An oxygen vacancy type Bi 2 O 2 CO 3 / MIL-101-NH 2 Composite catalyst, preparation method thereof and application

Abstract

The present invention discloses an oxygen vacancy type Bi2O2CO3 / MIL-101-NH2 composite catalyst, its preparation method and application, belonging to the technical fields of catalytic oxidation and water environment treatment. The composite catalyst provided by the present invention forms a heterojunction structure rich in oxygen vacancies by loading MIL-101-NH2 onto the surface of Bi2O2CO3; the Bi2O2CO3 is in the form of cluster flower-like structures with a diameter of 2-3 μm; the MIL-101-NH2 is in the form of spindle-shaped particles with a length of 500-1000 nm, rich in oxygen vacancies, and is dispersedly loaded in the stamens of the Bi2O2CO3. The composite catalyst provided by the present invention exhibits high catalytic oxidation performance in the test of photocatalytic activation of peroxymonosulfate (PMS) for treating antibiotic-containing water bodies, can effectively remove antibiotics in water in a short time, and has excellent application potential for antibiotic treatment.

Description

Technical Field

[0001] The present invention relates to the technical fields of photocatalytic materials, persulfate catalytic oxidation, and water environment treatment, and particularly relates to an oxygen vacancy type Bi 2 O 2 CO 3 / MIL-101-NH 2 composite catalyst, a preparation method thereof, and an application thereof. Background Technique

[0002] Antibiotics are widely used in human medicine, livestock production, and aquaculture. However, humans or livestock cannot completely absorb or metabolize antibiotics. Therefore, a large part of the ingested antibiotics will be discharged into the environment, resulting in the accumulation of antibiotics in the environment. The environmental release and pollution of antibiotics may promote the development and spread of antibiotic resistance, damage the effectiveness of human drug action, and seriously threaten human health and safety and environmental ecological safety. Therefore, it is necessary to further deepen the research on antibiotic treatment technologies, develop economical and efficient antibiotic treatment methods, and degrade the difficult-to-remove antibiotic molecules into low-toxicity small-molecule substances.

[0003] Advanced oxidation technologies can generate various reactive oxygen species (ROS) for degrading antibiotics and degrade antibiotics into low-toxicity small-molecule intermediates, showing great application potential in antibiotic wastewater treatment. Among them, photocatalysis and persulfate oxidation technologies have attracted much attention. Photocatalysis uses green and clean solar energy to excite photo-generated charges, and then generates ROS to degrade pollutants in water. The advanced oxidation technology based on persulfate activation can generate sulfate radicals (SO 4 -· ,E 0 = 2.5 - 3.1V) with strong adaptability and high reaction efficiency, which has attracted extensive attention from scholars at home and abroad.

[0004] A large number of studies have been carried out on photocatalytic technology in the past few decades. As a heterogeneous catalytic process, it has shown significant advantages in water treatment. However, compared with traditional advanced oxidation technologies, the application of photocatalysis in actual water treatment systems is very limited. The synergistic effect of photocatalysis and persulfate oxidation can promote the removal of antibiotics. Photo-generated electrons can be captured by persulfate and participate in the formation of sulfate radicals. At the same time, the consumption of photo-generated charges can inhibit the recombination of photo-generated charges and improve the photocatalytic activity. For example, Tong et al. synthesized boron-doped C 3 N 5For the degradation of 5 mg / L of tetracycline in a heterogeneous photocatalysis combined with peroxymonosulfate system, photocatalytic activation of persulfate was achieved within 120 minutes, realizing the efficient degradation of tetracycline (Wu.et al, Peroxymonosulfate activation by boron doped C3N5 metal-free materials with n→π* electronic transitions for tetracycline degradation under visible light: Insights into the generation of reactive species, Doi.org / 10.1016 / j.cej.2023.147693). However, its preparation method is complex and the reaction time is long.

