A metal-organic framework membrane, its preparation method and its application

Abstract

The application discloses a kind of metal organic framework films, preparation method and application thereof, it is related to antibiotic and mycotoxin removal technical field.The preparation method includes the following steps: metal source and organic ligand are added into solvent and mixed uniformly, obtain mixed solution;After using base material adsorbs the mixed solution, by in-situ growth method, in-situ growth polymerization metal organic framework crystal is carried out on the internal fiber surface of the base material, and the metal organic framework film is obtained;The metal source is zirconium salt;The organic ligand is tetra [4- (3,5-dicarboxyphenyl) ] tetraphenyl ethylene.This metal organic framework film can realize the high selectivity adsorption of antibiotic and mycotoxin by specific chemical structure and chemical composition, with the technical advantages of short antibiotic and mycotoxin adsorption time, high effect, low economic cost.

Description

Technical Field

[0001] This invention relates to the field of antibiotic and mycotoxin removal technology, and in particular to a metal-organic framework membrane, its preparation method, and its application. Background Technology

[0002] Antibiotics, as chemical agents that specifically inhibit or kill pathogenic microorganisms, have expanded their application beyond traditional medicine to industries such as agriculture and animal husbandry. During large-scale application, antibiotics are continuously introduced into aquatic systems through multiple pathways, including agricultural runoff, industrial wastewater, and domestic sewage. The resulting spread of antibiotic-resistant genes in bacteria has become a major challenge in public health. Mycotoxins, secondary metabolites produced by toxin-producing fungi, not only cause crop yield reduction and quality deterioration but can also accumulate at each stage of the food chain through bioaccumulation, leading to multiple health risks, including acute poisoning, immunosuppression, carcinogenicity, and teratogenicity.

[0003] The synergistic presence of these two types of pollutants in the aquatic environment has triggered significant ecological disturbances: firstly, it disrupts the structure of aquatic microbial communities, leading to the dominant growth of drug-resistant strains; secondly, it affects the metabolism and reproductive functions of aquatic organisms through bioaccumulation, thereby threatening the stability of aquatic ecosystems; and thirdly, it creates a complex pollution effect, exacerbating the safety risks of drinking water sources and aquaculture systems. Against the backdrop of accelerated industrialization and urbanization, traditional water treatment processes are insufficient in removing trace organic pollutants, making the development of new pollutant treatment technologies urgent. Adsorption methods, due to their simple operation, low operating costs, and high renewability, have shown promising application prospects in the field of water treatment. Among them, metal-organic frameworks (MOFs) have attracted much attention due to their unique structural characteristics: highly ordered crystal structures endow them with ultra-high specific surface area, tunable pore size distribution, and abundant surface functional groups, which enable them to exhibit excellent adsorption performance for various organic pollutants. However, MOFs prepared by conventional hydrothermal methods are mostly in nanoscale particle form, which limits their recycling, processing, and application. In practical applications, technical bottlenecks exist, such as difficulties in solid-liquid separation, insufficient mechanical strength, and poor reusability. Therefore, more synthesis and preparation technologies are needed to obtain materials that are easily recyclable and usable.

[0004] To address the aforementioned issues, current research focuses on two main technological directions: first, constructing magnetically responsive composite adsorbents by loading metal-organic frameworks onto magnetic supports (such as Fe3O4@SiO2) through in-situ growth; and second, preparing metal-organic framework aerogels using freeze-drying-crosslinking technology to enhance the structural stability of the materials. These technological innovations not only expand the engineering application scenarios of metal-organic framework materials but also provide new ideas for the synergistic optimization of efficient pollutant removal and green regeneration of adsorbents.

[0005] Based on the need for in-depth analysis of existing technological bottlenecks and innovative breakthroughs, this invention aims to prepare a novel adsorption membrane material and its preparation method based on a composite of metal-organic framework and glass microfiber filter paper, in order to achieve efficient enrichment and adsorption of antibiotics and mycotoxins. Summary of the Invention

[0006] The purpose of this invention is to provide a metal-organic framework membrane, its preparation method, and its application to solve the problems existing in the prior art. This metal-organic framework membrane, through its specific chemical structure and composition, can achieve highly selective adsorption of antibiotics and mycotoxins, possessing the technical advantages of short adsorption time, high efficiency, and low economic cost.

