Preparation method and application of phenylboronic acid functionalized urchin-like COFs material

Abstract

The invention provides a preparation method and application of a phenylboronic acid functionalized sea urchin-shaped COFs material, the COFs material is of a sea urchin-shaped structure, a covalent organic framework serves as a substrate, the substrate is modified through phenylboronic acid groups, the surface morphology of the COFs material is controlled by regulating and controlling the concentration of acetic acid, and functional sea urchin-shaped COFs materials with different morphologies are synthesized. The phenylboronic acid modified sea urchin COFs material not only has remarkable bactericidal performance, but also can specifically adsorb pollutants with vicinal diol structures in various water bodies, and shows remarkable application value in the field of water pollution control.

Description

Technical Field

[0001] The present invention belongs to the technical field of covalent organic framework materials, and in particular relates to a preparation method and application of a phenylboronic acid functionalized sea urchin-shaped COFs material. Background Art

[0002] Covalent organic frameworks (COFs), a class of crystalline porous polymers, are composed of organic molecular building blocks rich in light elements (such as carbon, hydrogen, oxygen, nitrogen, and boron) that form two-dimensional or three-dimensional crystal structures through condensation reactions, thereby constructing highly ordered periodic arrays. COFs have a regular and periodic pore structure, which not only has high thermal stability and large specific surface area, but also has the advantage of low density. Based on these excellent properties, they have shown extremely broad application prospects in many fields such as gas storage, photocatalysis, drug delivery, catalysis, and sensing, and have therefore attracted widespread attention from scientific researchers. Numerous studies have been published on the synthesis of COFs, encompassing a variety of methods, including room temperature, mechanical grinding, hot solvent, and microwave heating. However, the practical application of COFs remains limited. COFs possess a rich array of surface groups, and functional modification of these surface groups (e.g., with phenylboronic acid) can significantly expand their application. Commonly used modification methods include one-pot, post-modification, and ligand preassembly. Phenylboronic acid can complex with vicinal diols, resulting in modified COFs with specificity for these compounds. However, applications based on the inherent morphological characteristics of COFs remain largely unexplored. The room-temperature synthesis of COFs, combined with post-modification of their surface groups (e.g., with phenylboronic acid), allows for the selective recognition and adsorption of specific compounds, such as vicinal diols. This approach, combining the intrinsic adsorption properties of COFs with their unique morphological properties, promises to open up new applications. Summary of the Invention

[0003] Technical Problem to be Solved: This invention provides a method for preparing phenylboronic acid-functionalized sea urchin-like COFs and their applications. TTA-DVA-COFs are synthesized via an ammonia-aldehyde condensation reaction using the amino ligand 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TTA) and the aldehyde ligand 2,5-divinyl-1,4-benzenedicarboxaldehyde (DVA). These COFs are then post-modified with 4-mercaptophenylboronic acid to synthesize sea urchin-like COFs. The surface morphology of the COFs is regulated by acetic acid concentration, allowing the synthesis of functional sea urchin COFs with varying morphologies. These COFs not only exhibit mechanical bactericidal properties but also adsorb pollutants with vicinal diol structures in water.