[0005] CN117380285A provides a photocatalytic membrane system based on Bi 2 O 2 CO 3 -UIO-66-NH 2 heterojunction catalyst. Under the synergistic effect of photocatalysis and membrane filtration, the degradation rate of tetracycline can reach 100% within 50 min. However, this method still relies on photocatalytic degradation of pollutants and the degradation time is long. Summary of the Invention

[0006] In view of the above problems existing in the prior art, the present invention provides an oxygen vacancy type Bi 2 O 2 CO 3 / MIL-101-NH 2 composite catalyst, its preparation method and application. The composite catalyst provided by the present invention shows high catalytic oxidation performance in the test of photocatalytic activation of peroxymonosulfate (PMS) for treating antibiotic water bodies, can effectively remove antibiotics in water in a short time, and has excellent application potential for antibiotic treatment.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] An oxygen vacancy type Bi 2 O 2 CO 3 / MIL-101-NH 2 composite catalyst, wherein the composite catalyst is a composite material with a heterojunction structure in which MIL-101-NH 2 is loaded on the surface of Bi 2 O 2 CO 3 ;

[0009] The said Bi 2 O 2 CO 3 is a cluster flower-like structure with a diameter of 2 - 3 μm; the MIL-101-NH 2 is a spindle-shaped particle structure with an average particle size of 500 - 1000 nm, rich in oxygen vacancies, and closely adheres to the flower center of the flower-like Bi 2 O 2 CO 3 to form a novel Fe-Bi heterojunction.

[0010] Preferably, the MIL-101-NH 2 is synthesized by a solvothermal method. Dissolve FeCl 3 ·6H 2 O and 2-aminoterephthalic acid in N,N-dimethylformamide, i.e., DMF. After mixing evenly, carry out a solvothermal reaction to generate MIL-101-NH 2 ;

[0011] For every 1 - 2 mmol of FeCl 3 ·6H 2 O, 12 - 24 mL of DMF is required as a solvent. The molar ratio of FeCl 3 ·6H 2 O to 2-aminoterephthalic acid is 8 - 9:1 - 2.

[0012] Preferably, the solvothermal reaction temperature is 100 - 120 °C, and the reaction time is 22 - 26 hours.

[0013] Preferably, the Bi 2 O 2 CO 3 / MIL-101-NH 2 composite catalyst is synthesized by a hydrothermal method. Dissolve MIL-101-NH 2 , Bi(NO 3 ) 3 ·5H 2 O and C 6 H 5 Na 3 O 7 in deionized water. After mixing evenly, carry out a hydrothermal reaction to generate Bi 2 O 2 CO 3 / MIL-101-NH 2 ;

[0014] By mass ratio, Bi(NO 3 ) 3 ·5H 2O:C 6 H 5 Na 3 O 7 : MIL-101-NH 2 = 14 - 18:10 - 16:1 - 3;

[0015] The dosage of the deionized water is 34 - 69 mL of deionized water used as a solvent for every 1 - 2 g of Bi(NO 3 ) 3 ·5H 2 O added.

[0016] Preferably, the pH is adjusted to 9 - 10 with ammonia water before the hydrothermal reaction, the hydrothermal reaction temperature is 160 - 200 °C, and the reaction time is 22 - 25 hours.

[0017] The present invention also provides the application of the oxygen vacancy type Bi 2 O 2 CO 3 / MIL-101-NH 2 composite catalyst. Using the composite catalyst as a photocatalyst, activate persulfate under visible light irradiation to degrade antibiotics in water.

[0018] Furthermore, the specific method for degrading antibiotics is: adding Bi 2 O 2 CO 3 / MIL-101-NH 2 composite catalyst as a photocatalyst. After the photocatalyst reaches the adsorption - desorption equilibrium under dark conditions, add persulfate, and generate oxidative active substances under visible light irradiation to degrade antibiotics.

[0019] Preferably, the wavelength of the visible light is greater than 400 nm, and the persulfate is monopersulfate.

[0020] Preferably, the antibiotic is tetracycline; the pH range of the water containing antibiotics is 5 - 9.

[0021] Preferably, the addition concentration of the Bi 2 O 2 CO 3 / MIL-101-NH 2 composite catalyst is 0.1 - 0.3 g / L, and the addition concentration of the persulfate is 0.7 - 1.1 mM.

[0022] Furthermore, the concentration range of the antibiotics in the water is 0 - 100 mg / L, preferably 0.01 - 100 mg / L.

[0023] The beneficial technical effects of the present invention are as follows:

[0024] 1. Different from the traditional MIL-101-NH 2 in the preparation method, the molar ratio of FeCl 3 ·6H 2 O to 2-aminoterephthalic acid is set to 2:1. Instead, the dosing ratio of FeCl 3 ·6H 2 O to 2-aminoterephthalic acid is greatly increased to 8:1, obtaining MIL-101-NH 2 with more active sites of MOF metal clusters, thus improving the photocatalytic activity.