[0007] To achieve the above objectives, the present invention provides the following solution:

[0008] This invention provides a method for preparing a metal-organic framework membrane for enriching and adsorbing antibiotics and / or mycotoxins, comprising the following steps:

[0009] The metal source and organic ligand are added to the solvent and mixed evenly to obtain a mixed solution;

[0010] After the mixed solution is adsorbed onto the substrate material, polymeric metal-organic framework crystals are grown in situ on the surface of the internal fibers of the substrate material by an in-situ growth method to obtain the metal-organic framework film.

[0011] The metal source is a zirconium salt;

[0012] The organic ligand is tetrakis[4-(3,5-dicarboxyphenyl)]tetraphenylethylene;

[0013] Furthermore, the substrate material is glass microfiber filter paper.

[0014] Furthermore, the solvent is glacial acetic acid and / or N,N-dimethylformamide.

[0015] Preferably, the zirconium salt is ZrOCl2.

[0016] Furthermore, the mass ratio of the metal source to the organic ligand is 1:(1-4).

[0017] Preferably, the mass ratio of the metal source to the organic ligand is 1:1.25.

[0018] Furthermore, the in-situ growth method is performed at a temperature of 80-120℃ for a time of 4-16 hours.

[0019] The present invention also provides a metal-organic framework membrane prepared according to the above preparation method.

[0020] The present invention also provides the application of the above-described metal-organic framework membrane in the enrichment and adsorption of antibiotics and / or mycotoxins.

[0021] The present invention also provides a method for enriching and adsorbing antibiotics and / or mycotoxins, comprising the step of adsorbing a liquid sample containing antibiotics and / or mycotoxins using the above-described metal-organic framework membrane.

[0022] Furthermore, the liquid sample is selected from wastewater, milk, oil, feed, and feed ingredient extracts;

[0023] The antibiotic is selected from at least one of sulfamethoxypyrimidine, sulfao-methoxypyrimidine, sulfachlorpyridazine, sulfachlorpyridazine, sulfaquinoxaline, trimethoprim, norfloxacin, flumethin, sinofloxacin, ciprofloxacin, enrofloxacin, quinolone, chlortetracycline, oxytetracycline, oxifenesole, tivalmonin, erythromycin, tylosin, tylosin, lincomycin, nifuranhydrazone, monensin, salinomycin, tiamulin, amoxicillin, penicillin G, cephalexin, cefixime, nystatin, and berberine;

[0024] The mycotoxin is selected from at least one of the following: aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2, aflatoxin M1, aflatoxin M2, zearalenone, α-zearalenol, β-zearalenol, deoxynivalenol, ochratoxin A, ochratoxin B, T-2 toxin, HT-2 toxin, fumonisin B1, fumonisin B2, hydrolyzed fumonisin B1, and hydrolyzed fumonisin B2.

[0025] The present invention discloses the following technical effects:

[0026] This invention provides a novel metal-organic framework membrane that, through its specific chemical structure and composition, achieves highly selective adsorption of antibiotics and mycotoxins, offering advantages such as short adsorption time, high efficiency, and low cost. Furthermore, this metal-organic framework membrane exhibits chemical stability and excellent thermal stability, demonstrating a high adsorption capacity for antibiotics and mycotoxins at room temperature and pressure, making it suitable for the adsorption and separation of these substances. This metal-organic framework membrane can effectively adsorb antibiotics and mycotoxins from samples, achieving an adsorption rate of 90-99%, thus serving as a high-quality enrichment and adsorption material for antibiotics and mycotoxins.

[0027] The method for preparing metal-organic framework membranes provided by this invention has the technical advantages of simple preparation process, strong controllability, low cost, and large-scale production. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 The diagram shows metal-organic framework membranes with different metal sources; where A and D represent metal-organic framework membranes prepared using ZrOCl2, CuCl2, PbCl2, and ZnCl2 as metal sources, respectively.

