Multifunctional nano-catalyst, preparation method thereof and application of multifunctional nano-catalyst in water pollution treatment

Abstract

The invention provides a multifunctional nano-catalyst and a preparation method and application thereof in water pollution treatment, and the preparation method comprises the following steps: dissolving a cobalt source and glucose oxidase in deionized water, adjusting the pH value of the solution, reacting under a heating condition, and obtaining a Co (at) GOx nano-material after the reaction is completed; the method comprises the following steps: dissolving an iron source metal compound and trimesic acid in a solvent, mixing, and reacting under a heating condition to obtain the MIL-100 after the reaction is completed. According to the multifunctional nano-catalyst, the degradation rate of methylene blue dye by utilizing an MCG catalyst / glucose system exceeds 90%, the degradation rate of tetracycline hydrochloride can reach 80% or above, meanwhile, up to 99.9% of microorganism inactivation is achieved, and the multifunctional nano-catalyst has the advantages that the operation process is simple, H2O2 does not need to be added, the cost is low, and good stability is achieved; the method has very high application potential in the aspect of cascade catalysis, and is helpful for eliminating various organic pollutants and bacteria.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment, and in particular relates to a multifunctional nanocatalyst, its preparation method, and its application in water pollution treatment. Background Technology

[0002] With the rapid development of industry and agriculture, water pollution has reached alarming levels, particularly the widespread presence of various organic pollutants (such as methylene blue (MB) and tetracycline hydrochloride (TC-HCl)) and harmful microorganisms, seriously endangering the ecological environment and human health. Advanced catalytic oxidation processes are considered an effective method for treating organic dyes and antibiotics. Through Fe... 2+ The activation of hydrogen peroxide (H₂O₂) to generate reactive oxygen species (ROS) via a Fenton-like reaction can achieve highly efficient degradation of dyes and antibiotics such as MB and TC-HCl. Traditional Fenton-like reaction systems typically require strongly acidic conditions, which greatly limits their practical applications. Furthermore, Fenton-like reactions usually require high concentrations of H₂O₂, and directly adding high concentrations of H₂O₂ may damage easily oxidizable substances in the system. Large-scale production, storage, and transportation of H₂O₂ also pose extremely high safety risks, causing significant losses to individuals and society. Therefore, there is an urgent need to develop other safe and efficient new systems and methods. Summary of the Invention

[0003] In view of this, the present invention aims to overcome the defects of existing Fenton-like catalysts, such as poor stability and insufficient ROS generation capacity, and to prepare a multifunctional nanocatalyst for degrading pollutants such as antibiotics and organic dyes, while simultaneously achieving efficient sterilization.

[0004] To achieve the above objectives, the technical solution of the present invention is implemented as follows: A method for preparing a multifunctional nanocatalyst includes the following steps: (1) Dissolve the cobalt source and glucose oxidase in deionized water, adjust the pH of the solution, and react under heating conditions to obtain Co@GOx after the reaction is completed; (2) The metal compound and pyromellitic acid are dissolved in a solvent, mixed and reacted under heating conditions. After the reaction is completed, MIL-100 is obtained. (3) The MIL-100 and Co@GOx were added to deionized water and incubated to obtain the multifunctional nanocatalyst.

[0005] Furthermore, the mass ratio of cobalt source to glucose oxidase in step (1) is 4.5:3.6; the cobalt source in step (1) is at least one of water-soluble cobalt sources such as cobalt chloride, cobalt nitrate, and cobalt acetate.

[0006] Furthermore, the pH value in step (1) of adjusting the pH value of the solution is 8-9; the reaction temperature in step (1) is 37 ℃ and the time is 3 h.

[0007] Furthermore, in step (2), the solid-liquid ratio of the metal compound, pyromellitic acid, and solvent is 0.25-0.29 g: 0.19-0.23 g: 18-22 mL; the metal compound in step (2) is at least one of ferric chloride hexahydrate, anhydrous ferric chloride, ferric nitrate nonahydrate, or ferric sulfate; and the solvent in step (2) is N,N-dimethylformamide.

[0008] Furthermore, the reaction temperature in step (2) is 150 °C and the time is 12 h.

[0009] Furthermore, in step (3), the volume ratio of MIL-100, Co@GOx and deionized water is 0.6-0.8:0.4-0.6:0.2-0.3; the incubation step in step (3) is at room temperature for 0.8-1.2 hours.