[0025] 2. The present invention combines MIL-101-NH 2 with Bi 2 O 2 CO 3 . The MIL-101-NH 2 particles occupy the growth sites of Bi 2 O 2 CO 3 so that the originally randomly distributed nanosheets stack to form thick petals, forming the morphological effect of "buds blooming into flowers". From the perspective of optoelectronic properties, the surface is loaded with a transition metal MOF with excellent optoelectronic properties, effectively inhibiting the separation of photo-generated electrons and holes, and constructing a novel Fe-Bi heterojunction catalyst with excellent photocatalytic activity.

[0026] 3. The heterojunction material prepared by the present invention contains oxygen vacancies and transition metals, which can promote the charge transfer on the surface of the catalytic material and the valence state conversion of iron ions, enhance the activation ability of persulfate, and can continuously generate 1 O 2 and SO 4 -· to improve the degradation ability, which is beneficial to improving the removal effect of antibiotics.

[0027] 4. The Bi 2 O 2 CO 3 / MIL-101-NH 2 heterojunction material provided by the present invention can activate persulfate to generate a large amount of ROS through two ways: the photo-generated charges generated by photocatalysis and the transition metal ions of MOF, thereby efficiently degrading antibiotics.

[0028] 5. The Bi 2 O 2 CO 3 / MIL-101-NH 2Heterojunction materials show good cost - effectiveness and application prospects for treating tetracycline in wastewater. Compared with CN117380285A, whose degradation rate is about 84% in 20 minutes, the optimal degradation rate of the present invention can reach 100% in 20 minutes, which is of great significance for the development of efficient and economic antibiotic wastewater treatment. The present invention adopts a photocatalytic coupling persulfate system, which greatly enhances the application potential in actual water treatment systems. Description of the Drawings

[0029] Figure 1 SEM images of flower - shaped Bi 2 O 2 CO 3 (a), spindle - shaped MIL - 101 - NH 2 (b), and the composite material Bi 2 O 2 CO 3 / MIL - 101 - NH 2 (c - d) in Example 2;

[0030] Figure 2 XRD patterns of Bi 2 O 2 CO 3 , MIL - 101 - NH 2 , and the composite material Bi 2 O 2 CO 3 / MIL - 101 - NH 2 in Example 2;

[0031] Figure 3 ESR spectra of Bi 2 O 2 CO 3 , MIL - 101 - NH 2 , and the composite material Bi 2 O 2 CO 3 / MIL - 101 - NH 2 in Example 2;

[0032] Figure 4 Comparison chart of the degradation performance of Bi 2 O 2 CO 3 , MIL - 101 - NH 2 , and the composite material Bi 2 O 2 CO 3 / MIL - 101 - NH 2 composite materials for 10 mg / L tetracycline under visible light and 0.9 mM PMS conditions in Test Example 1;

[0033] Figure 5 For the material Bi obtained in Test Example 2 2 O 2 CO 3 / MIL-101-NH 2 Comparison chart of the degradation performance of tetracycline at different concentrations under visible light and 0.9 mM PMS conditions;

[0034] Figure 6 For the material Bi obtained in Test Example 3 2 O 2 CO 3 / MIL-101-NH 2 Comparison chart of the degradation performance of tetracycline solutions with different pH values under visible light and 0.9 mM PMS conditions;

[0035] Figure 7 For the material Bi obtained in Test Example 4 2 O 2 CO 3 / MIL-101-NH 2 Reusability chart of tetracycline degradation under visible light and 0.9 mM PMS conditions. Detailed implementation manners

[0036] The exemplary embodiments of the present disclosure will now be described in detail. Although the exemplary embodiments of the present disclosure are shown, it should be clear that the figures and embodiments shown in the exemplary embodiments of the present disclosure are only a part of the invention and should not be considered as a limitation to the present invention. These embodiments are provided to enable researchers in the field to have a clearer understanding of the present disclosure.

[0037] Example 1:

[0038] Dissolve 5 mmol of FeCl 3 ·6H 2 O and 0.625 mmol of 2-aminoterephthalic acid in 60 ml of DMF. After magnetic stirring for 0.5 h, place the mixed solution in a reaction kettle and react at a constant temperature of 110 °C for 24 h. After the reaction is completed, centrifuge and wash, and dry at 60 °C for 8 h to obtain MIL-101-NH 2 .

