CN116899589A - Yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics and preparation method and application thereof - Google Patents

Yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics and preparation method and application thereof Download PDF

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CN116899589A
CN116899589A CN202310681528.9A CN202310681528A CN116899589A CN 116899589 A CN116899589 A CN 116899589A CN 202310681528 A CN202310681528 A CN 202310681528A CN 116899589 A CN116899589 A CN 116899589A
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yolk
cuco
photocatalytic material
znin
composite micro
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何祖明
申龙�
林凯
苏江滨
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
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Abstract

The invention discloses a yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics, and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving nitrate in organic solution, heating and preserving heat in an autoclave, cooling, centrifuging, drying the product at 60 ℃ for 12 hours to obtain CuCo-glycerol microspheres which are used as carriers, and growing ZnIn on the surface in situ by a hydrothermal method 2 S 4 Ultra-thin nanosheets to obtain CuCo-Glycerol microsphere/ZnIn 2 S 4 A composite material; heating and annealing to obtain CuCo with yolk-eggshell structure 2 O 4 /ZnIn 2 S 4 Photocatalytic microspheres. The nano microsphere has high specific surface area, adjustable structure and rich active sites, has obvious degradation efficiency on pollutants in water, especially antibiotic-containing pollutants in visible light, is simple to operate, has good reproducibility and is easy for large-scale production.

Description

Yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics and preparation method and application thereof
Technical Field
The invention belongs to the field of photocatalytic materials, and relates to a yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics, and a preparation method and application thereof.
Background
In recent years, the pharmaceutical manufacturing industry has rapidly progressed, and the pharmaceutical market scale has been expanding. Antibiotics (tetracycline, oxytetracycline, ciprofloxacin, etc.) have been widely used for prevention and control of various pathogens in human, livestock and aquaculture for the past decades due to their broad-spectrum antibacterial activity and good bactericidal effect. However, untreated sewage or industrial wastewater is mixed with rainwater, and unexpected breakage of sewage or industrial wastewater pipes, etc., causes a large amount of antibiotics to be found in artificial environments, and more evidence is showing that overuse and abuse of antibiotics have had a certain influence on the entire ecological system. Sewage treatment is an important problem faced by sustainable development of water environment in recent years, particularly, the discharge of a large amount of organic wastewater and medical wastewater becomes an important pollution source of water resources, and the pollutant components of the wastewater are complex, contain a large amount of toxic and harmful substances, have great degradation difficulty, have severe influence on ecological environment and have serious harm to human health and safety.
Recently, spinel-structured ACo 2 O 4 The compounds of (a= Ni, cu, zn, ca) are receiving increasing attention for their wide application in lithium ion batteries, magnetism, catalysis, supercapacitors, oxygen evolution reaction electrocatalysts, photovoltaic devices and the like. In particular CuCo 2 O 4 The advantages of narrow energy band gap (about 1.60 eV), low cost, no toxicity, good photocatalytic activity and the like are brought into wide attention. For example, sheet and studySpinel MCo was found 2 O 4 (m=co, ni, cu) oxidation of acetone, wherein CuCo 2 O 4 Has the highest oxidation activity. Von et al prepared CuCo 2 O 4 Sulfomethylpyrimidine is removed by peroxymonosulfate activation. Also, by which et al synthesized CuCo by polyacrylamide gel method 2 O 4 Has better degradation effect on the oxytetracycline hydrochloride under the irradiation of visible light. Although CuCo 2 O 4 Has unique spinel structure and excellent photocatalytic performance. But due to photo-generated electron-hole (e - -h + ) Queue separation efficiency is still low, limiting its further practical application. To overcome these problems, accelerate e - -h + The rapid separation of the team reduces the recombination probability to enhance the photocatalytic performance, and the coupling with other suitable semiconductor materials forms an efficient heterojunction structure between the different components, which is critical to improving the charge separation efficiency. For example, maria et al report CuCo under simulated sunlight 2 O 4 /g-C 3 N 4 The degradation rate of the methyl orange dye reaches 97% within 60 min. Also, there are studies reporting Cu 2 O/CuCo 2 O 4 The microsphere shows good photocatalytic activity on chlortetracycline oxidation and nitrobenzene reduction under visible light irradiation. The above research results show that CuCo 2 O 4 The composite material can effectively improve the photocatalysis efficiency.
