A treatment method for removing beta-lactam antibiotics by using a COF / FeOF cascade self-fenton system

Abstract

This invention relates to the field of β-lactam antibiotic treatment technology, and discloses a method for removing β-lactam antibiotics using a COF / FeOF cascaded self-Fenton system. The method includes adding an urchin-shaped imine-type COF catalyst and an FeOF catalyst to wastewater containing β-lactam antibiotics, and carrying out a photocatalytic reaction under light irradiation to remove the β-lactam antibiotics. This method only requires mixing the COF and FeOF catalysts and adding them to the wastewater, avoiding the increased costs and safety hazards associated with traditional Fenton technology which requires the addition of H2O2. The entire system of this invention does not require high temperature or high pressure conditions for removing β-lactam antibiotics, significantly reducing energy consumption and process complexity, while avoiding safety hazards, and possessing significant potential for industrial scale-up.

Description

Technical Field

[0001] This invention relates to the field of β-lactam antibiotic treatment technology, specifically a treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system. Background Technology

[0002] Between 2016 and 2023, global antibiotic consumption increased from 29.5 billion defined daily doses to 34.3 billion, a growth rate of 16.3%. Approximately 70% of antibiotics are not completely metabolized by organisms, inevitably leading to their release into the environment and causing widespread aquatic pollution. β-lactam antibiotics account for 50% to 70% of global antibiotic use.

[0003] Photocatalytic in-situ synthesis of H2O2 using covalent organic frameworks (COFs) can effectively avoid the high storage and transportation costs and safety hazards associated with traditional exogenous addition methods. However, the key to constructing an efficient self-Fenton cascade system lies in introducing spatially separated Fenton active centers to achieve rapid capture and efficient activation of in-situ generated H2O2. Against this backdrop, although various iron-based materials have been widely used as H2O2 activators, iron fluoride oxyfluoride (FeOF), with its excellent properties, is considered a highly promising and ideal activating material for constructing this cascade system. Unlike traditional iron catalysts, the strong electronegativity of the incorporated fluorine atoms gives the iron centers in FeOF a unique Lewis acidity. This unique electronic structure provides a strong thermodynamic driving force for the capture of H2O2 and the subsequent breaking of the OO bonds. In summary, FeOF is an excellent heterogeneous catalyst for activating H2O2, capable of activating H2O2 over a wide pH range and under conditions free of iron sludge.

[0004] Therefore, it is necessary to design a treatment method that utilizes a COF / FeOF cascade self-Fenton system to remove β-lactam antibiotics. Summary of the Invention

[0005] The purpose of this invention is to provide a treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system, thereby solving the problems in the prior art.

[0006] The objective of this invention can be achieved through the following technical solutions: A treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system, the method comprising: adding an urchin-shaped imine-type COF catalyst and an FeOF catalyst to wastewater containing β-lactam antibiotics, and carrying out a photocatalytic reaction under light conditions to complete the removal of β-lactam antibiotics.

[0007] Furthermore, the preparation method of the sea urchin-shaped imine-type COF catalyst includes the following steps: S1. Add 1,4-dialdehyde-2,5-divinylbenzene to an acetic acid solution with a concentration of 3~8 mol / L and stir for 20~40 min; S2. Add 1,3,5-tris(4-aminophenyl)benzene to an acetonitrile solution and sonicate for 20-40 seconds. S3. After thoroughly mixing the solution from step S1 with the solution from step S2, let it stand for 48 to 80 h at a normal temperature of 10 to 40°C and a normal pressure of -0.02 to 0.1 MPa. Drain the supernatant, wash the sludge, and vacuum dry it to obtain the urchin-shaped imine-type COF catalyst.

[0008] Further, the mass ratio of 1,4-dialdehyde-2,5-divinylbenzene and 1,3,5-tris(4-aminophenyl)benzene in S1 and S2 is 1:1 to 1:3; the volume ratio of acetic acid and acetonitrile used in S1 and S2 is 0.5 to 2.5.

[0009] Furthermore, it includes the following steps: S1. Add iron powder to a fluorosilicic acid solution, stir vigorously at 30~80℃ for 5~15 h, filter, wash the filter residue and vacuum dry it. S2. The filter residue from step S1 is added to n-propanol and stirred for 10-40 min. After mixing, it is placed in a high-pressure reactor and heated at 150-250℃ for 5-15 h. After cooling, washing, and vacuum drying, the FeOF catalyst is obtained.

