Preparation method of a multi-level hole UiO-66 (SO3H) 2 material and application thereof in adsorbing trace fluorquinolone antibiotics

Abstract

The application provides a preparation method of a multi-level hole UiO-66(SO3H)2 material, which is prepared by a solvent thermal method assisted by double regulators and combined with in-situ oxidation and acidification, so that the effective pore diameter of the material is expanded while the internal active sites of the material are modified, rich mesoporous transmission channels (mesoporous pore diameters are concentrated in 3-10nm) are constructed, and the problem of mass transfer limitation of macromolecular drugs in the material is solved; in combination with the hydrophilic and negatively charged sulfonic acid groups (-SO3H) introduced by post-modification, strong electrostatic attraction and hydrogen bond effect between the material and fluoroquinolone drug molecules are generated. Strong synergy between physical channels and chemical target sites makes the material exhibit superfast adsorption rate far beyond conventional microporous materials, and solves the problem that trace antibiotics cannot be deeply removed in the prior art.

Description

Technical Field

[0001] This invention belongs to the field of environmental functional materials and water pollution control technology, specifically relating to a method for preparing a multi-level porous UiO-66(SO3H)2 material and its application in the adsorption of trace fluoroquinolone antibiotics. Background Technology

[0002] Metal-organic frameworks (MOFs), particularly the UiO-66 series, have shown great potential in water treatment due to their abundant coordination sites and excellent water stability. To further enhance the targeted adsorption capacity of UiO-66 for specific pollutants, researchers often modify its functional groups. One researcher successfully prepared sulfonic acid-functionalized UiO-66 materials by oxidizing thiol groups to sulfonic acid groups using a post-modification strategy. However, researchers discovered a major drawback in these materials: a simple pore structure and severely limited space. Introducing bulky sulfonic acid groups into the micropores further severely crowded out the already limited space, resulting in a sharp decrease in the BET specific surface area of ​​the obtained UiO-66(SO3H)2 material to only 35 m² / g. This single and extremely narrow pore structure generates a strong steric hindrance effect when facing fluoroquinolone drugs with large molecular volumes. The mass transfer resistance of the macromolecules is extremely high, making it very difficult for the macromolecular drugs to enter the chemical adsorption sites inside the material. This results in extremely slow adsorption kinetics and low pore utilization, which completely fails to meet the actual engineering requirements for "rapid removal" of low-concentration pollutants in water treatment.

[0003] Therefore, there is an urgent need in this field to develop a sulfonic acid-functionalized UiO-66 material capable of precise control over the material's pore structure to construct a hierarchical porous structure (combining micropores and mesopores). The aim is to utilize the hierarchical porous structure to overcome the mass transfer bottleneck caused by single micropores, and combine this with the abundant chemisorption sites provided by the -SO3H group to achieve rapid and near-complete adsorption of extremely low concentrations of fluoroquinolone drugs in water. Summary of the Invention

[0004] The purpose of this invention is to provide a hierarchical porous functionalized UiO-66 powder material UiO-66(SO3H)2, which significantly improves the adsorption rate and removal efficiency of low-concentration fluoroquinolone drugs by constructing hierarchical channels.

[0005] To achieve the above objectives, the present invention first provides the following technical solution: A method for preparing a hierarchical porous UiO-66(SO3H)2 material: S1: Dissolve zirconium salt and 2,5-dimercaptoterephthalic acid ligand in an organic solvent, and then sonicate them to disperse and dissolve them to prepare a mixed solution; S2: Add an inorganic acid regulator and a monocarboxylic acid regulator to the mixed solution. For every 1 gram of the zirconium salt, add 1.0 to 1.5 ml of the inorganic acid regulator. The volume ratio of the inorganic acid regulator to the monocarboxylic acid regulator is 1:1 to 1:1.2. Mix evenly to obtain a precursor solution. S3: After sealing the precursor solution, heat it to carry out a solvothermal reaction. After the reaction is completed, cool it naturally, and obtain the precursor material UiO-66(SH)2 after centrifugation, solvent washing and drying. S4: The precursor material UiO-66(SH)2 is dispersed in hydrogen peroxide solution for oxidation reaction. After the reaction is completed, it is centrifuged and then acidified with dilute sulfuric acid solution. Finally, it is washed until the system is neutral and dried to obtain the hierarchical porous UiO-66(SO3H)2 material with mesopore size concentrated in the range of 3-10 nm.

