A magnetic zirconium metal-organic framework material, preparation method and application thereof

Abstract

The present invention discloses a magnetic zirconium metal organic framework material, a preparation method and its application, and relates to the technical field of toxin purification. This new type of magnetic zirconium metal organic framework material can achieve highly selective adsorption of a variety of toxins. The material has the technical advantages of short toxin adsorption time, high efficiency, good purification effect, removal of many impurities, and low economic cost. Moreover, the chemical properties of the MOFs crystal material are stable and the thermal stability is excellent. It has a high toxin adsorption capacity at room temperature and pressure and can be used for the adsorption and separation of various toxins. After the above-mentioned magnetic zirconium metal organic framework material is mixed with a sample, the toxins in the sample can be effectively adsorbed. The sample adsorbed by the magnetic zirconium metal organic framework material provided by the present invention can be used as a purification material for toxin detection tests.

Description

Technical Field

[0001] The present invention relates to the technical field of toxin purification, and in particular to a magnetic zirconium metal organic framework material, a preparation method and applications thereof. Background Art

[0002] Mycotoxins are toxic secondary metabolites that contaminate grains and their products before harvest or during storage. Consuming contaminated grains can severely impact the health of humans and animals. Mycotoxins in grains and their products encompass a wide variety of types, each with its own harmful properties and unique characteristics. The presence of mycotoxins in grains and their products is a global concern. According to the Food and Agriculture Organization of the United Nations (FAO), 25% of global food is contaminated with mycotoxins. The mycotoxins that pose the greatest threat to the safety of grains and their products include aflatoxins (AFs), deoxynivalenol (DON), and zearalenone (ZEN).

[0003] As scientists continue to explore and research the toxicity of mycotoxins, the harm they pose to the national economy and public health has become increasingly clear. Consumers are increasingly concerned about food safety, and a growing number of companies and institutions are focusing on how to accurately detect mycotoxins in food. Many countries and regions have also introduced regulations setting limits for mycotoxins in food, significantly driving the development of various toxin detection technologies. Toxin residues and contamination have become a hot topic of international research.

[0004] To assess toxin residues and contamination, it is necessary to establish toxin detection methods. The difficulty in toxin detection and analysis lies in the separation of different toxin types and sample pretreatment techniques. Although significant progress has been made in toxin detection research, different toxin types often differ significantly, and the simultaneous separation and detection of multiple toxins remains challenging. Therefore, it is extremely important to provide a reliable adsorption material that can simultaneously target multiple toxins to meet the needs of toxin adsorption, separation, and purification.

[0005] Existing research indicates that metal-organic frameworks (MOFs) exhibit tremendous development potential in drug adsorption, removal, and selective separation. The diverse and tunable chemical structures of existing MOFs, along with their physical properties such as abundant pores and large surface area, allow for targeted design based on desired functional groups, making them a highly sought-after new purification material in sample pretreatment.

[0006] In view of this, the present invention is proposed. Summary of the Invention

[0007] The present invention aims to provide a zirconium metal-organic framework material, preparation method, and application thereof. This novel zirconium metal-organic framework (MOF) material significantly improves the material's adsorption performance for toxins, thereby providing a practical and effective solution to the bottleneck problem of limited toxin enrichment and purification. This new magnetic zirconium metal-organic framework material can be used for toxin detection.

[0008] The present invention is achieved in that:

[0009] In the first aspect, the present invention provides a magnetic zirconium metal organic framework material, the chemical formula of the magnetic zirconium metal organic framework material is: [Zr X L2]n, is a high symmetry space group of the trigonal system, wherein L represents an organic ligand; the organic ligand is selected from tetrakis[4-(3,5-dicarboxyphenyl)]tetraphenylethylene, and the unit cell parameters of the magnetic zirconium metal organic framework material are a=15.1, b=24.83, c=28.43; x=4; and n is a positive integer;

[0010] The structure of the magnetic zirconium metal-organic framework material is as follows: zirconium is connected to organic ligands to form a metal-organic framework material. Magnetic nano-iron particles are encapsulated in the metal-organic framework material (MOFs) material through metal nodes or material connections.