[0010] The present invention also provides a multifunctional nanocatalyst prepared by the aforementioned preparation method.

[0011] This invention also provides a catalytic material supported on a nanocatalyst, wherein the catalytic material is prepared by loading the multifunctional nanocatalyst onto a porous polyurethane elastomer material; the multifunctional nanocatalyst and a binder are dispersed in a solvent, and after ultrasonication, a mixed solution is obtained; the porous polyurethane elastomer material is immersed in the mixed solution, and after drying, the catalytic material is obtained; the solid-liquid ratio of the multifunctional nanocatalyst, polybutylene oxide, and solvent is (18-22 mg):(9-12 mg):(9-11 mL); the binder is polyvinyl butyral; the temperature of the immersion step is less than or equal to 45°C; the solvent is anhydrous ethanol or methanol; the pore size of the porous polyurethane elastomer material is 50-500 μm; and the ultrasonication time is 30-60 min.

[0012] The present invention also provides applications of the aforementioned multifunctional nanocatalyst, including its application in wastewater treatment; its application in the degradation of organic pollutants; and its application in the degradation of methylene blue or tetracycline hydrochloride.

[0013] Furthermore, the application method of the aforementioned multifunctional nanocatalyst includes the following steps: adding the nanocatalyst to wastewater, adding glucose to it, and the reaction is complete; the concentration of the glucose is 5 mM; the concentration of the nanocatalyst is 0.1 mg / mL; the reaction time is 0.1-180 min, and the temperature is 25-45℃.

[0014] This multifunctional nanocatalyst generates hydrogen peroxide and reactive oxygen species in situ based on a cascade catalytic reaction, enabling efficient degradation of organic pollutants and sterilization. The multifunctional nanocatalyst utilizes a biomineralization method to synthesize a cobalt-based glucose oxidase composite nanomaterial (Co@GOx), which not only possesses glucose oxidase properties but also peroxidase-like characteristics. Furthermore, through in-situ self-assembly, the metal-organic framework nanomaterial MIL-100 is combined with Co@GOx to successfully prepare a MIL-100 / Co@GOx (MCG) nanocatalyst with both high specific surface area and dual-enzyme activity. When the MCG nanocatalyst is mixed with pollutants and glucose is added, the MCG catalyst catalyzes the conversion of glucose to H2O2. On one hand, Co@GOx catalyzes the generation of reactive oxygen species (ROS) from H2O2; on the other hand, MIL-100 undergoes a Fenton-like reaction with H2O2 to continuously generate •OH (hydroxyl radicals). The continuous release of •OH can efficiently degrade organic pollutants such as antibiotics and dyes, while simultaneously achieving broad-spectrum sterilization. Considering practical applications in water pollution control, MCG catalysts were loaded onto polyurethane (PU) sponges using polyvinyl butyral (PVB) as a binder for the continuous removal of antibiotics, organic dyes, and bacteria from wastewater. Continuous large-scale experiments were conducted in a nanocatalytic system using MIL-100 / Co@GOX@PU (MCG@PU) as the catalyst. Results showed that the MCG@PU sponge achieved a degradation rate exceeding 90% for methylene blue (MB) dye and tetracycline hydrochloride (TC-HCl) in wastewater, while maintaining a microbial inactivation rate as high as 99.9%. The entire process requires no additional H2O2, exhibiting green, efficient, safe, and sustainable characteristics.

[0015] Compared with the prior art, the present invention has the following advantages: The multifunctional nanocatalyst described in this invention utilizes an MCG catalyst / glucose system to achieve a degradation rate of over 90% for methylene blue (MB) dye and over 80% for tetracycline hydrochloride (TC-HCl), while simultaneously achieving up to 99.9% microbial inactivation. It has the advantages of simple operation, no need for H2O2 addition, low cost, and good stability. This method has great potential in cascade catalysis and can help eliminate various organic pollutants and bacteria.

[0016] The multifunctional nanocatalyst described in this invention has good tandem enzyme activity, can catalyze the production of H2O2 from glucose, and then continuously generate •OH through peroxidase-like and Fenton-like reaction characteristics.