[0006] As a preferred embodiment of the present invention, the molar ratio of the zirconium salt to the 2,5-dimercaptoterephthalic acid in step S1 is 1:1.4-1:1.5.

[0007] As a preferred embodiment of the present invention, the zirconium salt in step S1 is either zirconium oxychloride octahydrate or zirconium tetrachloride.

[0008] As a preferred embodiment of the present invention, the organic solvent in step S1 is any one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), or N,N-diethylformamide (DEF).

[0009] As a preferred embodiment of the present invention, the inorganic acid regulator in S2 is either hydrochloric acid or hydrobromic acid.

[0010] As a preferred embodiment of the present invention, the monocarboxylic acid regulator in step S2 is one of acetic acid, formic acid, or benzoic acid.

[0011] As a preferred embodiment of the present invention, the heating temperature in step S3 is 100°C and the reaction time is 2 hours.

[0012] As a preferred technical solution of the present invention, the solvent washing in step S3 is to first add one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc) or N,N-diethylformamide (DEF) for centrifugation, and then wash multiple times with anhydrous ethanol. The centrifugation speed is preferably 8500 rpm.

[0013] As a preferred embodiment of the present invention, the mass fraction of the hydrogen peroxide solution in step S4 is 30%, and the oxidation reaction time is 1 hour. The concentration of the dilute sulfuric acid solution was 0.02M, and the acidification treatment time was 45 minutes.

[0014] The present invention also provides the application of the multi-level porous UiO-66(SO3H)2 material prepared according to any one of the above-described methods in the adsorption of trace amounts of fluoroquinolone antibiotics.

[0015] As a preferred embodiment of the present invention, the initial concentration of the fluoroquinolone antibiotic in the water is 0.1 ppb-100 ppb, and more specifically, the initial concentration of the fluoroquinolone antibiotic in the water is close to 1 ppb.

[0016] Compared with the prior art, the present invention has the following beneficial effects: 1. Precise and controllable pore structure: This invention overcomes the limitations of micropore blockage caused by the introduction of large functional groups by employing a solvothermal method assisted by dual regulators combined with in-situ oxidation and acidification. Compared with traditional single-microporous powders, this invention expands the effective pore size of the material while maintaining the active sites inside the material, constructing abundant mesoporous transport channels (mesopore sizes are concentrated in the 3-10 nm range), thereby solving the problem of limited mass transfer of large molecule drugs within the material.

[0017] 2. High mass transfer efficiency and excellent adsorption performance: The hierarchical porous (microporous and mesoporous) structure formed in this invention provides unobstructed physical mass transfer channels for macromolecules. Combined with the hydrophilic and negatively charged sulfonic acid groups (-SO3H) introduced through post-modification, this material generates strong electrostatic attraction and hydrogen bonding with fluoroquinolone drug molecules. The strong synergy between the physical channels and the chemical targeting sites enables this material to exhibit an ultrafast adsorption rate far exceeding that of conventional microporous materials.

[0018] 3. Possesses deep purification capabilities for trace antibiotics: Conventional adsorbents are often ineffective against antibiotic pollution in natural water bodies, which is often present at extremely low concentrations (e.g., ppb levels), due to insufficient driving force. The powder material of this invention can still achieve highly efficient capture of drug molecules, with a removal rate of up to 99.6%, even under extreme conditions where the initial concentration is only 1 ppb or even 0.1 ppb, solving the problem of the difficulty of achieving deep removal of trace antibiotics in existing technologies. Attached Figure Description

[0019] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the embodiments of the invention to explain the invention and do not constitute a limitation thereof.