[0004] Technical solution: A phenylboronic acid functionalized sea urchin-like COFs material is prepared by synthesizing TTA-DVA-COFs from the amino ligand 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TTA) and the aldehyde ligand 2,5-divinyl-1,4-benzenedicarboxaldehyde (DVA), and then post-modifying with 4-mercaptophenylboronic acid to synthesize the sea urchin COFs material. The preparation method of the phenylboronic acid functionalized sea urchin-shaped COFs material comprises the following steps: S1. Preparation of COFs material initial product: amino ligand TTA and aldehyde ligand DVA are dispersed in acetonitrile solution, ultrasonically mixed to obtain solution A, acetic acid is added to solution A and shaken to obtain mixed solution B, and mixed solution B is reacted to obtain COFs material initial product; S2. Preparation of sea urchin COFs material: The initial product of COFs material is washed with tetrahydrofuran and ethanol, and then filtered. 4-mercaptophenylboronic acid and azobisisobutyronitrile are added, mixed evenly, and then dispersed in tetrahydrofuran solution for ultrasonic treatment to obtain a mixed suspension A. The mixed suspension A is then stirred to react in an anhydrous and oxygen-free environment, washed with N,N-dimethylformamide, tetrahydrofuran, and acetone, and filtered and vacuum-dried to obtain the sea urchin COFs material. Preferably, the concentration of TTA and DVA in step S1 is 2-20 nmol / L. Preferably, the ultrasonic treatment time in step S1 is 10 to 15 minutes. Preferably, the concentration of acetic acid in step S1 is 12-17 mol / L. Preferably, the oscillation time in step S1 is 10 to 15 seconds. Preferably, the reaction temperature in step S1 is 23-25° C., and the reaction time is 70-72 h. Preferably, the mass ratio of 4-mercaptophenylboronic acid to the COFs primary product in step S2 is 1.8 to 2:1. Preferably, the mass ratio of azobis(ethylbutyronitrile) to the COFs primary product in step S2 is 1 to 1.5:10. Preferably, the ultrasonic treatment time in step S2 is 10 to 15 minutes. Preferably, the stirring reaction temperature in step S2 is 65-70° C., and the reaction time is 22-24 h. Preferably, the vacuum drying time in step S2 is 11 to 12 hours. The application of the above-mentioned phenylboronic acid functionalized sea urchin COFs material in sterilization and adsorption of water pollutants. The above-mentioned phenylboronic acid functionalized sea urchin COFs material is used to adsorb pollutants with vicinal diol structures in water bodies. Beneficial effects: 1. This invention enables precise control of the morphology of sea urchin-like COFs by adjusting the temperature and acetic acid concentration of the reaction system. This controllable synthesis method offers the following significant advantages: First, by precisely controlling the reaction conditions, nanoneedle-like structures with varying aspect ratios and high hardness can be produced, imparting mechanical bactericidal properties. Second, morphology manipulation simultaneously optimizes the material's pore size distribution and specific surface area, enhancing toxin adsorption and increasing adsorption capacity. This morphology manipulation strategy is not only simple to operate but also allows for tailoring material properties to specific water purification requirements, demonstrating significant technical advantages and application flexibility. 2. The phenylboronic acid-modified sea urchin-like COFs material prepared by the present invention can directly destroy bacterial cell structures through physical methods, such as nanoscale mechanical puncture and cell membrane tearing. This physical sterilization method is completely different from the biochemical action mechanism of traditional antibiotics, fundamentally avoiding the possibility of bacteria developing drug resistance through genetic mutation. In addition, this mechanical sterilization method is not limited by water quality conditions and has stable and reliable sterilization performance. The phenylboronic acid-modified sea urchin-like COFs material can not only specifically adsorb pollutants with a diol structure, but also has excellent toxin adsorption capacity, which can simultaneously remove endotoxins, heavy metal ions and organic pollutants in water, achieving "sterilization-purification" in one step. This synergistic effect greatly improves water treatment efficiency and simplifies the cumbersome process of traditional multi-stage treatment. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 Schematic diagram of the structure of amino ligand TTA and aldehyde ligand DVA; Figure 2 Schematic diagram of the synthesis routes of sea urchin COFs materials with different morphologies; Figure 3 SEM images of COFs materials prepared in Examples 1 to 3 and Comparative Examples 1 and 7 to 8; Figure 4 Young's modulus force curves of sea urchin COFs materials with different morphologies prepared in Examples 1 to 3; Figure 5 X-ray diffraction patterns of COFs materials prepared in Examples 1 to 3 and Comparative Example 1; Figure 6 Infrared absorption spectra (FTIR) of the COFs materials prepared in Examples 1 to 3 and Comparative Example 1; Figure 7 The specific surface area and pore size of the COFs materials prepared in Examples 1 to 3 and Comparative Example 1; Figure 8 XPS of COFs materials prepared in Examples 1 to 3 and Comparative Example 1; Figure 9 The sterilization effects of Examples 4 to 18 and Comparative Examples 2 to 6 are as follows; Figure 10 Electron microscopic images of Escherichia coli treated with sea urchin COFs materials with different morphologies prepared in Examples 1 to 3; Figure 11 Active oxygen staining of the sea urchin COFs materials with different morphologies prepared in Examples 1 to 3 after sterilization; Figure 12 This is the adsorption effect of Examples 19 to 33 on other