[0011] The inventors discovered that materials with this chemical composition and structure offer the technical advantages of fast and efficient toxin adsorption, high toxin adsorption performance, excellent purification effects, and high impurity removal at a low cost. When mixed with a sample, the magnetic zirconium metal-organic framework effectively adsorbs toxins from the sample, achieving a toxin adsorption rate of 90-99%. Samples adsorbed by the magnetic zirconium metal-organic framework provided by the present invention can be used as purification materials in toxin detection tests.

[0012] The magnetic zirconium metal-organic framework material has a relatively large microporous network structure, which can effectively adsorb toxins and has an extremely high specific surface area and porosity.

[0013] In a preferred embodiment of the present invention, the pore size of the magnetic zirconium metal organic framework material is 1.5 nm and the pore volume is 1.39 cm 3 / g.

[0014] In a second aspect, the present invention further provides a method for preparing a magnetic zirconium metal organic framework material, which comprises the following steps:

[0015] The raw materials and solvent are mixed and reacted at 80-120° C. for 12-16 hours. The raw materials include magnetic nano-iron particles, a zirconium source and an organic ligand. The mass ratio of the magnetic nano-iron particles, the zirconium source and the organic ligand is 1-2:2-4:1-2. The magnetic zirconium metal-organic framework material synthesized under the above ratio has a good adsorption effect.

[0016] For example, the mass ratio of magnetic nano-iron particles, zirconium source and organic ligand is 1:2:1, or 1:3:2; or 1:4:1; or 2:4:1, or 2:3:1.

[0017] In an optional embodiment, the mass ratio of the magnetic nano-iron particles, the zirconium source and the organic ligand is 1:2:1.

[0018] The above preparation method has the technical advantages of simple preparation process, strong controllability, low cost and large-scale production.

[0019] For example, the reaction is carried out at 80-90°C, 90-100°C, 100-120°C or 110-120°C for 12-16 hours, for example, for 12 hours, 13 hours, 14 hours, 15 hours or 16 hours.

[0020] The ratio of raw material to solvent is 240 mg: (5-50) mL;

[0021] Preferably, the average particle size of the magnetic nano-iron particles is 50-200 nm.

[0022] For example, the ratio of raw material to solvent is 240 mg: 5 mL; or 240 mg: 10 mL; or 240 mg: 20 mL; or 240 mg: 40 mL.

[0023] In a preferred embodiment of the present invention, the zirconium source is selected from zirconium salts, for example, at least one selected from ZrCl4, ZrOCl2, ZrO2, Zr(OH)4 and Zr(NO3)4.

[0024] In an alternative embodiment, the zirconium source is selected from ZrCl4.

[0025] In a preferred embodiment of the present invention, the ratio of raw material to solvent is 2 g:20 mL.

[0026] In an optional embodiment, the solvent is selected from at least one of glacial acetic acid and DMF solvent.

[0027] In a preferred embodiment of the present invention, the preparation method further comprises removing the solvent from the reaction solution after the mixed reaction, and washing and drying the product; the drying time is 14 to 16 hours, and the drying temperature is 40 to 60°C.

[0028] In an optional embodiment, the solvent is removed by centrifugation at 9000-11000 r / min for 4-6 min.

[0029] In a third aspect, the present invention also provides a magnetic zirconium metal organic framework material or a magnetic zirconium metal organic framework material prepared by the above preparation method for use in adsorbing toxins, purifying toxins or detecting toxins.

[0030] The magnetic zirconium metal-organic framework material exhibits excellent adsorption properties for a wide range of toxins, boasting high toxin adsorption rates and excellent purification performance, enabling rapid removal of a wide range of impurities. Samples adsorbed by the magnetic zirconium metal-organic framework material can be used as purification materials in toxin detection tests.