[0017] The catalytic material with supported nanocatalysts prepared in this invention exhibits excellent stability and has practical application potential for the efficient degradation of organic pollutants and the removal of microorganisms in complex water bodies. The entire process requires no additional H2O2, making it green, efficient, safe, and sustainable. In summary, this catalyst provides a new pathway for pollutant degradation. Attached Figure Description

[0018] Figure 1 The enzyme activities of Co@GOx, MIL-100, and MIL-100 / Co@GOx (0.1 mg / mL) under neutral conditions as described in the embodiments of the present invention are as follows: (a) UV-Vis absorption spectra of TMB catalyzed by Co@GOx, MIL-100, and MIL-100 / Co@GOx measured at 500-800 nm after 15 min of reaction at room temperature; (b) the absorbance of the products of Co@GOx, MIL-100, and MIL-100 / Co@GOx catalyzed by TMB as a function of time at 650 nm. Figure 2 The three catalysts Co@GOx, MIL-100, and MCG described in this embodiment of the invention adsorb / degrade MB and TC-HCl: (a) MB; (b) TC-HCl. (Under neutral conditions at room temperature, TC-HCl concentration: 0.05 mg / mL, MCG catalyst concentration: 0.1 mg / mL, and glucose concentration: 5 mM. Glucose was added at t=0 to adsorb / degrade MB and TC-HCl.) Figure 3 The effect of different glucose concentrations on the degradation of MB and TC-HCl by the MCG catalyst as described in the embodiments of the present invention: (a): MB; (b): TC-HCl. (Under neutral conditions at room temperature, MB concentration: 0.01 mg / mL, TC-HCl concentration: 0.05 mg / mL, MCG catalyst concentration: 0.1 mg / mL, glucose was added at t=0 to adsorb / degrade organic pollutants.) Figure 4 The effect of different MCG catalyst concentrations on the degradation of MB and TC-HCl described in the embodiments of the present invention: (a): MB; (b): TC-HCl. (Under neutral conditions at room temperature, MB concentration: 0.01 mg / mL, TC-HCl concentration: 0.05 mg / mL, and glucose concentration: 5 mM. Glucose was added at t=0 to adsorb / degrade MB.) Figure 5The effect of different pH values ​​on the degradation of MB and TC-HCl by the MCG catalyst as described in the embodiments of the present invention: (a): MB; (b): TC-HCl. (At room temperature, MB concentration: 0.01 mg / mL, TC-HCl concentration: 0.05 mg / mL, MCG catalyst concentration: 0.1 mg / mL, glucose concentration: 5 mM, glucose was added at t=0 to adsorb / degrade MB and TC-HCl.) Figure 6 The effect of different temperatures on the degradation of MB and TC-HCl by the MCG catalyst as described in the embodiments of the present invention: (a): MB; (b): TC-HCl. (Under neutral conditions, MB concentration: 0.01 mg / mL, TC-HCl concentration: 0.05 mg / mL, MCG catalyst concentration: 0.1 mg / mL, glucose concentration: 5 mM, glucose was added at t=0 to adsorb / degrade MB and TC-HCl.) Figure 7 The effects of different ions on the degradation of MB and TC-HCl by the MCG catalyst described in the embodiments of the present invention are shown. (a): MB; (b): TC-HCl. (Under neutral conditions at room temperature, MB concentration: 0.01 mg / mL, TC-HCl concentration: 0.05 mg / mL, MCG catalyst concentration: 0.1 mg / mL, glucose concentration: 5 mM. Glucose was added at t=0 to adsorb / degrade organic pollutants. The inorganic ion concentration in the MB degradation system was 0.01 mg / mL, and the inorganic ion concentration in the TC-HCl degradation system was 0.05 mg / mL.) Figure 8 The effects of different water samples on the degradation of MB and TC-HCl by the MCG catalyst described in this embodiment of the invention are as follows: (a) MB; (b) TC-HCl. (Under neutral conditions at room temperature, the concentrations of MB, TC-HCl, catalyst, and glucose were artificially added: 0.01 mg / mL, 0.05 mg / mL, 0.1 mg / mL, and 5 mM. Glucose was added at t=0 to adsorb / degrade organic pollutants.) Figure 9 The images show colonies formed after the kanamycin-resistant Escherichia coli (KREC) and methicillin-resistant Staphylococcus aureus (MRSA) model strains described in the embodiments of the present invention were treated with different systems and then co-incubated at 37°C for 3 hours.