substances. DETAILED DESCRIPTION The present invention will be further described below in conjunction with examples, which are provided to explain the present invention and are not limited to the following examples: Example 1 This example is the preparation of a sea urchin COFs material (UCOF-R) modified with phenylboronic acid at an acetic acid concentration of 12 mol / L, comprising the following steps: S1. Preparation of the primary product of COFs material: Disperse TTA and DVA in acetonitrile and shake well. Ultrasonicate for 15 minutes until the mixture is completely dissolved to obtain a mixed solution A, wherein the concentration of TTA is 4 mmol / L and the concentration of DVA is 3 mmol / L. Add 0.8 mL of 12 mol / L acetic acid solution to the mixed solution A, and rapidly shake for 15 seconds to obtain a mixed solution B. The mixed solution B is reacted at 25°C for 72 hours to obtain the primary product of COFs. S2. Preparation of sea urchin COFs material: The primary product of COFs material was washed with tetrahydrofuran and ethanol three times, and the solid product was collected. It was mixed with 4-mercaptophenylboronic acid in a mass ratio of 1:2, and 8 mg of azobisisobutyronitrile was added. After mixing evenly, the mixture was dispersed in tetrahydrofuran solution. The mixed solution was ultrasonically treated for 15 minutes to obtain a mixed suspension A. The mixed suspension A was stirred at 5000 rpm for 24 hours in an anhydrous and oxygen-free environment at 65°C to obtain the primary product of sea urchin COFs; the primary product of sea urchin COFs material was filtered and washed with N,N-dimethylformamide, tetrahydrofuran and acetone three times, and the solid product was collected. It was then vacuum dried at 60°C for 12 hours to obtain the sea urchin COFs material UCOF-R. Example 2 The difference between this embodiment and embodiment 1 is that the sea urchin COFs material UCOF-H is prepared when the acetic acid concentration in this embodiment is 15 mol / L. Example 3 The difference between this embodiment and embodiment 1 is that the sea urchin COFs material UCOF-S is prepared in this embodiment with an acetic acid concentration of 17 mol / L. Example 4 This example is a test of the sterilization performance of sea urchin COFs material UCOF-R against Escherichia coli, comprising the following steps: S1. Activation and cultivation of E. coli: E. coli was cultured in liquid culture medium at 37°C and 150 rpm for 12 h until its concentration reached 1×10 8 ~10 9 CFU / mL, the bacterial suspension was centrifuged at 9700 × g for 5 min to collect the bacteria, washed 2 to 3 times with sterile deionized water, and then diluted to adjust the concentration of E. coli to ×10 6 ~10 7 CFU / mL; S2. Testing the bactericidal properties of the UCOF-R material: 1 mL of diluted E. coli was transferred to a 1.5 mL centrifuge tube. 0.5 mg of the UCOF-R material was slowly added. The tube was allowed to stand for 15 minutes, and the bacterial concentration was measured. S3. Quantitative analysis: 0.2 mL of the liquid before and after treatment with UCOF-R material was diluted with sterile deionized water for 10 4 Take 0.2 mL of the diluted liquid and spread it on the culture medium. The culture medium was incubated at 37°C for 18 hours and the number of colonies on the culture dish was counted. The number of colonies on each culture dish was multiplied by 10. 4 , the bacterial concentration in the water sample can be obtained. Example 5 The difference between this embodiment and embodiment 4 is that the sea urchin COFs material used in this embodiment is UCOF-H. Example 6 The difference between this embodiment and embodiment 4 is that the sea urchin COFs used in this embodiment are made of material UCOF-S. Example 7 This example is a test of the sterilization performance of sea urchin COFs material UCOF-R against Salmonella, and the specific process is the same as that of Example 4. Example 8 The difference between this embodiment and embodiment 7 is that the sea urchin COFs material used in this embodiment is UCOF-H. Example 9 The difference between this embodiment and embodiment 7 is that the sea urchin COFs material used in this embodiment is UCOF-S. Example 10 This example is a test of the sterilization performance of sea urchin COFs material UCOF-R against Klebsiella pneumoniae, and the specific process is the same as that of Example 4. Example 11 The difference between this embodiment and embodiment 10 is that the sea urchin COFs material used in this embodiment is UCOF-H. Example 12 The difference between this embodiment and Example 10 is that the sea urchin COFs material used in this embodiment is UCOF-S. Example 13 This example is a test of the sterilization performance of sea urchin COFs material UCOF-R against Pseudomonas aeruginosa, and the specific process is the same as that of Example 4. Example 14 The difference between this embodiment and Example 13 is that the sea urchin COFs material used in this embodiment is UCOF-H. Example 15 The difference between this embodiment and Example 13 is that the sea urchin COFs material used in this embodiment is UCOF-S. Example 16 This example is a test of the sterilization performance of sea urchin COFs material UCOF-R against Acinetobacter baumannii, and the specific process is the same as that of Example 4. Example 17 The difference between this embodiment and Example 16 is that the sea urchin COFs material used in this embodiment is UCOF-H. Example 18 The difference between this embodiment and Example 16 is that the sea urchin COFs material used in this embodiment is UCOF-S. Example 19 This example tests the adsorption performance of UCOF-S, a sea urchin COF material, for lipopolysaccharide (LPS). The specific process is as follows: 10 mg of sea urchin COF material UCOF-S was added to 10 mL of a 100 μg / L LPS aqueous solution