[0020] Figure 1 The images shown are scanning electron microscope (SEM) images and physical pictures (illustrated) of the hierarchical porous functionalized UiO-66(SO3H)2 powder material prepared in Example 1 of this invention. Figure 2 The image shows the X-ray diffraction (XRD) pattern of the hierarchical porous functionalized UiO-66(SO3H)2 powder material prepared in Example 1 of this invention. Figure 3 The Fourier transform infrared (FT-IR) spectrum of the hierarchical porous functionalized UiO-66(SO3H)2 powder material prepared in Example 1 of this invention is shown below. Figure 4 This is a comparison of the adsorption kinetic curves of fluoroquinolone antibiotics (5 ppm) in water prepared by the materials obtained in Example 1 and the comparative example of the present invention. Figure 5 This is a comparison of the adsorption kinetic curves of fluoroquinolone antibiotics (1ppb) in water prepared by the materials prepared in Example 1 and the comparative example of the present invention. Detailed Implementation

[0021] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] In a typical embodiment of this application, a method for preparing a hierarchical porous UiO-66(SO3H)2 material is provided: S1: Dissolve zirconium salt and 2,5-dimercaptoterephthalic acid ligand in an organic solvent and sonicate to disperse and dissolve them to prepare a mixed solution; this step provides a uniformly distributed molecular precursor for the subsequent self-assembly reaction and is the basis for the formation of a regular crystal structure.

[0023] S2: Add an inorganic acid regulator and a monocarboxylic acid regulator to the mixed solution and mix them evenly to obtain a precursor solution; the introduction of this dual regulator system effectively regulates the nucleation and growth process of crystals through the dynamic coordination competition between the two acidic substances and the metal center, inhibits the excessive growth of grains, and thus induces the formation of a structure composed of nanoscale small grains, laying the foundation for the subsequent formation of hierarchical channels. Based on a mass-volume ratio, for every 1 gram of the zirconium salt, 1.0 to 1.5 milliliters of the inorganic acid regulator are added, with a volume ratio of the inorganic acid regulator to the monocarboxylic acid regulator of 1:1 to 1:1.2. This application achieves precise control of the material's pore structure through the combination of inorganic acid and monocarboxylic acid regulators. The present invention uses dual regulators to give the final product a higher specific surface area and mesopore volume. To obtain the pore structure with the best adsorption effect for fluoroquinolones, the volume ratio of the inorganic acid regulator to the monocarboxylic acid regulator is preferably 1:1. When the generated material pore size is too large, the number of effective adsorption sites decreases, which reduces the adsorption efficiency. If the generated material pore size is too small, macromolecules cannot enter the pores and therefore cannot be effectively adsorbed.

[0024] S3: The precursor solution is sealed and heated for a solvothermal reaction. After the reaction, it is allowed to cool naturally, and then centrifuged, washed with solvent, and dried to obtain the precursor material UiO-66(SH)2. In a high-temperature and high-pressure closed environment, zirconium ions coordinate with organic ligands to self-assemble, forming a stable metal-organic framework structure. Due to the pre-regulatory effect of the dual regulators, what is formed at this time is not a dense microporous crystal, but a hierarchical porous UiO-66(SH)2 precursor rich in mesopores, composed of stacked nanocrystals. Through this step, macromolecular mass transfer channels are successfully pre-constructed in the material structure.

[0025] S4: The precursor material UiO-66(SH)2 is dispersed in hydrogen peroxide solution for oxidation. After the reaction, it is centrifuged, then acidified with dilute sulfuric acid solution, and finally washed until the system is neutral and dried to obtain a hierarchical porous UiO-66(SO3H)2 material with mesopore sizes concentrated in 3-10 nm. This step is a post-modification process, the purpose of which is to convert the thiol groups (-SH) pre-embedded in the framework, which have a weak adsorption effect on the target pollutants, into sulfonic acid groups (-SO3H) with strong hydrophilicity, strong acidity, and strong electrostatic attraction and hydrogen bonding effect on fluoroquinolone antibiotics. Through this strategy of "building the framework first, then adding functions", a hierarchical porous functionalized UiO-66(SO3H)2 powder material with both efficient mass transfer channels (hierarchical pores) and strong chemisorption sites (sulfonic acid groups) is finally obtained.

[0026] As a preferred embodiment of the present invention, the molar ratio of the zirconium salt to the 2,5-dimercaptoterephthalic acid in step S1 is 1:1.4-1:1.5. If the ratio is too large, it will easily cause ligand loss, increase crystal defects, and cause serious agglomeration; if the ratio is too small, there will be excessive ligand residue, which will interfere with crystal growth and introduce impurities.

