Peroxidase nanocatalyst adsorption-catalysis combined treatment agent, preparation method and application thereof

Abstract

The application relates to a peroxide nanoenzyme adsorption-catalysis combined treatment agent, a preparation method and application thereof, and belongs to the technical field of biotechnology. The peroxide nanoenzyme adsorption-catalysis combined treatment agent can be applied to adsorption and degradation of tetracycline. First, an adsorption enrichment material PCN-222 is prepared, then the PCN-222 is reacted with cobalt chloride to prepare PCN-222 (Co); then, the PCN-222 and the PCN-222 (Co) are filled in two polypropylene chromatographic columns as column materials of adsorption columns and degradation columns, so that the peroxide nanoenzyme adsorption-catalysis combined treatment agent is obtained; tetracycline aqueous solution is added into the adsorption column, tetracycline in the tetracycline aqueous solution is adsorbed by the PCN-222, then the tetracycline adsorbed by the PCN-222 is eluted with an eluent and enters an elution column with the eluent; hydrogen peroxide aqueous solution and the PCN-222 (Co) are added into the elution column, and the tetracycline in the elution column is catalytically degraded.

Description

Technical Field

[0001] This invention belongs to the field of biotechnology, specifically relating to a peroxide nanoenzyme adsorption-catalysis combined treatment agent, its preparation method and its application. This peroxide nanoenzyme adsorption-catalysis combined treatment agent can be used in the adsorption and degradation of tetracycline. Background Technology

[0002] With the development of the pharmaceutical industry, antibiotics have been overused. Among them, tetracycline antibiotics (TCs), as broad-spectrum antibiotics, have broad-spectrum activity and are characterized by high quality and low cost, making them one of the main antibiotics for human treatment, animal disease control, and agricultural feed additives. Currently, pharmaceutical factories synthesize tetracyclines through fermentation, semi-synthesis, and total synthesis, with semi-synthesis (i.e., fermentation followed by chemical semi-synthesis) being the primary production method.

[0003] Numerous studies have shown that tetracycline is widely used worldwide. Tetracycline in wastewater may originate from direct discharge from pharmaceutical plants or from household and / or livestock wastewater. The majority (up to 75%) of total toxic substances (TCs) consumed by humans and livestock are excreted in inactive forms through feces and urine. Tetracycline itself has a complex structure, high hydrophilicity, high solubility, and low biodegradability, making it difficult to remove using conventional wastewater treatment methods. This results in the presence of tetracycline in aquatic environments such as surface water, rivers, groundwater, and wastewater. Although tetracycline is widely present in aquatic environments, it is generally found at low concentrations (in the range of ng / L to mg / L) (Xu LY, Zhang H, Xiong P, et al. Occurrence, fate, and risk assessment of typical tetracycline antibiotics in the aquatic environment: A review[J]. Science of the Total Environment, 2021, 753), although higher concentrations (less than 10 mg / L) have been observed in some rivers in northern China.

[0004] TCs (Tradecorneal Cyclones) have stable chemical structures. Their long-term presence in aquatic environments can inhibit the growth and development of aquatic species, exert toxicity on plants (such as altering metabolic and respiratory mechanisms), and exert selective pressure on antibiotic-resistant bacteria (ARBs) and antibiotic resistance genes (ARGs) in the environment. Furthermore, studies have found varying levels of antibiotic residues in meat, eggs, milk, and vegetables. Tetracyclines, through excessive accumulation in the food chain, can potentially affect human health, leading to various problems such as joint diseases, kidney disease, endocrine disorders, central nervous system defects, and bacterial pathogenicity. Moreover, long-term consumption of tetracycline-contaminated water can affect the development of teeth and bones and has a certain degree of hepatotoxicity. Therefore, removing tetracyclines from water bodies is extremely important for protecting the environment and human health.

