe2O4The amount of (A) is 0.6-1.6 g/L.
Further, the antibiotic is tetracycline, norfloxacin or sulfanilamide.
The invention has the beneficial effects that: the invention combines microwave catalysis and photocatalytic oxidation technology, designs the Z-type catalyst CdWO with dual-response activity4/ZnFe2O4Can fully utilize ultraviolet light and microwave energy and reduce electrons (e)-) And a cavity (h)+) The catalytic activity is improved, so that the rapid and complete degradation of the antibiotics in the water is realized.
Drawings
FIG. 1 is CdWO4X-ray diffraction pattern of (a).
FIG. 2 is ZnFe2O4X-ray diffraction pattern of (a).
FIG. 3 is CdWO4/ZnFe2O4X-ray diffraction pattern of (a).
FIG. 4 is CdWO4/ZnFe2O4Scanning electron microscopy of (a).
FIG. 5a is CdWO4、ZnFe2O4And CdWO4/ZnFe2O4Ultraviolet-visible diffuse reflection absorption spectrogram.
FIG. 5b is CdWO4And ZnFe2O4Ultraviolet-visible diffuse reflection absorption spectrogram.
FIG. 6 is CdWO4、ZnFe2O4And CdWO4/ZnFe2O4Photoluminescence spectrum of (a).
Detailed Description
Example 1
Z-type catalyst CdWO with dual-response activity4/ZnFe2O4The preparation method comprises the following steps:
1) synthesis of CdWO by microwave hydrothermal method4Nano-particles: adding 2.5mmol of Na2WO4·2H2O and 2.5mmol of Cd (NO)3)2·4H2O was dissolved in 25mL of deionized water. Na (sodium sulfate)2WO4·2H2O aqueous solution was added dropwise to Cd (NO)3)2·4H2Stirring the O aqueous solution for 30min under constant magnetic force, pouring the mixed solution into a polytetrafluoroethylene reaction tank, and transferring the reaction tank into a microwave hydrothermal synthesizer to react for 30min under the pressure of 1.5MPa and the temperature of 210 ℃. Washing the obtained product with deionized water, drying at 90 ℃ in an oven, calcining at 600 ℃ for 1h, and grinding to obtain the CdWO4And (3) nanoparticles.
2) ZnFe synthesis by microwave hydrothermal method2O4Nano-particles: in terms of mole ratio, Fe3+:Zn2+Accurately weigh 9.0mmol of Fe (NO) 2:13)3·9H2O and 4.5mmol ZnCl2Then 30mL of deionized water was added for dissolution and magnetic stirring was continued for 10 min. The pH of the resulting mixed solution was adjusted to 10-13 by adding NaOH dropwise with stirring at 500 rmp. Then continuously stirring for 15min, pouring the obtained mixed solution into a polytetrafluoroethylene reaction tank, transferring into a microwave hydrothermal synthesizer, reacting for 30min at the temperature of 210 ℃ and 1.5MP, washing the obtained product with deionized water for a plurality of times, measuring the pH value to be about 7.0, drying at the constant temperature of 105 ℃, finally calcining for 1h at the temperature of 600 ℃, and grinding to obtain ZnFe2O4And (3) nanoparticles.
3) Preparation of CdWO by isoelectric point method and high-temperature calcination method4/ZnFe2O4The compound is as follows: first, the CdWO is determined separately4And ZnFe2O4Isoelectric point of (d). Secondly, mixing the CdWO4And ZnFe2O4Dissolving the powder in deionized water at different particle ratios (1:4, 1:8, 1:12), ultrasonic dispersing for 30min, adjusting pH to 7.5 with NaOH or HCl, stirring, centrifuging, collecting precipitate, drying at 100 deg.C, and grinding. Finally, calcining the mixture for 2 hours in a muffle furnace at the temperature of 600 ℃, and grinding the mixture to obtain different productsTarget product CdWO of particle ratio4/ZnFe2O4A catalyst.
Characterization of the catalyst
As shown in fig. 1, CdWO4The characteristic peak of (A) was consistent with that of a standard card (JCPDS File No. 14-0676). The results show the successful preparation of CdWO4。
ZnFe prepared by microwave hydrothermal method, as shown in FIG. 22O4Can be matched with the characteristic peak of a standard card (JCPDSFileNo.22-1012), so that the synthesized ZnFe2O4No impurities.
FIG. 3 shows a Z-type catalyst CdWO4/ZnFe2O4From the XRD pattern of (A), CdWO can be found4And ZnFe2O4The characteristic peak position of the compound has no obvious movement, which shows that the structures of the compound and the compound are not changed, and also shows that the CdWO is successfully prepared4/ZnFe2O4And (3) compounding a catalyst.
FIG. 4 is CdWO4/ZnFe2O4Scanning electron microscopy of (a). As can be seen from the figure, the ZnFe is in the form of smaller spheres2O4Nanoparticles attached to larger, short rod-shaped CdWO4The test result shows that the CdWO is4And ZnFe2O4And (4) successfully compounding. In addition, as can be seen from the images, CdWO4Has a crystal size dispersed in about 190-220nm, ZnFe2O4Is dispersed at about 30-80 nm.
