Cu-MOF derivative material for antibiotic degradation and preparation method thereof

Abstract

The invention discloses a Cu-MOF derivative material for antibiotic degradation and a preparation method of the Cu-MOF derivative material, and belongs to the field of metal organic framework material preparation and the technical field of water treatment. The preparation method of the Cu-MOF derivative material comprises the following steps: preparing a high-crystallinity Cu-MOF precursor by adopting a hydrothermal synthesis method, washing for a plurality of times to remove impurities, drying, grinding the obtained Cu-MOF precursor, putting into a tubular furnace, calcining in a nitrogen atmosphere, and cooling to obtain the Cu-MOF derivative material. The preparation process is simple, the Cu-MOF precursor is synthesized through a hydrothermal synthesis method, the Cu-MOF derivative material is synthesized through programmed temperature control calcination modification, the raw material cost is low, the removal efficiency is high, and the application range is wide. The material is high in efficiency of degrading antibiotics, has anti-interference performance when being used for catalytically degrading tetracycline hydrochloride, can still keep relatively good degradation performance in the presence of inorganic ions such as PO4 < 3->, NO3 <-> and Cl <-> and humic acid HA, and has important application value in removal of tetracycline hydrochloride in actual water bodies.

Description

Technical Field

[0001] The invention belongs to the field of metal organic framework material preparation and water treatment technology, and specifically relates to a novel Cu-MOF derivative material for antibiotic degradation and a preparation method thereof. Background Art

[0002] Currently, tetracycline antibiotics (TCs) are continuously detected in environmental water bodies such as groundwater, surface water and drinking water. The widespread presence of antibiotics in the environment may induce bacterial resistance, especially posing a potential threat to aquatic organisms and human health.

[0003] Tetracycline hydrochloride (TCH) is a kind of tetracycline antibiotics, with strong antibacterial and broad-spectrum properties, and is widely used in clinical treatment and animal husbandry. Since tetracycline hydrochloride is directly discharged into the external environment without sufficient treatment during its use in medical treatment and animal husbandry, it will cause serious harm to the ecosystem and water environment. Therefore, these organic substances must be removed before the wastewater is discharged into the water environment. Due to the high chemical stability of tetracycline hydrochloride, it is difficult to completely remove it using biological or conventional physical methods. At present, there is an urgent need for efficient and energy-saving treatment methods to solve the problem of wastewater containing tetracycline hydrochloride.

[0004] Advanced Oxidation Processes (AOPs) with peroxyacetic acid has the advantages of fast speed and high removal efficiency, and is considered to be one of the effective technologies for removing antibiotics. Peroxyacetic acid (PAA), as an oxidant, can quickly and efficiently degrade organic pollutants, microorganisms and ozone precursors. It can decompose organic pollutants into harmless small molecules in a short time. During the use of AOPs, peroxyacetic acid will decompose into water and oxygen, and no secondary pollutants will be produced. This means that after the degradation of pollutants is completed, no harmful residues will be left in the treated water. The development of catalysts with high catalytic activity is one of the key factors in solving the above problems. Metal-organic frameworks (MOFs) are a new generation of crystalline porous materials with a pore structure formed by metal ions or clusters and organic ligands through coordination bonds. It has been a research hotspot in the field of coordination chemistry in the past 20 years. As a new type of multifunctional material, MOFs have the advantages of high porosity, low density, large specific surface area, adjustable pore size, diverse structures and tailorability, and are widely used in various fields, such as batteries, supercapacitors, electrocatalysis, photocatalysis, sensors, drug delivery, gas separation, adsorption and storage. Among the many metal or metal oxide catalyst materials, the development of copper-based metal organic framework materials is of great benefit to stimulate peracetic acid to improve the catalytic activity of the material. Therefore, there is an urgent need to develop a copper-based metal organic framework material to remove tetracycline antibiotics in water environments.