[0005] Adsorption and enzymatic methods offer significant advantages in wastewater treatment, but single methods are often less than ideal. Combining these two methods to improve overall performance is a wise approach. However, using bifunctional materials that simultaneously perform adsorption and enzyme-mimicking catalysis has limitations: incomplete catalysis can lead to occupied adsorption sites, affecting adsorption performance; and the adsorption sites are easily damaged by free radicals during pollutant oxidation, resulting in lower reusability and impacting practical applications. Furthermore, for low-concentration pollutants, simultaneous adsorption and enzyme-mimicking catalysis can lead to excessively long times for pollutants to reach the catalytic sites due to their low concentration. Therefore, adsorption and enzyme-mimicking catalysis are performed separately. First, large volumes of low-concentration wastewater are enriched through adsorption. Then, a small volume of eluent is used to desorb the enriched pollutants, followed by enzyme-mimicking catalysis. This shortens treatment time and reduces energy consumption.

[0006] Based on the above, it is crucial to prepare a combined system that can both adsorb tetracycline and catalyze its degradation. Summary of the Invention

[0007] This invention addresses the increasingly serious water pollution problems caused by the complex structure, poor biodegradability, low pollutant concentration, and water pollution of wastewater containing tetracycline and other drugs. Based on the design concept of a two-step adsorption-enzyme catalysis method, it provides a peroxide nanoenzyme adsorption-catalysis combined treatment agent, its preparation method, and its application in the adsorption and degradation of tetracycline.

[0008] The preparation method of the peroxide nanoenzyme adsorption-catalysis combined treatment agent of the present invention comprises the following steps:

[0009] (1) Preparation of adsorption and enrichment materials

[0010] Add 200-500 mg of zirconium oxychloride (ZrOCl2·8H2O) to 50-200 mL of N,N-dimethylformamide (DMF), mix and sonicate for 20-60 min. Add 50-100 mg of tetracarboxyphenylporphyrin (TCPP) and sonicate for 20-60 min. Add 50-100 mL of formic acid and mix thoroughly. Heat at 120-180 ℃ for 60-100 hours. Centrifuge at 8000-12000 rpm for 10-25 min and discard the supernatant. Resuspend the precipitate in 10-40 mL of DMF. Wash the precipitate repeatedly with DMF until the supernatant is clear and transparent. Dry the precipitate under vacuum at 100-140 ℃ for 5-10 h to obtain PCN-222.

[0011] Dissolve 20-50 mg of PCN-222 in 20-100 mL of DMF using ultrasound, add 0.5-1 mL of 6-10 M hydrochloric acid, and react at 120-160 °C for 10-15 h. After centrifugation at 8000-12000 rpm for 10-25 min, discard the supernatant and resuspend the precipitate in 10-40 mL of DMF. Wash the precipitate repeatedly with DMF until the supernatant is clear and transparent, and then vacuum dry the precipitate at 100-140 °C for 5-10 h to obtain activated PCN-222.

[0012] (2) Preparation of materials with peroxide nanozyme activity

[0013] Take 30-50 mg of PCN-222 prepared in step (1) and 150-300 mg of cobalt chloride (CoCl2·6H2O) and sonicate it into 8-10 mL of DMF. React at 100-150 °C for 16-24 hours. After centrifugation at 10000-15000 rpm for 8-15 min, discard the supernatant and suspend the precipitate in 10-40 mL of DMF. Wash the precipitate repeatedly with DMF until the supernatant is clear and transparent. Dry the precipitate under vacuum at 100-140 °C for 5-10 h to ensure no DMF residue, and obtain PCN-222 (Co).

[0014] (3) Preparation of peroxide nanoenzyme adsorption-catalysis combined treatment agent

[0015] The adsorption-degradation column consists of two Econo-Pac polypropylene chromatography columns, each 10-20 cm high and 1.0-2.0 cm in diameter, respectively filled with 20-300 mg of PCN-222 and PCN-222(Co) as the column stock for the adsorption and degradation columns. Before filling the columns, 2-3 polypropylene gaskets, 1.0-2.0 cm in diameter and 2-5 mm thick, are placed at the bottom of the columns to prevent the column stock from flowing out with the liquid due to small particle size. After filling, 1-2 polypropylene gaskets, 1.0-2.0 cm in diameter and 2-5 mm thick, are placed at the top of the columns to reduce damage to the column bed when liquid is added. A constant flow pump is connected to the lower end of the chromatography columns to control the flow rates of the adsorption and degradation columns, thereby obtaining the peroxide nanoenzyme adsorption-catalysis combined treatment agent.