[0027] As a preferred embodiment of the present invention, the zirconium salt in step S1 is either zirconium oxychloride octahydrate or zirconium tetrachloride.

[0028] As a preferred embodiment of the present invention, the organic solvent in step S1 is any one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), or N,N-diethylformamide (DEF).

[0029] Preferably, the zirconium salt in step S1 is zirconium oxychloride octahydrate (ZrOCl2·8H2O), and the organic solvent is N,N-dimethylformamide (DMF). Zirconium oxychloride octahydrate, as a commonly used zirconium source, exhibits good solubility and reactivity. N,N-dimethylformamide, as a high-boiling-point aprotic polar solvent, can effectively dissolve the reactants and provide a suitable reaction environment for the solvothermal reaction, which is beneficial for the formation of high-quality crystalline products.

[0030] As a preferred embodiment of the present invention, the inorganic acid regulator in step S2 is either hydrochloric acid or hydrobromic acid.

[0031] As a preferred embodiment of the present invention, the monocarboxylic acid regulator in step S2 is one of acetic acid, formic acid, or benzoic acid.

[0032] Preferably, the inorganic acid regulator in S2 is hydrochloric acid, and the monocarboxylic acid regulator is acetic acid. Hydrochloric acid, as a strong acid, provides a high concentration of protons, effectively regulating the pH of the reaction system, and forms an unstable chloride coordination intermediate with zirconium ions, promoting nucleation. Acetic acid, as a weak acid and monocarboxylic acid, allows its acetate ions to compete for coordination with organic ligands, acting as a "capping agent" and slowing down the crystal growth rate. It is this synergistic effect of strong acid promoting nucleation and weak acid slowing down growth that ultimately results in uniformly sized nanocrystals, thereby constructing a rich mesoporous structure.

[0033] In a preferred embodiment of the present invention, the heating temperature in step S3 is 100°C for 2 hours. Too low a temperature or too short a time may result in incomplete reaction and poor crystallinity; while too high a temperature or too long a time may lead to excessive grain growth, destroying the existing hierarchical porous structure and causing the regeneration of a dense microporous material. Therefore, reacting at 100°C for 2 hours provides a process window that ensures high crystallinity while better preserving the hierarchical porous structure.

[0034] As a preferred embodiment of the present invention, the solvent washing in step S3 involves first adding one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), or N,N-diethylformamide (DEF) to the mixture and centrifuging it, followed by multiple washes with anhydrous ethanol. The centrifugation speed is preferably 8500 rpm. This centrifugation and washing process ensures that the product is free of impurities.

[0035] As a preferred embodiment of the present invention, the mass fraction of the hydrogen peroxide solution in step S4 is 30%, and the oxidation reaction time is 1 hour. The concentration of the dilute sulfuric acid solution was 0.02M, and the acidification treatment time was 45 minutes.

[0036] In step S4, hydrogen peroxide acts as an oxidant, with water as its only reaction byproduct. It gently oxidizes thiol groups (-SH) to sulfonic acid groups (-SO3H), making it environmentally friendly. The subsequent treatment with dilute sulfuric acid ensures that all sulfonic acid groups exist in their protonated form (-SO3H), thus giving them strong acidity and the ability to interact with pollutants. This specific reagent selection guarantees the effective transformation of functional groups.

[0037] The beneficial effects of this application will be further illustrated below with reference to embodiments and comparative examples. Example

[0038] S1 Add 1.61 g of zirconium oxychloride octahydrate (ZrOCl2·8H2O) and 1.66 g of 2,5-dimercaptoterephthalic acid to 30 ml of N,N-dimethylformamide (DMF) and sonicate at room temperature for 15 minutes to dissolve completely. S2 Add 2 ml of hydrochloric acid and 2 ml of acetic acid as dual conditioning agents to the above clear solution and stir thoroughly to mix evenly; S3. Transfer the mixed solution to a reaction vessel (or a sealed glass reagent bottle) and heat it at 100°C for 2 hours. After the reaction, allow it to cool naturally to room temperature. Then, add 20 ml of DMF to the system, centrifuge for 5 minutes to separate the precipitate, and wash it three times with anhydrous ethanol to remove unreacted substances. The centrifugation speed for each wash is set to 8500 rpm. Place the washed solid in a 50°C oven to dry, and obtain UiO-66(SH)2 precursor powder with a hierarchical porous structure. S4 Take 200 mg of the above-mentioned hierarchical porous UiO-66(SH)2 precursor sample and add it to 20 ml of 30% hydrogen peroxide aqueous solution. Stir magnetically for 1 hour to carry out in-situ oxidation reaction. After centrifuging the solid, place it in 0.02 M sulfuric acid solution and continue stirring for 45 minutes to carry out protonation treatment. Then wash the sample multiple times with deionized water until the washing filtrate is neutral. Finally, place the washed sample in a 50℃ oven to dry, and the hierarchical porous functionalized UiO-66(SO3H)2 powder material is obtained.

