A phenyl ether-based bimetallic organic framework antifouling material and a preparation method thereof

Abstract

The application discloses a phenyl ether-based bimetallic organic framework antifouling material and a preparation method thereof, and relates to the technical field of functional antifouling MOF materials. The phenyl ether-based bimetallic organic framework antifouling material has a three-dimensional porous network structure and is self-assembled by a phenyl ether-based organic ligand and two different metal ions through coordination bonds. 2+ The two different metal ions are selected from any two of copper ions Cu 2+ , zinc ions Zn 2+ , cobalt ions Co 2+ , and nickel ions Ni . By introducing a phenyl ether-based benzotriazole organic ligand into the MOF structure, the hydrophobicity of the material surface is improved as a whole, and the initial attachment tendency of marine organisms on the material surface is effectively weakened.

Description

Technical Field

[0001] This invention relates to the field of functional antifouling MOF materials technology, specifically to a phenyl ether-based bimetallic organic framework antifouling material and its preparation method. Background Technology

[0002] Marine biofouling is a long-standing and serious challenge in the field of marine engineering. It refers to the formation of complex biofouling layers caused by the attachment and growth of microorganisms, algae, shellfish, barnacles, and other marine organisms on the surfaces of ships, offshore platforms, aquaculture cages, and other marine facilities. This phenomenon not only increases ship drag, fuel consumption, and accelerates equipment corrosion and aging, but also clogs aquaculture cage mesh, affects the normal operation of marine instruments and equipment, and causes huge economic losses to shipping, marine development, and aquaculture industries. At the same time, it also exacerbates the burden on the marine ecological environment.

[0003] To address the problem of marine biofouling, antifouling coatings have become the most widely used protective measure. Traditional antifouling coatings mainly rely on antifouling agents containing toxic substances such as mercury, lead, and organotin compounds, which inhibit biofouling by continuously releasing toxic components. However, while these toxic antifouling agents play a role in preventing biofouling, they also severely pollute the marine ecosystem, endangering the survival and reproduction of marine life, and even affecting human health through the food chain. With increasingly stringent environmental regulations and growing awareness of ecological protection, the development of environmentally friendly, efficient, and long-lasting new antifouling materials has become an urgent need for the industry.

[0004] Metal-organic frameworks (MOFs), as a novel type of functional material with a three-dimensional porous network structure, have shown great potential in the field of antifouling due to their advantages such as high specific surface area, controllable pore size, structural tunability, and good chemical stability. While MOF antifouling materials constructed with single metal ions possess certain antifouling properties, they still have shortcomings in terms of long-term antifouling effect, broad antibacterial spectrum, and environmental adaptability. Bimetallic organic frameworks, through the synergistic effect of two different metal ions, can optimize the electronic structure, porosity, and surface properties of the material, thereby improving antifouling efficacy and stability.

[0005] The phenyl ether functional group possesses excellent chemical stability, hydrophobicity, and biocompatibility. Introducing it into organic ligands to construct MOF materials holds promise for enhancing their resistance to marine environmental erosion and antifouling performance. Currently, research on phenyl ether-based bimetallic organic framework antifouling materials is not yet fully developed, and existing MOF antifouling materials still suffer from limitations such as a single antifouling mechanism and unsatisfactory practical application results. Therefore, developing a structurally controllable and high-performance phenyl ether-based bimetallic organic framework antifouling material is of significant practical importance for promoting the upgrading and development of marine antifouling technology and reducing the harm caused by marine biofouling. Summary of the Invention

