A method for removing oxytetracycline from water using boron nitride-modified copper ferrite-activated periodate.

Abstract

This invention discloses a method for removing oxytetracycline from water using boron nitride-modified copper ferrite-activated periodate. The catalytic material uses copper ferrite as the main material and boron nitride as a modifying material, wherein the mass ratio of boron nitride to copper ferrite is 1:5–20. The catalytic material used in this invention promotes charge transfer through surface support and the formation of interfacial Fe-N bonds, thereby achieving excellent oxytetracycline removal performance. The method for removing oxytetracycline from water using boron nitride-modified copper ferrite-activated periodate described in this invention has advantages such as low cost, simple operation, stable catalytic performance, wide applicable pH range, strong anti-interference ability, and high oxytetracycline removal efficiency, and has a promising application prospect for oxytetracycline wastewater treatment.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment, specifically relating to a method for removing oxytetracycline from water by using boron nitride-modified copper ferrite-activated periodate. Background Technology

[0002] Since the successful development of penicillin in the 1940s, antibiotics have played a crucial role in the treatment of human diseases. However, with the application of antibiotics in medicine, animal husbandry, and aquaculture, large quantities of antibiotics have entered the environment, causing pollution of water bodies, soil, and air, and adversely affecting ecosystems. Tetracycline antibiotics (TCs), such as oxytetracycline (OTC), are among the most widely used antibiotics globally. Because they are poorly absorbed by organisms, difficult to degrade in the environment, and difficult to completely remove in conventional wastewater treatment systems, they pose a serious threat to ecosystems and human health. In animal husbandry, antibiotics are used as feed additives to improve livestock immunity, promote growth, and increase economic benefits. The metabolites of these antibiotics mostly enter the environment through livestock excrement, causing pollution of rivers and oceans.

[0003] To date, various technologies, including biodegradation, adsorption, and advanced oxidation processes (AOPs), have been used to remove and degrade oxytetracycline from aquatic environments. Advanced oxidation processes (AOPs), due to their high efficiency, speed, environmental friendliness, and lack of secondary pollution, have shown significant advantages in treating recalcitrant organic matter, making them one of the important technologies in water treatment. Commonly used oxidants in AOPs include hydrogen peroxide (H₂O₂), ozone (O₃), and persulfate (S₂O₈). 2- PS), potassium permanganate (KMnO4), periodate (IO4) - These oxidants, such as PI, generate highly oxidizing free radicals, such as hydroxyl radicals (·OH), through different reaction mechanisms in advanced oxidation technologies, thereby effectively oxidizing and decomposing oxytetracycline in water.

[0004] As a novel oxidant, periodate (PI) has attracted attention due to its stability, ease of activation, and high detergency. AOPs based on PI as an oxidant possess strong oxidizing power and can efficiently degrade various oxytetracyclines over a wide pH range, showing good application potential in water treatment. PI in AOPs mainly works by generating reactive oxygen species (such as ·OH, ...). 1 O2 and O2 ·-PI (iodine) reacts with reactive iodine species (e.g., IO3· and IO4·) to eliminate pollutants. However, the oxidation capacity of PI itself is very limited (reduction potential of +1.6 eV). Researchers have explored various activation methods, including light, heat, metal catalysts, and carbon material catalysts, to enhance the activation capacity of periodate and apply it to the treatment of organic wastewater in water bodies. However, current PI-based AOPs water treatment technologies are still limited by high energy consumption and interference from water matrix components. Therefore, seeking a highly efficient, interference-resistant, widely applicable, reusable, and low-cost periodate catalytic material is of great significance for the treatment of organic wastewater. Summary of the Invention

[0005] To address the shortcomings and deficiencies of existing technologies, the primary objective of this invention is to provide a method for removing oxytetracycline from water using boron nitride-modified copper ferrite activation, which exhibits excellent catalytic performance, high stability, wide applicability, and environmental friendliness.

[0006] To solve the above-mentioned technical problems, the present invention achieves its objective through the following technical solution:

[0007] A method for removing oxytetracycline from water by activating periodate with boron nitride-modified copper ferrite is characterized in that boron nitride-modified copper ferrite activates periodate to degrade oxytetracycline in the water; the boron nitride-modified copper ferrite is prepared by in-situ growth of copper ferrite (CuFe2O4) on boron nitride (BN) as a base material and boron nitride (BN) as a modifying material; the mass ratio of boron nitride to copper ferrite in the boron nitride-modified copper ferrite is 1:5 to 20. Preferably, the copper ferrite is a three-dimensional nanosphere structure with a diameter of approximately 300-500 nm; the boron nitride is a two-dimensional porous nanosheet structure.

