Hindered Lewis acid-base pair type oxygen-defective vanadium oxyhydroxide Fenton catalyst and preparation method and application thereof

Abstract

The present invention discloses a vanadium hydroxide Fenton-type catalyst with oxygen-rich defects of hindered Lewis acid-base pair type, a preparation method and an application, and belongs to the field of water treatment technology. The preparation method comprises: adding vanadate to deionized water, ultrasonically stirring to obtain a vanadate solution; adding peroxodisulfate solution dropwise to the vanadate solution, stirring evenly and then adding ammonia water; hydrothermally reacting the suspension to obtain a precursor powder; spreading the precursor powder on a conductive glass, placing it in a plasma discharge device, passing gas after vacuuming, and then starting the discharge treatment to obtain vanadium hydroxide. The present invention produces oxygen defects on the material through a discharge treatment process, thereby changing the local coordination environment of the adjacent space of V and OH, so that the unbonded Lewis acid and Lewis base close to the steric hindrance form a hindered Lewis acid-base pair, which can enhance the activation of peroxides to produce a large number of active oxidizing species to degrade antibiotic pollutants as a Fenton-type catalyst.

Description

Technical Field

[0001] The invention belongs to the technical field of water treatment, and in particular relates to a hindered Lewis acid-base pair type oxygen-rich defect vanadium oxyhydroxide Fenton catalyst, a preparation method and an application thereof. Background Art

[0002] In recent years, antibiotic pollution has become a global environmental problem. Various antibiotics frequently detected in natural water bodies such as surface water and groundwater pose a serious threat to public health and ecological security. Therefore, it is necessary to adopt efficient, economical and environmentally friendly methods to treat antibiotic pollutants in water bodies.

[0003] Advanced oxidation technology is a deep water treatment technology that has been widely used in the treatment of environmental organic pollution wastewater and has achieved remarkable results. Among them, Fenton-like oxidation technology, as one of the typical representatives of advanced oxidation technology, has attracted much attention due to its advantages such as simple conditions, fast reaction speed, wide application range and good treatment effect. Fenton-like systems do not require special reaction equipment and external energy input. They activate peroxides such as hydrogen peroxide (H2O2), persulfate (PS) and peracetic acid (PAA) through solid-phase catalysts to produce free radicals and non-free radicals and other active oxidizing species, which can decompose highly toxic and difficult-to-degrade organic pollutants into small molecules until they are mineralized into CO2, H2O and inorganic salts.

[0004] Designing and preparing high-performance catalysts is the key to fully utilize the performance of activated peroxides in degrading mineralized pollutants in Fenton-like oxidation technology. x O y , M represents metal, x and y represent atomic numbers) has always been an important member of the Fenton-like catalyst family, and the metal redox pairs (M (n+1)+ / M n+ ) is crucial in determining the activation process and direction of peroxides. (n+1)+ Towards low valence state M n+ The high reaction energy barrier for conversion leads to low intrinsic cycle efficiency of metal redox pairs, which is one of the main factors that currently hinder transition metal oxides from becoming high-performance Fenton-like catalysts.

[0005] Constructing hindered Lewis acid-base pairs (FLPs) on materials based on micro-mesoscopic surface structure and electronic structure regulation to improve local spatial electronic polarization is a feasible solution to improve the cycling efficiency of metal redox pairs. Metal oxyhydroxides contain Lewis acids (M cations) and Lewis bases (-OH anions), which have the basic conditions for constructing hindered Lewis acid-base pairs. Vanadium oxyhydroxide is an ideal precursor material due to its low toxicity, low price and high activity.

[0006] The present invention adopts a plasma discharge surface modification treatment method, creates oxygen defects on a vanadium oxyhydroxide material, changes the local coordination environment of the space adjacent to V and -OH, and makes the unbonded Lewis acid and Lewis base that are sterically hindered to form a hindered Lewis acid-base pair, thereby preparing a hindered Lewis acid-base pair type oxygen-defect-rich vanadium oxyhydroxide catalyst; the catalyst is used to activate peroxide to treat antibiotic wastewater, thereby improving the treatment effect of antibiotic pollutants in water bodies. Summary of the invention

[0007] The purpose of the present invention is to provide a hindered Lewis acid-base pair type oxygen-rich defect vanadium oxyhydroxide Fenton catalyst and a preparation method and application thereof, wherein the catalyst can enhance the activation of peroxides and achieve efficient degradation and removal of antibiotic pollutants in polluted water. The catalyst is simple to prepare, has good economic efficiency, and has good catalytic degradation performance for a variety of antibiotic pollutants.