[0030] Figure 2 Illustrations of metal-organic framework membranes prepared for different substrate materials; wherein, the substrate materials of AC are glass microfiber filter paper, qualitative filter paper and quantitative filter paper, respectively;

[0031] Figure 3 TEM images of glass microfiber filter paper (A) and metal-organic framework membrane (B);

[0032] Figure 4 XPS images of glass microfiber filter paper and metal-organic framework membrane; where ac represents the detection results of Zr 3d, O 1s and C1s signals, respectively; A represents glass microfiber filter paper and B represents metal-organic framework membrane.

[0033] Figure 5 This is a statistical graph showing the adsorption capacity of typical antibiotics and mycotoxins on the zirconium metal source metal-organic frame membrane synthesized in Example 1.

[0034] Figure 6 Statistical chart of the adsorption capacity of the metal-organic framework material FMSL-AL for 16 antibiotics and 6 mycotoxins;

[0035] Figure 7 A statistical chart showing the adsorption capacity of the metal-organic framework material MOF-808(Zr) for 16 antibiotics and 6 mycotoxins;

[0036] Figure 8 A statistical chart showing the adsorption capacity of the metal-organic framework material MIL-101(Cr) for 16 antibiotics and 6 mycotoxins;

[0037] Figure 9 A statistical chart showing the adsorption capacity of the metal-organic framework material UIO-66 for 16 antibiotics and 6 mycotoxins;

[0038] Figure 10 Statistical chart of adsorption capacity of ZN-MOF metal-organic framework for 16 antibiotics and 6 mycotoxins;

[0039] Figure 11 This is a statistical chart showing the adsorption capacity of the zirconium metal-sourced metal-organic frame membrane synthesized in Example 1 for 16 antibiotics and 6 mycotoxins. Detailed Implementation

[0040] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0041] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0042] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0043] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0044] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0045] Example 1

[0046] 1. Experimental Methods

[0047] 1.1 Screening of Metal Sources

[0048] Metal-organic framework (MOF) membranes were prepared using ZrOCl2, CuCl2, PbCl2, and ZnCl2 as metal sources, respectively. The preparation effects of different MOF membranes were compared to screen suitable metal sources. The preparation methods of MOF membranes are as follows:

[0049] Take 160 mg of the metal source and 200 mg of tetrakis[4-(3,5-dicarboxyphenyl)]tetraphenylethylene (T4CPE) (organic ligand) and add them to a 100 mL glass bottle. Add 2 mL of glacial acetic acid and 40 mL of N,N-dimethylformamide (DMF) solvent, and dissolve by sonication. To ensure uniform mixing of the raw materials, vortex mix for 2 min to obtain a homogeneous solution. Soak glass microfiber filter paper in DMF overnight, discard the DMF, dry at 80 °C for 12 h, cut into 2 × 2 cm pieces with scissors, and then freeze for later use.

[0050] 1000 mg of prepared glass microfiber filter paper (substrate material) and 40 mL of mixed solution were added to a polytetrafluoroethylene reaction vessel and ultrasonically vibrated for 30 min to ensure complete absorption of the mixed solution by the glass microfiber filter paper. Then, the reaction was carried out in a constant-temperature shaking incubator at 80 °C for 4 h. After the reaction was completed, the solvent was removed by centrifugation (10000 r / min, 5 min). The metal-organic framework membrane was then washed twice with 10 mL of deionized water, followed by two washes with 5 mL of DMF solvent. Finally, it was dried at 50 °C for 12 h to obtain the metal-organic framework membrane.

[0051] 1.2 Screening of substrate materials

[0052] Metal-organic framework membranes were prepared using glass microfiber filter paper, qualitative filter paper, and quantitative filter paper as substrate materials, respectively. The preparation effects of different metal-organic framework membranes were compared to screen suitable substrate materials. The preparation method of metal-organic framework membranes is the same as in 1.1, and ZrOCl2 is used as the metal source.