[0008] A further improvement to the above method involves using boron nitride-modified copper ferrite to activate periodate for the degradation of oxytetracycline in water. This method includes the following steps: mixing boron nitride-modified copper ferrite with water containing oxytetracycline for half an hour to achieve adsorption-desorption equilibrium between the catalyst and oxytetracycline; and then conducting an oxytetracycline degradation experiment under conditions of further addition of periodate. The amount of boron nitride-modified copper ferrite added is 0.3g to 0.7g per liter of pollutant solution.

[0009] In a further improvement to the above method, the water body is an oxytetracycline-containing water body; the concentration of the oxytetracycline-containing water body is 5-25 mg / L; the pH value of the oxytetracycline-containing water body is 3.0-11.0; the periodate in the degradation experiment is sodium periodate (NaIO4); the concentration of periodate in the degradation experiment is 0.4-1.2 mM; the time for the catalyst to reach adsorption-desorption equilibrium is 30-60 min; and the reaction time of the degradation experiment is 0-60 min.

[0010] A further improvement to the above method, the preparation method of the boron nitride modified copper ferrite, includes the following steps:

[0011] S1. Boric acid and melamine are dispersed in a beaker containing deionized water and heated to dissolve. The mixture is stirred to obtain a homogeneous solution. The solution is then refrigerated to precipitate a white solid. The white solid is collected by filtration and further dried to obtain a boron nitride precursor. Subsequently, the boron nitride precursor is calcined twice in a tube furnace to obtain boron nitride.

[0012] S2. The boron nitride obtained in step S1 is ultrasonically dispersed in ethylene glycol and further stirred to obtain a homogeneous suspension. Then, copper nitrate trihydrate and ferric nitrate nonahydrate are added to the above suspension and stirred until completely dissolved to obtain a transparent reddish-brown solution A. Anhydrous sodium acetate is dissolved in ethylene glycol and stirred evenly to form a white solution B. Subsequently, solution B is added dropwise to the stirred solution A and stirred evenly to obtain solution C. Finally, the above solution C is transferred to a polytetrafluoroethylene reactor for hydrothermal reaction. The reaction product is separated, washed, and dried to obtain the precursor of boron nitride modified copper ferrite.

[0013] S3. The precursor of boron nitride modified copper ferrite obtained in step S2 is placed in a muffle furnace for calcination treatment to obtain a boron nitride modified copper ferrite.

[0014] In a further improvement to the above method, in step S1, the ratio of melamine, boric acid, and water is 0.756g:0.742g:100mL; the ultrasonication time is 30–60 min; the heating temperature is 80–90℃; the stirring is carried out at a speed of 500 r / min–800 r / min; the refrigeration temperature is 0–4℃; the drying treatment is carried out at a temperature of 60℃–80℃; the drying treatment time is 8 h–12 h; the calcination is carried out under a N2 atmosphere; the first calcination temperature is 600℃, the calcination heating rate is 5℃ / min, and the calcination time is 3 h; the second calcination temperature is 700℃, the calcination heating rate is 5℃ / min, and the calcination time is 2 h.

[0015] The above method is further improved in step S2 as follows: the mass ratio of boron nitride to stoichiometric copper ferrite is 1:5-20; the ultrasonic time of solution A is 30-60 min; the ratio of copper nitrate trihydrate, ferric nitrate nonahydrate, anhydrous sodium acetate, and ethylene glycol in solution C is 1 mmol:2 mmol:3 mmol:15 mL; the stirring time is 30-60 min, and the stirring is carried out at a speed of 500 r / min-800 r / min; the ethylene glycol content ratio of solutions A and B is 7 mL:2 mL; the stirring time is 30-60 min, and the stirring is carried out at a speed of 500 r / min-800 r / min; the hydrothermal reaction temperature is 180-200℃, and the hydrothermal reaction time is 18 h; the solid separation method is magnetic precipitation separation; the drying treatment is carried out at a temperature of 60℃-80℃; and the drying treatment time is 8 h-12 h.

[0016] The above method is further improved in step S3, wherein the calcination temperature is 400-450℃, the calcination heating rate is 5℃ / min, and the calcination time is 2-3h.

