CN113332988A - Porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst and preparation method and application thereof - Google Patents
Porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 35
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 55
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 37
- 239000002351 wastewater Substances 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 32
- 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 abstract description 31
- 229960001180 norfloxacin Drugs 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003115 biocidal effect Effects 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims description 126
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims description 17
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- 229960001763 zinc sulfate Drugs 0.000 claims description 17
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 17
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 11
- 235000017281 sodium acetate Nutrition 0.000 claims description 11
- 239000001632 sodium acetate Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010981 drying operation Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910016516 CuFe2O4 Inorganic materials 0.000 abstract description 11
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 40
- 230000003197 catalytic effect Effects 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 238000006385 ozonation reaction Methods 0.000 description 11
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 9
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- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 2
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- 208000035473 Communicable disease Diseases 0.000 description 1
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- 239000005751 Copper oxide Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
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- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 229910052598 goethite Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
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- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J23/80—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 zinc, cadmium or mercury
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- B01J35/33—
-
- B01J35/51—
-
- B01J35/60—
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
A porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst and a preparation method and application thereof relate to the field of water treatment materials, in particular to a catalyst and a preparation method and application thereof. Objects of the inventionTo solve the problem of the existing CuFe2O4Catalyst particles or ZnFe2O4The catalyst particles are easy to agglomerate, the specific surface area is small, the number of active sites is small, and the conductivity is poor. The chemical formula of the catalyst is Cux‑Cu(0.5‑x)Zn0.5Fe2O(4‑x)(ii) a Is in the shape of a porous sphere. The method comprises the following steps: firstly, preparing a solution A; secondly, preparing a solution B; thirdly, preparing a precursor; fourthly, carrying out hydrothermal reaction to obtain a hydrothermal reaction product; fifthly, washing and drying. The catalyst is used together with ozone to treat antibiotic waste water. The advantages are that: good dispersibility, large specific surface area, strong electron transfer capacity, remarkable effect of catalyzing, ozonizing and degrading norfloxacin wastewater, good circulation stability and no secondary pollution.
Description
Technical Field
The invention relates to the field of water treatment materials, and particularly relates to a catalyst, and a preparation method and application thereof.
Background
Antibiotics are widely used and used in large amounts as drugs for treating infectious diseases. However, antibiotics can not be completely metabolized after entering human bodies or animal bodies, and are enriched in water environment after being discharged out of the bodies, so that water body pollution is caused, human health is harmed, and even ecological balance is damaged. The traditional municipal sewage treatment plant mostly adopts an activated sludge process to remove organic pollutants, but has poor antibiotic removal effect, and needs to develop an effective method for degrading residual antibiotics in wastewater.
Heterogeneous catalytic ozonation technology utilizes solid catalyst to promote ozone decomposition to generate hydroxylThe free radicals can thoroughly mineralize organic pollutants and are suitable for the advanced treatment of antibiotic wastewater. Common heterogeneous catalysts include metal oxides, carbon-based materials, metal or metal oxide-supported composite materials, mineral materials, and the like. Wherein the metal oxide (e.g. Al)2O3、Fe2O3、MnO2Etc.), but the catalytic activity is lower, the metal ions are easy to leach out, and the solid-liquid separation of the powdery catalyst is difficult; carbon-based materials (such as activated carbon, carbon nanotubes, graphene, etc.) overcome the problem of dissolution of metal ions, but are volatile after being oxidized by ozone; the composite material loaded with metal or metal oxide has strong stability and large specific surface area, but the preparation process is complex and the cost is high; mineral materials (such as zeolite, goethite, montmorillonite, etc.) have high thermal stability and mechanical properties, can reduce metal ion dissolution, but have low catalytic efficiency and difficult recovery. CuFe2O4And ZnFe2O4As the spinel type metal oxide, the size of the spinel type metal oxide can reach a nanoscale size, mass transfer resistance from reactants to the surface of the catalyst is favorably reduced, and the spinel type metal oxide has magnetism, is easy to recover and has low preparation cost. But CuFe2O4Catalyst particles or ZnFe2O4The catalyst particles are easy to agglomerate, the specific surface area is small, the number of active sites is small, the conductivity is poor, the contact probability of the catalyst and organic matters and the electron transfer process are hindered, and the catalytic efficiency is influenced. At present, methods such as noble metal doping or porous material loading and the like are mostly adopted to improve the dispersibility, the number of active sites and the electron transfer capacity of the catalyst, but the cost of the noble metal is higher, and the preparation process of the composite material is complex.