[0005] In the prior art, there have been some achievements in the preparation method of Cu-MOF-derived materials, such as Chinese Patent No. 202310313440.1, published on August 4, 2023, which discloses a patent document entitled "A Cu-MOF-derived N-doped porous carbon material and its preparation method and application". The patent mixes and stirs the HKUST-1 precursor solution and the oil phase solution, and carbonizes, alcohol washes and dries the product to obtain a Cu-MOF-derived N-doped porous carbon material, which is used to activate persulfate to degrade p-nitrophenol. However, the preparation method of this material is complicated, and p-nitrophenol is a phenol compound, and tetracycline hydrochloride is a broad-spectrum antibiotic with a polycyclic structure, so the removal process is significantly different. In addition, China Patent Application No.: 202310762888.1, published on September 22, 2023, discloses a patent document entitled "Preparation method and application of a new Cu-MOF-derived magnetic Fe3O4@Cu / C composite material for antibiotic degradation". The patent is to compound the obtained new Cu-MOF with Fe2O3 in a high-pressure reactor, and calcine it in an inert gas atmosphere to obtain a magnetic Fe3O4@Cu / C composite material, thereby improving its ability to activate persulfate to degrade oxytetracycline. However, the synthesis cost of the material is high, and the material is recycled after use. Faced with challenges, practical application is relatively difficult; Chinese patent application number: 202310945093.4, publication date December 15, 2023, disclosed a patent document entitled "A SCN-Cu-MOFs nanomaterial and its preparation method and application". The patent proposes to carry out thiocyanate composite modification of copper-based metal organic framework materials (Cu-MOF), synthesize SCN-Cu-MOFs nanomaterials by hydrothermal method, and apply SCN-Cu-MOFs nanomaterials to catalytic degradation of tetracycline. However, the material's anti-interference ability and acid-base resistance are unknown, and the actual application effect is still unclear.

[0006] There are also related patents in the research technology of activated peracetic acid. For example, Chinese patent number: 202310630219.9, published on September 1, 2023, discloses a patent entitled "A thermally activated peracetic acid catalyst for rapid degradation of tetracycline hydrochloride wastewater and its preparation and application method". The cobalt ferrite-doped biochar composite catalyst prepared by the invention is used to treat tetracycline hydrochloride wastewater at a set temperature. However, thermal activation of peracetic acid requires strict control of temperature and reaction conditions. The actual operation is relatively complicated and it is not easy to achieve industrial-scale application. In addition, the cobalt ferrite-doped biochar composite catalyst may have the problem of cobalt ion dissolution, thereby causing secondary pollution; Chinese patent application number: 202310055569.7, published on November 24, 2023, discloses a patent document entitled "A method for treating wastewater by activating peracetic acid with molybdenum carbide". The pH range for the efficient removal of antibiotics by this material is relatively narrow, thereby limiting the removal of antibiotics in acidic and alkaline environments; Chinese patent application number: 202410173538.6, published on March 26, 2024, discloses a patent document entitled "A porous biochar and its preparation method and application of activated peracetic acid to remove pollutants in water". Compared with metal organic framework materials, biocarbon materials have weaker catalytic activity, long catalytic time and low selectivity, and are difficult to regenerate.

[0007] In the research technology of tetracycline hydrochloride removal, there are already some better methods, for example, China Patent Application No.: 202410639968.2, application publication date June 25, 2024, the patent document named "Metal cobalt-doped modified orange peel biochar and its preparation method and application", the invention pyrolyzes orange peel powder to obtain biochar; the biochar, cobalt, salt and water are mixed and reacted to obtain metal cobalt-doped modified orange peel biochar, which is used to activate percarbonate to remove tetracycline hydrochloride, but the recycling performance of this material is unknown, and there is a risk of cobalt ion dissolution; China Patent Application No.: 202410751879.7, application publication date July 16, 2024, a patent document named "Preparation method and application of CdS / Ni3C nanowire catalyst with photocatalytic performance" is disclosed. Although the photocatalytic material has low cost, the preparation process is complicated and the photocatalytic process requires a long processing time. Summary of the invention

[0008] In view of the defects and shortcomings of the existing technology for removing antibiotics from water and the stability of the catalyst, the purpose of the present invention is to provide a new Cu-MOF derivative material for antibiotic degradation and a preparation method thereof, in order to provide a technical reference for the actual removal of antibiotics from water.

[0009] To solve the above problems, the present invention adopts the following technical solutions.