[0017] Compared with the prior art, the advantages of the present invention are as follows:

[0018] (1) This invention provides a method for removing oxytetracycline from water by using boron nitride-modified copper ferrite-activated periodate. The method involves mixing boron nitride-modified copper ferrite with water containing oxytetracycline, followed by the addition of periodate to initiate the oxytetracycline degradation reaction, thus achieving highly efficient removal of oxytetracycline from the water. This method has advantages such as simple operation, high pollutant removal efficiency, and no secondary pollution, and has a promising application prospect in the field of organic wastewater treatment. Using boron nitride-modified copper ferrite-activated periodate to degrade oxytetracycline in water for 60 minutes can remove more than 91.02% of the oxytetracycline, achieving highly efficient removal of oxytetracycline from water, which is of great significance for the treatment of water bodies polluted by oxytetracycline.

[0019] (2) This invention provides a method for removing oxytetracycline from water by activating periodate with boron nitride-modified copper ferrite. The method involves mixing boron nitride-modified copper ferrite with water containing oxytetracycline, followed by the addition of periodate for catalytic reaction, thereby achieving efficient removal of oxytetracycline from the water. It has a wide applicable pH range (3.0–11.0) and is suitable for inorganic anions (SO42- ... 2- NO3 - CO3 2- HCO3 - Cl -It exhibits good oxytetracycline removal performance even under certain conditions and demonstrates strong resistance to environmental interference. Furthermore, after five cycles of use, it still maintains high pollutant degradation performance, demonstrating high stability.

[0020] (3) In this invention, the boron nitride modified copper ferrite uses copper ferrite as the main material, and the Fe in the copper ferrite... 2+ / Fe 3+ and Cu + / Cu 2+ The resulting bimetallic redox cycle can continuously promote the activation of periodate and the generation of active species such as free radicals, exhibiting excellent catalytic performance. Using boron nitride as a modifying material, its porous two-dimensional nanosheet structure has a large specific surface area, allowing copper ferrite to be uniformly dispersed on its surface, effectively solving the problem of copper ferrite aggregation and deactivation.

[0021] (4) The boron nitride-modified copper ferrite of the present invention can effectively disperse copper ferrite nanospheres by adjusting the ratio of boron nitride to copper ferrite in the composite material, thereby ensuring the effective exposure of active sites in the material. Moreover, the porosity and large specific surface area of ​​boron nitride can effectively improve the adsorption performance of the material for periodate. At the same time, the nitrogen atoms in boron nitride interact with the metallic iron atoms in copper ferrite to form covalent Fe(δ+)-N(δ-) chemical bonds. These interfacial chemical bonds can serve as interfacial charge transfer channels, further accelerating charge migration and promoting the delocalization of electrons at the iron atom center to trigger the catalytic process.

[0022] (5) The method of removing oxytetracycline from water by boron nitride-modified copper ferrite activation of periodate in this invention has the advantages of mild reaction conditions, simple process flow and easy control of operating conditions, and is suitable for large-scale application. Attached Figure Description

[0023] Figure 1 The images are scanning electron microscope (SEM) images of the boron nitride-modified copper ferrite (CFBN10), copper ferrite (CuFe2O4), and boron nitride (BN) prepared in Example 1 of this invention.

[0024] Figure 2 The X-ray diffraction patterns are of boron nitride-modified copper ferrites (CFBN5, CFBN10, CFBN15, CFBN20), copper ferrites (CuFe2O4), and boron nitride (BN) prepared in Example 1 of this invention.

[0025] Figure 3 The infrared spectra of boron nitride modified copper ferrite (CFBN5, CFBN10, CFBN15, CFBN20), copper ferrite (CuFe2O4) and boron nitride (BN) prepared in Example 1 of this invention are shown.

[0026] Figure 4 The graph shows the degradation effect of boron nitride modified copper ferrite (CFBN5, CFBN10, CFBN15, CFBN20), copper ferrite (CuFe2O4), and boron nitride (BN) activated periodate on oxytetracycline in Example 1 of this invention.

[0027] Figure 5 This is a diagram showing the degradation effect of boron nitride modified copper ferrite (CFBN10) on oxytetracycline by periodate activated under different anion conditions in Example 2 of the present invention.

[0028] Figure 6 The graph shows the degradation effect of boron nitride modified copper ferrite (CFBN10) on oxytetracycline by periodate under different pH conditions in Example 3 of the present invention.

[0029] Figure 7 This is a curve showing the cycle number versus degradation effect when boron nitride-modified copper ferrite (CFBN10) activates periodate to degrade oxytetracycline in Example 4 of the present invention. Detailed Implementation

[0030] The present invention will be further described below with reference to the accompanying drawings and specific preferred embodiments, but this does not limit the scope of protection of the present invention.

[0031] The raw materials and instruments used in the following embodiments are all commercially available. Unless otherwise specified, the processes and equipment used in these embodiments are conventional, and the data obtained are the average values ​​of three repeated experiments.