Disclosure of Invention
The invention aims to solve the problem of the existing CuFe2O4Catalyst particles or ZnFe2O4The problems of easy agglomeration of catalyst particles, small specific surface area, small number of active sites and poor conductivity are solved, and the porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst, the preparation method and the application thereof are provided.
A porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst, its preparation methodChemical formula is Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)X is 0.3 to 0.35; is in a porous spherical shape, and the particle size is concentrated between 120nm and 180 nm.
A preparation method of a porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst comprises the following steps:
firstly, preparing a solution A: dissolving copper nitrate, zinc sulfate and ferric nitrate in ethylene glycol, stirring at the temperature of 20-40 ℃ until the copper nitrate, the zinc sulfate and the ferric nitrate are completely dissolved, then adding sodium acetate powder, and stirring uniformly to obtain a solution A; the molar ratio of the copper nitrate, the zinc sulfate and the ferric nitrate is 0.5:0.5: 2;
secondly, preparing a solution B: dissolving cetyl trimethyl ammonium bromide in isopropanol, and stirring until the cetyl trimethyl ammonium bromide is completely dissolved to obtain a solution B;
thirdly, preparing a precursor: adding the solution B into the solution A, and uniformly stirring at the temperature of 20-40 ℃ to obtain a catalyst precursor;
fourthly, hydrothermal reaction: placing the catalyst precursor in a reaction kettle lined with polytetrafluoroethylene for hydrothermal reaction to obtain a hydrothermal reaction product;
fifthly, washing and drying: taking out the hydrothermal reaction product, washing and drying to obtain the porous magnetic conductive self-doped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)A catalyst.
The application of the porous magnetic conductive self-doped copper-zinc ferrite catalyst is that the porous magnetic conductive self-doped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)The catalyst is used as a catalyst and is used together with ozone for treating antibiotic wastewater.
The principle and the advantages of the invention are as follows:
firstly, Cu self-doped with Cu is prepared by adopting a solvothermal methodx-Cu(0.5-x)Zn0.5Fe2O(4-x)Catalyst, with CuFe2O4Catalyst or ZnFe2O4Compared with the catalyst, the multicomponent metallic oxide contains more lattice defects and is beneficial to organicPollutants are adsorbed on the surface of the catalyst and are further oxidized by active species, and meanwhile, the synergistic effect and the electron transfer among multiple metals are beneficial to improving the catalytic performance.
Secondly, the porous magnetic conductive self-doped Cu obtained by the inventionx-Cu(0.5-x)Zn0.5Fe2O(4-x)The catalyst is in a porous spherical shape, and the specific surface area of the catalyst is increased by a porous structure, so that the transmission and diffusion of substances are facilitated;
thirdly, the invention adopts glycol and isopropanol with strong reducibility as solvents, controls the adding amount of the alkali source sodium acetate and can induce Cu0.5Zn0.5Fe2O4The crystal generates intrinsic defects, and the chemical formula of the final product is Cu0.5Zn0.5Fe2O4To Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)The method realizes in-situ self-doping of Cu, the copper simple substance provides more active sites and oxygen vacancies, the electron transfer in the catalytic reaction process is facilitated, a large amount of surface active oxygen is generated, in addition, the self-doping does not need to introduce exogenous ions, the preparation cost is low, the method is simple and convenient, and the operation is safe.
And fourthly, modifying the surface of the catalyst by adopting hexadecyl trimethyl ammonium bromide, which is not only favorable for dispersing particles and avoiding agglomeration, but also prevents the surface of simple substance copper from generating copper oxide and reduces the conductivity.
The porous magnetic conductive self-doped Cu obtained by the inventionx-Cu(0.5-x)Zn0.5Fe2O(4-x)The catalyst has good dispersibility, large specific surface area, strong electron transfer capacity, remarkable effect of catalyzing, ozonizing and degrading the norfloxacin wastewater (under the condition that the dosage of the catalyst is 0.5g/L and the dosage of ozone is 1.52mg/L, when the concentration of norfloxacin is 10mg/L, the norfloxacin removal rate can reach 92.48 percent after the catalytic ozonization treatment is carried out for 30 min), easy separation and recovery (the recovery rate can reach 97.98 percent at most), good cycle stability (after the catalyst is recycled for 30 times, the norfloxacin removal rate is still maintained above 84 percent), and Cu2+、Zn2+、Fe3+The leaching is less than 0.5mg/L, and no secondary pollution exists, so the porous magnetic conductive self-doping C obtained by the inventionux-Cu(0.5-x)Zn0.5Fe2O(4-x)The catalyst is suitable for the advanced treatment of antibiotic wastewater.