and mixed evenly. After centrifugation and washing, the residual substance in the aqueous solution was quantitatively analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES), ultraviolet analysis, fluorescence analysis, and liquid chromatography at regular intervals until equilibrium was reached. The amount of substance adsorbed at equilibrium was calculated according to the mass balance equation: qe = V(C0 - Ce) / m, where qe (mg / g) is the amount of adsorbent adsorbed per gram at equilibrium, C0 (mg / mL) is the initial concentration of the substance in the aqueous solution, Ce (mg / mL) is the concentration of the final solution at equilibrium, and m (g) is the mass of the adsorbent used. Example 20 This example tests the adsorption performance of sea urchin COFs material UCOF-S on microcystin-LR (MC-LR), and the specific process is the same as Example 19. Example 21 This example tests the adsorption performance of sea urchin COFs material UCOF-S on DNA, and the specific process is the same as Example 19. Example 22 This example tests the adsorption performance of sea urchin COFs material UCOF-S on humic acid (HA), and the specific process is the same as Example 19. Example 23 This example tests the adsorption performance of sea urchin COFs material UCOF-S on perfluorooctanoic acid (PFOA), and the specific process is the same as Example 19. Example 24 This example tests the adsorption performance of sea urchin COFs material UCOF-S on imidacloprid, and the specific process is the same as that of Example 19. Example 25 This example tests the adsorption performance of sea urchin COFs material UCOF-S on triadimefon, and the specific process is the same as that of Example 19. Example 26 This example tests the adsorption performance of sea urchin COFs material UCOF-S on malachite green, and the specific process is the same as Example 19. Example 27 This example tests the adsorption performance of sea urchin COFs material UCOF-S on naphthalene, and the specific process is the same as Example 19. Example 28 This example tests the adsorption performance of sea urchin COFs material UCOF-S on phenol, and the specific process is the same as Example 19. Example 29 This example tests the adsorption performance of sea urchin COFs material UCOF-S for lead (Pb), and the specific process is the same as that of Example 19. Example 30 This example tests the adsorption performance of sea urchin COFs material UCOF-S on chromium (Cr), and the specific process is the same as Example 19. Example 31 This example tests the adsorption performance of sea urchin COFs material UCOF-S on cadmium (Cd), and the specific process is the same as Example 19. Example 32 This example tests the adsorption performance of sea urchin COFs material UCOF-S for mercury (Hg), and the specific process is the same as Example 19. Example 33 This example tests the adsorption performance of sea urchin COFs material UCOF-S on arsenic (As), and the specific process is the same as Example 19. Comparative Example 1 The difference between this comparative example and Example 1 is that in this comparative example, the amino ligand TTA is replaced by 1,3,5-tris(4-aminopheny l)benzene (TPB) to prepare the COFs material SCOF. Comparative Example 2 This comparative example is a test of the sterilization performance of SCOF material against Escherichia coli, and the specific process is the same as that of Example 4. Comparative Example 3 This comparative example is a test of the sterilization performance of SCOF material against Salmonella, and the specific process is the same as that of Example 4. Comparative Example 4 This comparative example is a test of the sterilization performance of SCOF material against Klebsiella pneumoniae, and the specific process is the same as that of Example 4. Comparative Example 5 This comparative example is a test of the sterilization performance of the SCOF material against Pseudomonas aeruginosa, and the specific process is the same as that of Example 4. Comparative Example 6 This comparative example is a test of the sterilization performance of SCOF material against Acinetobacter baumannii, and the specific process is the same as that of Example 4. Comparative Example 7 The difference between this comparative example and Example 1 is that the concentration of acetic acid in this comparative example is 6 mol / L. Comparative Example 8 The difference between this comparative example and Example 1 is that the reaction temperature in this comparative example is 15°C. Figure 3 The SEM images of the sea urchin COFs materials with different morphologies prepared in Examples 1 to 3 and the COFs materials prepared in Comparative Examples 1, 7 and 8 are shown. Figure 3 As shown, the surface hardness of sea urchin COFs is affected by acetic acid concentration. Post-modification has little effect on the morphology of UCOF-R (Example 1), UCOF-H (Example 2), and UCOF-S (Example 3). SCOF (Comparative Example 1) also showed no morphological changes after the above process. If the acetic acid concentration is less than 12 mol / L (Comparative Example 7) or the reaction temperature is not optimal (Comparative Example 8), the prepared COFs do not have sea urchin morphology and lack mechanical sterilization ability. Figure 4 The Young's modulus force curves of sea urchin COFs materials with different morphologies prepared in Examples 1 to 3 are shown in FIG. Figure 4 As shown in Figure 3, with the increase of acetic acid concentration, the surface of sea urchin COFs material gradually softens. Figure 5 The X-ray diffraction patterns of sea urchin COFs materials with different morphologies prepared in Examples 1 to 3 and the SCOF material prepared in Comparative Example 1 are shown. Figure 5As shown, the XRD curve before and after modification with 4-mercaptophenylboronic acid has a slight rightward shift. This is because the