[0032] Example 1

[0033] A method for removing oxytetracycline from water using boron nitride-modified copper ferrite activated periodate, specifically involving the removal of oxytetracycline from water using boron nitride-modified copper ferrite under activated periodate conditions, includes the following steps:

[0034] Weigh 25 mg each of boron nitride (BN), copper ferrite (CuFe2O4), and boron nitride-modified copper ferrite (CFBN5, CFBN10, CFBN15, CFBN20), and add them to 50 mL of a solution containing oxytetracycline (20 mg / L) (pH 4.5). Use a circulating cooling device to control the reaction temperature at 25 °C. Stir for 30 min to allow the catalytic materials to reach adsorption-desorption equilibrium for oxytetracycline. Then add periodate to make the concentration in the solution reach 1 mM to trigger the catalytic reaction. React for 60 min to remove oxytetracycline from the water.

[0035] Blank control group: Take 50 mL of solution containing oxytetracycline (20 mg / L), without adding any catalyst, only add periodate (1 mM), and carry out the reaction under the same conditions to serve as a control.

[0036] During the activation of periodate, 1 mL of reaction solution was aspirated every 10 min, filtered through a 0.22 μm filter, and then added to 20 μL of sodium thiosulfate solution (1 M concentration). Finally, the concentration of oxytetracycline in the solution was detected by high performance liquid chromatography to evaluate the degradation performance of the catalytic material.

[0037] In this embodiment, the boron nitride modified copper ferrite includes boron nitride, copper ferrite, and boron nitride modified copper ferrite.

[0038] In this embodiment, the copper ferrite is a three-dimensional nanosphere structure with a diameter of approximately 300-500 nm; the boron nitride is a two-dimensional porous nanosheet structure.

[0039] In this embodiment, the preparation method of boron nitride material includes the following steps: 0.756g of melamine and 0.742g of boric acid are ultrasonically dispersed in 100mL of aqueous solution, and heated and stirred at 80℃ to obtain a homogeneous solution. Then, the above solution is naturally cooled and placed in a refrigerator for 12h, precipitating a white solid, which is filtered, collected, and dried to obtain a boron nitride precursor. The obtained boron nitride precursor is calcined in a tube furnace at 600℃ for 3h at a heating rate of 5℃ / min, and then calcined at 700℃ for 2h at a heating rate of 5℃ / min to obtain boron nitride (denoted as BN).

[0040] In this embodiment, the preparation method of copper ferrite material includes the following steps: 6 mmol of copper nitrate trihydrate and 12 mmol of ferric nitrate nonahydrate are added to 70 mL of ethylene glycol and stirred under magnetic stirring until completely dissolved to form solution A. 18 mmol of anhydrous sodium acetate is added to 20 mL of ethylene glycol and stirred until completely dissolved to form solution B. Then, solution B is slowly added dropwise to solution A and stirred under magnetic stirring for 1 h until uniformly mixed. Subsequently, the above solution is transferred to a 100 mL polytetrafluoroethylene reaction vessel and reacted at 180 °C for 18 h. After naturally cooling to room temperature, the product is collected by magnetic attraction, washed several times with ethanol and deionized water, and the final solid is dried in a vacuum drying oven at 60 °C for 12 h to obtain copper ferrite material (denoted as CuFe2O4).

[0041] In this embodiment, the mass ratio of boron nitride to copper ferrite in boron nitride modified copper ferrite (CFBN10) is 1:10.

[0042] In this embodiment, the preparation method of boron nitride modified copper ferrite includes the following steps: 82 mg of the boron nitride obtained above is ultrasonically dispersed in 70 mL of ethylene glycol. Then, 6 mmol of copper nitrate trihydrate and 12 mmol of ferric nitrate nonahydrate are added, and the mixture is stirred under magnetic stirring until completely dissolved to form solution A. 18 mmol of anhydrous sodium acetate is added to 20 mL of ethylene glycol and stirred until completely dissolved to form solution B. Then, solution B is slowly added dropwise to solution A and stirred under magnetic stirring for 1 h until uniformly mixed. Subsequently, the above solution is transferred to a 100 mL polytetrafluoroethylene autoclave and reacted at 180 °C for 18 h. After naturally cooling to room temperature, the product is collected by magnetic attraction, washed several times with ethanol and deionized water, and the final solid is dried in a vacuum drying oven at 60 °C for 12 h to obtain boron nitride modified copper ferrite (denoted as CFBN10).