[0031] In a preferred embodiment of the present invention, the toxin is selected from at least one of Aflatoxin B1 (aflatoxin B1), Aflatoxin B2 (aflatoxin B2), Aflatoxin G1 (aflatoxin G1), Aflatoxin G2 (aflatoxin G2), Aflatoxin M1 (aflatoxin M1), Aflatoxin M2 (aflatoxin M2), Fumonisin B1 (fumonisin B1), Fumonisin B2 (fumonisin B2), T-2toxin (T-2 toxin), HT-2toxin (HT-2 toxin), Zearalenone (zearalenone), Ochratoxin (ochratoxin), deoxynivalenol, trichothecenes, citrinin, penicillic acid, beauvericin and patulin.

[0032] For example, toxins Aflatoxin B1 and Aflatoxin B2 can be adsorbed or purified at the same time; or toxins Aflatoxin, Fumonisin, and Zearalenone can be adsorbed or purified at the same time; or toxins Ochratoxin, Deoxynivalenol, Citrinin, and Penicillic Acid can be adsorbed or purified at the same time.

[0033] The magnetic zirconium metal-organic framework material provided by the present invention can simultaneously adsorb aflatoxin B1, aflatoxin B2, T-2 toxin, ochratoxin and zearalenone. Compared with the existing FMSL-AL, MOF-808 (Zr), MIL-101 (Cr), UIO-66, ZN-MOF and other MOF materials, it has a significantly higher adsorption rate and has a toxin adsorption effect of 90-99%.

[0034] In a fourth aspect, the present invention further provides a method for adsorbing or purifying toxins, comprising the following steps:

[0035] The magnetic zirconium metal organic framework material or the magnetic zirconium metal organic framework material prepared by the above preparation method is mixed with a sample containing toxins, and then the toxins in the sample are adsorbed by magnetic attraction, and the toxins are separated by elution.

[0036] The magnetic zirconium metal organic framework material adsorbing the toxin is adsorbed by a magnet or a substance that can provide a magnetic field, thereby removing the liquid in the sample, and then the toxin is separated from the magnetic zirconium metal organic framework material by elution.

[0037] The above method has a high recovery rate for toxins and can directly and selectively measure multiple toxins in a high-throughput manner, thereby achieving rapid and simple toxin detection.

[0038] The time for mixing the magnetic zirconium metal organic framework material and the sample containing toxins is, for example, 30s-600s.

[0039] In an optional embodiment, the sample containing toxins is a sample extracted with an extracting solution, and the extracting solution is selected from a mixed solution of methanol, acetonitrile and water in a volume ratio of 7 to 9:1:1; the usage ratio of the sample containing toxins to the magnetic zirconium metal organic framework material is 2 to 5 mL: 10 mg.

[0040] The dosage ratio of the sample containing toxin to the extract is 2-5 g:20 mL. Within the above range, the toxin in the analyte can be fully extracted.

[0041] In an optional embodiment, magnetic attraction is to use an electromagnet or a magnet to adsorb toxins in the sample.

[0042] In an optional embodiment, before elution, an eluent is added to the container to be eluted, vortexed, and the magnetic zirconium metal organic framework material is adsorbed by an electromagnet or a magnet to collect the eluent containing the toxin;

[0043] The eluent is selected from an aqueous solution of 1-5% formic acid and acetonitrile.

[0044] In an optional embodiment, the sample is selected from feed and feed raw materials, including but not limited to concentrated feed, additive premix feed, concentrate supplement, corn, soybean meal, rapeseed meal, etc.

[0045] The toxin is selected from at least one of Aflatoxin B1 (aflatoxin B1), Aflatoxin B2 (aflatoxin B2), Aflatoxin G1 (aflatoxin G1), Aflatoxin G2 (aflatoxin G2), Aflatoxin M1 (aflatoxin M1), Aflatoxin M2 (aflatoxin M2), Fumonisin B1 (fumonisin B1), Fumonisin B2 (fumonisin B2), T-2toxin (T-2 toxin), HT-2toxin (HT-2 toxin), Zearalenone (zearalenone), Ochratoxin (ochratoxin), deoxynivalenol, trichothecenes, citrinin, penicillic acid, beauvericin and patulin.