[0039] Mix 50 mg of the pre-prepared MIL-101-NH 2 , 1.5 mmol of Bi(NO 3 ) 3 ·5H 2 O (0.73 g) and 2.25 mmol of C 6 H 5 Na 3O 7 (0.58 g) was dissolved in 25 mL of deionized water. After stirring evenly, the mixed solution was adjusted to pH = 9 with ammonia water. Subsequently, after magnetic stirring evenly, the mixed solution was transferred to a reaction kettle and reacted at 180 °C for 24 hours. The reacted material was washed repeatedly with ethanol and deionized water, and the sample obtained after drying overnight at 60 °C was recorded as Bi 2 O 2 CO 3 / MIL-101-NH 2 -50 composite catalyst.

[0040] Example 2:

[0041] Same as Example 1, the only difference is that the dosage of MIL-101-NH 2 was 100 mg, and the finally obtained sample was recorded as Bi 2 O 2 CO 3 / MIL-101-NH 2 -100 composite catalyst.

[0042] The SEM of the material prepared by the above method is as shown in Figure 1 Figure. It can be seen from Figure 1 (a) that the surface of Bi 2 O 2 CO 3 has many fine and curly nanosheet "petals" forming a cluster-like flower bud structure; it can be seen from (b) that MIL-101-NH 2 shows a typical spindle structure with an average particle size of 500 - 1000 nm, and most of the crystal sizes are similar and angular; it can be seen from (c) that the surface morphology of the composite material has changed compared with Bi 2 O 2 CO 3 The fine flower buds gradually disperse, and the nanosheets gather to form thick petals with an average diameter of 2 - 3 μm. The MIL-101-NH 2 O 2 CO 3 particles are embedded in the flower core, forming a new type of Fe-Bi heterojunction; it can be seen from (d) that the edges of the MIL-101-NH 2 crystals are gradually passivated to form smooth particles, which are embedded in the flower core of Bi 2 O 2 CO 2 CO 3 .

[0043] The XRD pattern of the material prepared by the above method is as shown in the appendix Figure 2 Figure. It can be seen from the figure that MIL-101-NH2 A distinct diffraction peak was shown at the 9.4° position, while for Bi 2 O 2 CO 3 the characteristic peaks were all indexed with tetragonal Bi 2 O 2 CO 3 (JCPDS 84-1752). Bi 2 O 2 CO 3 / MIL-101-NH 2 -100 retained the characteristic diffraction peaks of MIL-101-NH 2 and Bi 2 O 2 CO 3 However, the diffraction intensities corresponding to the (013) and (110) crystal planes at 30.3° and 32.7° decreased to some extent, which might be attributed to the stacking of nanosheets into thick petals and the lattice distortion caused by the embedding of MIL-101-NH 2 -100.

[0044] The ESR spectra of the prepared materials are as Figure 3 shown. It can be seen that different signal peaks at g = 2.013 were observed in all the prepared photocatalysts, indicating the existence of oxygen vacancies. However, the oxygen vacancy signal of Bi 2 O 2 CO 3 / MIL-101-NH 2 -100 was weaker than that of MIL-101-NH 2 , which might be attributed to the collapse of some oxygen vacancies during the synthesis process.

[0045] Example 3:

[0046] Same as Example 1, except that the dosage of MIL-101-NH 2 was 150 mg, and the finally obtained sample was recorded as Bi 2 O 2 CO 3 / MIL-101-NH 2 -150 composite catalyst.

[0047] Test Example 1: Comparison of tetracycline degradation between the composite catalyst and monomer materials in the PMS system

[0048] Accurately weigh 20 mg of Bi 2 O 2 CO 3 / MIL-101-NH 2 -100 composite photocatalytic material, single cluster flower-like Bi with a diameter of 2-3 μm2 O 2 CO 3 Spindle-shaped MIL-101-NH with a particle size of 500-1000 nm 2 materials were respectively added to 100 mL of tetracycline solution with a concentration of 10 mg / L. After 30 min of dark reaction to reach the adsorption-desorption equilibrium, the xenon lamp was turned on, and 0.9 mM PMS was added simultaneously. Samples were taken at certain time intervals (0, 2, 5, 10, 20 min), and the remaining tetracycline concentration was measured using a high-performance liquid chromatograph to evaluate the degradation efficiency of each catalyst for tetracycline.