[0043] In this embodiment, the preparation method of boron nitride modified copper ferrite (CFBN5) is basically the same as that of boron nitride modified copper ferrite (CFBN10), except that the mass ratio of boron nitride to copper ferrite in boron nitride modified copper ferrite (CFBN5) is 1:5.

[0044] In this embodiment, the preparation method of boron nitride modified copper ferrite (CFBN15) is basically the same as that of boron nitride modified copper ferrite (CFBN10), the only difference being that the mass ratio of boron nitride to copper ferrite in boron nitride modified copper ferrite (CFBN15) is 1:15.

[0045] In this embodiment, the preparation method of boron nitride modified copper ferrite (CFBN20) is basically the same as that of boron nitride modified copper ferrite (CFBN10), except that the mass ratio of boron nitride to copper ferrite in boron nitride modified copper ferrite (CFBN20) is 1:20.

[0046] Figure 1 These are scanning electron microscope (SEM) images of the boron nitride-modified copper ferrite (CFBN10), boron nitride (BN), and copper ferrite (CuFe2O4) prepared in Example 1 of this invention. (a) shows BN, (b) shows CuFe2O4, and (c) shows the CFBN10 composite material. Figure 1 It is known that boron nitride has a two-dimensional nanosheet structure, while copper ferrite has a three-dimensional nanosphere structure with a diameter of approximately 300–500 nm. In the CFBN10 composite material, BN nanosheets are uniformly attached to CuFe2O4 nanospheres.

[0047] Figure 2 The images show X-ray diffraction patterns of boron nitride-modified copper ferrites (CFBN5, CFBN10, CFBN15, CFBN20), boron nitride (BN), and copper ferrite (CuFe2O4) prepared in Example 1 of this invention. Figure 2 As can be seen, all characteristic peaks of CuFe2O4 point well to the cubic phase of CuFe2O4. The characteristic peaks in the BN sample located at 2θ = 26.2° and 43.5° correspond to the (002) and (101) planes of boron nitride, respectively. Characteristic peaks corresponding to BN and CuFe2O4 can be observed in all boron nitride-modified copper ferrites (CFBN5, CFBN10, CFBN15, CFBN20), indicating that the modified materials were successfully prepared.

[0048] Figure 3 The images show the infrared spectra of boron nitride-modified copper ferrites (CFBN5, CFBN10, CFBN15, CFBN20), boron nitride (BN), and copper ferrites (CuFe2O4) prepared in Example 1 of this invention. Figure 3 It can be seen that for boron nitride (BN), located at 1401 cm⁻¹ -1 and 1074cm -1 The absorption peak belongs to BN or BO bonds, 792 cm⁻¹ -1 and 3259cm -1 The absorption peaks are due to the transverse stretching vibrations of BNB and the stretching vibrations of NH. For copper ferrite (CuFe2O4), the peak is 581 cm⁻¹. -1 and 449cm -1 The two peaks at 3418 cm⁻¹ represent the tensile vibrations of Fe-O and Cu-O. Furthermore, a peak at 3418 cm⁻¹ is present in all samples. -1 The peaks belong to surface-adsorbed -OH groups. It can be seen that characteristic peaks of BN and CuFe2O4 can be observed in almost all boron nitride-modified copper ferrites (CFBN5, CFBN10, CFBN15, CFBN20). In addition, the peaks at approximately 486 cm⁻¹ are also observed. -1 A new peak was also observed, which is a characteristic peak of the Fe-N bond. These results confirm that CuFe₂O₄ and BN form a tight chemically coupled structure through Fe-N bonds.

[0049] The results above show that the present invention uses boron nitride to modify copper ferrite, thereby achieving effective loading of copper ferrite on boron nitride nanosheets and forming a chemically coupled structure connected by Fe-N bonds.

[0050] Figure 4 This image shows the degradation effect of boron nitride-modified copper ferrites (CFBN5, CFBN10, CFBN15, CFBN20), boron nitride (BN), and copper ferrites (CuFe2O4) on oxytetracycline under activated periodate conditions in Example 1 of this invention. Figure 4It is evident that the boron nitride-modified copper ferrite activated periodate of this invention exhibits a good degradation effect on oxytetracycline, and the degradation effect continuously increases with the increase of boron nitride content in the boron nitride-modified copper ferrite. The optimal degradation effect on oxytetracycline is achieved when the mass ratio of boron nitride to copper ferrite reaches 1:10 (i.e., CFBN10). However, if the mass ratio of boron nitride to copper ferrite is further increased to 1:5 (i.e., CFBN5), the degradation effect of the composite material on oxytetracycline decreases. This is because excessive boron nitride reduces the total number of metal active sites in the material and decreases the number of Fe-N interface structures. The optimal mass ratio of boron nitride to copper ferrite is 1:10. Therefore, the boron nitride-modified copper ferrite (CFBN10) activated periodate prepared in Example 1 of this invention exhibits the best degradation effect on oxytetracycline, degrading 91.02% (20 mg / L) of oxytetracycline after 60 min of activation. The CFBN10 composite material exhibits optimal periodate activation performance in degrading oxytetracycline primarily due to the significant increase in specific surface area resulting from boron nitride modification. This enhances the exposure of active sites on the material surface and fosters the formation of a chemically coupled structure linked by Fe-N bonds. The increased specific surface area effectively improves the material's adsorption capacity for periodate while simultaneously promoting the formation of reactive species such as high-valence metal oxygen species. Furthermore, the interfacial Fe-N bonds act as charge transfer channels, further accelerating electron migration at the iron centers and enhancing the generation rate of free radicals and other reactive species, thus promoting the degradation of oxytetracycline.