[0010] The present invention provides a method for preparing a Cu-MOF derivative material for antibiotic degradation, and the specific steps are as follows:

[0011] (1) Dissolve copper nitrate trihydrate and polyvinyl pyrrolidone in N,N-dimethylformamide to obtain solution A; dissolve 1,3,5-benzenetricarboxylic acid in N,N-dimethylformamide to obtain solution B. The molar ratio of copper nitrate trihydrate to 1,3,5-benzenetricarboxylic acid is 1.5-2.5:1.

[0012] (2) Solution A and solution B were mixed and stirred evenly. The mixture was then transferred to a polytetrafluoroethylene reactor and placed in an oven at 80°C for 24 hours.

[0013] (3) After the polytetrafluoroethylene reactor is cooled, the supernatant is removed after centrifugation and stratification, and methanol is added for washing three times, and then placed in an oven at 60°C for drying for 24 hours to obtain a Cu-MOF precursor.

[0014] (4) The obtained Cu-MOF precursor is ground and placed in a tubular furnace, and calcined under a nitrogen atmosphere. After cooling, the Cu-MOF derivative material can be obtained.

[0015] Furthermore, in step (1), the molar ratio of copper nitrate trihydrate to 1,3,5-benzenetricarboxylic acid is 1.7:1.

[0016] Furthermore, in step (4), the obtained Cu-MOF precursor is placed in a tubular furnace for calcination, wherein the temperature is raised to 500° C. at a heating rate of 2° C. / min under a N 2 atmosphere and calcined for 120 min, and then cooled at room temperature.

[0017] The copper-based metal framework (Cu-MOF) derived material obtained by the above preparation method can be used to remove tetracycline from water.

[0018] The specific principle is speculated as follows:

[0019] Tetracycline hydrochloride molecules in the wastewater are first adsorbed onto the surface of the Cu-MOF derivative material through its porous structure. The Cu species and surface functional groups in the Cu-MOF derivative material are the main active sites for PAA activation. ·OH, 1 O2 and RO·, where 1 O2 plays a leading role in the degradation of TCH. These strong oxidizing free radicals destroy the molecular structure of tetracycline hydrochloride through oxidation reactions, ultimately achieving degradation.

[0020] Compared with the prior art, the present invention has the following technical effects:

[0021] (1) The preparation process of the present invention is simple. The Cu-MOF precursor is synthesized by a hydrothermal synthesis method, and the Cu-MOF derivative material is synthesized by programmed temperature controlled calcination modification. The raw material cost is low, the removal efficiency is high, and the application range is wide.

[0022] (2) The Cu-MOF derivative material prepared by the present invention can effectively remove tetracycline hydrochloride from water. Under the conditions of an initial TCH concentration of 10 mg / L, a PAA dosage of 0.2 mM, and an adjusted solution pH of 7, the Cu-MOF derivative material activated PAA to degrade TCH with a removal rate of 88.7% after 30 minutes of reaction, and the reaction process reached equilibrium within 15 minutes.

[0023] (3) The Cu-MOF derivative material prepared by the present invention has high efficiency in degrading antibiotics, and the material has anti-interference performance when catalyzing the degradation of tetracycline hydrochloride. 3- 、NO 3- , Cl - And when humic acid HA is present, it can still maintain good degradation performance, and the removal of tetracycline hydrochloride in water is less affected by the acidity and alkalinity of the environment.

[0024] (4) The Cu-MOF material prepared by the present invention can oxidize peracetic acid to degrade tetracycline hydrochloride at room temperature without the need for specific lighting conditions, with high processing efficiency and low use cost.

[0025] (5) The Cu-MOF material prepared by the present invention has good recyclability and still has a good catalytic effect after being recycled four times. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a scanning electron microscope image of the morphology of the Cu-MOF derived material obtained in Example 2 of the present invention.

[0027] Figure 2 This is a diagram showing the removal effect of PAA activated by Cu-MOF derivative materials (Examples 1-5) obtained at different calcination temperatures to degrade tetracycline hydrochloride;

[0028] As shown in the figure, when the calcination temperature is 400°C to 800°C, the removal rates of Cu-MOF derived materials to activate PAA to degrade tetracycline hydrochloride are 73.5%, 88.7%, 88.1%, 87.9% and 88.1%, respectively.