[0010] Furthermore, in S1, the ratio of iron powder to fluorosilicic acid solution is 1:8 to 1:12 g / mL; in S2, the ratio of filter residue to n-propanol is 1:120 g / mL to 1:180 g / mL.

[0011] An application of a COF / FeOF cascade self-Fenton system for the removal of β-lactam antibiotics is disclosed. The method comprises: feeding the COF catalyst and FeOF catalyst into wastewater containing β-lactam antibiotics; and conducting a photocatalytic reaction under visible light irradiation to remove the β-lactam antibiotics; wherein the visible light intensity is 10~200 mW / cm². 2 .

[0012] An application of a COF / FeOF cascade self-Fenton system in H2O2 generation, employing the aforementioned method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system, includes: weighing 20 mg of COF catalyst, adding it to 100 mL of pure water, sonicating for 5 min, stirring in the dark for 30 min to allow surface adsorption equilibrium, and then reacting at 10–200 mW / cm². 2 The photocatalytic reaction was carried out under xenon lamp irradiation for 30 minutes to complete the generation of H2O2.

[0013] An application of a treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system in altering the pH environment for amoxicillin degradation.

[0014] The beneficial effects of this invention are: 1. This invention provides a method for removing β-lactam antibiotics using a COF / FeOF cascaded self-Fenton system. It only requires mixing and adding a COF catalyst and a FeOF catalyst to the wastewater containing β-lactam antibiotics, avoiding the increased costs and safety issues associated with traditional Fenton technology which requires the addition of H2O2. The entire system of this invention does not require high temperature or high pressure conditions for removing β-lactam antibiotics, significantly reducing energy consumption and process complexity, while avoiding safety hazards, and possessing significant potential for industrial scale-up.

[0015] 2. This invention provides a method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system. This dual-catalyst design employs a spatially decoupled architecture to achieve the cascade effect, separating the photocatalytic H2O2 generation center (COF) from the activation center (FeOF), rather than relying on complex interfacial chemical bonding. This avoids the complexity of the process flow caused by the complex multi-step protocol usually required to construct a tightly bound heterojunction with precise dual active sites.

[0016] 3. This invention also provides a method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system. The FeOF catalyst used has superior H2O2 activation ability. Since FeOF is a heterogeneous catalyst, unlike traditional homogeneous catalysts, the Fenton reaction does not need to be carried out in an acidic pH range. At the same time, homogeneous catalysts are not easy to separate from the solution, but FeOF is a heterogeneous catalyst, so it is easy to separate, thereby achieving reuse and saving costs. Attached Figure Description

[0017] The invention will now be further described with reference to the accompanying drawings.

[0018] Figure 1This is a scanning electron microscope image of the COF catalyst in the COF / FeOF cascade self-Fenton system in Example 1 of the present invention.

[0019] Figure 2 This is an X-ray diffraction pattern of the FeOF catalyst in the COF / FeOF cascade self-Fenton system in Example 1 of the present invention.

[0020] Figure 3 This is a diagram showing the generation of H2O2 by the COF catalyst in Example 2 of the present invention.

[0021] Figure 4 The graph shows the degradation effect of COF catalyst and different iron catalysts cascaded in the Fenton system on amoxicillin in Example 3 of this invention.

[0022] Figure 5 This is a graph showing the degradation effect of the COF / FeOF cascade self-Fenton system on penicillin in Example 3 of the present invention.

[0023] Figure 6 This is a graph showing the degradation effect of the COF / FeOF cascade self-Fenton system on β-lactam antibiotics under different pH conditions in Example 4 of the present invention. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] A method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system, specifically involving the preparation of a sea urchin-type COF catalyst and an FeOF catalyst, includes the following steps: In this embodiment, the preparation method of the sea urchin-type COF catalyst includes the following steps: S1. Add 0.06 mmol of 1,4-dialdehyde-2,5-divinylbenzene to 2 mL of 4.38 mol / L acetic acid solution and stir for 20-40 min.

[0026] S2. Add 0.04 mmol of 1,3,5-tris(4-aminophenyl)benzene to 2 mL of acetonitrile solution and sonicate for 20-40 s.

[0027] S3. Mix the solution from step S1 with the solution from step S2, let it stand at room temperature and pressure, wash it, and dry it under vacuum to obtain the sea urchin-type COF catalyst.

[0028] The conditions for ambient temperature and pressure are as follows: ambient temperature is 10~40℃, ambient pressure is -0.02~0.1 MPa, the solution is allowed to stand for 48~80 h, the supernatant is discharged, and the sediment is washed.