[0051] Example 2

[0052] A method for removing oxytetracycline from water by boron nitride-modified copper ferrite activation of periodate includes the following steps:

[0053] Weigh out 6 portions of boron nitride modified copper ferrite (CFBN10), 25 mg each, and add them separately to a solution containing 5 mmol / L SO4. 2- NO3 - CO3 2- HCO3 - Cl - In a 50 mL solution containing oxytetracycline (20 mg / L) without any added ions (pH 4.5), the reaction temperature was controlled at 25 °C using a circulating cooling device. The mixture was stirred for 30 min to allow the catalytic material to reach adsorption-desorption equilibrium for oxytetracycline. Then, periodate was added to bring the concentration in the solution to 1 mM to trigger the catalytic reaction. The reaction was carried out for 60 min to remove oxytetracycline from the water.

[0054] During the activation of periodate, 1 mL of reaction solution was aspirated every 10 min, filtered through a 0.22 μm filter, and then added to 20 μL of sodium thiosulfate solution (1 M concentration). Finally, the concentration of oxytetracycline in the solution was detected by high performance liquid chromatography (HPLC) to evaluate the degradation performance of oxytetracycline by boron nitride-modified copper ferrite (CFBN10) activated periodate under different anion conditions. The results are as follows: Figure 5 As shown.

[0055] Figure 5 This image shows the degradation effect of boron nitride-modified copper ferrite (CFBN10) on oxytetracycline by periodate activated under different anion conditions in Example 2 of this invention. Figure 5 It can be seen that the boron nitride-modified copper ferrite (CFBN10) of this invention, without the addition of any ions, effectively degrades periodate to oxytetracycline, achieving a degradation rate of 91.02% (20 mg / L) of oxytetracycline after 60 minutes. (In SO4) 2- and Cl - In the presence of SO42-, boron nitride-modified copper ferrite (CFBN10) activated periodate did not significantly inhibit the degradation of oxytetracycline, indicating that SO42-... 2- and Cl - The presence of CO3 has little effect on the degradation of oxytetracycline. 2- HCO3 - and NO3 - In the presence of boron nitride-modified copper ferrite (CFBN10), activated periodate exhibits some inhibitory effect on the degradation of oxytetracycline, but still retains high degradation performance. The decrease in periodate catalytic activity is partly due to CO3... 2- HCO3 - and NO3 - It can act as a free radical scavenger, combining with highly reactive free radicals to generate substances with relatively weaker activity, leading to a decrease in the degradation performance of oxytetracycline; on the other hand, it is due to CO3... 2- and HCO3 - The addition of [a substance] will cause the solution pH to rise, resulting in some periodate being converted or polymerized into iodine species with lower reduction potential, thus producing fewer active species to act on the degradation of oxytetracycline.

[0056] Example 3

[0057] A method for removing oxytetracycline from water by boron nitride-modified copper ferrite activation of periodate includes the following steps:

[0058] Five portions of boron nitride modified copper ferrite (CFBN10), each 25 mg, were weighed and added to 50 mL solutions containing oxytetracycline (20 mg / L) with pH values ​​of 3.0, 7.0, 9.0, 11.0, and 4.5 (pH value of the solution was not adjusted). The reaction temperature was controlled at 25 °C using a circulating cooling device. The mixture was stirred for 30 min to allow the catalytic material to reach adsorption-desorption equilibrium for oxytetracycline. Then, periodate was added to bring the concentration in the solution to 1 mM to trigger the catalytic reaction. The reaction was allowed to proceed for 60 min to remove oxytetracycline from the water.