[0006] The purpose of this invention is to address the problems existing in the prior art by providing a phenyl ether-based bimetallic organic framework antifouling material and its preparation method. This invention provides a phenyl ether-based bimetallic organic framework antifouling material with controllable structure and excellent hydrophobicity (water contact angle greater than 90°). Through the synergistic effect of the bimetallic components and the characteristics of the phenyl ether ligands, it achieves efficient, environmentally friendly, and long-lasting antifouling performance, suitable for marine environment applications.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is: a phenyl ether-based bimetallic organic framework antifouling material, wherein the material has a three-dimensional porous network structure and is formed by the self-assembly of phenyl ether-based organic ligands and two different metal ions through coordination bonds; The two different metal ions are selected from copper ions (Cu). 2+ Zinc ions (Zn) 2+ Cobalt ions (Co) 2+ Nickel ions Ni 2+ Any two of them; The phenyl ether organic ligand is a benzotriazole-bridged isophthalic acid derivative; The phenyl ether organic ligand is a compound represented by Formula 1; Formula 1 ; In Formula 1, R1 and R2, which may be the same or different, are selected from any one of hydrogen and alkyl groups having 1-5 carbon atoms; Or R1 and R2 in Formula 1 may fuse to form a six-membered aromatic ring; The phenyl ether-based organic ligand is a benzotriazole-bridged isophthalic acid derivative.

[0008] Furthermore, the two different metal ions are any one of copper-zinc Cu-Zn, copper-cobalt Cu-Co, or copper-nickel Cu-Ni, and the molar ratio of the two metal ions is from 1:0.1 to 1:10.

[0009] Furthermore, the benzotriazole-bridged isophthalic acid derivative is any one of 4-(2-(2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid, 4-(2-(5,6-dimethyl-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid, and 4-(2-(2H-naphtho[2,3-d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid.

[0010] Furthermore, the structure of the 4-(2-(2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid is as follows: .

[0011] Furthermore, the structure of the 4-(2-(5,6-dimethyl-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid is as follows: .

[0012] Furthermore, the structure of the 4-(2-(2H-naphtho[2,3-d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid is as follows: .

[0013] Furthermore, the antifouling material has a water contact angle greater than 90°.

[0014] A method for preparing a phenyl ether-based bimetallic organic framework antifouling material includes the following steps: (1) Solution preparation: Dissolve the phenyl ether organic ligand in an organic solvent to form a ligand solution, and dissolve two different metal salts in solvent A to form a mixed metal salt solution; (2) Mixing: The ligand solution and the mixed metal salt solution are mixed evenly to obtain a precursor solution; (3) Solvothermal reaction: The precursor solution is placed in a closed reaction vessel and a solvothermal reaction is carried out. After the reaction is completed, it is cooled to room temperature. (4) Post-processing: The reaction product is centrifuged and washed alternately with organic solvent and deionized water. After vacuum drying and activation, the phenyl ether-based bimetallic organic framework antifouling material is obtained.

[0015] Furthermore, the metal salt mentioned in step (1) is a metal nitrate, chloride, acetate, or sulfate.

[0016] Furthermore, the organic solvent is selected from one or more mixtures of N,N-dimethylformamide, N,N-diethylformamide, ethanol, methanol, or acetone; Solvent A is deionized water.

[0017] Furthermore, in step (3), the temperature of the solvothermal reaction is 80°C to 160°C, and the reaction time is 12 hours to 72 hours; In step (2), the ratio of the total number of moles of metal ions to the number of moles of ligands in the mixed precursor solution is 1:0.5 to 1:3.

[0018] A marine antifouling coating comprises the above-mentioned phenyl ether-based bimetallic organic framework antifouling material as an antifouling agent, as well as a film-forming resin, solvent, and additives.

[0019] Furthermore, the amount of the phenyl ether-based bimetallic organic framework antifouling material added to the coating is 1% to 20% by weight.