[0029] Figure 3 This is a diagram showing the effect of the dosage of Cu-MOF derivative materials obtained in Example 2 of the present invention on the degradation of tetracycline hydrochloride by activated PAA.

[0030] Figure 4This is a diagram showing the removal effect of activated PAA on tetracycline hydrochloride degradation by the Cu-MOF derivative material obtained according to Example 2 of the present invention at different PAA dosages.

[0031] Figure 5 This is a diagram showing the removal effect of the Cu-MOF derivative material obtained according to Example 2 of the present invention on the degradation of tetracycline hydrochloride by activated PAA at different pH values ​​of the initial solution.

[0032] Figure 6 This is a test chart of the recyclability of the Cu-MOF derived material obtained according to Example 2 of the present invention.

[0033] Figure 7 The Cu-MOF derived material obtained in Example 2 of the present invention activates PAA to degrade tetracycline hydrochloride to resist NO 3- Performance test chart.

[0034] Figure 8 The Cu-MOF derived material obtained in Example 2 of the present invention activates PAA to degrade tetracycline hydrochloride and resists Cl - Performance test chart.

[0035] Fig. 9 The Cu-MOF derived material obtained in Example 2 of the present invention activates PAA to degrade tetracycline hydrochloride to resist PO4 3- Performance test chart.

[0036] Fig.10 This is a test diagram of the anti-humic acid performance of the Cu-MOF derivative material activated PAA to degrade tetracycline hydrochloride according to Example 2 of the present invention. DETAILED DESCRIPTION

[0037] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments, but is not intended to be a specific limitation of the present invention.

[0038] Example 1

[0039] This embodiment provides a method for preparing a novel Cu-MOF derivative material for activating PAA to degrade antibiotics (the molar ratio of Cu(NO3)2·3H2O to H3BTC is 1.7:1), the method comprising the following steps:

[0040] Preparation of Cu-MOF precursor: 0.875g Cu(NO3)2·3H2O and 0.3g PVP were dissolved in 40ml DMF to form solution A, and 0.42g H3BTC was dissolved in 30ml DMF to form solution B. Then solution B was mixed with solution A and stirred for 10 minutes. The mixture was then transferred to a 100mL polytetrafluoroethylene reactor and placed in an oven at 80°C for 24h. After centrifugation and stratification, the supernatant was removed, and after washing three times with methanol, it was placed in an oven at 60°C and dried for 24h to obtain the Cu-MOF precursor.

[0041] Preparation of Cu-MOF derivative materials: The obtained Cu-MOF precursor was placed in a tubular furnace and calcined under a N2 atmosphere. The temperature was increased to 400°C at a heating rate of 2°C / min and calcined for 120 min. The temperature was cooled at room temperature and the product was collected.

[0042] Example 2

[0043] This embodiment provides a method for preparing a novel Cu-MOF derivative material for activating PAA to degrade antibiotics, the method comprising the following steps:

[0044] Preparation of Cu-MOF precursor: 0.875g Cu(NO3)2·3H2O and 0.3g PVP were dissolved in 40ml DMF to form solution A, and 0.42g H3BTC was dissolved in 30ml DMF to form solution B. Then. Solution B was mixed with solution A and stirred for 10 minutes. The mixture was then transferred to a 100mL polytetrafluoroethylene reactor and placed in an oven at 80°C for 24h. After centrifugation and stratification, the supernatant was removed, and after washing three times with methanol, it was placed in an oven at 60°C and dried for 24h to obtain the Cu-MOF precursor.

[0045] Preparation of Cu-MOF derivative materials: The obtained Cu-MOF precursor was placed in a tubular furnace and calcined under a N2 atmosphere. The temperature was increased to 500°C at a heating rate of 2°C / min and calcined for 120 min. The temperature was then cooled at room temperature and the product was collected.

[0046] Figure 1 This is a scanning electron microscope image of the morphology of the Cu-MOF derivative material prepared in this example.