[0046] The present invention has the following beneficial effects:

[0047] The present invention provides a new magnetic zirconium metal-organic framework material, which can achieve highly selective adsorption of a variety of toxins through its specific chemical structure and chemical composition, and has the technical advantages of short toxin adsorption time, high efficiency, high toxin adsorption performance, good purification effect, removal of many impurities, and low economic cost. In addition, the MOFs crystal material has stable chemical properties and excellent thermal stability. It has a high toxin adsorption capacity at room temperature and pressure and can be used for the adsorption and separation of various toxins. After the above-mentioned magnetic zirconium metal-organic framework material is mixed with a sample, the toxins in the sample can be effectively adsorbed, and the toxin adsorption rate in the sample reaches 90-99%. The sample adsorbed by the magnetic zirconium metal-organic framework material provided by the present invention can be used as a purification material for toxin detection tests.

[0048] The preparation method of the magnetic zirconium metal organic framework material provided by the present invention has the technical advantages of simple preparation process, strong controllability, low cost and large-scale production.

[0049] The method for adsorbing or purifying toxins provided by the present invention has the technical advantages of short adsorption time and good toxin purification effect, reduces matrix effect and improves detection accuracy. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0051] Figure 1 The structural analysis diagram of the infrared spectrum of the ligand and the synthesized MOFs;

[0052] Figure 2 The X-ray diffraction structure analysis diagram of the ligand and the synthesized MOFs;

[0053] Figure 3 A comparison of the adsorption effects of different MOF materials on various toxins (from left to right, the adsorption effects of material A on Aspergillus flavus B1, Aspergillus flavus B2, T-2, Aspergillus ochraceus A, and ZEN, respectively, and the adsorption effects of material BF on the same toxins are shown);

[0054] Figure 4 Schematic diagram of toxin detection and analysis;

[0055] Figure 5 Specific chromatograms for 12 mycotoxins;

[0056] Figure 6 Schematic diagram of the structure of magnetic zirconium metal-organic framework materials. DETAILED DESCRIPTION

[0057] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0058] The features and performance of the present invention are further described in detail below with reference to the embodiments.

[0059] Example 1

[0060] This embodiment provides a magnetic zirconium metal organic framework material, the preparation method of which is as follows:

[0061] Combine 60 mg of magnetic nano-iron particles, 120 mg of zirconium chloride, and 60 mg of tetrakis[4-(3,5-dicarboxyphenyl)]tetraphenylethylene. Add these to a reaction kettle, along with 0.3 mL of glacial acetic acid and 5 mL of DMF. To ensure uniform mixing, vortex mix the mixture for 2 minutes and shake it on a constant-temperature shaker for 2 hours. The mixture is then reacted at 120°C for 16 hours, centrifuged at 9000 rpm for 4 minutes, and the solvent removed. The centrifuged product is then washed twice with 5 mL of DMF until free of impurities, and then dried at 40-60°C for 12 hours to obtain a magnetic zirconium metal-organic framework.

[0062] The structure of the prepared magnetic zirconium metal organic framework material is analyzed as follows: Zirconium is connected with organic ligands to form a metal organic framework material. Magnetic nano-iron particles are coated in the MOFs material through metal nodes or material connections. The structural diagram is shown in Figure 2. Figure 6shown.

[0063] Example 2

[0064] This embodiment provides a method for adsorbing toxins. The adsorption flow chart is shown in FIG. Figure 4 As shown, the specific steps include:

[0065] (1) Toxin extraction step: 5 g of Da Bei Nong's compound feed and the extract were added to 50 mL centrifuge tubes, mixed by vortexing for 20 seconds, and ultrasonically extracted for 20 minutes. The mixture was then centrifuged at 7500 rpm for 4 minutes, and the supernatant was collected for later use. The extract consisted of methanol, acetonitrile, and aqueous solution in a volume ratio of 7:1:1.