[0049] The degradation effect results of each catalyst for tetracycline are as Figure 4 shown. As can be seen from Figure 4 that after 20 min of reaction under visible light irradiation and 0.9 mM PMS conditions, the removal rates of the single materials Bi 2 O 2 CO 3 and MIL-101-NH 2 are 77.8% and 89.2% respectively. Under the same conditions, the degradation efficiency of the composite material Bi 2 O 2 CO 3 / MIL-101-NH 2 is significantly improved, and the degradation rate is increased to 100%, which is significantly better than the monomer materials. The photocatalytic activity of the monomer materials is low. The construction of the heterojunction effectively inhibits the recombination of photogenerated carriers, improves the photocatalytic activity, and promotes the migration of photogenerated carriers. Compared with the simple photocatalytic system, the photocatalytic activation PMS system adopted in the present invention not only activates PMS through the photogenerated electrons generated by photocatalysis in addition to degrading pollutants through the traditional photocatalytic pathway, but also the Fe transition metal in the heterojunction material can activate PMS to generate a large amount of ROS, showing a more efficient and rapid degradation effect on tetracycline.

[0050] Test Example 2: Comparison of the degradation effects of composite catalysts on tetracycline with different concentrations

[0051] Accurately weigh 20 mg of Bi 2 O 2 CO 3 / MIL-101-NH 2 -100 composite material and add it to 100 mL of tetracycline solution with initial concentrations of 5, 10, and 20 mg / L. After 30 min of dark reaction to reach the adsorption-desorption equilibrium, the xenon lamp was turned on, and 0.9 mM PMS was added simultaneously. Samples were taken at certain time intervals (0, 2, 5, 10, 20 min), and the remaining tetracycline concentration was measured using a high-performance liquid chromatograph to evaluate the degradation efficiency of each catalyst for tetracycline.

[0052] The degradation effect of the heterojunction material catalyst on tetracycline at different concentrations is as follows Figure 5 shown. It can be seen from Figure 5 that when the tetracycline concentration is increased from 5 mg / L to 20 mg / L, the degradation efficiency of Bi 2 O 2 CO 3 / MIL-101-NH 2 decreases from 100% to 82.6%. This is because as the tetracycline concentration increases, more tetracycline molecules will consume the free radicals and holes of the catalyst, thus reducing the removal efficiency of tetracycline.

[0053] Test Example 3: Comparison of the degradation effect of different reaction pH on tetracycline

[0054] Accurately weigh 20 mg of Bi 2 O 2 CO 3 / MIL-101-NH 2 -100 composite material and add it to 100 mL of tetracycline solution with a concentration of 10 mg / L at different solution pH values (3, 5, 7, 9, 11). After 30 minutes of dark reaction to reach the adsorption-desorption equilibrium, turn on the xenon lamp, and simultaneously add 0.9 mM PMS. Sample at certain time intervals (0, 2, 5, 10, 20 min), and use a high-performance liquid chromatograph to measure the remaining tetracycline concentration to evaluate the degradation efficiency of each catalyst on tetracycline.

[0055] The degradation effect of different reaction pH on tetracycline is as follows Figure 6 shown. It can be seen from Figure 6 that the optimal degradation pH of Bi 2 O 2 CO 3 / MIL-101-NH 2 is between 5 and 9. When the degradation solution is acidic, especially at pH = 3, the degradation rate drops to 70.8%. This is because under acidic conditions, the free radical O 2 - excited by the photocatalyst is easily consumed by H + , resulting in a decrease in the concentration of reactive oxygen species and a reduction in the photocatalytic degradation efficiency.

[0056] Test Example 4: Reusability

[0057] Accurately weigh 20 mg of Bi 2 O 2 CO 3 / MIL-101-NH 2-100 composite materials were added to 100 mL of tetracycline solution with a concentration of 10 mg / L. After 30 minutes of dark reaction to reach the adsorption and desorption equilibrium, the xenon lamp was turned on, and 0.9 mM PMS was added simultaneously to start the degradation reaction. The dark reaction plus the light reaction treatment for 50 minutes was taken as one cycle. After one cycle, the reaction solution was centrifuged and dried to collect the catalyst, and the next cycle was carried out. The remaining tetracycline concentration was measured using a high-performance liquid chromatograph to evaluate the degradation efficiency of each catalyst for tetracycline. It should be noted that each cycle included the 30 minutes required for adsorption equilibrium.