[0047] Example 3

[0048] This embodiment provides a method for preparing a novel Cu-MOF derivative material for activating PAA to degrade antibiotics, the method comprising the following steps:

[0049] Preparation of Cu-MOF precursor: 0.875g Cu(NO3)2·3H2O and 0.3g PVP were dissolved in 40ml DMF to form solution A, and 0.42g H3BTC was dissolved in 30ml DMF to form solution B. Then. Solution B was mixed with solution A and stirred for 10 minutes. The mixture was then transferred to a 100mL polytetrafluoroethylene reactor and placed in an oven at 80°C for 24h. After centrifugation and stratification, the supernatant was removed, and after washing three times with methanol, it was placed in an oven at 60°C and dried for 24h to obtain the Cu-MOF precursor.

[0050] Preparation of Cu-MOF derivative materials: The obtained Cu-MOF precursor was placed in a tubular furnace and calcined under a N2 atmosphere. The temperature was increased to 600°C at a heating rate of 2°C / min and calcined for 120 min. The temperature was lowered at room temperature and the product was collected.

[0051] Example 4

[0052] This embodiment provides a method for preparing a novel Cu-MOF derivative material for activating PAA to degrade antibiotics, the method comprising the following steps:

[0053] Preparation of Cu-MOF precursor: 0.875g Cu(NO3)2·3H2O and 0.3g PVP were dissolved in 40ml DMF to form solution A, and 0.42g H3BTC was dissolved in 30ml DMF to form solution B. Then. Solution B was mixed with solution A and stirred for 10 minutes. The mixture was then transferred to a 100mL polytetrafluoroethylene reactor and placed in an oven at 80°C for 24h. After centrifugation and stratification, the supernatant was removed, and after washing three times with methanol, it was placed in an oven at 60°C and dried for 24h to obtain the Cu-MOF precursor.

[0054] Preparation of Cu-MOF derivative materials: The obtained Cu-MOF precursor was placed in a tubular furnace and calcined under a N2 atmosphere. The temperature was increased to 700°C at a heating rate of 2°C / min and calcined for 120 min. The temperature was cooled at room temperature and the product was collected.

[0055] Example 5

[0056] This embodiment provides a method for preparing a novel Cu-MOF derivative material for activating PAA to degrade antibiotics, the method comprising the following steps:

[0057] Preparation of Cu-MOF precursor: 0.875g Cu(NO3)2·3H2O and 0.3g PVP were dissolved in 40ml DMF to form solution A, and 0.42g H3BTC was dissolved in 30ml DMF to form solution B. Then. Solution B was mixed with solution A and stirred for 10 minutes. The mixture was then transferred to a 100mL polytetrafluoroethylene reactor and placed in an oven at 80°C for 24h. After centrifugation and stratification, the supernatant was removed, and after washing three times with methanol, it was placed in an oven at 60°C and dried for 24h to obtain the Cu-MOF precursor.

[0058] Preparation of Cu-MOF derivative materials: The obtained Cu-MOF precursor was placed in a tubular furnace and calcined under a N2 atmosphere. The temperature was increased to 800°C at a heating rate of 2°C / min and calcined for 120 min. The temperature was cooled at room temperature and the product was collected.

[0059] Example 6

[0060] This embodiment provides a method for preparing a novel Cu-MOF derivative material for activating PAA to degrade antibiotics (the molar ratio of Cu(NO3)2·3H2O to H3BTC is 1.5:1), the method comprising the following steps:

[0061] Preparation of Cu-MOF precursor: 0.875g Cu(NO3)2·3H2O and 0.3g PVP were dissolved in 40ml DMF to form solution A, and 0.50g H3BTC was dissolved in 30ml DMF to form solution B. Then. Solution B was mixed with solution A and stirred for 10 minutes. The mixture was then transferred to a 100mL polytetrafluoroethylene reactor and placed in an oven at 80°C for 24h. After centrifugation and stratification, the supernatant was removed, and after washing three times with methanol, it was placed in an oven at 60°C and dried for 24h to obtain the Cu-MOF precursor.

[0062] Preparation of Cu-MOF derivative materials: The obtained Cu-MOF precursor was placed in a tubular furnace and calcined under a N2 atmosphere. The temperature was increased to 500°C at a heating rate of 2°C / min and calcined for 120 min. The temperature was then cooled at room temperature and the product was collected.