modification of the phenylboronic acid group causes the interplanar spacing of the COFs material to decrease, causing the curve to shift to the right. The sea urchin COFs material has a strong diffraction peak at 2.8 (2θ), indicating that sea urchin COFs materials with different morphologies were successfully synthesized at different acetic acid concentrations. The diffraction peak of the SCOF material (Comparative Example 1) also has a slight rightward shift before and after modification with phenylboronic acid. The crystallinity is not lost much before and after modification, proving that the SCOF material was successfully synthesized. Figure 6 The infrared absorption spectra (FTIR) of the sea urchin COFs materials with different morphologies prepared in Examples 1 to 3 and the SCOF material prepared in Comparative Example 1 are shown. Figure 6 As shown in a, the infrared spectra of the COFs materials synthesized under three different acetic acid concentrations are basically the same. The -NH of the amino ligand TTA (3457 and 3322 cm -1 ) stretching vibration and the -CH(2920 and 2857 cm) of the aldehyde ligand DVA -1 ) stretching vibration and -C=O(1694cm - 1) Stretching vibration does not appear in COFs materials. -1 A new peak appeared, which is the -C=N- peak, indicating that the two ligands successfully formed COFs materials through the ammonia-aldehyde condensation reaction; Figure 6 As shown in b, 1075cm -1 The emergence of the new peak -CS- can well illustrate the successful modification of 4-mercaptophenylboronic acid. Figure 7 The specific surface area and pore size of the sea urchin COFs materials with different morphologies prepared in Examples 1 to 3 and the SCOF material prepared in Comparative Example 1. Figure 7 As shown in the figure, with the increase of acetic acid concentration, the specific surface area of ​​sea urchin COFs material gradually increases, which is related to the size change of sea urchin COFs material. With the increase of acetic acid concentration, the diameter of a single sea urchin ball will become smaller; the pore size of sea urchin COFs material has basically not changed, and remains at about 1.7nm. This is because the three COFs materials have the same structural formula. The SCOF (Comparative Example 1) has a different structure, and a pore structure of 2.58nm is present. Figure 8 The XPS graphs of sea urchin COFs materials with different morphologies prepared in Examples 1 to 3 and the SCOF material prepared in Comparative Example 1 are shown. Figure 8 As shown in the figure, C 1s, O 1s, and N 1s are the characteristic peaks of COFs, which can indicate that the COFs material is successfully synthesized. In contrast, two new peaks, B1s and S2p, appear after modification, which is caused by the modification of 4-mercaptophenylboronic acid. Figure 9The bactericidal effects of different COFs materials in Examples 4 to 18 and Comparative Examples 2 to 6 are shown. Figure 9 As shown, compared with SCOF (Comparative Examples 2 to 6), the three sea urchin-like COFs materials (Examples 4 to 18) all exhibited relatively considerable bactericidal effects. Combining the Young's modulus of the three sea urchin-like COFs materials, we found that UCOF-S with a small modulus exhibited a better bactericidal effect. Figure 10 Electron micrographs of Escherichia coli treated with sea urchin COFs of different morphologies prepared in Examples 1 to 3. Figure 10 As shown, all three materials exhibited a strong ability to capture E. coli, which was due to the binding of phenylboronic acid on the surface of the material to the diol structure on the surface of the bacterial membrane, and a large number of holes appeared on the surface of the bacteria, which was the effect of mechanical force. Figure 11 The active oxygen staining of the sterilized sea urchin COFs with different morphologies prepared in Examples 1 to 3. Figure 11 As shown, the red fluorescence observed from the sea urchin spines upon contact with bacteria indicates a significant increase in intracellular reactive oxygen species (ROS) levels. In E. coli, the urchin-like covalent organic framework's spikes cleave electron transport chain complex I and oxidative stress defense proteins, generating ROS that rapidly kill the bacteria. Although superoxide anions are typically non-cytotoxic, fluorescence microscopy imaging shows that they can be rapidly converted into cytotoxic intermediates, including peroxides. Figure 12 The adsorption effect of sea urchin COFs material UCOF-S on other substances in Examples 19 to 33 is shown. Figure 12 As shown in the figure, the initial concentrations of 15 pollutants including lipopolysaccharide LP (Example 19), microcystin-LR (Example 20), DNA, humic acid HA (Example 21), perfluorooctanoic acid PFOA (Example 23), imidacloprid (Example 24), triadimefon (Example 25), malachite green (Example 26), naphthalene (Example 27), phenol (Example 28), lead (Example 29), chromium (Example 30), cadmium (Example 31), mercury (Example 32), and arsenic (Example 33) were set to 100 μg / L. After adsorption by UCOF-S, the water quality containing these pollutants met the drinking water standard. The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Any person skilled in the art can, without departing from the spirit and technical solution of the present invention, use the methods and technical contents disclosed above to make many possible changes and modifications to the technical solution of the present invention, or modify it into an equivalent embodiment with equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention shall still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A phenylboronic acid functionalized sea urchin COFs material, characterized by: The COFs material has a sea urchin-like structure and has radially distributed nano needle-like or thorn-like protrusions.