FIG. 5a is CdWO4、ZnFe2O4And CdWO4/ZnFe2O4Ultraviolet-visible diffuse reflection absorption spectrogram. FIG. 5b is CdWO4And ZnFe2O4Ultraviolet-visible diffuse reflection absorption spectrogram. As shown in FIG. 5a, the prepared CdWO4/ZnFe2O4The nanoparticles have an absorption wavelength between 200 and 800 nm. Further, as shown in FIG. 5b, CdWO was obtained by calculation based on the ultraviolet-visible diffuse reflectance absorption spectrum4And ZnFe2O4Respectively at 3.74eV and 1.92 eV.
FIG. 6 is CdWO4、ZnFe2O4And CdWO4/ZnFe2O4Photoluminescence spectrum of (a). As can be seen from the figure, CdWO4/ZnFe2O4The photoluminescence intensity of the compound is the weakest, and the test result shows that the compound CdWO4/ZnFe2O4The most efficient and the most excellent photocatalytic performance is achieved.
Example 2
Influence of different particle ratios of cadmium tungstate and zinc ferrite on tetracycline degradation rate
Ultraviolet light-microwave (UV + MW) catalytic degradation: 20.0mL of tetracycline solution (25mg/L TC) was measured, and 1.0g/L of catalyst powder (CdWO) was added to each solution at different particle ratios4/ZnFe2O4) Mixing, irradiating with 200W ultraviolet light and 100W microwave for 25min at a rotation speed of 200 r/min. Cooling to room temperature, centrifuging, filtering, and measuring ultraviolet spectrum of the supernatant at 200-800 nm. And calculating the degradation rate of the tetracycline by taking the absorbance at 358 nm.
Percent degradation (%) - (C)0-C)/C0X 100% (wherein C)0: the concentration of the stock solution; c: concentration of sample).
TABLE 1 Effect of different particles of cadmium tungstate and zinc ferrite on the degradation rate (%) of tetracycline
As can be seen from Table 1, in the UV-microwave catalytic system, the degradation degree of tetracycline shows a tendency of increasing first and then decreasing with the increase of the zinc ferrite content, and the particle ratio of the tetracycline to the zinc ferrite is CdWO4:ZnFe2O4When the ratio is 1:8, the degradation rate of tetracycline is the highest. In order to obtain good degradation effect and reduce cost so as to be put into practical production, the invention selects CdWO4:ZnFe2O4The optimal particle ratio was 1: 8.
(II) Effect of different conditions on the degradation Rate of Tetracycline over time
Changing the composition technology and degradation time, wherein the microwave power is 100W, the ultraviolet light power is 200W, the rotating speed r is 200r/min, the irradiation time is 0-35min, the tetracycline is 25.0mg/L, and the adding amount of the catalyst (the particle ratio is 1:8) is 1.0 g/L. The results are shown in Table 2.
TABLE 2 Effect of UV-microwave different composition techniques on tetracycline degradation Rate over time
As can be seen from table 2, the degradation rate increased with increasing irradiation time. When MW was combined with UV, the degradation rate of tetracycline was higher than when MW or UV was used alone, demonstrating a synergistic effect of MW and UV. CdWO when UV + MW irradiation is 35min4/ZnFe2O4The degradation rate in the system is 68.10%. In comparison, in the range of 0-35min, CdWO4/ZnFe2O4The degradation efficiency of the/UV + MW system is always highest.
(III) influence of microwave power change with time on tetracycline degradation rate
Changing the microwave power, ultraviolet light 200W, rotating speed r 200r/min, irradiating for 0-35min, tetracycline 25.0mg/L, and catalyst (particle ratio 1:8) adding amount 1.0 g/L. The results are shown in Table 3.
TABLE 3 Effect of microwave power over time on tetracycline degradation
As can be seen from Table 3, the degradation rate is positively correlated to the Microwave (MW) power. The higher microwave power is shown, the high microwave irradiation intensity can be obtained, the catalyst is favorable for absorbing more microwave energy, and more tetracycline can be degraded. Moreover, when the microwave power is 400W and the UV + MW irradiation time is 35min, the degradation rate of the tetracycline is maximum and reaches 87.30%.
(IV) influence of different adding amounts of catalyst on tetracycline degradation rate
Ultraviolet light of 200W, rotating speed r of 200r/min, irradiating for 30min under microwave of 100W, tetracycline of 25.0mg/L, and only changing the adding amount of the catalyst (particle ratio of 1: 8). The results are shown in Table 4.
TABLE 4 Effect of different dosages on the degradation rate of tetracycline
As can be seen from Table 4, the degradation rate of tetracycline showed a tendency to increase and then gradually decrease as the amount of catalyst added was increased. When the catalyst addition is 1.0g/L, the CdWO4/ZnFe2O4The degradation rate in the UV + MW system was 66.12%.