[0016] (4) Adsorption and degradation of tetracycline by peroxide nanoenzyme adsorption-catalysis combined treatment agent

[0017] The peroxide nanozyme adsorption-catalysis combined treatment agent obtained in step (3) was used to adsorb and degrade tetracycline. The eluent was a methanol aqueous solution of 0.1 M HCl, wherein the volume content of methanol was 10%~90%. The adsorption column flow rate was 1~2 mL, the elution column flow rate was 0.5~2 mL, the tetracycline aqueous solution concentration was 20~100 mg / L, and the hydrogen peroxide aqueous solution concentration was 3~40 mM H2O2. The tetracycline aqueous solution was added to the adsorption column, and the tetracycline in the tetracycline aqueous solution was adsorbed by PCN-222. Then, the tetracycline adsorbed by PCN-222 was eluted with the eluent and entered the elution column. Hydrogen peroxide aqueous solution and PCN-222 (Co) were added to the elution column, and the tetracycline in the elution column was catalytically degraded. Attached Figure Description

[0018] Figure 1 These are scanning electron microscope (SEM) images and EDS energy dispersive spectroscopy (EDS) images of the materials in Example 1; where Figure a is a 1000x magnified image of PCN-222, Figure b is a 1500x magnified image of PCN-222(Co), and Figure c is a 3000x magnified image of PCN-222(Co) EDS energy dispersive spectroscopy (EDS) image.

[0019] Figure 2 This is the UV-Vis absorption spectrum of the product in Example 1. The spectrum shows that after Co binding, the Soret band absorption peak at 410 nm shifts to 431 nm. As shown in the inset, the Q band decreases from three absorption peaks at 528 nm, 566 nm, and 653 nm to two absorption peaks at 551 nm and 590 nm. The UV-Vis absorption spectrum here characterizes the porphyrin ligand. The porphyrin ligand of PCN-222 is TCPP, while the porphyrin ligand of PCN-222(Co) is the metallized TCPP-Co.

[0020] Figure 3 The image shows the X-ray diffraction pattern of the product in Example 1, indicating that the material synthesized in Example 1 has a stable crystal structure and that the structure remains essentially unchanged after Co coordination.

[0021] Figure 4 The pore size curve (a) and specific surface area curve (b) of the product in Example 1 are shown; it was found that the specific surface area and pore size of PCN-222(Co) are smaller than those of PCN-222.

[0022] Figure 5 The image shows the tetracycline UV-Vis spectrum of the PCN-222 obtained in Example 1 as it adsorbs tetracycline over time; the adsorption time ranges from 0 to 300 min (0, 2, 5, 8, 12, 16, 30, 60, 180, and 300 min from top to bottom), and the tetracycline absorption signal gradually decreases at 357 nm.

[0023] Figure 6 The curve is a peroxidase-like activity assay of PCN-222(Co) obtained in Example 1; PCN-222(Co) can change the color of TMB and thus have an absorption signal at 652nm only when H2O2 is added.

[0024] Figure 7 The degradation curve of tetracycline by PCN-222(Co) obtained in Example 1 is shown; the characteristic absorption peak of TC at 357 nm is reduced in the presence of PCN-222(Co) and H2O2.

[0025] Figure 8 This is a schematic diagram comparing the toxicity of tetracycline after degradation by PCN-222(Co) obtained in Example 1; after tetracycline was degraded by PCN-222(Co), the inhibition zone of E. coli and S. aureus decreased, which was basically the same as that of the control group.

[0026] Figure 9 The diagram shows the construction pattern (a) and physical image (b) of the peroxide nanoenzyme adsorption-catalysis combined treatment agent.

[0027] Figure 10 This is a curve showing the adsorption and degradation effect of tetracycline on the peroxide nanozyme adsorption-catalysis combined treatment agent. After adsorption and degradation, the concentration of tetracycline in the solution decreases. Detailed Implementation

[0028] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0029] Example 1

[0030] This embodiment provides a method for synthesizing a peroxide nanozyme adsorption-catalysis combined treatment agent, the required reagents being as follows:

[0031] TCPP (tetracarboxyphenylporphyrin) was purchased from TCI Reagent Co., Ltd. of Japan; CH2O2 (formic acid), DMF (N,N-dimethylformamide), KBr (potassium bromide), ZrOCl2·8H2O (zirconium oxychloride), and CoCl2·6H2O (cobalt chloride) were purchased from Aladdin Reagent Co., Ltd. of Shanghai; and glacial acetic acid, concentrated hydrochloric acid, and sodium hydroxide were purchased from Sinopharm Chemical Reagent Co., Ltd.