[0039] Comparative Example 1: Preparation of Hierarchical Porous UiO-66(SH)2 Powder Material Repeat steps S1 to S3 in Example 1, but do not perform the oxidation and acidification treatment in step S4. Directly collect the powder after drying in an oven at 50°C to obtain the hierarchical porous UiO-66(SH)2 material containing thiol groups (-SH).

[0040] Comparative Example 2: Preparation of Microporous UiO-66(SO3H)2 Powder Material In step S2 of Example 1, only 4 ml of acetic acid was added as a single regulator (hydrochloric acid was not added). The operation process, reaction reagents, and parameter conditions of the remaining steps S1, S3, and S4 were exactly the same as in Example 1. Finally, UiO-66(SO3H)2 powder material with only microporous structure was obtained.

[0041] Example

[0042] 100 mg of each of the materials from Example 1, Comparative Example 1, and Comparative Example 2 were weighed and divided into 10 groups. Each group was placed in a 5 ppm of ofloxacin aqueous solution and subjected to adsorption experiments on a shaker. The adsorption time for each group was different, with a time gradient of 5, 10, 20, 30, 40, 50, 60, 80, 90, 100, and 120 min. After the specified time, samples from the corresponding groups were taken for analysis to determine the adsorption amount. The adsorption results are shown in the attached figure. Figure 4 As shown.

[0043] Example

[0044] 100 mg of each of the materials from Example 1, Comparative Example 1, and Comparative Example 2 were weighed and divided into 10 groups. Each group was placed in a 1 ppb of ofloxacin aqueous solution and subjected to adsorption experiments on a shaker. The adsorption time for each group was different, with a time gradient of 5, 10, 20, 30, 40, 50, 60, 80, 90, 100, and 120 min. After the specified time, samples from the corresponding groups were taken for analysis to determine the adsorption amount. The adsorption results are shown in the attached figure. Figure 5 As shown.

[0045] The structure of UiO-66(SO3H)2 prepared in this invention and its effect on the adsorption of fluoroquinolone antibiotics will be described below with reference to the accompanying drawings: according to Figure 1 According to scanning electron microscopy (SEM), the material prepared by this invention exhibits a microsphere morphology formed by irregular aggregation of nano-sized particles, with a large number of clearly visible gaps between the particles. This surface morphology and abundant interparticle porosity, together with the intrinsic defects of mesopores inside the material, constitute a well-developed multi-level pore transport system.

[0046] according to Figure 2 X-ray diffraction (XRD) analysis showed that the main diffraction peak positions of the material prepared in this invention (red line) were highly consistent with the characteristic peak positions of the standard UiO-66 material (black line), indicating that the dual-regulator method and post-modification process of this invention yielded a stable UiO-66 material with its inherent crystal framework structure.

[0047] according to Figure 3 The chemical bonds of the final product of this invention (UiO-66(SO3H)2) and the product of Comparative Example 1 (UiO-66(SH)2) were compared by Fourier transform infrared spectroscopy (FT-IR). It can be observed that the chemical bonds are more closely related to the final product by approximately 2550 cm⁻¹ in the spectrum of Comparative Example 1. -1 The stretching vibration peak of the -SH group present at [location] was no longer detected in the spectrum of the final product of this invention; meanwhile, at approximately 1035 cm⁻¹, [further details are needed]. -1 and 1150 cm -1 New characteristic peaks appeared at the point, belonging to the symmetric and asymmetric stretching vibrations of the S=O group in the -SO3H group, respectively. This series of changes indicates that the -SH group was converted into the -SO3H group through the oxidative acidification treatment in step S4.