[0066] (2) Toxin adsorption (purification) step: Take the first supernatant in a centrifuge tube, add 8 mL of phosphate buffer solution and the magnetic zirconium metal organic framework material prepared in Example 1, and the ratio of the first supernatant to the magnetic zirconium metal organic framework material is 2 mL:10 mg. Vortex mix for 30 seconds, adsorb the magnetic zirconium metal organic framework material with a magnet, and discard the supernatant. Add an elution solution containing 1% formic acid and acetonitrile, vortex mix for 30 seconds, adsorb the magnetic zirconium metal organic framework material with a magnet, and collect the elution solution containing the toxin.

[0067] Refer to the structural analysis diagram of the infrared spectrum of the ligand and the synthesized MOFs Figure 1 As shown, the X-ray diffraction structure analysis diagram of the ligand and the synthesized MOFs is shown in Figure 2 shown.

[0068] Example 3

[0069] This embodiment provides a method for detecting toxins, comprising the following detection steps:

[0070] The toxin-containing eluate prepared in Example 2 was concentrated using a nitrogen purge at 35°C, and the concentrated product was dissolved in a sample diluent comprising 0.1% by volume formic acid and 10% by volume acetonitrile. The diluted concentrated product was filtered through a 0.22 μm filter and analyzed by column chromatography and liquid chromatography-mass spectrometry.

[0071] Mass spectrometry conditions

[0072] The mass spectrometer used an electrospray ionization source, positive and negative ion switching, and multiple reaction monitoring (MRM) mode; the spray voltage was 3.2 kV; the ion source temperature was 350°C; the curtain gas was air and the collision gas was nitrogen. The flow rates of each gas were adjusted before use to ensure that the mass spectrometer sensitivity met the detection requirements. Segmented acquisition was used. The specific parameters are shown in Table 1.

[0073] Table 1 LC-MS / MS mass spectrometry conditions for 11 mycotoxins

[0074]

[0075]

[0076] Chromatographic column: Waters BEH C18 column (100 mm × 3.0 mm, 1.7 μm); column temperature: 40 °C; injection volume: 1 μL; mobile phase flow rate: 0.4 mL / min. The mobile phase composition and elution gradient are shown in Table 2. The specific chromatograms of the 11 mycotoxins are shown in Figure 5 .

[0077] Table 2 Chromatographic conditions for 7 mycotoxins detection using the 6500 LC-MS / MS

[0078]

[0079] Example 4

[0080] This embodiment provides a magnetic zirconium metal organic framework material, the preparation method of which is as follows:

[0081] Combine 60 mg of magnetic nano-iron particles, 360 mg of zirconium chloride, and 60 mg of tetrakis[4-(3,5-dicarboxyphenyl)]tetraphenylethylene. Add these to a reaction kettle, along with 0.3 mL of glacial acetic acid and 10 mL of DMF. To ensure uniform mixing, vortex mix the mixture for 2 minutes and shake it on a constant-temperature shaker for 2 hours. The mixture is then reacted at 120°C for 16 hours, centrifuged at 9000 rpm for 4 minutes, and the solvent removed. The centrifuged product is then washed twice with 10 mL of DMF until free of impurities, and then dried at 40-60°C for 12 hours to obtain a magnetic zirconium metal-organic framework.

[0082] Example 5

[0083] This embodiment provides a magnetic zirconium metal organic framework material, the preparation method of which is as follows:

[0084] Combine 40 mg of magnetic nano-iron particles, 160 mg of zirconium chloride, and 40 mg of tetrakis[4-(3,5-dicarboxyphenyl)]tetraphenylethylene. Add the raw materials to a reactor, along with 0.3 mL of glacial acetic acid and 6 mL of DMF. Mix thoroughly for 2 minutes using a vortex mixer and shake on a constant-temperature shaker for 2 hours. Then, react at 100°C for 14 hours, centrifuge at 9000 rpm for 4 minutes, and remove the solvent. Wash the centrifuged product twice with 6 mL of DMF until free of impurities, then dry at 40-60°C for 12 hours to obtain a magnetic zirconium metal-organic framework.