[0019] Figure 10The MCG@PU sponge described in this embodiment of the invention degrades MB and TC-HCl in a continuous reaction device. (a): Degradation effect of MB in the MCG / Glucose system; (b): Degradation effect of TC-HCl in the MCG / Glucose system. Detailed Implementation

[0020] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.

[0021] The present invention will be described in detail below with reference to the embodiments.

[0022] Example 1 A method for preparing a multifunctional nanocatalyst includes the following steps: (1) Synthesis of Co@GOx by biomineralization: Cobalt chloride (4.5 mg) and glucose oxidase (3.6 mg) were dissolved in 2.5 mL of deionized water, and 35 µL of sodium hydroxide (1 mol / mL) was added. The mixture was reacted in a water bath at 37 °C for 3 h. (2) Synthesis of MIL-100: 0.270 g, 1 mM ferric chloride hexahydrate and 0.210 g, 1 mM pyromellitic acid were dissolved in 20 mL N,N-dimethylformamide and placed in an 80 mL Teflon-lined autoclave. The mixture was then sonicated for 5 min, sealed in the autoclave, and heated in an oven at 150 °C for 12 h. (3) Preparation of MCG catalyst: 0.25 mL of deionized water was added to a mixed solution of 0.75 mL of 1.7 mg / mL MIL-100 and 0.5 mL of 1.6 mg / mL Co@GOx. The MCG catalyst was obtained after incubation at room temperature for 1 h. (4) Preparation of MCG@PU sponge: 20 mg of MCG catalyst and 10 mg of polybutyl vinyl were dispersed in 10 mL of ethanol and sonicated for half an hour. A 2*2 cm cylindrical polyurethane (PU) sponge was immersed in the mixed liquid and air-dried to obtain MCG@PU sponge.

[0023] Experimental Example 1: Dual-enzyme activity verification: Under neutral conditions, MCG catalyst (50 μL, 20 μg / mL), glucose (100 μL, 100 mM), and 3,3',5,5'-tetramethylbenzidine (TMB, 8 μL, 10 mM) were reacted in a 96-well plate at room temperature for 15 min. The absorbance at 650 nm or the UV-Vis absorption curve was then recorded using a microplate reader. Recordings were taken every 20 s to obtain the change in absorbance over time. A blank control group (without glucose) was included in the experiment, and the results were discarded.

[0024] The results are as follows Figure 1 As shown, from Figure 1 As can be seen from a and b, Co@GOx and MCG catalysts exhibit dual enzyme activities of glucose oxidase and peroxidase-like enzymes, enabling rapid oxidation of TMB. Among them, the MCG catalyst exhibits the best dual enzyme activity. The improvement of the dual enzyme activity of the MCG catalyst is due to: (1) the integration of nanozymes and glucose oxidase through spatial confinement effect, which enhances substrate transfer efficiency; (2) the multi-level synergistic catalytic mechanism of active sites reduces the diffusion loss of intermediate products, thereby improving the cascade catalytic efficiency, making it superior to Co@GOx and MIL-100 in the cascade oxidation reaction of glucose-TMB.

[0025] Experimental Example 2: Feasibility verification: The absorbance of contaminants (MB and TC-HCl) was measured using an ELISA reader under the following conditions (e.g.) Figure 2 (As shown): a: Synthetic MCG to remove / degrade MB; b: TC-HCl. In the above system, the concentration of MB is 0.01 mg / mL, the concentration of TC-HCl is 0.05 mg / mL, the concentration of MCG catalyst is 0.1 mg / mL, and the concentration of Glucose is 5 mM. Glucose is added at the beginning of the reaction.

[0026] The results are as follows Figure 2 As shown, from Figure 2 Figures a and b show that the adsorption kinetics and Fenton-like catalytic degradation performance of the synthesized MCG catalyst nanocomposite material were evaluated using MB and TC-HCl as simulated pollutants. The catalytic degradation became very rapid after the addition of glucose, confirming that the MCG catalyst possesses Fenton-like catalytic activity. When Co@GOx or MIL-100 was used alone, the degradation efficiency for MB and TC-HCl was significantly lower than that of the MIL-100 / Co@GOx (MCG) composite material prepared in Example 1 of this invention. This demonstrates that the combination of MIL-100 and Co@GOx produces a synergistic catalytic effect, rather than a simple superposition of the functions of the individual components. The MCG catalyst exhibited the highest removal efficiency for both MB and TC-HCl.