[0008] The technical solution of the present invention is as follows:

[0009] The method for preparing vanadium oxyhydroxide with hindered Lewis acid-base pair type oxygen-defective vanadium oxyhydroxide comprises the following steps:

[0010] (1) adding vanadate to deionized water and stirring with ultrasonic waves to obtain a vanadate solution;

[0011] (2) Add the peroxodisulfate solution dropwise to the vanadate solution, stir evenly, then add aqueous ammonia, and continue stirring to form a uniform suspension;

[0012] (3) subjecting the suspension to a hydrothermal reaction, and after the reaction is completed, centrifuging, washing, and drying to obtain a precursor powder;

[0013] (4) Spread the precursor powder on conductive glass, place it in a plasma discharge device, evacuate the vacuum, introduce gas, and then start the discharge treatment to obtain vanadium oxide hydroxide with oxygen-rich defects of the hindered Lewis acid-base pair type.

[0014] In a further embodiment, the vanadate in step (1) is one of orthovanadate, metavanadate and pyrovanadate;

[0015] The concentration of the vanadate solution is 4 to 8 mg / mL;

[0016] The temperature of the ultrasonic stirring is 50-80°C.

[0017] In a further embodiment, the peroxodisulfate solution in step (2) comprises a sodium peroxodisulfate solution or a potassium peroxodisulfate solution;

[0018] The concentration of the peroxodisulfate solution is 1 mol / L, and the amount added is 0.5 to 2 mL;

[0019] The mass concentration of the ammonia water is 25-28%, and the amount added is 3-8 mL.

[0020] In a further embodiment, the hydrothermal reaction in step (3) is carried out in a closed reactor at a temperature of 110 to 130° C. for 2 to 6 hours.

[0021] In a further embodiment, in step (4), the discharge power of the plasma discharge device is 20 to 40 W, and the discharge treatment time is 10 to 30 minutes.

[0022] The second object of the present invention is to provide a hindered Lewis acid-base pair type oxygen-defect-rich vanadium oxyhydroxide prepared by the above preparation method.

[0023] The third invention objective of the present invention is to provide the application of the above-mentioned hindered Lewis acid-base pair type oxygen-defective vanadium oxyhydroxide, which is used to degrade antibiotics in polluted water.

[0024] In a further embodiment, the step of degrading the antibiotic in the contaminated water includes: uniformly dispersing the hindered Lewis acid-base pair type oxygen-rich defect vanadium oxyhydroxide in the contaminated water containing the antibiotic;

[0025] Then add peroxide and stir;

[0026] Then, the degradation reaction was carried out in a water bath at 25 to 35°C for 10 to 60 minutes;

[0027] After the reaction is completed, the hindered Lewis acid-base pair type oxygen-rich defect vanadium oxide hydroxide is recovered by filtration.

[0028] In a further embodiment, the antibiotic comprises tetracycline, oxytetracycline, sulfadiazine, sulfamethoxazole, norfloxacin or ofloxacin;

[0029] The peroxide is hydrogen peroxide, persulfate or peracetic acid, and the persulfate is any one of potassium peroxymonosulfate, sodium peroxymonosulfate, potassium peroxodisulfate and sodium peroxodisulfate;

[0030] The water bath degradation reaction was carried out in a shaker at 180 ~ 250 rpm.

[0031] In a further embodiment, the mass ratio of vanadium oxyhydroxide to antibiotics in the contaminated water is 5 to 15:1, and the concentration of peroxide is 0.1 to 5 mM.

[0032] The metal oxyhydroxide in the hindered Lewis acid-base pair type oxygen-deficient vanadium oxyhydroxide prepared by the present invention contains Lewis acid (metal cation) and Lewis base (hydroxyl anion), that is, oxygen defects are produced on the material through a discharge treatment process, thereby changing the local coordination environment of the Lewis acid and Lewis base in the adjacent space, and inducing adaptive adjustment of the bonding length and angle. Among them, the unbonded Lewis acid and Lewis base that are close to each other in steric hindrance constitute a hindered Lewis acid-base pair, which in turn generates a polar activation cloud, enhances the confined electron mass transfer and mediation on the surface of the material, and promotes the circulation efficiency of the metal redox pair; at the same time, the hydroxyl groups on the material can also provide active sites as electron donors, improve its activation of peroxides, adsorption of pollutants, and the redox reaction between the generated active oxidative species and antibiotics.