So far, although researchers have surrounded CuCo 2 O 4 Extensive research work has been done, but there is no temporary reference to the yolk-eggshell structure CuCo 2 O 4 /ZnIn 2 S 4 And (5) researching a composite micro-nano photocatalytic material.
Disclosure of Invention
To solve the existing single CuCo 2 O 4 The invention aims to provide a CuCo with a yolk eggshell structure, which aims to solve the problem of low photocatalysis efficiency of a nano photocatalysis material catalyst 2 O 4 /ZnIn 2 S 4 Preparation method and application of composite micro-nano photocatalytic material, and CuCo prepared by adopting method 2 O 4 /ZnIn 2 S 4 The composite micro-nano catalyst is mainly applied to the treatment of organic pollutants in medical wastewater. The specific technical scheme is as follows:
a preparation method of a yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics comprises the following steps:
(1) Dissolving copper nitrate and cobalt nitrate in an organic solution, stirring uniformly to obtain a mixed solution A, adding the mixed solution A into an autoclave, heating and preserving heat, cooling to room temperature, centrifuging to obtain precipitate, cleaning, and drying to obtain CuCo-glycerol microspheres;
(2) Dispersing CuCo-glycerol microspheres in a mixed solution of ultrapure water/absolute ethyl alcohol by ultrasonic, adding a surfactant, then dropwise adding indium nitrate and zinc chloride, magnetically stirring for 30min, adding thioacetamide, and continuously stirring until a suspension solution B is formed;
(3) Transferring the suspension solution B into an autoclave, heating and preserving heat, cooling to room temperature, centrifuging to collect a product, cleaning and drying to obtain CuCo-glycerol microsphere/ZnIn 2 S 4 ；
(4) CuCo-glycerol microsphere/ZnIn 2 S 4 Heating and annealing in a tube furnace, and preserving heat to obtain the composite micro-nano photocatalytic material.
Preferably, in step (1), the molar ratio of copper nitrate to cobalt nitrate is 1:2.
Preferably, in the step (1), the heating temperature is 140-160 ℃, and the heat preservation time is 12-24 hours; the drying temperature is 60 ℃ and the drying time is 12-24 hours. .
Preferably, the organic solution comprises glycerin and isopropanol, and the mass fraction of the glycerin is 20% -80%.
Preferably, in step (2), the surfactant is dopamine or polyvinylpyrrolidone.
Preferably, in the step (2), the molar ratio of the CuCo-glycerol microsphere, the surfactant, the indium nitrate, the zinc chloride and the thioacetamide is (0.2-0.4): (0.13-0.26): 2:1 (4-5).
Preferably, in the step (3), the heating temperature is 140-180 ℃, and the heat preservation time is 12-24 hours; the drying temperature is 60 ℃ and the drying time is 12-24 hours.
Preferably, in the step (4), the heating annealing temperature is 300-450 ℃ and the time is 2-5 h.
The invention also provides the yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics, which is prepared by the preparation method and is characterized in that the composite micro-nano photocatalytic material has a yolk-eggshell structure and is prepared by CuCo 2 O 4 Is egg yolk with ZnIn 2 S 4 Is eggshell.
The invention also provides application of the yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics, which is prepared by the preparation method, in treating organic pollutants in medical wastewater.
Compared with the prior art, the invention has the beneficial effects that:
CuCo with yolk-eggshell structure prepared by the invention 2 O 4 /ZnIn 2 S 4 The micro-nano material is favorable for separating electrons and holes, and the CuCo 2 O 4 /ZnIn 2 S 4 The micro-nanospheres have the diameter of about 2 mu m and the appearance of the micro-nanospheres are of yolk-eggshell structures, have higher photocatalysis efficiency, can effectively degrade organic dyes in wastewater under visible light, and particularly have the photocatalysis degradation efficiency of 97% for Carbamazepine (CBZ) organic solution.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention, wherein:
FIG. 1 is a view of CuCo 2 O 4 、ZnIn 2 S 4 With CuCo obtained in example 1 2 O 4 /ZnIn 2 S 4 X-ray diffraction (XRD) pattern of micro-nanospheres.
FIG. 2 is a CuCo obtained in example 1 2 O 4 /ZnIn 2 S 4 Scanning Electron Microscope (SEM) image of the micro-nanospheres.
FIG. 3 is a CuCo obtained in example 1 2 O 4 /ZnIn 2 S 4 TEM image of micro-nanospheres.
FIG. 4 is a CuCo obtained in example 1 2 O 4 /ZnIn 2 S 4 And the degradation efficiency of the micro-nanospheres on methylene blue organic solution is shown in the figure.