[0063] Example 7

[0064] This embodiment provides a method for preparing a novel Cu-MOF derivative material for activating PAA to degrade antibiotics (the molar ratio of Cu(NO3)2·3H2O to H3BTC is 2.5:1), the method comprising the following steps:

[0065] Preparation of Cu-MOF precursor: 0.875g Cu(NO3)2·3H2O and 0.3g PVP were dissolved in 40ml DMF to form solution A, and 0.30g H3BTC was dissolved in 30ml DMF to form solution B. Then. Solution B was mixed with solution A and stirred for 10 minutes. The mixture was then transferred to a 100mL polytetrafluoroethylene reactor and placed in an oven at 80°C for 24h. After centrifugation and stratification, the supernatant was removed, and after washing three times with methanol, it was placed in an oven at 60°C and dried for 24h to obtain the Cu-MOF precursor.

[0066] Preparation of Cu-MOF derivative materials: The obtained Cu-MOF precursor was placed in a tubular furnace and calcined under a N2 atmosphere. The temperature was increased to 500°C at a heating rate of 2°C / min and calcined for 120 min. The temperature was then cooled at room temperature and the product was collected.

[0067] The novel Cu-MOF derivative materials prepared in Examples 2, 6 and 7 were tested for degradation of tetracycline hydrochloride by activated peracetic acid, respectively, under the conditions of 10 mg / L TCH initial concentration, 0.2 mM PAA dosage, 200 mg / L material dosage, pH of the solution was adjusted to 7, 30 minutes oxidation degradation time, 25°C water temperature, and 200 rpm / min oscillation speed. The test data show that the novel Cu-MOF derivative materials obtained in Examples 2, 6 and 7 of the present invention have a significant effect on degradation of tetracycline hydrochloride by activated peracetic acid (as shown in Table 1).

[0068] Table 1 Experimental results of different examples of activated peracetic acid to remove tetracycline hydrochloride

[0069] Different embodiments Example 2 Example 6 Example 7 Tetracycline hydrochloride removal rate (%) 88.70 87.98 88.35

[0070] Example 8

[0071] This example shows the removal rate of tetracycline hydrochloride catalytically degraded by PAA activated by the Cu-MOF derivative material prepared in Example 2.

[0072] The Cu-MOF derivative material prepared in Example 2 was used to synergistically stimulate PAA to degrade tetracycline hydrochloride (TCH), as follows:

[0073] Weigh 10 mg of Cu-MOF modified material and place it in a 100 mL glass bottle, add 50 mL of TCH (initial concentration is 10 mg / L) solution, PAA dosage is 0.2 mmol / L, and adjust to pH = 7 with NaOH (0.1 mol / L) and H2SO4 (0.1 mol / L). The degradation experiment was carried out in a constant temperature water bath oscillator at 200 rpm / min. At regular intervals, 2 mL of the reaction solution was taken, filtered with a 0.45 μm filter membrane, and quenched with 100 mM sodium thiosulfate. The experimental time was 30 min, and the concentration change was measured with a UV-visible spectrophotometer to calculate the degradation rate. Figure 2 As shown, when the material prepared in Example 1 is used to activate PAA to degrade tetracycline hydrochloride, the degradation rate can reach 88.7% in 30 minutes.

[0074] Example 9

[0075] This example shows the effect of the dosage of the Cu-MOF derivative material prepared in Example 2 on the removal rate of tetracycline hydrochloride catalytic degradation by activated PAA.

[0076] The degradation experiment of Example 8 was carried out when the dosage of the Cu-MOF derivative material in Example 8 was 100 mg / L, 200 mg / L, 300 mg / L, and 400 mg / L, respectively. Figure 3 As shown in the figure, when the dosage of Cu-MOF derivatives increased from 100 mg / L to 400 mg / L, the degradation rate of TCH in 30 min increased from 83.3% to 92.4%. With the increase of the dosage of Cu-MOF derivatives, the degradation rate of TC gradually increased, and the reaction basically reached equilibrium in 15 min.

[0077] Example 10

[0078] This example shows the effect of the PAA dosage on the removal rate of PAA-catalyzed degradation of tetracycline hydrochloride by the Cu-MOF derivative material prepared in Example 2.