[0033] Therefore, in the present application, the hindered Lewis acid-base pair type oxygen-deficient vanadium oxide obtained by plasma discharge modification and optimization treatment is used as a catalyst and peroxide to form a Fenton-like oxidation system, which is used to enhance the activation of peroxide to produce active oxidative species (free radicals and non-free radicals) to degrade and remove antibiotics in water.

[0034] Furthermore, the vanadium oxyhydroxide prepared in the present application can be applied to Fenton-like degradation of other simulated antibiotic-contaminated water and actual antibiotic-contaminated water, wherein the simulated antibiotic-contaminated water includes antibiotic-contaminated water prepared with pure water, tap water, river water, lake water, and river water.

[0035] The present invention adopts relatively low-priced ammonium vanadate, potassium peroxodisulfate and ammonia water, and prepares hindered Lewis acid-base pair type oxygen-rich defect vanadium oxide hydroxide through solvothermal method and plasma discharge surface modification treatment. The vanadium oxide hydroxide is used as a Fenton-like catalyst to enhance the generation of active oxidative species by activated peroxide, so as to achieve the purpose of degrading and removing antibiotics in water. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 are SEM images, wherein a is a SEM image of the precursor powder VOOH-0 prepared in Example 1, and b is a SEM image of the hindered Lewis acid-base pair type oxygen-rich defect vanadium oxyhydroxide material VOOH-1 prepared in Example 1;

[0037] Figure 2 This is an XRD pattern of the hindered Lewis acid-base pair type oxygen-defect-rich vanadium oxyhydroxide material prepared in Example 1;

[0038] Figure 3 This is an EPR image of the hindered Lewis acid-base pair type oxygen-defect-rich vanadium oxyhydroxide material prepared in Example 1;

[0039] Figure 4This is a diagram showing the effect of activating potassium peroxymonosulfate to degrade tetracycline using the hindered Lewis acid-base pair type oxygen-defective vanadium oxyhydroxide material prepared in Example 1. DETAILED DESCRIPTION

[0040] The present invention is further described below in conjunction with specific embodiments, but the essence of the present invention is not limited to the following embodiments. The methods are conventional methods unless otherwise specified, and the materials can be obtained from public commercial channels unless otherwise specified. Those skilled in the art should know that any simple transformation or substitution based on the essence of the present invention belongs to the protection scope claimed by the present invention.

[0041] In the following examples, a FEI-Quanta 200 scanning electron microscope (SEM) was used to characterize the morphology;

[0042] Use PANalytical X-ray diffractometer (XRD) to characterize the crystal form and structural characteristics of the material;

[0043] A Bruker EMX X plus-10 / 12 electron paramagnetic resonance spectrometer (EPR) was used to semi-quantitatively characterize the oxygen defect concentration;

[0044] The concentration of antibiotics in the treated water samples was measured using an Agilent 1220 high performance liquid chromatograph.

[0045] Example 1

[0046] (1) Dissolve 0.468 g of ammonium metavanadate in 90 mL of deionized water, stir ultrasonically at 60°C to dissolve it, and cool it to obtain a yellow-green ammonium metavanadate solution;

[0047] (2) Add 1 mL of potassium peroxodisulfate solution (concentration: 1 mol / L) dropwise to the ammonium metavanadate solution. After stirring evenly, add 5 mL of ammonia water (mass concentration: 26%) to the above solution and continue stirring at room temperature for 30 minutes to form a uniform suspension.

[0048] (3) The suspension was transferred to a polytetrafluoroethylene-lined reactor, sealed and subjected to hydrothermal reaction at 120 °C for 4 h. After the reaction, the suspension was centrifuged and washed with distilled water and ethanol three times to remove any possible residues. The suspension was then vacuum dried at 60 °C for 10 h to obtain a precursor powder, which was designated as VOOH-0.