[0085] Experimental Example 1

[0086] Investigation of the properties of synthetic materials.

[0087] In this experiment, five toxins, including Aspergillus flavus B1, B2, T-2, Aspergillus ochraceus A, and ZEN, were selected as adsorption targets of MOF materials (the specific adsorption conditions were the same as those in Example 2). The purification effects of six different MOF materials were compared. The results are shown in Table 2. Figure 3 The adsorption effect is calculated by dividing the measured toxin content by the amount of added toxin. The formula is as follows: X = A0 / A1

[0088] X---Adsorption effect

[0089] A0---Measured toxin content

[0090] A1---Amount of toxin added

[0091] The specific six different MOF materials are shown in Table 3 below: (Materials AE were purchased from Xi'an Qiyue Biotechnology Co., Ltd.)

[0092] Table 3 Six different MOF materials

[0093]

[0094] from Figure 3 As can be seen, the newly synthesized MOFs (F, New MOFs) showed the best adsorption efficiency for the five toxins, with adsorption efficiencies ranging from 90% to 99%. The other MOF materials, on the other hand, performed poorly, with values ​​above 60%, indicating that they did not adsorb toxins at all. This comprehensive comparison shows that the newly synthesized MOFs can be used as purification materials for toxin detection experiments, with the advantage of excellent adsorption efficiency.

[0095] Experimental Example 2

[0096] Method validation.

[0097] To evaluate the effectiveness of this method, its quantitative characteristics were evaluated under optimal conditions, including LOD (based on the signal-to-noise ratio (S / N) equal to 3), limit of quantification (LOQ, S / N = 10), and precision (expressed as relative standard deviation). The results are shown in Tables 4 and 5.

[0098] Table 4 Linear equation and correlation coefficient of matrix addition standard curve

[0099]

[0100]

[0101] Table 5 Recovery and precision of different mycotoxins added to feed

[0102]

[0103] Calibration curves were constructed using matrix-matched standard solutions spiked into blank feed at five concentrations (each replicated three times). Matrix-matched calibration curves exhibited excellent linearity for the analytes, with correlation coefficients ≥ 0.9905. Limits of detection and quantification were 0.02–0.8 μg / kg and 0.06–2.5 μg / kg, respectively. Due to the superior selectivity and sensitivity of LC-MS / MS, the LODs and LOQs were lower than those reported in the literature.

[0104] The recovery rates and intra- and inter-day repeatability for feed were summarized. Feed recoveries ranged from 77.5% to 98.4%, with intra-day RSDs of 0.84% ​​to 11.9% and inter-day RSDs of 1.84% to 13.2%. The deviations for all analytes were ≤15%. This indicates that the recovery rates of the LC-MS / MS developed in this study were not significantly different from those of previously reported methods, meeting the recovery requirements for mycotoxin detection in feed to a certain extent. This demonstrates that this method has good ability to measure analytes in the presence of potential interferences in the sample.

[0105] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A magnetic zirconium metal organic framework material, characterized in that: The magnetic zirconium metal organic framework material is a trigonal high symmetry space group, wherein the organic ligand is selected from tetrakis[4-(3,5-dicarboxyphenyl)]tetraphenylethylene, and the unit cell parameters of the magnetic zirconium metal organic framework material are a=15.1, b=24.83, and c=28.43; The structure of the magnetic zirconium metal-organic framework material is as follows: zirconium is connected to the organic ligand to form a metal-organic framework material; magnetic nano-iron particles are connected or coated in the metal-organic framework material through metal nodes or material gaps; The preparation method comprises the following steps: mixing raw materials and a solvent, and reacting at 80-120°C for 12-16 hours. The raw materials comprise magnetic nano-iron particles, a zirconium source and an organic ligand. The mass ratio of the magnetic nano-iron particles, the zirconium source and the organic ligand is 1-2:2-4:1-2.

2. The magnetic zirconium metal organic framework material according to claim 1, characterized in that The magnetic zirconium metal organic framework material has a pore diameter of 1.5 nm and a pore volume of 1.39 cm 3 / g.