Drawings
FIG. 1 shows Cu of the present inventionx-Cu(0.5-x)Zn0.5Fe2O(4-x)The crystal generates an electron transfer process schematic diagram of an intrinsic defect;
FIG. 2 shows the porous magnetically conductive autodoped Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67Scanning electron micrographs of the catalyst;
FIG. 3 is the porous magnetically conductive autodoped Cu of FIG. 20.33-Cu0.17Zn0.5Fe2O3.67The particle size distribution diagram of the catalyst;
FIG. 4 is an XRD pattern in which A represents CuFe obtained in comparative example 12O4XRD pattern of catalyst, B represents ZnFe obtained in comparative example 22O4XRD pattern of catalyst, C shows porous magnetic conductive autodoped Cu obtained from example 10.33-Cu0.17Zn0.5Fe2O3.67XRD pattern of the catalyst;
FIG. 5 is an XPS spectrum of Cu element, in which A represents CuFe obtained in comparative example 12O4XPS spectrum of Cu element of the catalyst; b represents the porous magnetically conductive autodoped Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67XPS spectrum of Cu element of the catalyst;
FIG. 6 is a degradation curve of norfloxacin wastewater, wherein T is a degradation curve of norfloxacin wastewater obtained in example 4, comparative example A is a degradation curve of norfloxacin wastewater obtained in comparative example 3, ● is a degradation curve of norfloxacin wastewater obtained in comparative example 4, and ■ is a degradation curve of norfloxacin wastewater obtained in comparative example 5;
FIG. 7 is a graph showing the cycle count-removal rate curve obtained in example 4 at ■, the cycle count-removal rate curve obtained in comparative example 3 at comparative example A, and the cycle count-removal rate curve obtained in comparative example 4 at ●.
Detailed Description
The first embodiment is as follows: the embodiment is a porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst with a chemical formula of Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)X is 0.3 to 0.35; is in a porous spherical shape, and the particle size is concentrated between 120nm and 180 nm.
The porous magnetic conductive copper-doped copper-zinc ferrite catalyst has intrinsic defects, is self-doped with Cu in situ, and the copper simple substance provides more active sites and oxygen vacancies, thereby being beneficial to electron transfer in the catalytic reaction process and having a large amount of surface active oxygen.
The second embodiment is as follows: the embodiment is a preparation method of a porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst, which is specifically completed by the following steps:
firstly, preparing a solution A: dissolving copper nitrate, zinc sulfate and ferric nitrate in ethylene glycol, stirring at the temperature of 20-40 ℃ until the copper nitrate, the zinc sulfate and the ferric nitrate are completely dissolved, then adding sodium acetate powder, and stirring uniformly to obtain a solution A; the molar ratio of the copper nitrate, the zinc sulfate and the ferric nitrate is 0.5:0.5: 2;
secondly, preparing a solution B: dissolving cetyl trimethyl ammonium bromide in isopropanol, and stirring until the cetyl trimethyl ammonium bromide is completely dissolved to obtain a solution B;
thirdly, preparing a precursor: adding the solution B into the solution A, and uniformly stirring at the temperature of 20-40 ℃ to obtain a catalyst precursor;
fourthly, hydrothermal reaction: placing the catalyst precursor in a reaction kettle lined with polytetrafluoroethylene for hydrothermal reaction to obtain a hydrothermal reaction product;
fifthly, washing and drying: taking out the hydrothermal reaction product, washing and drying to obtain the porous magnetic conductive self-doped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)An oxidizing agent.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that: the volume ratio of the total amount of the copper nitrate, the zinc sulfate and the ferric nitrate to the glycol in the first step is 3mmol (8-24) mL; the mass ratio of the total mass of the copper nitrate, the zinc sulfate and the ferric nitrate to the mass of the sodium acetate powder is 1 (1-2). The rest is the same as the second embodiment.
The fourth concrete implementation mode: the present embodiment differs from the second or third embodiment in that: and in the second step, the concentration of the hexadecyl trimethyl ammonium bromide in the solution B is 0.05 g/mL-0.1 g/mL. The other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: the second to fourth embodiments are different from the first to fourth embodiments in that: the volume ratio of the solution B to the solution A in the third step is 4: 1. The other points are the same as those in the second to fourth embodiments.