[0049] (4) The precursor powder was placed in a plasma discharge device, and before discharge, it was first evacuated and then nitrogen was passed for 5 minutes, and then the discharge was treated at a power of 30 W for 10 minutes to obtain a hindered Lewis acid-base pair type oxygen-rich vanadium oxyhydroxide material, which was recorded as VOOH-1.

[0050] Test example 1:

[0051] The precursor powder VOOH-0 in Example 1 was used as the comparative example 1 and the vanadium oxyhydroxide material VOOH-1 prepared in Example 1 was characterized as follows: SEM image (such as Figure 1 ) show that both have sea urchin-like structures; XRD patterns (such as Figure 2 ) shows that the crystal structure of the vanadium oxyhydroxide material does not change significantly after plasma discharge treatment.

[0052] Comparative Example 2:

[0053] The same as Example 1, except that the discharge power of the plasma discharge device is 10 W, and the obtained hindered Lewis acid-base pair type oxygen-defective vanadium oxyhydroxide material is denoted as VOOH-2.

[0054] Embodiment 2:

[0055] The same as Example 1, except that the discharge power of the plasma discharge device is 20 W, and the obtained hindered Lewis acid-base pair type oxygen-defective vanadium oxyhydroxide material is denoted as VOOH-3.

[0056] Embodiment 3:

[0057] The same as Example 1, except that the discharge power of the plasma discharge device is 40 W, and the obtained hindered Lewis acid-base pair type oxygen-defective vanadium oxyhydroxide material is denoted as VOOH-4.

[0058] Embodiment 4:

[0059] The same as Example 1, except that the discharge power of the plasma discharge device is 30 W, the treatment time is 30 minutes, and the obtained hindered Lewis acid-base pair type oxygen-rich vanadium oxyhydroxide material is recorded as VOOH-5.

[0060] Test example 2:

[0061] The oxygen defect concentrations of VOOH-0 and VOOH-2 in Comparative Examples 1 and 2 and vanadium oxyhydroxide materials VOOH-1, VOOH-3, VOOH-4 and VOOH-5 prepared in Examples 1 to 4 were semi-quantitatively characterized using a Bruker EMX X plus-10 / 12 electron paramagnetic resonance spectrometer (EPR). The EPR spectra are shown in FIG. Figure 3As shown, it is shown that under the same treatment time, as the plasma discharge power increases, the oxygen defect concentration in the vanadium oxyhydroxide material increases accordingly. However, when the power exceeds 30 W, or under the same power, the discharge treatment time is too long, which will affect the meso-microstructure of the material, and the concentration of oxygen defects decreases slightly. Therefore, the discharge power of the plasma discharge device in this application is 20 ~ 40 W, and the discharge treatment time is 10 ~ 30 minutes.

[0062] Specifically, the precursor powder VOOH-0 in the comparative example has the lowest oxygen defect concentration because it has not been subjected to plasma discharge treatment;

[0063] The oxygen defect concentration of VOOH-2 prepared in Comparative Example 2 is greater than that of VOOH-0, but less than that of VOOH-1;

[0064] The oxygen defect concentration of VOOH-3 prepared in Example 2 is greater than that of VOOH-0 and VOOH-2, but less than that of VOOH-1;

[0065] The oxygen defect concentration of VOOH-4 prepared in Example 3 is greater than that of VOOH-0, VOOH-2, and VOOH-3, but less than that of VOOH-1;

[0066] The oxygen defect concentration of VOOH-5 prepared in Example 4 is greater than that of VOOH-0, VOOH-2, and VOOH-3, but less than that of VOOH-1 and VOOH-4.

[0067] Test example 3:

[0068] Experiment on degradation of tetracycline pollutants in wastewater by activated peroxymonosulfate (PMS):

[0069] Weigh 10 mg each of the precursor powders VOOH-0 and VOOH-2 prepared in Comparative Examples 1 and 2 and the vanadium oxyhydroxide materials VOOH-1, VOOH-3, VOOH-4, and VOOH-5 prepared in Examples 1-4, and add them to 100 mL of a water sample containing 20 mg / L of tetracycline (denoted as C0), and then add 0.2 mM potassium peroxymonosulfate to each of them, and react at 25°C. The pH value of each water sample is 7, which is suitable for actual water bodies and does not require further adjustment. After fully shaking at 180 rpm in a shaker, samples are taken at certain time intervals (such as taking water samples at 0, 5, 10, 15, 20, 25, and 30 minutes respectively), and the tetracycline content in the water sample is detected after filtering (denoted as C), as shown in detail. Figure 4As shown in the figure, after 30 minutes of reaction, VOOH-1 activated PMS can remove 98% of tetracycline pollutants, while the removal rate of the precursor powder VOOH-0 / PMS system is only 43%. The removal rates of tetracycline by VOOH-2, VOOH-3, VOOH-4, and VOOH-5 activated PMS are 69%, 85%, 92%, and 89%, respectively.