[0027] Experiment Example 3: Glucose concentration: MB and TC-HCl were mixed with 0.1 mg / mL MCG catalyst and reacted at room temperature for 30 min to allow the MCG catalyst to reach adsorption equilibrium for the organic dye. Then, different concentrations of glucose were added, and the mixtures were incubated at room temperature for different times (0, 30, 60, 90, 120, 150, and 180 min). Next, the mixtures were centrifuged at 25°C and 8000 rpm for 5 min, and the absorption spectra of the supernatant were recorded using a microplate reader. The concentrations of MB, TC-HCl, and MCG catalyst in the above systems were: MB: 0.01 mg / mL, TC-HCl: 0.05 mg / mL, MCG catalyst: 0.1 mg / mL, and glucose: 5 mM.

[0028] result Figure 3 As shown, from Figure 3 As shown in a and b, the removal rates of MB and TC-HCl both increase with the increase of glucose concentration from 0.1 mM to 5 mM. However, as the glucose concentration further increases by 20 mM from 5 mM, the removal rate gradually decreases. This indicates that the MCG catalyst can effectively degrade MB and TC-HCl at 5 mM glucose concentration.

[0029] Experiment Example 4: MCG catalyst concentration: MB and TC-HCl were mixed with different concentrations of MCG catalyst and reacted at room temperature for 30 min to allow the MCG catalyst to reach adsorption equilibrium for MB and TC-HCl. Then, 5 mM glucose was added, and the mixture was incubated at room temperature for different times (0, 30, 60, 90, 120, 150, and 180 min). Next, the mixture was centrifuged at 25 ℃ and 8000 rpm for 5 min, and the absorption spectrum of the supernatant was recorded using a microplate reader. The concentrations of MB, TC-HCl, and glucose in the above systems were: MB: 0.01 mg / mL, TC-HCl: 0.05 mg / mL, and glucose: 5 mM.

[0030] result Figure 4 As shown, from Figure 4 As shown in a and b, the removal rate increases with increasing catalyst dosage, mainly affecting the catalyst's adsorption efficiency. However, excessive dosage may lead to aggregation and a decrease in degradation rate. The 0.1 mg / mL MCG catalyst exhibits the best degradation effect.

[0031] Experiment Example 5: pH: 0.01 mg / mL MB (or 0.05 mg / mL TC-HCl) was mixed with 0.1 mg / mL MCG catalyst in aqueous solutions at different pH values ​​and reacted at room temperature for 30 min to allow the MCG catalyst to reach adsorption equilibrium for MB and TC-HCl. Then, 5 mM glucose was added, and the mixture was incubated at room temperature for different times (0, 30, 60, 90, 120, 150, and 180 min). Next, the mixture was centrifuged at 25 °C and 8000 rpm for 5 min, and the absorption spectrum of the supernatant was recorded using a microplate reader. In the above systems, the concentration of MCG catalyst was 0.1 mg / mL, and the concentration of glucose was 5 mM.

[0032] result Figure 5 As shown, from Figure 5 As shown in a and b, we observed that MCG exhibits highly efficient catalytic activity for the degradation of MB and TC-HCl over a wide pH range of 2-12. The removal rates of MB and TC-HCl are higher at pH values ​​of 5, 6, and 7. The optimal pH for MCG degradation of pollutants is 6, with removal efficiencies of 96.95% and 76.77% for MB and TC-HCl, respectively. This indicates that the catalyst can maximize its Fenton-like activity under weakly acidic conditions, which is close to the pH values ​​of most real wastewater. It is worth noting that the practicality of operating under near-neutral pH conditions may offer potential for the practical application of Fenton-like systems.

[0033] Experimental Example 6: Temperature: MB and TC-HCl were mixed with 0.1 mg / mL MCG catalyst and reacted at room temperature for 30 min to allow the MCG catalyst to reach adsorption equilibrium for MB and TC-HCl. Then, 5 mM glucose was added, and the mixture was incubated at different temperatures (4, 25, 37, 45, 55, 65, 75, 85, and 95 °C) for different times. Next, the mixture was centrifuged at 25 °C and 8000 rpm for 5 min, and the absorption spectrum of the supernatant was recorded using a microplate reader. The concentrations of MB, TC-HCl, MCG catalyst, and glucose in the above systems were: MB: 0.01 mg / mL, TC-HCl: 0.05 mg / mL, MCG catalyst: 0.1 mg / mL, and glucose: 5 mM.