3. The method for preparing a magnetic zirconium metal organic framework material according to any one of claims 1 to 2, characterized in that: It includes the following steps: The raw materials and solvent are mixed and reacted at 80-120° C. for 12-16 hours. The raw materials include magnetic nano-iron particles, a zirconium source, and an organic ligand. The mass ratio of the magnetic nano-iron particles, the zirconium source, and the organic ligand is 1-2:2-4:1-2.

4. The preparation method according to claim 3, characterized in that The mass ratio of the magnetic nano-iron particles, the zirconium source and the organic ligand is 1:2:

1.

5. The preparation method according to claim 3, characterized in that The usage ratio of the raw material to the solvent is 240 mg: (5-50) mL.

6. The preparation method according to claim 3, characterized in that The average particle size of the magnetic nano-iron particles is 50-200 nm.

7. The preparation method according to claim 3, characterized in that The zirconium source is selected from zirconium salts.

8. The preparation method according to claim 7, characterized in that The zirconium source is selected from at least one of ZrCl4, ZrOCl2, ZrO2, Zr(OH)4 and Zr(NO3)4.

9. The preparation method according to claim 8, characterized in that The zirconium source is selected from ZrCl4.

10. The preparation method according to claim 3, characterized in that The solvent is selected from at least one of glacial acetic acid and DMF solvent.

11. The preparation method according to claim 3, characterized in that The preparation method further comprises removing the solvent from the reaction liquid after the mixed reaction, and washing and drying the product; the drying time is 14 to 16 hours, and the drying temperature is 40 to 60°C.

12. The preparation method according to claim 11, characterized in that The solvent is removed by centrifugation at 9000-11000 r / min for 4-6 min.

13. Use of the magnetic zirconium metal organic framework material according to any one of claims 1 to 2 or the magnetic zirconium metal organic framework material prepared by the preparation method according to any one of claims 3 to 12 in adsorbing toxins, purifying toxins or detecting toxins.

14. The use according to claim 13, characterized in that The toxin is selected from at least one of aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2, aflatoxin M1, aflatoxin M2, fumonisin B1, fumonisin B2, T-2 toxin, HT-2 toxin, zearalenone, ochratoxin, deoxynivalenol, trichothecenes, citrinin, penicillic acid, beauvericin and patulin.

15. A method for adsorbing or purifying toxins, characterized in that: It includes the following steps: The magnetic zirconium metal organic framework material according to any one of claims 1-2 or the magnetic zirconium metal organic framework material obtained by the preparation method according to any one of claims 3-12 is mixed with a sample containing toxins, and then the toxins in the sample are adsorbed by magnetic attraction, and the toxins are separated by elution.

16. The method for adsorbing or purifying toxins according to claim 15, characterized in that: The toxin-containing sample is a sample extracted with an extracting solution, and the extracting solution is selected from a mixed solution of methanol, acetonitrile and water with a volume ratio of 7~9:1:1; the usage ratio of the toxin-containing sample to the magnetic zirconium metal organic framework material is 2~5mL:10mg.

17. The method for adsorbing or purifying toxins according to claim 15, characterized in that: The magnetic attraction is to use an electromagnet or a magnet to adsorb the toxins in the sample.

18. The method for adsorbing or purifying toxins according to claim 15, characterized in that: Before the elution, an eluent is added to the container to be eluted, vortexed, and the magnetic zirconium metal organic framework material is adsorbed by an electromagnet or a magnet to collect the eluent containing the toxin; The eluent is selected from an aqueous solution of 1-5% formic acid and acetonitrile.

19. The method for adsorbing or purifying toxins according to claim 15, characterized in that: The sample is selected from feed and feed raw materials; the toxin is selected from at least one of aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2, aflatoxin M1, aflatoxin M2, fumonisin B1, fumonisin B2, T-2 toxin, HT-2 toxin, zearalenone, ochratoxin, deoxynivalenol, trichothecenes, citrinin, penicillic acid, beauvericin and patulin.

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