[0059] During the activation of periodate, 1 mL of reaction solution was aspirated every 10 min, filtered through a 0.22 μm filter, and then added to 20 μL of sodium thiosulfate solution (1 M concentration). Finally, the concentration of oxytetracycline in the solution was detected by high-performance liquid chromatography (HPLC) to evaluate the degradation performance of oxytetracycline by boron nitride-modified copper ferrite (CFBN10) activated periodate under different pH conditions. The results are as follows: Figure 6 As shown.

[0060] Figure 6 This image shows the degradation effect of boron nitride-modified copper ferrite (CFBN10) on oxytetracycline under different pH conditions in Example 3 of this invention. Figure 6 It can be seen that the boron nitride-modified copper ferrite (CFBN10) of this invention has a high degradation effect on oxytetracycline by activating periodate under natural conditions, and can degrade 91.02% of oxytetracycline (20 mg / L) after 60 min. However, the degradation effect on oxytetracycline is reduced under slightly alkaline conditions. The lower degradation effect of oxytetracycline at pH 11.0 is because some periodate is converted or polymerized into iodine species with lower reduction potential, thus affecting the catalytic performance. Conversely, the degradation of oxytetracycline is accelerated under slightly acidic conditions. In particular, when the pH of the solution is 3.0, 94.29% of oxytetracycline (20 mg / L) can be degraded within 60 min. The enhanced catalytic effect under acidic conditions is due to the increased H+ under acidic conditions. + The presence of [a specific substance] promotes the generation of active species. However, it can be seen that the periodate catalyst exhibits the best catalytic performance within a weakly acidic range (pH 3–7). Since most actual water bodies are weakly acidic, the boron nitride-modified copper ferrite in this invention has a wide range of applicability.

[0061] Example 4

[0062] The stability of boron nitride-modified copper ferrite-activated periodate degradation of oxytetracycline in water includes the following steps:

[0063] (1) Weigh 25 mg of boron nitride modified copper ferrite (CFBN10) and add it to 50 mL of a solution containing oxytetracycline (20 mg / L) (the pH of the solution is 4.5). Use a circulating cooling device to control the reaction temperature at 25 °C. Stir for 30 min to allow the catalytic material to reach the adsorption and desorption equilibrium of oxytetracycline. Then add periodate to make its concentration in the solution reach 1 mM to trigger the catalytic reaction. React for 60 min to remove oxytetracycline from the water.

[0064] (2) During the activation of periodate, 1 mL of reaction solution was taken every 10 min, filtered through a 0.22 μm filter, and added to 20 μL of sodium thiosulfate solution (concentration of 1 M). Finally, the concentration of oxytetracycline in the solution was detected by high performance liquid chromatography to evaluate the degradation performance of periodate activated by boron nitride modified copper ferrite (CFBN10) on oxytetracycline.

[0065] (3) After each reaction, the catalyst was collected using a magnet. The catalyst was then washed several times with deionized (DI) water and 70% ethanol solution, resuspended in the ethanol solution, sonicated for 30 min, and finally collected again using a magnet. This step was repeated three times to dissolve and remove oxytetracycline adsorbed on the catalyst surface. The collected material was then dried under vacuum at 60°C.

[0066] (4) Repeat steps (1) to (3) five times to investigate the performance and stability of boron nitride-modified copper ferrite (CFBN10) in activating periodate to degrade oxytetracycline. The results are as follows: Figure 7 As shown.

[0067] Figure 7 This is a curve showing the cycle number versus degradation effect during the cyclic degradation of oxytetracycline by boron nitride-modified copper ferrite (CFBN10) activated periodate in Example 4 of this invention. Figure 7 It can be seen that after five cycles, the boron nitride modified copper ferrite (CFBN10) still exhibits high degradation performance of oxytetracycline. This indicates that the boron nitride modified copper ferrite of the present invention has the advantages of stable catalytic performance, strong corrosion resistance, and high degradation efficiency of oxytetracycline. It is a novel composite catalytic material with high degradation performance and good repeatability.

[0068] The above embodiments are preferred embodiments of the present invention, but the scope of protection of the present invention is not limited to the above embodiments. Any changes, modifications, combinations, substitutions, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the scope of protection of the present invention.

Claims

1. A method for removing oxytetracycline from water by using boron nitride-modified copper ferrite-activated periodate, characterized in that, Boron nitride-modified copper ferrite was used to activate periodate for the degradation of oxytetracycline in water. The boron nitride-modified copper ferrite used copper ferrite as the base material and modified with boron nitride. The mass ratio of boron nitride to copper ferrite in the boron nitride-modified copper ferrite was 1:5 to 20. The copper ferrite was a three-dimensional nanosphere structure with a diameter of 300-500 nm. The boron nitride was a two-dimensional porous nanosheet structure.