[0032] The specific synthesis method is as follows:

[0033] (1) Preparation of adsorption and enrichment materials:

[0034] 375 mg of zirconium oxychloride (ZrOCl2·8H2O) and 100 mL of N,N-dimethylformamide (DMF) were mixed in a 250 mL dry beaker and sonicated for 30 min to dissolve ZrOCl2·8H2O in DMF. Then, 65 mg of tetracarboxyporphyrin was added, and sonication was continued for another 30 min. Finally, 70 mL of formic acid was added to the mixture, and after thorough mixing, it was dispensed into liquid scintillation vials (approximately 17 mL each). The mouths of the liquid scintillation vials were covered with thick aluminum foil, the caps were tightened, and the vials were placed in a digital display constant temperature drying oven at 130 °C for 80 h. After the reaction was completed, the product was observed to have a rod-shaped crystal morphology under an optical microscope. After centrifugation at 10,000 rpm for 20 min, the supernatant was discarded, and the precipitate was resuspended in 15 mL of DMF. The precipitate was repeatedly washed with DMF until the supernatant was clear and transparent. The precipitate was then placed in a vacuum drying oven and dried at 120 °C for 8 h to obtain PCN-222 with a product mass of 160 mg.

[0035] 30 mg of PCN-222 was sonicated and dissolved in 20 mL of DMF. Then, 0.75 mL of HCl (8 M) was added and the mixture was reacted at 120 °C for 12 h. After centrifugation at 10,000 rpm for 20 min, the supernatant was discarded and the precipitate was resuspended in 15 mL of DMF. The precipitate was repeatedly washed with DMF until the supernatant was clear and transparent. The precipitate was then placed in a vacuum drying oven and dried at 120 °C for 8 h to obtain successfully activated PCN-222 with a product mass of 22 mg.

[0036] (2) Preparation of peroxide nanozyme active materials

[0037] Based on step (1), 40 mg of activated PCN-222 and 200 mg of CoCl2·6H2O were ultrasonically dissolved in 10 mL of DMF and reacted at a constant temperature of 130℃ for 18 h. After centrifugation at 12000 rpm for 20 min, the supernatant was discarded and the precipitate was resuspended in 15 mL of DMF. The precipitate was repeatedly washed with DMF until the supernatant was clear and transparent. The precipitate was then placed in a vacuum drying oven and vacuum dried at 120℃ for 8 h to ensure no DMF residue, thus obtaining PCN-222 (Co) with a product mass of 70 mg.

[0038] Example 2

[0039] This embodiment uses SEM imaging and EDS analysis to perform SEM imaging and EDS analysis on the peroxide nanozyme adsorption-catalysis material obtained in Example 1. The imaging results in Example 1 are as follows: Figure 1 As shown, both PCN-222 and PCN-222(Co) are rod-shaped with a length of approximately 100 μm, and there is no significant difference between them in terms of morphology and size. EDS spectroscopy results show that PCN-222(Co) has a clear Co element signal with a relatively uniform distribution, which characterizes the successful cobalt metallization of PCN-222(Co).

[0040] Example 3

[0041] This embodiment characterizes the peroxide nanoenzyme adsorption-catalysis material obtained in Example 1 using ultraviolet spectroscopy. The ultraviolet spectral results of Example 1 are as follows: Figure 2 As shown in the figure, the Soret absorption peak of the PCN-222 ligand is at 410 nm, with three Q-band absorption peaks; the Soret absorption peak of the PCN-222(Co) ligand is at 431 nm, showing a redshift compared to PCN-222; there are two Q-band absorption peaks, one less than PCN-222. This result is consistent with the report in the literature (Choi MY, Pollard JA, Webb MA, et al. Counterion-dependent excitonic spectra of tetra(p-carboxyphenyl)porphyrin aggregates in acidic aqueous solution[J]. Journal of the American Chemical Society, 2003, 125(3): 810-820) that the Q-band absorption peak decreases after the porphyrin molecule is inserted into a metal, indicating that the porphyrin center of PCN-222(Co) is successfully metallized.