[0053] 2. Experimental Results

[0054] 2.1 Results of Metal Source Screening

[0055] Comparison of different metal-organic framework membranes prepared in 1.1 revealed that when PbCl2 and ZnCl2 were used as metal sources, MOF crystals were not generated, and no corresponding MOF coating was found on the filter paper (see [link to article]). Figure 1 (C and D). When CuCl2 is used as the metal source, the ligands react incompletely with CuCl2, failing to generate denser MOF layers (see C and D). Figure 1 (B) When ZrOCl2 is used as the metal source, it exhibits uniform epitaxial growth characteristics, achieving full-coverage loading on the fiber surface (coverage > 98%), forming a continuous and stable porous functional layer (see B). Figure 1 (A). Therefore, PbCl2 was selected as the optimal metal source.

[0056] 2.2 Results of substrate material screening

[0057] like Figure 2 As shown, comparing the metal-organic framework membranes prepared in 1.2, it was found that when glass microfiber filter paper was used as the substrate, the MOF crystals exhibited uniform epitaxial growth characteristics. The nanoscale grains achieved full-coverage loading (coverage > 98%) on the fiber surface through the coordination and anchoring effect of surface silanol groups (-Si-OH) with metal nodes, forming a continuous and stable porous functional layer. In contrast, the qualitative filter paper, due to the topological roughness and chemically inert interface of cellulose fibers, resulted in localized island-like aggregation of MOF crystals (coverage ≈ 35%), and significant uneven crystal size distribution. The quantitative filter paper, limited by its dense pore structure (porosity < 40%) and hydrophobic surface characteristics (contact angle > 100°), showed almost no effective MOF loading (coverage < 0.5%). Based on a comprehensive analysis of crystal loading density, interfacial bonding strength, and structural stability, this invention selected glass microfiber filter paper as the optimized substrate material for preparing MOF composite membranes.

[0058] Example 2

[0059] A method for preparing a metal-organic framework membrane:

[0060] Add 160 mg ZrOCl2 and 160 mg T4CPE to a 100 mL glass bottle, along with 2 mL glacial acetic acid and 40 mL DMF solvent. Dissolve by sonication. To ensure homogeneous mixing, vortex mix for 2 minutes to obtain a uniform solution. Soak glass microfiber filter paper in DMF overnight, discard the DMF, dry at 80°C for 12 hours, cut into 2*2 cm pieces, and freeze for later use.

[0061] 2000 mg of prepared glass microfiber filter paper and 60 mL of mixed solution were added to a polytetrafluoroethylene reaction vessel and ultrasonically vibrated for 30 min to ensure complete absorption of the mixed solution by the glass microfiber filter paper. Then, the reaction was carried out in a constant-temperature shaking bed at 90 °C for 16 h. After the reaction was completed, the solvent was removed by centrifugation (9000 r / min, 6 min). The metal-organic framework membrane was then washed twice with 10 mL of deionized water, followed by two washes with 5 mL of LDM solvent. Finally, it was dried at 40 °C for 16 h to obtain the metal-organic framework membrane.

[0062] Example 3

[0063] A method for preparing a metal-organic framework membrane:

[0064] Add 160 mg ZrOCl2 and 640 mg T4CPE to a 100 mL glass bottle, along with 2 mL glacial acetic acid and 40 mL DMF solvent. Dissolve by sonication. To ensure uniform mixing, vortex mix for 2 minutes to obtain a homogeneous solution. Soak glass microfiber filter paper in DMF overnight, discard the DMF, dry at 80°C for 12 hours, cut into 2*2 cm pieces, and freeze for later use.

[0065] 5000 mg of prepared glass microfiber filter paper and 100 mL of mixed solution were added to a polytetrafluoroethylene reaction vessel and ultrasonically vibrated for 30 min to allow the glass microfiber filter paper to completely absorb the mixed solution. Then, the reaction was carried out in a constant temperature shaker at 120 °C for 8 h. After the reaction was completed, the solvent was removed by centrifugation (11000 r / min, 4 min). The metal-organic framework membrane was then washed twice with 10 mL of deionized water and twice with 5 mL of DMF solvent. Finally, it was dried at 60 °C for 14 h to obtain the metal-organic framework membrane.