The sixth specific implementation mode: the second to fifth embodiments are different from the first to fifth embodiments in that: the operation parameters of the hydrothermal reaction in the fourth step are as follows: the hydrothermal temperature is 160-200 ℃, the hydrothermal time is 10-16 h, and the filling degree of the reaction kettle lined with polytetrafluoroethylene is 50-70%. The rest is the same as the second to fifth embodiments.
The seventh embodiment: the present embodiment differs from one of the second to sixth embodiments in that: the washing operation process in the step five is as follows: and washing with ethanol and deionized water alternately for 3 times. The rest is the same as the second to sixth embodiments.
The specific implementation mode is eight: the second embodiment differs from the first embodiment in that: the drying operation process in the step five is as follows: vacuum drying at 60 deg.c for 6-10 hr. The rest is the same as the second to seventh embodiments.
The specific implementation method nine: the embodiment is an application of a porous magnetic conductive self-doped copper-zinc ferrite catalyst, and the porous magnetic conductive self-doped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)The catalyst is used as a catalyst and is used together with ozone for treating antibiotic wastewater.
The detailed implementation mode is ten: the present embodiment differs from the ninth embodiment in that: the antibiotic wastewater is norfloxacin-containing wastewater. The rest is the same as in the ninth embodiment.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The following tests are adopted to verify the effect of the invention:
example 1: a preparation method of a porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst comprises the following steps:
firstly, preparing a solution A: dissolving 1.25mmol of copper nitrate, 1.25mmol of zinc sulfate and 5mmol of ferric nitrate in 20mL of ethylene glycol, stirring at 40 ℃ for 30min (solid is completely dissolved), adding 15mmol of sodium acetate powder, and stirring uniformly to obtain a solution A;
secondly, preparing a solution B: dissolving 0.5g of hexadecyl trimethyl ammonium bromide in 5mL of isopropanol, and stirring for 30min (completely dissolving the solid) to obtain a solution B;
thirdly, preparing a precursor: adding the solution B obtained in the step two into the solution A obtained in the step one, and magnetically stirring for 30min at the temperature of 30 ℃ to obtain a catalyst precursor;
fourthly, hydrothermal reaction: placing a catalyst precursor in a reaction kettle lined with polytetrafluoroethylene for hydrothermal reaction, wherein the volume of the reaction kettle lined with polytetrafluoroethylene is 50mL, and obtaining a hydrothermal reaction product;
fifthly, washing and drying: taking out the hydrothermal reaction product, washing and drying to obtain the porous magnetic conductive self-doped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)A catalyst.
The operating parameters for the hydrothermal reaction described in example 1, step four were as follows: the hydrothermal temperature is 200 ℃ and the hydrothermal time is 10 h.
The washing procedure described in step five of example 1 is as follows: and washing with ethanol and deionized water alternately for 3 times.
The drying procedure described in step five of example 1 is as follows: drying under vacuum at 60 deg.C for 10 h.
For the porous magnetic conductive self-doped Cu obtained in example 1x-Cu(0.5-x)Zn0.5Fe2O(4-x)The peak fitting analysis of the Cu element in the XPS spectrum of the catalyst revealed that x is 0.33, i.e., the porous magnetic conductive autodoped Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67A catalyst.
For the porous magnetic conductive self-doped Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67The catalyst is subjected to a scanning electron microscope, as shown in figure 2, and figure 2 shows the porous magnetic conductive self-doped Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67Scanning electron micrographs of the catalyst; as can be seen from FIG. 2, the porous magnetically conductive autodoped Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67The catalyst is in porous spherical shape, and the particle size distribution diagram is drawn according to FIG. 2, as shown in FIG. 3, FIG. 3 is the porous magnetic conductive self-doped Cu in FIG. 20.33-Cu0.17Zn0.5Fe2O3.67The particle size distribution of the catalyst is shown in FIG. 3, which shows that the porous magnetic conductive autodoped Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67The particle size of the catalyst is concentrated between 120nm and 180 nm.