(V) Effect of different initial concentrations on the degradation Rate of Tetracycline
Ultraviolet light of 200W, rotating speed r of 200r/min, irradiating for 30min under microwave of 100W, adding 1.0g/L catalyst (particle ratio of 1:8), and only changing the initial concentration of tetracycline solution. The results are shown in Table 5.
TABLE 5 Effect of different initial concentrations on the degradation Rate of Tetracycline
As can be seen from Table 5, the degradation rate increased with decreasing initial concentration of tetracycline. CdWO when the initial concentration of tetracycline is 10.0mg/L4/ZnFe2O4The degradation rate in the UV + MW system was 81.46%.
(VI) Effect of changing catalyst usage times on tetracycline degradation rate
Ultraviolet light of 200W, rotating speed r of 200r/min, irradiating for 30min under microwave of 100W, tetracycline of 25.0mg/L, and catalyst dosage of 1.0 g/L. The results are shown in Table 6.
The effect of the number of uses on the photodegradation of the antibiotic-tetracycline, the results are given in table 6.
TABLE 6 Effect of number of applications on tetracycline degradation
As can be seen from Table 6, the degradation rate of tetracycline is more stable. This means that in five consecutive cycles, the CdWO is4/ZnFe2O4the/UV + MW catalytic system exhibits very good degradation activity. Therefore, when the pollutants in water are removed, the catalyst can be reused for 5 times, and the catalytic system still has good stability.
In the above examples, tetracycline is used as the antibiotic, but the present invention is not limited to tetracycline, and the method of the present invention is suitable for degrading any antibiotic, such as norfloxacin, sulfanilamide, etc.
Claims (9)
1. Z-type catalyst CdWO with dual-response activity4/ZnFe2O4Characterized in that the Z-type catalyst CdWO4/ZnFe2O4From CdWO4And ZnFe2O4Prepared according to the particle ratio of CdWO4:ZnFe2O4＝1:(4～12)。
2. The Z-type catalyst CdWO with dual-response activity as claimed in claim 14/ZnFe2O4The preparation method is characterized by comprising the following steps: in terms of particle ratio, CdWO4:ZnFe2O4Taking CdWO (4-12) ═ 14And ZnFe2O4Dissolving the powder in deionized water, ultrasonically dispersing for 30min, adjusting pH to 7.5 with NaOH or HCl, stirring and mixing uniformly, centrifuging, collecting precipitate, drying the precipitate at 100 deg.C, grinding, calcining at 600 deg.C for 2-3h, and grinding again to obtain the target product Z-type catalyst CdWO4/ZnFe2O4。
3. The method of claim 2, wherein the CdWO is a CdWO4The preparation method comprises the following steps: dropwise adding a sodium tungstate dihydrate aqueous solution into a cadmium nitrate tetrahydrate aqueous solution, magnetically stirring for 30min, pouring the mixed solution into a polytetrafluoroethylene reaction tank, and transferring the reaction tank into a microwave hydrothermal synthesizer to react for 30min at 1.5MPa and 210 ℃; washing the obtained product with deionized water, drying at 90 deg.C, calcining at 600 deg.C for 1-2h, and grinding to obtain CdWO4And (3) nanoparticles.
4. The method according to claim 2, characterized in that the ZnFe is used as a catalyst2O4The preparation method comprises the following steps: in terms of mole ratio, Fe3+:Zn2+Weighing ferric nitrate nonahydrate and zinc chloride, adding deionized water to dissolve, magnetically stirring for 10min, dropwise adding NaOH to adjust the pH value of the solution to 10-13 under the condition of continuously stirring at 500rmp of the obtained mixed solution, continuously stirring for 15min, pouring the obtained mixed solution into a polytetrafluoroethylene reaction tank, transferring the mixed solution into a microwave hydrothermal synthesizer, washing the obtained product with deionized water until the pH value is neutral, drying the product at the constant temperature of 105 ℃, calcining the product at the constant temperature of 600 ℃ for 1-2h, and grinding the product to obtain ZnFe2O4And (3) nanoparticles.
5. The Z-type catalyst CdWO with dual-response activity as claimed in claim 14/ZnFe2O4The application of the catalytic degradation of the antibiotics in water under the synergistic action of ultraviolet light and microwave.
6. Use according to claim 5, characterized in that the method is as follows: the addition of the Z-type catalyst with dual-response activity, CdWO, according to claim 1, to a solution containing antibiotics4/ZnFe2O4And performing catalytic degradation for 5-35min under the microwave power of 100-400W and the ultraviolet light power of 200W.
7. Use according to claim 6, characterized in that the initial concentration of antibiotic is 10.0-30.0 mg/L.
8. Use according to claim 7, characterized in that the Z-type catalyst with dual-response activity, CdWO4/ZnFe2O4The amount of (A) is 0.6-1.6 g/L.
9. The use according to any one of claims 5 to 8, wherein the antibiotic is tetracycline, norfloxacin or sulfonamide.
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