[0066] Example 4

[0067] The metal-organic framework films of zirconium metal source prepared in Example 1 were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS).

[0068] TEM scan results show that this invention has successfully achieved the controllable growth and stable loading of metal-organic framework materials on glass microfiber filter paper substrates. Figure 3 The results clearly show that after in-situ synthesis, the surface of cellulose fibers exhibits significant morphological modification characteristics—the originally smooth fiber surface is covered with a large number of nanoscale metal-organic framework crystals, forming a composite interface with a three-dimensional porous structure. This indicates that the microstructure of the substrate fibers plays a template-guiding role in the heterogeneous nucleation and directional growth of metal-organic framework crystals.

[0069] SEM and EDS were used to analyze the elemental distribution of glass microfiber filter paper and metal-organic framework (MOF) membranes. Analysis of the glass microfiber filter paper revealed a uniform distribution of carbon (C, 13%), silicon (Si, 35.8 at%), and oxygen (O, 35.8 at%), with no zirconium (Zr) signal detected. After loading the MOF, EDS surface scanning results showed a high spatial correlation among C, O, silicon, and Zr in the composite membrane. The characteristic signal of Zr (5.2 at%) was detected for the first time, and its distribution completely overlapped with the morphology of the MOF crystals, directly confirming the successful introduction of metal-oxygen clusters into the MOF. Regarding carbon (C) and oxygen (O): C content increased while O content decreased, consistent with the trend observed in XPS results. The decrease in C is attributed to the physical covering of cellulose fibers by the MOF crystals, resulting in partial shielding of the C signal from the substrate; the decrease in O is due to the contribution of carboxylic acid ligands and metal-oxygen clusters within the MOF.

[0070] In-depth analysis of the surface chemical composition and bonding state of glass microfiber filter paper and metal-organic framework membranes based on X-ray photoelectron spectroscopy was conducted, and the results were obtained ( Figure 4 This indicates a significant change in the types of elements on the material surface and the chemical environment, providing direct evidence for the successful synthesis of metal-organic frameworks (MOFs) and interfacial interactions. The XPS full spectrum of the glass microfiber filter paper only showed characteristic peaks for carbon (C 1s, 284.8 eV) and oxygen (O 1s, 532.5 eV), consistent with the abundant COC and hydroxyl (-OH) structures in cellulose molecules. However, after loading with a MOF, the full spectrum of the MOF membrane showed the addition of characteristic bimodal peaks for zirconium (Zr3d, 182.5 eV and 184.8 eV), with an atomic percentage of 5.7%, while both the C1s and O1s peaks shifted. This shift directly confirms that the MOF crystals have been successfully anchored to the fiber surface—the introduction of Zr originates from the generation of metal nodes (such as Zr-O clusters) within the MOF, while the shift in O content may be related to the contributions of organic ligands (such as carboxylic acids or oxygen-containing aromatic ligands) and metal-oxygen clusters within the MOF, and the shift in C content is attributed to the partial shielding of carbon signals on the cellulose surface caused by the MOF covering. XPS data synthesis indicates that the metal-organic framework (MOF) and glass microfiber filter paper not only have physical coating but also form chemical bonds through coordination bonds between metal-oxygen clusters and Si-O, and π-π stacking of organic ligands and Si-O. This strong interfacial synergistic effect effectively inhibits the shedding or structural collapse of MOF crystals during dynamic use, which corroborates the long-term stability results observed by TEM in the past, providing theoretical chemical support for the practical application of composite membranes in humid environments or under mechanical stress.