Example 2: a preparation method of a porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst comprises the following steps:
firstly, preparing a solution A: dissolving 0.5mmol of copper nitrate, 0.5mmol of zinc sulfate and 2mmol of ferric nitrate in 24mL of ethylene glycol, stirring for 30min at the temperature of 20 ℃ (the solid is completely dissolved), then adding 3mmol of sodium acetate powder, and stirring uniformly to obtain a solution A;
secondly, preparing a solution B: dissolving 0.5g of hexadecyl trimethyl ammonium bromide in 6mL of isopropanol, and stirring for 20min (the solid is completely dissolved) to obtain a solution B;
thirdly, preparing a precursor: adding the solution B obtained in the step two into the solution A obtained in the step one, and magnetically stirring for 40min at the temperature of 40 ℃ to obtain a catalyst precursor;
fourthly, hydrothermal reaction: placing a catalyst precursor in a reaction kettle lined with polytetrafluoroethylene for hydrothermal reaction, wherein the volume of the reaction kettle lined with polytetrafluoroethylene is 50mL, and obtaining a hydrothermal reaction product;
fifthly, washing and drying: taking out the hydrothermal reaction product, washing and drying to obtain the porous magnetic conductive self-doped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)A catalyst.
The operating parameters for the hydrothermal reaction described in example 2, step four, were as follows: the hydrothermal temperature is 160 ℃, and the hydrothermal time is 16 h.
The washing procedure described in step five of example 2 is as follows: and washing with ethanol and deionized water alternately for 3 times.
The drying procedure in step five of example 2 is as follows: drying under vacuum at 60 deg.C for 6 h.
For the porous magnetic conductive self-doped Cu obtained in example 2x-Cu(0.5-x)Zn0.5Fe2O(4-x)When the catalyst was subjected to peak-to-peak fitting analysis of Cu element in XPS spectrum, it was found that x was 0.35, i.e., the porous magnetic conductive autodoped Cu obtained in example 20.35-Cu0.15Zn0.5Fe2O3.65A catalyst.
Example 3: a preparation method of a porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst comprises the following steps:
firstly, preparing a solution A: dissolving 1mmol of copper nitrate, 1mmol of zinc sulfate and 4mmol of ferric nitrate in 28mL of ethylene glycol, stirring at the temperature of 30 ℃ for 40min (the solid is completely dissolved), then adding 9mmol of sodium acetate powder, and stirring uniformly to obtain a solution A;
secondly, preparing a solution B: dissolving 0.5g of hexadecyl trimethyl ammonium bromide in 7mL of isopropanol, and stirring for 20min (the solid is completely dissolved) to obtain a solution B;
thirdly, preparing a precursor: adding the solution B obtained in the step two into the solution A obtained in the step one, and magnetically stirring for 40min at the temperature of 30 ℃ to obtain a catalyst precursor;
fourthly, hydrothermal reaction: placing a catalyst precursor in a reaction kettle lined with polytetrafluoroethylene for hydrothermal reaction, wherein the volume of the reaction kettle lined with polytetrafluoroethylene is 50mL, and obtaining a hydrothermal reaction product;
fifthly, washing and drying: taking out the hydrothermal reaction product, washing and drying to obtain the porous magnetic conductive self-doped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)A catalyst.
The operating parameters for the hydrothermal reaction described in example 3, step four, were as follows: the hydrothermal temperature is 180 ℃ and the hydrothermal time is 14 h.
Example 3 the washing procedure described in step five is as follows: and washing with ethanol and deionized water alternately for 3 times.
Example 3 the drying procedure described in step five is as follows: drying under vacuum at 60 deg.C for 8 h.
For the porous magnetic conductive self-doped Cu obtained in example 3x-Cu(0.5-x)Zn0.5Fe2O(4-x)When the catalyst was subjected to peak-to-peak fitting analysis of Cu element in XPS spectrum, it was found that x was 0.3, i.e., the porous magnetic conductive autodoped Cu obtained in example 30.3-Cu0.2Zn0.5Fe2O3.7A catalyst.