[0048] according to Figure 4At a concentration of 5 ppm, the adsorption kinetics of Example 1, Comparative Example 1 (lacking sulfonic acid groups), and Comparative Example 2 (lacking hierarchical pores) were compared. The results showed that the material of this invention reached adsorption equilibrium within 10 minutes, exhibiting the fastest adsorption rate and the highest equilibrium adsorption capacity. This demonstrates that the synergistic effect of hierarchical pores (Comparative Example 2) and sulfonic acid groups (Comparative Example 1) is crucial for achieving rapid, high-capacity adsorption.

[0049] according to Figure 5 Adsorption experiments were conducted under trace conditions with an initial concentration of only 1 ppb. The material of this invention achieves rapid and deep purification of trace pollutants. In contrast, the material prepared in Comparative Example 2 exhibits poor adsorption performance due to high mass transfer resistance. This demonstrates that the present invention has a significant effect on the removal of trace pollutants compared to existing technologies, supporting application scenarios with initial concentrations close to 1 ppb.

Claims

1. A method for preparing a hierarchical porous UiO-66(SO3H)2 material, characterized in that, Includes the following steps: S1: Dissolve zirconium salt and 2,5-dimercaptoterephthalic acid ligand in an organic solvent, and then sonicate them to disperse and dissolve them to prepare a mixed solution; S2: Add an inorganic acid regulator and a monocarboxylic acid regulator to the mixed solution. According to the mass-volume ratio, for every 1 gram of the zirconium salt, add 1.0 to 1.5 ml of the inorganic acid regulator. The volume ratio of the inorganic acid regulator to the monocarboxylic acid regulator is 1:1 to 1:1.

2. Mix evenly to obtain a precursor solution. S3: After sealing the precursor solution, heat it to carry out a solvothermal reaction. After the reaction is completed, cool it naturally, and obtain the precursor material UiO-66(SH)2 after centrifugation, solvent washing and drying. S4: The precursor material UiO-66(SH)2 is dispersed in hydrogen peroxide solution for oxidation reaction. After the reaction is completed, it is centrifuged and then acidified with dilute sulfuric acid solution. Finally, it is washed until the system is neutral and dried to obtain the hierarchical porous UiO-66(SO3H)2 material with mesopore size concentrated in the range of 3-10 nm.

2. The method for preparing the hierarchical porous UiO-66(SO3H)2 material as described in claim 1, characterized in that, The molar ratio of the zirconium salt to the 2,5-dimercaptoterephthalic acid in step S1 is 1:1.4-1:1.

5.

3. The preparation method of the hierarchical porous UiO-66(SO3H)2 material as described in claim 1, characterized in that, The zirconium salt mentioned in step S1 is either zirconium oxychloride octahydrate or zirconium tetrachloride.

4. The method for preparing the hierarchical porous UiO-66(SO3H)2 material as described in claim 1, characterized in that, The organic solvent mentioned in step S1 is any one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N,N-diethylformamide (DEF).

5. The method for preparing the hierarchical porous UiO-66(SO3H)2 material as described in claim 1, characterized in that, The inorganic acid regulator mentioned in S2 is either hydrochloric acid or hydrobromic acid.

6. The method for preparing the hierarchical porous UiO-66(SO3H)2 material as described in claim 1, characterized in that, The monocarboxylic acid regulator mentioned in step S2 is one of acetic acid, formic acid, or benzoic acid.

7. The method for preparing the hierarchical porous UiO-66(SO3H)2 material as described in claim 1, characterized in that, The solvent washing in step S3 involves first adding one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), or N,N-diethylformamide (DEF) for centrifugation, followed by multiple washes with anhydrous ethanol.

8. The application of the hierarchical porous UiO-66(SO3H)2 material prepared by the method described in any one of claims 1-7 in the adsorption of trace amounts of fluoroquinolone antibiotics.

9. The application of the hierarchical porous UiO-66(SO3H)2 material as described in claim 8 in the adsorption of trace fluoroquinolone antibiotics, characterized in that, The initial concentration of the fluoroquinolone antibiotics in the water body is 0.1 ppb-100 ppb.

Images