[0071] Example 5

[0072] The metal-organic frame membrane with zirconium metal source synthesized in Example 1 was used to conduct adsorption experiments on liquid samples containing different antibiotics or mycotoxins. The removal efficiency of the metal-organic frame membrane for different antibiotics and mycotoxins was compared. The method is as follows:

[0073] Take 10 mL of liquid sample containing antibiotics or mycotoxins into a centrifuge tube, adjust the pH to 6.0 with phosphate buffer, mix well, and centrifuge. Add the supernatant to a funnel equipped with a zirconium metal-organic framework membrane prepared in Example 1, with a supernatant to metal-organic framework membrane volume ratio of 4 mL:100 mg. Allow to flow naturally to enrich and remove antibiotics or mycotoxins. Detect the antibiotic or mycotoxin content in the supernatant and filtrate. The adsorption effect is calculated using the following formula:

[0074] X = (1 - A0 / A1) × A1 / M;

[0075] Where X: maximum adsorption capacity (mg / g); A0: antibiotic or mycotoxin content in the filtrate (mg); A1: antibiotic or mycotoxin content in the supernatant (mg); M: mass of the metal-organic framework membrane (g).

[0076] from Figure 5 It can be seen that the metal-organic framework membrane exhibits good adsorption effects on 30 antibiotics and 19 mycotoxins, with adsorption capacities ranging from 352 to 2320 mg / g. Therefore, the metal-organic framework membrane prepared in this invention can be used as a removal material for antibiotics and mycotoxins, and can be applied to the adsorption, removal, and detection of these substances.

[0077] Example 5

[0078] Sixteen typical antibiotics and six mycotoxins were selected as adsorption targets for metal-organic frameworks (MOFs). The removal efficiency of the six different MOFs was compared, using the same method as in Example 4. The specific six different MOFs are shown in Table 1.

[0079] Table 16 different metal-organic framework materials

[0080]

[0081]

[0082] from Figure 6-11It can be seen that the zirconium metal-based metal-organic framework membrane prepared in Example 1 showed the best adsorption effect on antibiotics and mycotoxins, with adsorption capacities ranging from 353 to 2248 mg / g. Material A showed strong adsorption only for tylosin, lincomycin, and berberine (300 mg / g), but weak adsorption capacity for other toxins. Material B showed some adsorption capacity for quinolone (663.28 mg / g), enrofloxacin (555.47 mg / g), and aflatoxin B1 (189.95 mg / g). Other metal-organic framework materials showed poor adsorption effects on antibiotics and mycotoxins, with measured values ​​ranging from 22 to 600 mg / g. Some metal-organic framework materials showed no adsorption, indicating that they did not adsorb antibiotics and mycotoxins. In summary, the metal-organic framework membrane prepared in this invention can be used as a removal material for antibiotic and mycotoxin detection tests, with the advantage of good adsorption performance.

[0083] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. Use of a metal organic framework membrane for the enrichment adsorption of antibiotics, characterized in that, The preparation method of the metal organic framework film comprises the following steps: adding a metal source and an organic ligand into a solvent and mixing them uniformly to obtain a mixed solution; after the substrate material adsorbs the mixed solution, growing polymerized metal organic framework crystals in-situ on the internal fiber surface of the substrate material by an in-situ growth method to obtain the metal organic framework film; the metal source is a zirconium salt; the organic ligand is tetrakis[4-(3,5-dicarboxyphenyl)]tetraphenyl ethylene; the substrate material is a glass microfiber filter paper.

2. Use according to claim 1, characterized in that, the solvent is glacial acetic acid and / or N,N-dimethylformamide.

3. Use according to claim 1, characterized in that, the zirconium salt is ZrOCl2.

4. Use according to claim 1, characterized in that, the mass ratio of the metal source to the organic ligand is 1:(1-4).

5. The use according to claim 1, characterized in that, the mass ratio of the metal source to the organic ligand is 1:1.

25.

6. Use according to claim 1, characterized in that, the temperature of the in-situ growth method is 80-120℃, and the time is 4-16h.

7. A method of enriching adsorbing an antibiotic, characterized by, the method comprises the step of adsorbing a liquid sample containing an antibiotic by using the metal organic framework film in the application of any one of claims 1-6.

Images