[0034] result Figure 6 As shown, from Figure 6 As can be seen from a and b, both excessively high and low temperatures will affect the activity of glucose oxidase, thereby affecting the degradation efficiency of MB and TC-HCl. The degradation efficiency is highest at 45 ℃.

[0035] Experiment Example 7: Different ions: MB and TC-HCl were mixed with 0.1 mg / mL MCG catalyst and reacted at room temperature for 30 min to allow the MCG catalyst to reach adsorption equilibrium for MB and TC-HCl. 5 mM glucose was added to the MB degradation system (0.01 mg / mL) and the TC-HCl degradation system (0.05 mg / mL). The mixtures were incubated at room temperature for different times (0, 30, 60, 90, 120, 150, and 180 min). Next, the mixtures were centrifuged at 25 ℃ and 8000 rpm for 5 min, and the absorption spectra of the supernatant were recorded using a microplate reader. The concentrations of MB, TC-HCl, MCG catalyst, and glucose in the above systems were: MB: 0.01 mg / mL, TC-HCl: 0.05 mg / mL, MCG catalyst: 0.1 mg / mL, and glucose: 5 mM.

[0036] result Figure 7 As shown, from Figure 7 As shown in a and b, it maintains stable degradation performance even in the presence of multiple inorganic ions, indicating that its chemical structure has strong tolerance to ion interference and is not easily affected by common inorganic components in the environment. In practical complex water sample treatment, it has the potential to cope with situations where multiple ions coexist, and efficiently exert its functions of degrading pollutants and sterilization.

[0037] Experiment Example 8: Detection of different water samples: MB and TC-HCl were mixed with 0.1 mg / mL MCG catalyst in different aqueous solutions (deionized water, tap water, and lake water), and reacted at room temperature for 30 min to allow the MCG catalyst to reach adsorption equilibrium for MB and TC-HCl. The mixtures were then incubated at room temperature for different times (0, 30, 60, 90, 120, 150, and 180 min). Next, the mixtures were centrifuged at 25 ℃ and 8000 rpm for 5 min, and the absorption spectrum of the supernatant was recorded using a microplate reader. The artificially added concentrations in the above systems were: MB 0.01 mg / mL, TC-HCl 0.05 mg / mL, MCG catalyst 0.1 mg / mL, and Glucose 5 mM.

[0038] like Figure 8 As shown, from Figure 8 As can be seen from a and b, we selected three water samples to explore the Fenton-like degradation performance of the MCG catalyst. The degradation rate of MB by the MCG catalyst reached over 90% under different water environments, and over 80% for TC-HCl. This shows that the MCG catalyst has good practical application potential in the treatment of polluted water bodies.

[0039] Experiment Example 9: Antibacterial activity of MCG@PU sponge: The antibacterial activity of common kanamycin-resistant Escherichia coli (KREC) and methicillin-resistant Staphylococcus aureus (MRSA) strains against MCG@PU was studied in the presence of 5 mM glucose. Typically, the control group (containing only bacteria), PU, ​​MCG@PU, and MCG@PU + 5 mM glucose were tested at 10 μL each. 6 After mixing the CFU / mL bacterial solution and incubating at 37 °C for 3 h, 30 μL of the resulting solution was spread onto an agar plate and incubated at 37 °C for another 12 h.

[0040] from Figure 9 As can be seen, compared with the control group, treatment with PU and MCG@PU significantly inhibited the growth of both bacteria. Furthermore, when 5 mM glucose was added to MCG@PU, almost no colonies formed in the MRSA and KREC groups, indicating that MCG@PU achieved complete bactericidal effect (99.9%). These results demonstrate that MCG@PU has high antibacterial activity against KREC and MRSA.

[0041] Experiment Example 10: Continuous reactor experiment: The prepared MCG@PU functionalized sponge was integrated into a continuous flow reactor to construct a dynamic catalytic degradation system. Simulated organic dye wastewater with an initial concentration of 0.01 mg / mL MB and a 100 mM glucose solution were prepared as reaction substrates and simultaneously injected into the reactor via a single-channel peristaltic pump (flow rate 1 rpm / min) to achieve continuous reactant supply.