[0042] Example 4

[0043] This embodiment analyzes the specific surface area and pore size of the peroxide nanoenzyme adsorption-catalysis material obtained in Example 1, such as... Figure 4 As shown, the specific surface area of ​​PCN-222 was found to be 2050 m². 2 g -1 The pore sizes are concentrated between 10 Å and 35 Å; the specific surface area of ​​PCN-222(Co) is 347 m². 2 g -1 The pore sizes are concentrated between 9 Å and 23 Å. Both synthesized materials include both micropores (<2 nm) and mesopores (between 2 and 50 nm). The specific surface area of ​​both porous materials includes the sum of the surface areas of all pores. Compared to PCN-222, PCN-222(Co) has a smaller specific surface area and pore size, indicating that some metallic Co occupies the channels of PCN-222(Co).

[0044] Example 5

[0045] This embodiment monitors the adsorption of PCN-222 obtained in Example 1 onto tetracycline solution (10 mg / L) over 5 h (including 0, 2, 5, 8, 12, 16, 30, 60, 180, and 300 min). Figure 5 As shown, the peak value of the characteristic absorption peak of tetracycline decreases continuously over time, indicating that adsorption is ongoing.

[0046] Example 6

[0047] This embodiment detects the peroxidase activity of PCN-222(Co) from Example 1 using 3,3',5,5'-tetramethylbenzidine (TMB) as a substrate. The determination process is as follows: 1 mL reaction system (1 mL reaction system includes: 922 μL, pH 3.0 Gly-HCl buffer + 8 μL, 50 mM TMB + 20 μL H2O2 + 50 μL, 0.25 mg / mL PCN-222(Co); the pH 3.0 buffer system was chosen because PCN-222(Co) exhibits the best catalytic oxidation effect on TMB under these conditions; pH 3.0 Gly-HCl buffer: 50 mL, 0.2 M Gly solution + 11.4 mL, 0.2 M HCl, diluted to 200 mL with deionized water); the UV absorption (652 nm) of TMB was measured using a UV-2700 UV-Vis spectrophotometer. Figure 6As shown, in the control group (i.e., without PCN-222(Co) or H2O2), the solution did not change color and no oxTMB characteristic peak appeared. In the experimental group (i.e., with both H2O2 and PCN-222(Co) present), PCN-222(Co) caused TMB to change color, and the absorption peak intensity of oxTMB at 652 nm continuously increased within 60 s, representing the continuous generation of oxTMB. This indicates that PCN-222(Co) has peroxidase activity and can catalyze the oxidation of TMB in the presence of H2O2.

[0048] Example 7

[0049] This example further verifies the degradation of tetracycline by PCN-222(Co) in Example 1. The reaction system consisted of 680 μL of pH 3.0 Gly-HCl buffer + 30 μL of PCN-222(Co) + 100 μL of 200 mg / mL TC + 190 μL of 500 mM H2O2. Figure 7 As shown, when PCN-222(Co) and H2O2 exist alone or together, the characteristic absorption peak of TC at 357 nm will not appear because tetracycline is not present. When tetracycline exists alone, when TC and PCN-222(Co) coexist, or when TC and H2O2 coexist, tetracycline will not be degraded and will show the highest concentration in the figure. When TC, PCN-222(Co) and H2O2 are present together, the characteristic absorption peak of TC at 357 nm decreases after 10 min of reaction, indicating that the enzyme-mimicking activity of PCN-222(Co) can be used to degrade tetracycline.

[0050] Example 8

[0051] This embodiment compares the toxicity of tetracycline after degradation by PCN-222(Co) in Example 1. The changes in tetracycline toxicity are determined by the inhibition zones produced by two common bacteria, E. coli and Staphylococcus aureus, before and after degradation. Figure 8 As shown, since tetracycline does not produce biotoxicity, neither control group produced an inhibition zone; the two groups before degradation were made by soaking 6.00 mm diameter neutral filter paper in 0.05 mg / mL TC solution, and both groups showed large inhibition zones, demonstrating the biotoxicity of tetracycline to the two bacteria; degradation The last two groups are Neutral filter paper discs were immersed in a solution containing 50 mM H2O2 + 0.05 mg / mL TC + 1 mg / mL PCN-222(Co) for 12 h after degradation. The inhibition zones produced in these two groups were smaller than those in the two groups before degradation, indicating that the toxicity of tetracycline decreased after degradation.