Detailed Description
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not themselves indicate the relationship between the various embodiments and/or arrangements discussed.
Example 1
A preparation method of a yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics comprises the following steps:
(1): dissolving 0.01mmol of copper nitrate and 0.02mmol of cobalt nitrate in an isopropanol mixed organic solution containing 50% of glycerin content, and magnetically stirring for 1h uniformly to obtain a mixed solution A;
(2) Adding the mixed solution A into a 100ml autoclave, heating the mixed solution to 160 ℃, preserving heat for 24 hours, naturally cooling to room temperature, centrifuging to obtain a product, washing with ethanol and ultrapure water for three times, and drying at 60 ℃ for 24 hours to obtain the CuCo-glycerol microsphere.
(3) 0.2g of CuCo-glycerol microspheres are dispersed in a mixed solution of ultrapure water/absolute ethyl alcohol (volume ratio of the two is 1:1) by ultrasonic, 0.1g of dopamine is added as a surfactant, then 0.01mmol of indium nitrate and 0.005mmol of zinc chloride are added dropwise, after magnetic stirring is carried out for 30min, 0.02mmol of thioacetamide is added, and magnetic stirring is carried out for 30min to form a suspension solution B.
(4) Transferring the suspension solution B into an autoclave, heating to 180 ℃, preserving heat for 24 hours, naturally cooling to room temperature, centrifugally collecting a product, washing with ethanol and ultrapure water for 3 times, and drying at 60 ℃ for 24 hours to obtain CuCo-glycerol microspheres/ZnIn 2 S 4 。
(5) CuCo-glycerol microsphere/ZnIn 2 S 4 Heating to 350 ℃ in a tube furnace, annealing and preserving heat for 5 hours to finally prepare the CuCo with the yolk-eggshell structure 2 O 4 /ZnIn 2 S 4 The micro-nano sphere photocatalytic material is marked as 10-CuCo 2 O 4 /ZnIn 2 S 4 Micro-nano spheres.
Comparative example 1
For comparison, pure CuCo was prepared separately 2 O 4 And ZnIn 2 S 4 . Dissolving 0.01mmol of copper nitrate and 0.02mmol of cobalt nitrate in an isopropanol mixed organic solution containing 50% of glycerin content, and magnetically stirring for 1h uniformly to obtain a mixed solution A; adding the mixed solution A into a 100ml autoclave, heating the mixed solution to 160 ℃, preserving heat for 24 hours, naturally cooling to room temperature, centrifuging to obtain a product, washing with ethanol and ultrapure water for three times, and drying at 60 ℃ for 24 hours to obtain the CuCo-glycerol microsphere. Placing CuCo-glycerol microsphere in a tube furnace, heating to 350 ℃ for annealing and preserving heat for 5 hours, and finally obtaining the CuCo 2 O 4 Micro-nano sphere photocatalysis material.
After magnetically stirring 0.01mmol of indium nitrate and 0.005mmol of zinc chloride for 30min, 0.02mmol of thioacetamide was added thereto, and magnetically stirred for another 30min to form a suspension solution. Transferring the suspension solution into an autoclave, heating to 180 ℃, preserving heat for 24 hours, naturally cooling to room temperature, centrifugally collecting a product, washing with ethanol and ultrapure water for 3 times, and drying at 60 ℃ for 24 hours to obtain ZnIn 2 S 4 Micro-nano. CuCo prepared in example 1 2 O 4 /ZnIn 2 S 4 CuCo prepared in comparative example 1 2 O 4 And ZnIn 2 S 4 As shown in FIG. 1, the comparison of the spectrum of the diffraction peak with the standard card shows that the egg yolk eggshell CuCo prepared in this example 2 O 4 /ZnIn 2 S 4 The micro-nano spheres are pure and free of impurities; cuCo prepared in example 1 2 O 4 /ZnIn 2 S 4 As shown in fig. 2, the size of the micro-nanospheres is about 2 μm; cuCo prepared in example 1 2 O 4 /ZnIn 2 S 4 The TEM results of (A) are shown in FIG. 3, the prepared CuCo 2 O 4 /ZnIn 2 S 4 The micro-nano sphere has a yolk-eggshell structure.