[0042] Experimental results are as follows Figure 10 As shown in a and b, MB or TC-HCl solutions containing glucose solution are passed through the reaction apparatus at a uniform rate to complete the catalytic reaction. After 6 hours of continuous reaction, the degradation efficiencies of MB and TC-HCl remain above 99.83% and 98.39%, respectively, indicating that MCG@PU can catalyze the long-term glucose oxidase-triggered Fe... 2+ A Fenton-like mediated reaction was used to degrade H₂O₂ and generate abundant ·OH groups to degrade organic pollutants. In summary, the continuous flow experimental setup exhibited excellent performance in the degradation of MB and TC-HCl in the presence of glucose. Therefore, the prepared MCG@PU has the potential to achieve large-scale degradation of MB and TCl.

[0043] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a multifunctional nanocatalyst, characterized by: It comprises the following steps: (1) Dissolve the cobalt source and glucose oxidase in deionized water, adjust the pH value of the solution, and react under heating conditions. After the reaction is completed, Co@GOx is obtained; (2) Dissolve the iron source metal compound and trimesic acid in a solvent, mix and react under heating conditions. After the reaction is completed, MIL-100 is obtained; (3) Add the MIL-100 and the Co@GOx to deionized water, and incubate to obtain the multifunctional nanocatalyst.

2. The method for preparing multifunctional nanocatalyst according to claim 1, characterized in that: The mass ratio of the cobalt source to glucose oxidase in step (1) is 4.0-5.0:3.2-4.0; the cobalt source in step (1) is at least one of water-soluble cobalt sources such as cobalt chloride, cobalt nitrate, and cobalt acetate.

3. The method for preparing multifunctional nanocatalyst according to claim 1, characterized in that: The pH value in the pH value adjusting step in step (1) is 8-9; the temperature of the reaction in step (1) is 35-40℃, and the time is 2.5-3.5h.

4. The method for preparing multifunctional nanocatalysts according to claim 1, characterized in that: The solid-liquid ratio of the metal compound, trimesic acid, and solvent in step (2) is 0.25-0.29g:0.19-0.23g:18-22mL; the metal compound in step (2) is at least one of iron trichloride hexahydrate, anhydrous iron chloride, iron nitrate nonahydrate, or iron sulfate; the solvent in step (2) is N,N-dimethylformamide.

5. The method for preparing the multifunctional nanocatalyst according to claim 1, characterized by: The temperature of the reaction in step (2) is 140-160℃, and the time is 10-16h.

6. The method for preparing the multifunctional nanocatalyst according to claim 1, characterized in that: The volume ratio of MIL-100, Co@GOx, and deionized water in step (3) is 0.6-0.8:0.4-0.6:0.2-0.3; the temperature of the incubation step in step (3) is room temperature, and the time is 0.8-1.2h.

7. A multifunctional nanocatalyst prepared by the preparation method of any one of claims 1-6.

8. A catalytic material loaded with nanocatalysts, characterized in that: The catalytic material is prepared by loading the multifunctional nanocatalyst of claim 7 on a porous polyurethane elastomer material; the multifunctional nanocatalyst and the binder are dispersed in a solvent, and after ultrasonic treatment, a mixed solution is obtained; the porous polyurethane elastomer material is immersed in the mixed solution, and after drying, the catalytic material is obtained; the solid-liquid ratio of the multifunctional nanocatalyst, polybutylvinyl, and the solvent is 18-22mg:9-12m:9-11mL; the binder is polyvinyl butyral ester; the temperature of the immersion step is less than or equal to 45℃; the solvent is anhydrous ethanol or methanol; the pore size of the porous polyurethane elastomer material is 50-500μm; and the time of the ultrasonic treatment step is 30-60min.

9. Use of the multifunctional nanocatalyst according to claim 7, characterized in that: The multifunctional nanocatalyst is used in the field of wastewater treatment; the multifunctional nanocatalyst is used in the field of degrading organic pollutants; and the multifunctional nanocatalyst is used in the field of degrading methylene blue or tetracycline hydrochloride.

10. Use of multifunctional nanocatalysts according to claim 9, characterized in that: The application method of the multifunctional nanocatalyst comprises the following steps: adding the nanocatalyst into sewage, adding glucose into the sewage, and obtaining the product after the reaction is completed; the concentration of the glucose is 4-6 mM; the concentration of the nanocatalyst is 0.08-0.12 mg / mL; the reaction time is 0.1-180 min, and the reaction temperature is 25-45 DEG C.

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