[0029] In S1 and S2, the mass ratio of 1,4-dialdehyde-2,5-divinylbenzene and 1,3,5-tris(4-aminophenyl)benzene is 1:1 to 1:3; the volume ratio of acetic acid and acetonitrile used in S1 and S2 is 0.5 to 2.5.

[0030] In this embodiment, the preparation method of the FeOF catalyst includes the following steps: S1. Add 10 g of iron powder to 100 mL of fluorosilicic acid solution, stir vigorously at 30~80℃ for 5~15 h, filter, wash the filter residue and dry it under vacuum. S2. Add 0.5 g of the filter residue from S1 to 75 mL of n-propanol, stir for 10-40 min, mix well, and then put it into a high-pressure reactor. Heat at 150-250℃ for 5-15 h, cool, wash, and vacuum dry to obtain the FeOF catalyst.

[0031] In S1, the ratio of iron powder to fluorosilicic acid solution is 1:8 to 1:12 g / mL; in S2, the ratio of filter residue to n-propanol is 1:120 g / mL to 1:180 g / mL. Example

[0032] A method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system, specifically involving the preparation of a sea urchin-type COF catalyst and an FeOF catalyst, includes the following steps: In this embodiment, the preparation method of the sea urchin-type COF catalyst includes the following steps: S1. Add 0.06 mmol of 1,4-dialdehyde-2,5-divinylbenzene to 2 mL of 4.38 mol / L acetic acid solution and stir for 30 min.

[0033] S2. Add 0.04 mmol of 1,3,5-tris(4-aminophenyl)benzene to 2 mL of acetonitrile solution and sonicate for 30 s.

[0034] S3. Mix the solution from step S1 with the solution from step S2, let stand at room temperature and pressure for 72 h, wash, and vacuum dry to obtain the sea urchin-type COF catalyst.

[0035] In this embodiment, the preparation method of the FeOF catalyst includes the following steps: S1. Add 10 g of iron powder to 100 mL of fluorosilicic acid solution, stir vigorously at 50°C for 12 h, filter, wash the filter residue and dry it under vacuum. S2. Add 0.5 g of the filter residue from S1 to 75 mL of n-propanol, stir for 30 min, mix well, and then put it into a high-pressure reactor. Heat at 200℃ for 10 h, cool, wash, and vacuum dry to obtain the FeOF catalyst.

[0036] Figure 1 The image shows a scanning electron microscope (SEM) image of the COF catalyst in the COF / FeOF cascade self-Fenton system in Example 1 of this invention. It can be seen that the prepared COF catalyst is of the sea urchin type.

[0037] Figure 2 This is the X-ray diffraction pattern of the FeOF catalyst in the COF / FeOF cascade self-Fenton system in Example 1 of this invention. The diffraction peaks of the FeOF catalyst correspond to the standard cards, proving the successful preparation of FeOF. Example

[0038] An application of removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system specifically involves: generating H2O2 using a COF catalyst, including the following steps: Weigh 20 mg of COF catalyst and add it to 100 mL of pure water. Sonicate for 5 min, then stir in the dark for 30 min to allow surface adsorption equilibrium to be reached. Then, maintain the reaction temperature at 10–200 mW / cm³. 2 The photocatalytic reaction was carried out for 30 min under xenon lamp (λ>420 nm) irradiation to complete the generation of H2O2.

[0039] Figure 3 The diagram shows the generation of H2O2 by the COF catalyst in Example 2 of this invention. The COF catalyst generated 978.75 μmol / g of H2O2 after 30 min of light irradiation. Example

[0040] An application of removing β-lactam antibiotics using a COF / FeOF cascade Fenton system specifically involves treating wastewater containing β-lactam antibiotics using a COF / FeOF cascade Fenton system, including the following steps: Weigh 20 mg of COF catalyst and 1 mg of FeOF catalyst, and add them together to 100 mL of wastewater containing 10 mg / L β-lactam antibiotics. Sonicate for 1 min, then stir in the dark for 30 min to allow surface adsorption equilibrium to be reached. Finally, react at 100 mW / cm². 2 The removal of β-lactam antibiotics was achieved by photocatalytic reaction under xenon lamp (λ>420 nm) irradiation for 30 min.

[0041] Blank group: removal of β-lactam antibiotics by adding different iron catalysts, single COF catalysts, or single FeOF catalysts, with other conditions being the same.

[0042] Figure 4 The graph shows the degradation effect of COF catalyst and different iron catalysts cascaded in the Fenton system on amoxicillin in Example 3 of this invention.