[0070] Embodiment 5:

[0071] (1) Dissolve 0.4 g of sodium orthovanadate in 100 mL of deionized water, stir ultrasonically at 50°C to dissolve it, and cool it to obtain a sodium orthovanadate solution;

[0072] (2) Add 0.5 mL of potassium peroxodisulfate solution (concentration: 1 mol / L) dropwise to the sodium orthovanadate solution, stir evenly, then add 3 mL of ammonia water (mass concentration: 25%) to the above solution, and continue stirring at room temperature for 30 minutes to form a uniform suspension;

[0073] (3) The suspension was transferred to a polytetrafluoroethylene-lined reactor, sealed and subjected to hydrothermal reaction at 130 °C for 2 h. After the reaction, the suspension was centrifuged, washed with distilled water and ethanol three times to remove any possible residues, and then vacuum dried at 60 °C for 10 h to obtain a precursor powder.

[0074] (4) The precursor powder was placed in a plasma discharge device, and before discharge, it was first evacuated and then nitrogen was passed for 5 minutes, and then the discharge was treated at a power of 30 W for 10 minutes to obtain a vanadium oxyhydroxide material with oxygen-rich defects of the hindered Lewis acid-base pair type, which was recorded as VOOH-6.

[0075] Embodiment 6:

[0076] (1) Dissolve 0.8 g of sodium pyrovanadate in 100 mL of deionized water, stir ultrasonically at 80°C to dissolve it, and cool it to obtain a sodium pyrovanadate solution;

[0077] (2) Add 2 mL of sodium peroxodisulfate solution (concentration: 1 mol / L) dropwise to the sodium pyrovanadate solution, stir evenly, then add 8 mL of ammonia water (mass concentration: 28%) to the above solution, and continue stirring at room temperature for 30 minutes to form a uniform suspension;

[0078] (3) The suspension was transferred to a polytetrafluoroethylene-lined reactor, sealed and subjected to hydrothermal reaction at 110 °C for 6 h. After the reaction, the suspension was centrifuged, washed with distilled water and ethanol three times to remove any possible residues, and then vacuum dried at 60 °C for 10 h to obtain a precursor powder.

[0079] (4) The precursor powder is placed in a plasma discharge device, and before discharge, it is first evacuated and then nitrogen is passed for 5 minutes, and then the discharge treatment is performed at a power of 20 W for 20 minutes to obtain a vanadium oxyhydroxide material with oxygen-rich defects of the hindered Lewis acid-base pair type, which is recorded as VOOH-7.

[0080] As in Test Example 3, 30 mg of each vanadium oxyhydroxide material prepared in Examples 5 and 6 were added to 100 mL of sulfadiazine (20 mg / L) water sample, and then 5 mM peracetic acid was added to each sample. After being fully shaken at 200 rpm in a shaker at 25°C, samples were taken after 30 minutes. The sulfadiazine content in the water samples was detected after filtration, and the removal rates were 97% and 94%, respectively.

[0081] Comparative Example 3:

[0082] The same as Example 1, except that the discharge power is 50 W and the time is 10 minutes, and a hindered Lewis acid-base pair type oxygen-rich vanadium oxyhydroxide material is obtained, which is recorded as VOOH-8.

[0083] Comparative Example 4:

[0084] The same as Example 1, except that the discharge power is 15 W and the discharge time is 30 minutes, and a hindered Lewis acid-base pair type oxygen-rich vanadium oxyhydroxide material is obtained, which is recorded as VOOH-9.

[0085] Similar to Test Example 3, 20 mg of each vanadium oxyhydroxide material prepared in Comparative Examples 3 and 4 was added to 100 mL of norfloxacin (20 mg / L) water sample, and then 0.1 mM potassium peroxymonosulfate was added to each sample. After being fully shaken at 250 rpm in a shaker at 25°C, samples were taken after 30 minutes to detect the norfloxacin content in the water samples, and the removal rates were 57% and 49%, respectively.