Example 2
Step (1): dissolving 0.01mmol of copper nitrate and 0.02mmol of cobalt nitrate in an isopropanol mixed organic solution containing 30% of glycerol, and magnetically stirring for 50min uniformly to obtain a mixed solution A;
(2) Adding the mixed solution A into a 100ml autoclave, heating the mixed solution to 160 ℃, preserving heat for 20 hours, naturally cooling to room temperature, centrifuging to obtain a product, washing with ethanol and ultrapure water for three times, and drying at 60 ℃ for 20 hours to obtain the CuCo-glycerol microsphere.
(3) 0.12g of CuCo-glycerol microspheres are dispersed in a mixed solution of ultrapure water and absolute ethanol by ultrasonic, 0.1g of bar polyamine is added as a surfactant, then 0.01mmol of indium nitrate and 0.005mmol of zinc chloride are added dropwise, and after magnetic stirring for 30min, 0.025mmol of thioacetamide is added, and magnetic stirring is carried out for 30min to form a suspension solution B.
(4) Transferring the suspension solution B into an autoclave, heating to 160 ℃, preserving heat for 12 hours, naturally cooling to room temperature, centrifugally collecting a product, washing with ethanol and ultrapure water for 3 times, and drying at 60 ℃ for 24 hours to obtain CuCo-glycerol microspheres/ZnIn 2 S 4 。
(5) CuCo-glycerol microsphere/ZnIn 2 S 4 Heating to 450 ℃ in a tube furnace, annealing and preserving heat for 3 hours to finally prepare the CuCo with the yolk-eggshell structure 2 O 4 /ZnIn 2 S 4 The micro-nano sphere photocatalytic material is marked as 5-CuCo 2 O 4 /ZnIn 2 S 4 Micro-nano spheres.
Example 3
Step (1): dissolving 0.01mmol of copper nitrate and 0.02mmol of cobalt nitrate in an isopropanol mixed organic solution containing 80% of glycerin content, and magnetically stirring for 30min uniformly to obtain a mixed solution A;
(2) Adding the mixture solution A into a 100ml autoclave, heating the mixture solution to 140 ℃, preserving heat for 12 hours, naturally cooling to room temperature, centrifuging to obtain a product, washing with ethanol and ultrapure water for three times, and drying at 60 ℃ for 12 hours to obtain the CuCo-glycerol microsphere.
(3) 0.25g of CuCo-glycerol microspheres are dispersed in a mixed solution of ultrapure water and absolute ethyl alcohol by ultrasonic, 0.2g of dopamine is added as a surfactant, then 0.01mmol of indium nitrate and 0.005mmol of zinc chloride are added dropwise, after magnetic stirring is carried out for 30min, 0.02mmol of thioacetamide is added, and a suspension solution B is formed after magnetic stirring is carried out for 30 min.
(4) Transferring the suspension solution B into an autoclave, heating to 140 ℃, preserving heat for 24 hours, naturally cooling to room temperature, centrifugally collecting a product, washing with ethanol and ultrapure water for 3 times, and drying at 60 ℃ for 24 hours to obtain CuCo-glycerol microspheres/ZnIn 2 S 4 。
(5) CuCo-glycerol microsphere/ZnIn 2 S 4 Heating to 400 ℃ in a tube furnace, annealing and preserving heat for 4 hours to finally prepare the CuCo with the yolk-eggshell structure 2 O 4 /ZnIn 2 S 4 The micro-nano sphere photocatalytic material is marked as 15-CuCo 2 O 4 /ZnIn 2 S 4 Micro-nano spheres.
CuCo prepared in examples 1 to 3 2 O 4 /ZnIn 2 S 4 Micro-nano material and CuCo prepared in comparative example 1 2 O 4 And ZnIn 2 S 4 Respectively applied to the treatment of the organic pollutants in the medical wastewater. Namely, 0.1g of 5-CuCo is taken respectively 2 O 4 /ZnIn 2 S 4 、10-CuCo 2 O 4 /ZnIn 2 S 4 、15-CuCo 2 O 4 /ZnIn 2 S 4 Micro-nano material and CuCo 2 O 4 And ZnIn 2 S 4 Respectively adding into 100mL and 20mg/L carbamazepine solution, and placing under 500W ultraviolet-visible light lamp for photocatalytic reaction, wherein the distance between the light source and the reaction liquid surface is 20cm. As a result, as shown in FIG. 4, 5-CuCo was obtained as the reaction time passed 2 O 4 /ZnIn 2 S 4 、10-CuCo 2 O 4 /ZnIn 2 S 4 And 15-CuCo 2 O 4 /ZnIn 2 S 4 The residual concentration of the treated Carbamazepine (Carbamazepine) organic solution is substantially zero, such as 10-CuCo after 120 minutes of photocatalysis 2 O 4 /ZnIn 2 S 4 The catalytic degradation effect is best, the degradation rate reaches 97.0 percent, and CuCo 2 O 4 And ZnIn 2 S 4 The residual concentration of the treated carbamazepine organic solution is still maintained above 60 percent, so that the catalyst prepared by the invention can effectively degrade the carbamazepine organic solution.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention herein. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that the invention is not limited to the precise arrangements and instrumentalities shown in the drawings, which have been described above, and that various modifications and changes may be effected without departing from the scope thereof. The scope of the invention is limited only by the appended claims.