Comparative example 1: CuFe2O4The preparation method of the catalyst is specifically completed according to the following steps: :
firstly, dissolving 2.5mmol of copper nitrate and 5mmol of ferric nitrate in 20mL of water, magnetically stirring for 30min at the temperature of 40 ℃, then adding 3.6g of sodium acetate powder, and uniformly stirring to obtain a solution A;
secondly, dissolving 0.5g of hexadecyl trimethyl ammonium bromide in 5mL of water, and stirring for 30min to obtain a solution B;
thirdly, adding the solution B obtained in the second step into the solution A obtained in the first step, and magnetically stirring the solution A at the temperature of 30 ℃ for 30min to obtain CuFe2O4A catalyst precursor;
fourthly, mixing CuFe2O4Placing the catalyst precursor in a reaction kettle lined with polytetrafluoroethylene to perform hydrothermal reaction, wherein the volume of the reaction kettle lined with polytetrafluoroethylene is 50mL at the hydrothermal temperature of 200 ℃ for 10 hours to obtain a hydrothermal reaction product;
fifthly, washing and drying: taking out the hydrothermal reaction product, washing and drying to obtain CuFe2O4A catalyst.
Comparative example 1 the washing procedure described in step five was as follows: and washing with ethanol and deionized water alternately for 3 times.
Comparative example 1 the drying procedure described in step five was as follows: drying under vacuum at 60 deg.C for 6 h.
Comparative example 2: ZnFe2O4The preparation method of the catalyst is specifically completed according to the following steps: :
firstly, dissolving 2.5mmol of zinc sulfate and 5mmol of ferric nitrate in 20mL of water, magnetically stirring for 30min at the temperature of 40 ℃, then adding 3.6g of sodium acetate powder, and uniformly stirring to obtain a solution A;
secondly, dissolving 0.5g of hexadecyl trimethyl ammonium bromide in 5mL of water, and stirring for 30min to obtain a solution B;
thirdly, adding the solution B obtained in the second step into the solution A obtained in the first step, and magnetically stirring the solution A at the temperature of 30 ℃ for 30min to obtain ZnFe2O4A catalyst precursor;
fourthly, ZnFe is mixed2O4Placing the catalyst precursor in a reaction kettle lined with polytetrafluoroethylene to perform hydrothermal reaction, wherein the volume of the reaction kettle lined with polytetrafluoroethylene is 50mL at the hydrothermal temperature of 200 ℃ for 10 hours to obtain a hydrothermal reaction product;
fifthly, washing and drying: taking out the hydrothermal reaction product, washing and drying to obtain ZnFe2O4A catalyst.
Comparative example 2 the washing procedure described in step five was as follows: and washing with ethanol and deionized water alternately for 3 times.
Comparative example 2 the drying procedure described in step five was as follows: drying under vacuum at 60 deg.C for 10 h.
For the porous magnetic conductive self-doped Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67Catalyst, CuFe obtained in comparative example 12O4Catalyst and ZnFe obtained in comparative example 22O4The catalyst was subjected to XRD characterization, as shown in FIG. 4, where FIG. 4 is an XRD pattern, and A represents CuFe obtained in comparative example 12O4XRD pattern of catalyst, B represents ZnFe obtained in comparative example 22O4XRD pattern of catalyst, C shows porous magnetic conductive autodoped Cu obtained from example 10.33-Cu0.17Zn0.5Fe2O3.67XRD pattern of the catalyst, from FIG. 3, Cu0.33-Cu0.17Zn0.5Fe2O3.67The catalyst shows a characteristic peak of a Cu simple substance on the basis of keeping the original spinel structure, and indicates that Cu is successfully doped.
For the porous magnetic conductive self-doped Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67Catalyst and CuFe obtained in comparative example 12O4XPS analysis of Cu element is carried out on the catalyst, as shown in FIG. 5, FIG. 5 is the XPS spectrum of Cu element, and A in the graph represents CuFe obtained in comparative example 12O4XPS spectrum of Cu element of the catalyst; b represents the porous magnetically conductive autodoped Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67XPS spectrum of Cu element of the catalyst; as can be seen from FIG. 5, CuFe obtained in comparative example 12O4Cu elements in the catalyst are Cu2+And Cu obtained in example 10.33-Cu0.17Zn0.5Fe2O3.67The Cu element in the catalyst is 67.24 percent of Cu2+And 32.76% Cu0Composition, showing Cu0.33-Cu0.17Zn0.5Fe2O3.67Electron transfer to the surface of the catalyst, Cu0The self-doping is successful, and meanwhile, oxygen vacancies are generated, which is beneficial to improving the catalytic performance.