[0058] The results of the reusability performance are as Figure 7 shown. The abscissa is the degradation time (Time), and the ordinate is the tetracycline degradation rate (C t / C 0 ), where C 0 is the initial concentration of tetracycline, and C t is the real-time concentration. After four degradation cycles, the Bi 2 O 2 CO 3 / MIL-101-NH 2 -persulfate system could still maintain a tetracycline degradation efficiency of 84.5%, showing excellent reusability performance.

[0059] Although the embodiments of the present invention have been disclosed above, it is not limited to only the applications listed in the specification and embodiments. It can be fully applied to various fields suitable for the present invention. For those familiar with the field, for ordinary technical personnel in the field, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirits of the present invention. Therefore, without departing from the general concept defined by the claims and the equivalent scope, the present invention is not limited to specific details.

Claims

1. An oxygen vacancy type Bi2O2CO3 / MIL-101-NH2 composite catalyst, characterized in that: The composite catalyst is a composite material with a heterojunction structure in which MIL-101-NH2 is loaded on the surface of Bi2O2CO3; The Bi2O2CO3 is a clustered flower-like structure with a diameter of 2-3 μm; the MIL-101-NH2 is a spindle-like particle structure with an average particle size of 500-1000 nm, rich in oxygen vacancies, and tightly fits in the center of the flower-like Bi2O2CO3 to form a Fe-Bi heterojunction; The MIL-101-NH2 is synthesized by a solvothermal method, wherein FeCl3·6H2O and 2-aminoterephthalic acid are dissolved in N,N-dimethylformamide (DMF), mixed evenly, and then subjected to a solvothermal reaction to generate MIL-101-NH2; 12-24 mL of DMF is required as solvent for each addition of 1-2 mmol of FeCl3·6H2O, and the molar ratio of FeCl3·6H2O to 2-aminoterephthalic acid is 8-9:1-2.

2. The composite catalyst according to claim 1, characterized in that The solvent thermal reaction temperature is 100-120° C., and the reaction time is 22-26 hours.

3. The composite catalyst according to claim 1, characterized in that The Bi2O2CO3 / MIL-101-NH2 composite catalyst is synthesized by a hydrothermal method, wherein MIL-101-NH2, Bi(NO3)3·5H2O and C6H5Na3O7 are dissolved in deionized water, mixed evenly and then subjected to a hydrothermal reaction to generate Bi2O2CO3 / MIL-101-NH2; According to the mass ratio, Bi(NO3)3·5H2O:C6H5Na3O7:MIL-101-NH2=14-18:10-16:1-3; The amount of deionized water used is 34-69 mL of deionized water as a solvent for every 1-2 g of Bi(NO3)3·5H2O added.

4. The composite catalyst according to claim 3, characterized in that Before the hydrothermal reaction, the pH is adjusted to 9-10 with ammonia water, the hydrothermal reaction temperature is 160-200° C., and the reaction time is 22-25 hours.

5. Use of the oxygen vacancy type Bi2O2CO3 / MIL-101-NH2 composite catalyst according to any one of claims 1 to 4, characterized in that: The composite catalyst is used as a photocatalyst to activate persulfate to degrade antibiotics in water under visible light irradiation.

6. The use according to claim 5, characterized in that: The specific method for degrading antibiotics is: adding Bi2O2CO3 / MIL-101-NH2 composite catalyst as a photocatalyst to water containing antibiotics, adding persulfate after the photocatalyst reaches adsorption-desorption equilibrium under dark conditions, and generating oxidative active substances to degrade antibiotics under visible light irradiation.

7. The use according to claim 6, characterized in that: The wavelength of the visible light is greater than 400 nm, and the persulfate is peroxymonosulfate.

8. The use according to claim 6, characterized in that: The antibiotic is tetracycline; the pH range of the water containing the antibiotic is 5-9.

9. The use according to claim 6, characterized in that: The added concentration of the Bi2O2CO3 / MIL-101-NH2 composite catalyst is 0.1-0.3 g / L, and the added concentration of the persulfate is 0.7-1.1 mM.

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