[0079] When the PAA dosage was adjusted to 0.05mmol / L, 0.1mmol / L, 0.2mmol / L, and 0.3mmol / L, respectively, the degradation experiment of Example 8 was carried out. Figure 4 As shown in the figure, with the increase of PAA dosage, the degradation rate of TCH gradually increased. When the PAA dosage in the system increased from 0.05mmol / L to 0.3mmol / L, the degradation rate of TCH increased from 80.6% to 89.1% after 30min of reaction. When the PAA dosage increased to 0.2mmol / L, the degradation rate of TCH increased significantly to 88.7%.

[0080] Embodiment 11

[0081] This example shows the removal rate of tetracycline hydrochloride by the Cu-MOF derivative material in Example 2 at different pH ranges. The degradation experiment of Example 8 was carried out when the initial pH of the reaction system in Example 8 was adjusted to 3, 5, 7, 9, and 11, respectively. Figure 5 As shown, when the pH value of the reaction system solution is adjusted to 3-11, the Cu-MOF derived material can still exert a good catalytic degradation effect.

[0082] Example 12

[0083] This example is a test on the recyclability of the Cu-MOF derived material prepared in Example 2.

[0084] In practical use, the catalyst needs to be not only efficient and convenient, but also reusable and stable. The degradation effect of Cu-MOF derivative materials on TCH during the four-time reuse process is shown in Figure 2. Figure 6 As shown in the figure, the degradation rates of TCH after four reuses were 88.7%, 84.3%, 82.8% and 82.5% respectively. When the catalyst was reused four times, it still had a good removal effect on TCH.

[0085] Comparative Example:

[0086] This comparative example is an anti-interference test of the Cu-MOF derivative material prepared in Example 2 when activating PAA to degrade tetracycline hydrochloride.

[0087] In the degradation performance test of Example 8, 0.5-5 mmol / L of interfering ions NO were added respectively. 3- 、Cl-、PO4 3- or 0.5-5mg / L humic acid, such as Figure 7 , Figure 8 , Fig.10 As shown in the figure, compared with the system without anti-interference ions, adding NO 3- , Cl - The degradation rate of tetracycline hydrochloride by PAA activated by Cu-MOF derivative materials was almost unaffected by humic acid and NO 3- , Cl - Or the concentration of humic acid added increased, which had almost no effect on the degradation rate of tetracycline hydrochloride by PAA activated by Cu-MOF derived materials; Fig. 9 As shown, add PO4 3- After that, the TCH degradation efficiency only decreased by about 19%, and with the increase of PO4 3- The increase in concentration

[0088] Add, PO4 3- The degradation rate of tetracycline hydrochloride activated by PAA of Cu-MOF derivative material did not change much, proving that the material has strong anti-interference ability.

Claims

1. A method for preparing a Cu-MOF derivative material for antibiotic degradation, characterized in that The steps include: (1) dissolving copper nitrate trihydrate and polyvinyl pyrrolidone in N,N-dimethylformamide to obtain solution A; dissolving 1,3,5-benzenetricarboxylic acid in N,N-dimethylformamide to obtain solution B; The molar ratio of copper nitrate trihydrate to 1,3,5-benzenetricarboxylic acid is 1.5-2.5:1; (2) Mix solution A and solution B and stir them evenly; then transfer the mixture to a polytetrafluoroethylene reactor and place it in an oven at 80°C for 24 hours; (3) After the polytetrafluoroethylene reactor is cooled, the supernatant is removed after centrifugation and stratification, and methanol is added for washing, and then placed in an oven at 60° C. for drying for 24 h to obtain a Cu-MOF precursor; (4) The obtained Cu-MOF precursor is ground, placed in a tubular furnace, and calcined under a nitrogen atmosphere, and then cooled to obtain a Cu-MOF derivative material.

2. The method for preparing a Cu-MOF derivative material for antibiotic degradation according to claim 1, characterized in that: In step (1), the molar ratio of copper nitrate trihydrate to 1,3,5-benzenetricarboxylic acid is 1.7:

1.

3. The method for preparing a Cu-MOF derivative material for antibiotic degradation according to claim 1, characterized in that: In step (4), the calcination conditions are: heating to 500° C. at a heating rate of 2° C. / min and calcining for 120 min.

4. The Cu-MOF derived material prepared by the method according to any one of claims 1 to 3.

5. Use of the Cu-MOF derivative material according to claim 4 in removing tetracycline from water.

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