Example 4: application of porous magnetic conductive self-doped copper-zinc ferrite catalyst, namely porous magnetic conductive self-doped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)The catalyst is used as a catalyst and is used together with ozone for treating antibiotic wastewater: the antibiotic wastewater is norfloxacin-containing wastewater, and the porous magnetic conductive self-doped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)Catalyst is porous magnetic conductive self-doped Cu prepared in example 10.33-Cu0.17Zn0.5Fe2O3.67A catalyst; the specific implementation process is as follows:
firstly, placing 1L of norfloxacin wastewater with the concentration of 10mg/L into a glass reaction kettle, and introducing 1.52mg/L ozone for 2 min; then 0.5g of porous magnetic conductive self-doped Cu is added0.33-Cu0.17Zn0.5Fe2O3.67A catalyst;
continuously carrying out catalytic ozonation for 30min, sampling 10mL by using a peristaltic pump every 5min, filtering the sample by using a 0.22-micrometer filter membrane, detecting the concentration of the residual norfloxacin in the wastewater at 276nm by using an ultraviolet spectrophotometry, drawing a degradation curve of the norfloxacin wastewater according to detected data, calculating the removal rate, carrying out magnetic recovery after the catalyst ozonation is finished, and calculating the recovery rate;
thirdly, the porous magnetic conductive self-doped Cu obtained by magnetic recovery0.33-Cu0.17Zn0.5Fe2O3.67And (3) washing and drying the catalyst, recycling according to the first step and the second step for 29 times, calculating the norfloxacin removal rate in each recycling, and drawing a cycle number-removal rate curve.
The calculation shows that the porous magnetic conductive self-doping Cu is obtained in the second step of the example 40.33-Cu0.17Zn0.5Fe2O3.67The recovery rate of the catalyst was 97.98%, and Cu2+、Zn2+And Fe3+The leaching is less than 0.5mg/L, and no secondary pollution is caused.
Comparative example 3: this comparative example is different from example 4The same points are that: using CuFe2O4Catalyst for replacing porous magnetic conductive self-doped Cu0.33-Cu0.17Zn0.5Fe2O3.67A catalyst. The rest is the same as in example 4.
Comparative example 4: the comparative example differs from example 4 in that: using ZnFe2O4Catalyst for replacing porous magnetic conductive self-doped Cu0.33-Cu0.17Zn0.5Fe2O3.67A catalyst. The rest is the same as in example 4.
Comparative example 5: blank control without catalyst:
1L of norfloxacin wastewater with the concentration of 10mg/L is placed in a glass reaction kettle, and 1.52mg/L of ozone is introduced for 2 min; independently carrying out ozonization for 30min, sampling 10mL by using a peristaltic pump every 5min, filtering by using a 0.22-micrometer filter membrane, detecting the concentration of the residual norfloxacin in the wastewater at 276nm by adopting an ultraviolet spectrophotometry, drawing a degradation curve of the norfloxacin wastewater according to detected data, and calculating the removal rate;
summarizing the degradation curves of the norfloxacin wastewater obtained in example 4 and comparative examples 3 to 5, as shown in fig. 6, fig. 6 is the degradation curve of norfloxacin wastewater, wherein xxx represents the degradation curve of norfloxacin wastewater obtained in example 4, in the graph, comparative example a-solidup represents the degradation curve of norfloxacin wastewater obtained in comparative example 3, in the graph, ● represents the degradation curve of norfloxacin wastewater obtained in comparative example 4, and in the graph, ■ represents the degradation curve of norfloxacin wastewater obtained in comparative example 5; fig. 6 shows that the norfloxacin removal rate after 30min of catalytic ozonation treatment in example 4 is 92.48%, the norfloxacin removal rate after 30min of catalytic ozonation treatment in comparative example 3 is 72.22%, the norfloxacin removal rate after 30min of catalytic ozonation treatment in comparative example 4 is 86.86%, the norfloxacin removal rate after 30min of single ozonation treatment in comparative example 5 is 62.37%, and fig. 6 shows that the porous magnetic conductive self-doped Cu prepared in example 1 is in fig. 60.33-Cu0.17Zn0.5Fe2O3.67The catalytic ozonization efficiency is improved by 30.11 percent compared with that of the ozone alone, and the catalytic ozonization efficiency is improved by CuFe2O4And ZnFe2O4Compared with obvious improvement of watchThe porous magnetic conductive self-doped Cu obtained by the inventionx-Cu(0.5-x)Zn0.5Fe2O(4-x)The synergistic effect and electron transfer among multiple metals in the catalyst are beneficial to improving the catalytic performance.