Claims (10)

1. The preparation method of the yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics is characterized by comprising the following steps of:
(1) Dissolving copper nitrate and cobalt nitrate in an organic solution, stirring uniformly to obtain a mixed solution A, adding the mixed solution A into an autoclave, heating and preserving heat, cooling to room temperature, centrifuging to obtain precipitate, cleaning, and drying to obtain CuCo-glycerol microspheres;
(2) Dispersing the CuCo-glycerol microspheres in a mixed solution of ultrapure water/absolute ethyl alcohol by ultrasonic, adding a surfactant, then dropwise adding indium nitrate and zinc chloride, magnetically stirring for 30min, adding thioacetamide, and continuously stirring until a suspension solution B is formed;
(3) Transferring the suspension solution B into an autoclave, heating and preserving heat, cooling to room temperature, centrifuging to collect a product, cleaning and drying to obtain CuCo-glycerol microsphere/ZnIn 2 S 4 ；
(4) The CuCo-glycerol microsphere/ZnIn 2 S 4 Heating and annealing in a tube furnaceAnd (3) heating to prepare the composite micro-nano photocatalytic material.
2. A yolk eggshell structure CuCo for degrading antibiotics according to claim 1 2 O 4 /ZnIn 2 S 4 The preparation method of the composite micro-nano photocatalytic material is characterized in that in the step (1), the molar ratio of the copper nitrate to the cobalt nitrate is 1:2.
3. The method for preparing the composite micro-nano photocatalytic material with the yolk-eggshell structure for degrading antibiotics according to claim 1, wherein in the step (1), the heating temperature is 140-160 ℃, and the heat preservation time is 12-24 hours; the drying temperature is 60 ℃, and the drying time is 12-24 hours. .
4. The preparation method of the yolk-eggshell structured composite micro-nano photocatalytic material for degrading antibiotics according to claim 1, wherein the organic solution comprises glycerin and isopropanol, and the mass fraction of the glycerin is 20% -80%.
5. The method for preparing the composite micro-nano photocatalytic material with the yolk-eggshell structure for degrading antibiotics according to claim 1, wherein in the step (2), the surfactant is dopamine or polyvinylpyrrolidone.
6. The preparation method of the yolk-eggshell structured composite micro-nano photocatalytic material for degrading antibiotics according to claim 1, wherein in the step (2), the molar ratio of the CuCo-glycerol microsphere, the surfactant, the indium nitrate, the zinc chloride and the thioacetamide is (0.2-0.4): (0.13-0.26): 2:1 (4-5).
7. The method for preparing the composite micro-nano photocatalytic material with the yolk-eggshell structure for degrading antibiotics according to claim 1, wherein in the step (3), the heating temperature is 140-180 ℃, and the heat preservation time is 12-24 hours; the drying temperature is 60 ℃, and the drying time is 12-24 hours.
8. The method for preparing the composite micro-nano photocatalytic material with the yolk-eggshell structure for degrading antibiotics according to claim 1, wherein in the step (4), the heating annealing temperature is 300-450 ℃ and the time is 2-5 h.
9. The composite micro-nano photocatalytic material with yolk-eggshell structure for degrading antibiotics prepared by the preparation method of any one of claims 1 to 8, which is characterized in that the composite micro-nano photocatalytic material has a yolk-eggshell structure and is prepared by CuCo 2 O 4 Is egg yolk with ZnIn 2 S 4 Is eggshell.
10. The application of the yolk eggshell structure composite micro-nano photocatalytic material for degrading antibiotics prepared by the preparation method of any one of claims 1-8 in treating organic pollutants in medical wastewater.
CN202310681528.9A 2023-06-09 2023-06-09 Yolk-eggshell structure composite micro-nano photocatalytic material for degrading antibiotics and preparation method and application thereof Pending CN116899589A (en)

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