[0086] From the above, it can be concluded that by regulating the appropriate plasma discharge treatment process (discharge power, treatment time, etc.), oxygen defects can be created on the vanadium oxyhydroxide material, thereby changing the local coordination environment of the space adjacent to V and -OH, so that the unbonded Lewis acid and Lewis base that are sterically close to each other form a hindered Lewis acid-base pair, which in turn produces a polar activation cloud, enhances the confined electron mass transfer and mediation on the material surface, and promotes the circulation efficiency of the metal redox pair; at the same time, the hydroxyl groups on the material can also act as electron donors to provide active sites, further improving the removal of pollutants, and the removal rate basically reaches more than 85%.

[0087] Finally, it should be noted that the above embodiments are only preferred implementations of the present invention and are only used to explain the present invention, not to limit the present invention. For those skilled in the art, they can still modify the technical solutions recorded in the above embodiments, or replace some of the technical features therein with equivalents. Any changes, replacements and modifications made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing vanadium oxyhydroxide with hindered Lewis acid-base pair type oxygen-rich defects, characterized in that: The following steps are involved: (1) adding vanadate to deionized water and stirring with ultrasonic waves to obtain a vanadate solution; (2) Add the peroxodisulfate solution dropwise to the vanadate solution, stir evenly, then add aqueous ammonia, and continue stirring to form a uniform suspension; (3) subjecting the suspension to a hydrothermal reaction, and after the reaction is completed, centrifuging, washing, and drying to obtain a precursor powder; (4) Spread the precursor powder on conductive glass, place it in a plasma discharge device, evacuate the vacuum, introduce gas, and then turn on the device for discharge treatment for 10 to 30 minutes with a discharge power of 20 to 40 W to obtain vanadium oxide hydroxide with oxygen-rich defects of the hindered Lewis acid-base pair type.

2. The preparation method according to claim 1, characterized in that: The vanadate in step (1) is one of orthovanadate, metavanadate and pyrovanadate; The concentration of the vanadate solution is 4 to 8 mg / mL; The temperature of the ultrasonic stirring is 50-80°C.

3. The preparation method according to claim 1, characterized in that: The peroxodisulfate solution in step (2) includes a sodium peroxodisulfate solution or a potassium peroxodisulfate solution; The concentration of the peroxodisulfate solution is 1 mol / L, and the amount added is 0.5-2 mL; The mass concentration of the ammonia water is 25-28%, and the amount added is 3-8 mL.

4. The preparation method according to claim 1, characterized in that: The hydrothermal reaction in step (3) is carried out in a closed reaction vessel at a temperature of 110 to 130° C. for 2 to 6 hours.

5. Vanadium oxyhydroxide with oxygen-rich defects of hindered Lewis acid-base pair type obtained by the preparation method according to any one of claims 1 to 4.

6. The use of the hindered Lewis acid-base pair type oxygen-defective vanadium oxyhydroxide according to claim 5, characterized in that: It is used to degrade antibiotics in polluted water.

7. The use according to claim 6, characterized in that: The steps of degrading antibiotics in contaminated water include: uniformly dispersing hindered Lewis acid-base pair type oxygen-deficient vanadium oxyhydroxide in contaminated water containing antibiotics; Then add peroxide and stir; Then, a water bath degradation reaction is carried out at 25 to 35°C for 10 to 60 minutes; After the reaction is completed, the hindered Lewis acid-base pair type oxygen-rich defect vanadium oxide hydroxide is recovered by filtration.

8. The use according to claim 7, characterized in that: The antibiotics include tetracycline, oxytetracycline, sulfadiazine, sulfamethoxazole, norfloxacin or ofloxacin; The peroxide is hydrogen peroxide, persulfate or peracetic acid, and the persulfate is any one of potassium peroxymonosulfate, sodium peroxymonosulfate, potassium peroxodisulfate and sodium peroxodisulfate; The water bath degradation reaction was carried out in a shaker at 180-250 rpm.

9. The use according to claim 7, characterized in that: The mass ratio of vanadium oxyhydroxide to antibiotics in the polluted water is 5-15:1, and the concentration of peroxide is 0.1-5 mM.

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