Summarizing the cycle count-removal rate curves obtained in example 4 and comparative examples 3 to 5, as shown in FIG. 7, FIG. 7 is a cycle count-removal rate curve, ■ in the graph indicates the cycle count-removal rate curve obtained in example 4, comparative example A in the graph indicates the cycle count-removal rate curve obtained in comparative example 3, ● in the graph indicates the cycle count-removal rate curve obtained in comparative example 4, and it can be seen from FIG. 7 that the porous magnetic conductive autodoped Cu in example 4 is obtained by the porous magnetic conductive autodoped Cu0.33-Cu0.17Zn0.5Fe2O3.67After the agent is recycled for 30 times, the norfloxacin removal rate still reaches over 84 percent (84.21 percent), so the porous magnetic conductive self-doped Cu obtained by the inventionx-Cu(0.5-x)Zn0.5Fe2O(4-x)The catalyst has good stability.
Claims (10)
1. A porous magnetic conductive copper-doped copper-zinc ferrite catalyst is characterized in that the chemical formula of the porous magnetic conductive copper-doped copper-zinc ferrite catalyst is Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)X is 0.3 to 0.35; is in a porous spherical shape, and the particle size is concentrated between 120nm and 180 nm.
2. The preparation method of the porous magnetic conductive copper-self-doped copper-zinc ferrite catalyst according to claim 1, characterized by comprising the following steps:
firstly, preparing a solution A: dissolving copper nitrate, zinc sulfate and ferric nitrate in ethylene glycol, stirring at the temperature of 20-40 ℃ until the copper nitrate, the zinc sulfate and the ferric nitrate are completely dissolved, then adding sodium acetate powder, and stirring uniformly to obtain a solution A; the molar ratio of the copper nitrate, the zinc sulfate and the ferric nitrate is 0.5:0.5: 2;
secondly, preparing a solution B: dissolving cetyl trimethyl ammonium bromide in isopropanol, and stirring until the cetyl trimethyl ammonium bromide is completely dissolved to obtain a solution B;
thirdly, preparing a precursor: adding the solution B into the solution A, and uniformly stirring at the temperature of 20-40 ℃ to obtain a catalyst precursor;
fourthly, hydrothermal reaction: placing the catalyst precursor in a reaction kettle lined with polytetrafluoroethylene for hydrothermal reaction to obtain a hydrothermal reaction product;
fifthly, washing and drying: taking out the hydrothermal reaction product, washing and drying to obtain the porous magnetic conductive self-doped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)A catalyst.
3. The preparation method of the porous magnetic conductive self-doped copper zinc ferrite catalyst according to claim 2, wherein the volume ratio of the total amount of copper nitrate, zinc sulfate and ferric nitrate to glycol in the step one is 3mmol (8-24) mL; the mass ratio of the total mass of the copper nitrate, the zinc sulfate and the ferric nitrate to the mass of the sodium acetate powder is 1 (1-2).
4. The method according to claim 3, wherein the concentration of cetyltrimethylammonium bromide in the solution B in the second step is 0.05 g/mL-0.1 g/mL.
5. The method for preparing the porous magnetic conductive self-doped copper zinc ferrite catalyst according to claim 4, wherein the volume ratio of the solution B to the solution A in the third step is 4: 1.
6. The method for preparing the porous magnetic conductive self-doped copper zinc ferrite catalyst according to claim 5, wherein the operational parameters of the hydrothermal reaction in the fourth step are as follows: the hydrothermal temperature is 160-200 ℃, the hydrothermal time is 10-16 h, and the filling degree of the reaction kettle lined with polytetrafluoroethylene is 50-70%.
7. The method for preparing the porous magnetic conductive self-doped copper zinc ferrite catalyst according to claim 6, wherein the washing operation in step five is as follows: and washing with ethanol and deionized water alternately for 3 times.
8. The method for preparing the porous magnetic conductive self-doped copper zinc ferrite catalyst according to claim 7, wherein the drying operation in the fifth step is as follows: vacuum drying at 60 deg.c for 6-10 hr.
9. The use of the porous magnetic conductive autodoped copper zinc ferrite catalyst as claimed in claim 1 wherein the porous magnetic conductive autodoped Cux-Cu(0.5-x)Zn0.5Fe2O(4-x)The catalyst is used as a catalyst and is used together with ozone for treating antibiotic wastewater.
10. The use of the porous magnetic conductive self-doped copper zinc ferrite catalyst according to claim 9, wherein the antibiotic wastewater is norfloxacin-containing wastewater.
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