[0052] Example 9

[0053] Figure 9 To construct the schematic diagram and physical object diagram, Figure 9 As shown in Figure a, 200 mL of 200 mg / L tetracycline aqueous solution was prepared as the solution to simulate tetracycline wastewater. The solution flowed through a PCN-222 packed adsorption column, where tetracycline was adsorbed. The switch at position ① was opened, and tetracycline-free treated wastewater was obtained. Then, 100 mL of eluent (0.1 M HCl: methanol: water volume ratio = 1:1:8) was used to elute and desorb the tetracycline on the adsorption column. After desorption for 20 min, 100 mL of 20 mM H2O2 was added and mixed. The switch at position ② was opened, and the mixed solution containing eluent, tetracycline, and H2O2 entered the PCN-222 (Co) packed degradation column for catalytic degradation, finally obtaining tetracycline-free treated wastewater.

[0054] Figure 9 Figure b shows the physical model of the adsorption-degradation column. The adsorption-degradation column consists of two Econo-Pac polypropylene chromatography columns, each 14 cm high and 1.5 cm in diameter, with a column volume of 20 mL. Each column is filled with 200 mg of PCN-222 and PCN-222(Co) as the column stock, respectively. Before filling, two 3 mm thick polypropylene gaskets are placed in the column to prevent the column stock from flowing out with the liquid due to small particles. After filling, another polypropylene gasket is placed to reduce damage to the column bed when liquid is added. An HL-2N digital display constant flow pump is connected to the bottom of the column to control the flow rate. After the tetracycline-containing solution to be treated enters the adsorption column, a three-way valve controls the flow direction of the solution: either into a beaker (the treated solution without tetracycline) or into the degradation column (the tetracycline solution obtained after eluting the adsorption column with the eluent). The conduit below the adsorption column can be connected to a flow rate regulator with a pulley to control the flow rate. The conduit below the degradation column is connected to an HL-2N digital display constant flow pump, which can control the speed at which the fluid flows through the degradation column.

[0055] Example 10

[0056] The adsorption-catalysis combined with the constructed peroxide nanozyme was used to perform adsorption degradation experiments on tetracycline. 200 mL and 200 mg / L tetracycline solutions were passed through adsorption and degradation columns filled with 200 mg PCN222 and PCN222(Co), respectively. UV absorption spectra of the solutions at different stages of the adsorption-enrichment-elution-desorption-catalytic degradation process were obtained, as shown in the figures. Figure 10As shown, the absorption peak of the tetracycline solution (corresponding to the "Untreated TC" curve in the figure) decreases after flowing through the adsorption column (corresponding to the "Remaining after Adsorption" curve in the figure), indicating that tetracycline is adsorbed onto the adsorption column. Eluting with deionized water removes a small portion of the poorly adsorbed tetracycline (corresponding to the "Water Washing after Adsorption" curve in the figure). Most of the tetracycline is eluted using the eluent (corresponding to the "Eluting after Adsorption" curve in the figure). The eluted tetracycline undergoes catalytic degradation in the degradation column, and its characteristic absorption peak decreases (corresponding to the "After Degradation" curve in the figure), indicating that the tetracycline in the eluent can be degraded. The absence of a 357nm absorption peak in the "Eluting after Degradation" curve in the figure indicates that catalytic degradation mainly occurs in the degradation column, with almost no adsorption. This demonstrates the applicability of the adsorption-degradation column model.