[0043] Depend on Figure 4 It is evident that FeOF catalyst alone has almost no degradation effect on amoxicillin; when using only the co-COF catalyst, the degradation rate of amoxicillin is only about 40% after 30 minutes of illumination. Neither FeOCl nor Fe3O4 can improve the degradation efficiency of amoxicillin. Conversely, the introduction of FeOF into the COF system forms a cascaded self-Fenton system, achieving complete degradation of amoxicillin within 30 minutes.

[0044] Figure 5 This is a graph showing the degradation effect of the COF / FeOF cascade self-Fenton system on penicillin in Example 3 of the present invention.

[0045] Depend on Figure 5 It is known that the FeOF catalyst alone has a limited effect on penicillin degradation; when only the co-COF catalyst is used, the degradation rate of amoxicillin is only about 30% after 30 min of illumination. Under the condition of 30 min of illumination in the COF / FeOF cascade self-Fenton system, penicillin is completely degraded. Example

[0046] An application of a COF / FeOF cascade self-Fenton system for removing β-lactam antibiotics is basically the same as in Example 3, except that the pH environment for the degradation of amoxicillin is changed in Example 4.

[0047] Figure 6 This is a graph showing the degradation effect of the COF / FeOF cascade self-Fenton system on β-lactam antibiotics under different pH conditions in Example 4 of this invention. Figure 6 It can be seen that the COF / FeOF cascade self-Fenton system can degrade wastewater containing amoxicillin within the pH range of 3 to 9.

[0048] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system, characterized in that, The treatment method includes: adding urchin-shaped imine-type COF catalyst and FeOF catalyst to wastewater containing β-lactam antibiotics, and carrying out a photocatalytic reaction under light conditions to complete the removal of β-lactam antibiotics.

2. The treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system according to claim 1, characterized in that, The preparation method of the sea urchin-shaped imine-type COF catalyst includes the following steps: S1. Add 1,4-dialdehyde-2,5-divinylbenzene to an acetic acid solution with a concentration of 3~8 mol / L and stir for 20~40 min; S2. Add 1,3,5-tris(4-aminophenyl)benzene to an acetonitrile solution and sonicate for 20-40 seconds. S3. After thoroughly mixing the solution from step S1 with the solution from step S2, let it stand for 48 to 80 h at a normal temperature of 10 to 40°C and a normal pressure of -0.02 to 0.1 MPa. Discharge the supernatant, wash the sludge, and vacuum dry it to obtain the urchin-shaped imine-type COF catalyst.

3. The treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system according to claim 2, characterized in that, The mass ratio of 1,4-dialdehyde-2,5-divinylbenzene and 1,3,5-tris(4-aminophenyl)benzene in S1 and S2 is 1:1 to 1:3; the volume ratio of acetic acid and acetonitrile used in S1 and S2 is 0.5 to 2.

5.

4. The treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system according to claim 1, characterized in that, Includes the following steps: S1. Add iron powder to a fluorosilicic acid solution, stir vigorously at 30~80℃ for 5~15 h, filter, wash the filter residue and vacuum dry it. S2. The filter residue from step S1 is added to n-propanol and stirred for 10-40 min. After mixing, it is placed in a high-pressure reactor and heated at 150-250℃ for 5-15 h. After cooling, washing, and vacuum drying, the FeOF catalyst is obtained.

5. The treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system according to claim 4, characterized in that, The ratio of iron powder to fluorosilicic acid solution in S1 is 1:8 to 1:12 g / mL; the ratio of filter residue to n-propanol in S2 is 1:120 g / mL to 1:180 g / mL.

6. An application of removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system, comprising the treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system as described in any one of claims 1-5, characterized in that, include: The COF and FeOF catalysts were fed into wastewater containing β-lactam antibiotics, and a photocatalytic reaction was carried out under visible light irradiation to remove the β-lactam antibiotics; the visible light intensity was 10~200 mW / cm². 2 .

7. An application of a COF / FeOF cascade self-Fenton system in the generation of H2O2, employing the treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system as described in any one of claims 1-5, characterized in that... include: Weigh 20 mg of COF catalyst and add it to 100 mL of pure water. Sonicate for 5 min, then stir in the dark for 30 min to allow surface adsorption equilibrium to be reached. Then, maintain the reaction temperature at 10–200 mW / cm³. 2 The photocatalytic reaction was carried out under xenon lamp irradiation for 30 minutes to complete the generation of H2O2.

8. The application of the treatment method for removing β-lactam antibiotics using a COF / FeOF cascade self-Fenton system as described in any one of claims 1-5 in altering the pH environment for the degradation of amoxicillin.

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