2. The method for removing oxytetracycline from water by boron nitride-modified copper ferrite activation of periodate according to claim 1, characterized in that, The degradation of oxytetracycline in water by activating periodate with boron nitride-modified copper ferrite includes the following steps: mixing boron nitride-modified copper ferrite with water containing oxytetracycline, and carrying out the oxytetracycline degradation reaction under the condition of adding periodate to complete the degradation treatment of oxytetracycline in the water; the amount of boron nitride-modified copper ferrite added is 0.3g to 0.7g per liter of oxytetracycline solution.

3. The method for removing oxytetracycline from water by boron nitride-modified copper ferrite activation of periodate according to claim 1 or 2, characterized in that, The water body is an oxytetracycline-containing water body; the concentration of the oxytetracycline-containing water body is 5-25 mg / L; the pH value of the oxytetracycline-containing water body is 3.0-11.0; the periodate is sodium periodate; the concentration of the periodate is 0.4-1.2 mM; the time for the boron nitride-modified copper ferrite to reach adsorption-desorption equilibrium is 30-60 min; the degradation reaction time is 60 min.

4. A method for preparing boron nitride-modified copper ferrite in a method for removing oxytetracycline from water using boron nitride-modified copper ferrite activation as described in any one of claims 1 to 3, characterized in that, Includes the following steps: S1. Boric acid and melamine are ultrasonically dispersed in a beaker containing deionized water and heated to dissolve. The mixture is stirred to obtain a homogeneous solution. The solution is then placed in a refrigerator to precipitate a white solid. The white solid is collected by filtration and further dried to obtain a boron nitride precursor. Subsequently, the boron nitride precursor obtained above is calcined twice in a tube furnace to obtain boron nitride. S2. The boron nitride obtained in step S1 is ultrasonically dispersed in ethylene glycol and further stirred to obtain a uniform suspension. Then, copper nitrate trihydrate and ferric nitrate nonahydrate are added to the suspension and stirred until completely dissolved to obtain a transparent reddish-brown solution A. Anhydrous sodium acetate is dissolved in ethylene glycol and stirred evenly to form a white solution B. Subsequently, solution B is added dropwise to the stirred solution A and stirred evenly to obtain solution C. Finally, solution C is transferred to a polytetrafluoroethylene reactor for hydrothermal reaction. The reaction product is separated by solids, washed, and dried to obtain the precursor of boron nitride modified copper ferrite. S3. The precursor of boron nitride modified copper ferrite obtained in step S2 is placed in a muffle furnace for calcination treatment to obtain a boron nitride modified copper ferrite.

5. The method for preparing boron nitride modified copper ferrite according to claim 4, characterized in that, In step S1: the ratio of melamine, boric acid, and water is 0.756g:0.742g:100mL; the ultrasonic time is 30-60min; the heating temperature is 80-90℃; the stirring is carried out at a speed of 500r / min-800r / min; the refrigeration temperature is 0-4℃; the drying treatment is carried out at a temperature of 60℃-80℃; the drying time is 8h-12h; the calcination is carried out under a N2 atmosphere; the first calcination temperature is 600℃, the calcination heating rate is 5℃ / min, and the calcination time is 3h; the second calcination temperature is 700℃, the calcination heating rate is 5℃ / min, and the calcination time is 2h.

6. The method for preparing boron nitride modified copper ferrite according to claim 4, characterized in that, In step S2, the mass ratio of boron nitride to stoichiometric copper ferrite is 1:5-20; the ultrasonic time for solution A is 30-60 min; the ratio of copper nitrate trihydrate, ferric nitrate nonahydrate, anhydrous sodium acetate, and ethylene glycol in solution C is 1 mmol:2 mmol:3 mmol:15 mL; the stirring time is 30-60 min, and the stirring is carried out at a speed of 500 r / min-800 r / min; the ethylene glycol content ratio in solutions A and B is 7 mL:2 mL; the hydrothermal reaction temperature is 180-200℃, and the hydrothermal reaction time is 18 h; the solid separation method is magnetic precipitation separation; the drying treatment is carried out at a temperature of 60℃-80℃; and the drying treatment time is 8 h-12 h.

7. The method for preparing boron nitride modified copper ferrite according to claim 4, characterized in that, In step S3, the calcination temperature is 400-450℃, the calcination heating rate is 5℃ / min, and the calcination time is 2-3h.

8. A boron nitride modified copper ferrite material prepared by the preparation method according to any one of claims 4 to 7.

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