2. The phenylboronic acid functionalized sea urchin COFs material according to claim 1, characterized in that: The COFs material is based on a covalent organic framework and is modified with phenylboronic acid groups.

3. The method for preparing the phenylboronic acid functionalized sea urchin COFs material according to claim 1 or 2, characterized in that: The following steps are involved: S1. Preparation of COFs material initial product: amino ligand and aldehyde ligand are dispersed in acetonitrile solution, ultrasonically mixed and then added with acetic acid and shaken to obtain COFs material initial product after reaction; S2. Preparation of sea urchin COFs material: The initial product of COFs material was washed with tetrahydrofuran and ethanol and then filtered. 4-mercaptophenylboronic acid and azobisisobutyronitrile were added, mixed evenly and dispersed in tetrahydrofuran solution for ultrasonic treatment. The mixture was stirred and reacted in an anhydrous and oxygen-free environment. The product was washed with N,N-dimethylformamide, tetrahydrofuran and acetone. The sea urchin COFs material was obtained after filtration and vacuum drying.

4. The preparation method according to claim 3, wherein: In step S1, the amino ligand is 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, and the aldehyde ligand is 2,5-divinyl-1,4-benzenedicarboxaldehyde; and / or, The concentration of the amino ligand and the aldehyde ligand in step S1 is 2 to 20 nmol / L; and / or, The ultrasonic treatment time in step S1 is 10 to 15 minutes; and / or, The acetic acid concentration in step S1 is 12 to 17 mol / L; and / or, The oscillation time in step S1 is 10 to 15 seconds; and / or, The reaction temperature in step S1 is 23-25° C. and the reaction time is 70-72 h; and / or, The mass ratio of 4-mercaptophenylboronic acid to the COFs primary product in step S2 is 1.8 to 2:1; and / or, The mass ratio of azobis(ethylbutyronitrile) to the COFs primary product in step S2 is 1 to 1.5:10; and / or, The ultrasonic treatment time in step S2 is 10 to 15 minutes; and / or, The stirring reaction temperature in step S2 is 65-70° C. and the reaction time is 22-24 h; and / or, The vacuum drying time in step S2 is 11 to 12 hours.

5. Use of the phenylboronic acid functionalized sea urchin COFs material according to claim 1 or 2 in sterilization and adsorption of water pollutants.

6. Use of the phenylboronic acid functionalized sea urchin COFs material according to claim 1 or 2 in adsorbing pollutants with vicinal diol structures in water.

7. The use according to claim 5, characterized in that: The bacteria are any one or more of Escherichia coli, Salmonella, Klebsiella pneumoniae, Pseudomonas aeruginosa, and Acinetobacter baumannii.

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