Claims

1. A method for preparing a peroxide nanoscale enzyme adsorption-catalysis combined treatment agent, comprising the following steps: (1) Preparation of a material with adsorption enrichment function Take 200-500 mg of zirconium oxychloride and add it to 50-200 mL of N, N-dimethylformamide, mix and ultrasonically shake for 20-60 min, then add 50-100 mg of tetracarboxyphenyl porphyrin and ultrasonically shake for 20-60 min, then add 50-100 mL of formic acid and mix thoroughly, and then heat at a constant temperature of 120-180 ℃ for 60-100 hours; centrifuge for 10-25 min, discard the supernatant, and suspend the precipitate with 10-40 mL of DMF; repeatedly wash the obtained precipitate with DMF until the supernatant is clear and transparent, and then vacuum dry the precipitate at 100-140 ℃ for 5-10 h to obtain PCN-222; Dissolve 20-50 mg of PCN-222 in 20-100 mL of DMF by ultrasonic, add 0.5-1 mL of 6-10 M hydrochloric acid, and heat at a constant temperature of 120-160 ℃ for 10-15 h; centrifuge at 8000-12000 rpm for 10-25 min, discard the supernatant, and suspend the precipitate with 10-40 mL of DMF; repeatedly wash the obtained precipitate with DMF until the supernatant is clear and transparent, and then vacuum dry the precipitate at 100-140 ℃ for 5-10 h to obtain activated PCN-222; (2) Preparation of a material with peroxide nanoscale enzyme activity Take 30-50 mg of PCN-222 prepared in step (1) and 150-300 mg of cobalt chloride, and ultrasonically dissolve them in 8-10 mL of DMF, and then heat at a constant temperature of 100-150 ℃ for 16-24 hours; centrifuge at 10000-15000 rpm for 8-15 min, discard the supernatant, and suspend the precipitate with 10-40 mL of DMF; repeatedly wash the obtained precipitate with DMF until the supernatant is clear and transparent, and then vacuum dry the precipitate at 100-140 ℃ for 5-10 h to ensure that there is no DMF residue, and then obtain PCN-222(Co); (3) Preparation of a peroxide nanoscale enzyme adsorption-catalysis combined treatment agent The adsorption-degradation column is composed of two Econo-Pac polypropylene chromatography columns with a height of 10-20 cm and a diameter of 1.0-2.0 cm, and the column is filled with 20-300 mg of PCN-222 and PCN-222(Co) as column materials of the adsorption column and the degradation column respectively; a constant flow pump is connected to the lower end of the chromatography column to control the flow rate of the adsorption column and the flow rate of the degradation column, thereby obtaining the peroxide nanoscale enzyme adsorption-catalysis combined treatment agent.

2. The preparation method of a peroxide nanoszyme adsorption-catalysis combined treatment agent according to claim 1, characterized in that: In step (3), before filling the column material, 2-3 polypropylene gaskets with a diameter of 1.0-2.0 cm and a thickness of 2-5 mm are laid at the bottom of the chromatography column to prevent the column material from flowing out with the liquid due to being too small; after filling the column material, 1-2 polypropylene gaskets with a diameter of 1.0-2.0 cm and a thickness of 2-5 mm are laid at the top of the chromatography column to reduce the damage to the column bed when the liquid is added.

3. A peroxide nanoszyme adsorption-catalysis combined treatment agent, characterized in that: The peroxide nanoscale enzyme adsorption-catalysis combined treatment agent is prepared by the method of claim 1 or 2.

4. The use of the peroxide nanoscale enzyme adsorption-catalysis combined treatment agent of claim 3 in adsorbing and degrading tetracycline.

5. The use of a peroxide nanozyme adsorption-catalysis combined treatment agent in the adsorption and degradation of tetracycline according to claim 4, characterized in that: The peroxide nanoscale enzyme adsorption-catalysis combined treatment agent is used to adsorb and degrade tetracycline, and the eluent is a 0.1 M HCl methanol aqueous solution, wherein the volume content of methanol is 10% to 90%; the flow rate of the adsorption column is 1 to 2 mL, the flow rate of the elution column is 0.5 to 2 mL, the concentration of the tetracycline aqueous solution is 20 to 100 mg / L, and the concentration of the hydrogen peroxide aqueous solution is 3 to 40 mM H2O2; the tetracycline aqueous solution is added to the adsorption column, the tetracycline in the tetracycline aqueous solution is adsorbed by PCN-222, and then the tetracycline adsorbed by PCN-222 is eluted with the eluent and enters the elution column with the eluent; the hydrogen peroxide aqueous solution and PCN-222 (Co) are added to the elution column, and the tetracycline in the elution column is catalytically degraded.

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