[0020] This invention precisely addresses the technical problems of toxic pollution in traditional antifouling materials, insufficient long-term effectiveness of single MOF antifouling materials, narrow antibacterial spectrum, and poor environmental adaptability through the synergistic formulation of a phenyl ether-based organic ligand with two specific metal ions. The phenyl ether-based organic ligand (benzotriazole-bridged isophthalic acid derivative) possesses excellent chemical stability, hydrophobicity (ensuring a water contact angle greater than 90°), and biocompatibility, enhancing the material's resistance to marine environmental erosion while reducing initial attachment of marine organisms through its hydrophobic properties; the two ligands are selected from Cu... 2+ Zn 2+ Co 2+ Ni 2+ The metal ions (preferably a combination of Cu-Zn, Cu-Co, and Cu-Ni, with a molar ratio of 1:0.1 to 1:10) form a bimetallic synergistic effect, optimizing the electronic structure and porosity of the material, broadening the antibacterial spectrum and improving the long-term antifouling effect, thus avoiding the performance limitations of single-metal MOFs. At the same time, the ratio of the total molar number of metal ions to the molar number of ligands of 1:0.5 to 1:3, combined with the solvothermal reaction process, ensures that the material forms a three-dimensional porous network with controllable structure, further enhancing hydrophobicity and antifouling activity, and ultimately achieving an environmentally friendly, efficient, and long-lasting antifouling effect, which is suitable for the stringent requirements of marine environments for antifouling materials.

[0021] Compared with the prior art, the beneficial effects of the present invention are: 1) By introducing phenyl ether benzotriazole organic ligands into the MOF structure, the overall hydrophobicity of the material surface is improved, effectively weakening the initial attachment tendency of marine organisms to the material surface; 2) The MOF framework is constructed using a bimetallic structure, which shows a more stable and synergistic enhancement in antibacterial and algae-inhibiting properties compared to a single metal system, and provides a more comprehensive antifouling effect. 3) While maintaining a good crystalline structure and stability, the material achieves a synergistic improvement in hydrophobicity, antifouling activity and environmental adaptability, which is conducive to obtaining a more durable and balanced comprehensive antifouling effect. Attached Figure Description

[0022] Figure 1 The images show the XRD patterns of the MOF materials prepared in Examples 1 to 5 and Comparative Examples 1 to 4 of this invention.

[0023] Figure 2 The static water contact angle on the hydrophobic surface of the MOF material prepared in Example 1 of this invention; In the figure: (a) is a representative image of a water droplet with angle measurement marks, and (b) is the statistical distribution of contact angles obtained from multiple measurements. Detailed Implementation

[0024] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely 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.

[0025] Preparation Example 1 Preparation of 4-(2-(2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid: ; At room temperature, 5 g of 4-(2-bromophenoxy)isophthalic acid, 2.65 g of 2H-benzo[d][1,2,3]triazole, 16.91 g of cesium carbonate, and 0.53 g of 1,10-phenanthroline were added sequentially to a dry reaction vessel. The mixture was evacuated three times with nitrogen purging, and then 0.28 g of cuprous iodide and 60 ml of DMSO were added. After thorough mixing, the temperature was raised to 110 °C and stirred for 12 h, during which nitrogen gas was continuously introduced. The reaction solution was then cooled to room temperature. Add to 300 mL of water, filter with diatomaceous earth, extract the aqueous phase with ethyl acetate (100 mL × 2), slowly add 2 mol / L hydrochloric acid to the aqueous phase with stirring to adjust the pH to 2-3, filter and collect the solid, wash the filter cake with water until neutral, dissolve the crude product in 50 mL of hot ethanol, decolorize with activated carbon, cool and crystallize, filter, dry to obtain 4.21 g of 4-(2-(2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid; Mass spectrometry (MS+H) of 4-(2-(2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid + 376.

[0026] Preparation Example 2 Preparation of 4-(2-(5,6-dimethyl-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid: ; Following the preparation method of Preparation Example 1, the 2H-benzo[d][1,2,3]triazole was replaced with 5,6-dimethyl-2H-benzo[d][1,2,3]triazole, and the rest remained the same as in Preparation Example 1; Mass spectrometry (MS+H) of 4-(2-(5,6-dimethyl-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid + :404.

[0027] Preparation Example 3 Preparation of 4-(2-(2H-naphtho[2,3-d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid: ; Following the preparation method of Preparation Example 1, the 2H-benzo[d][1,2,3]triazole was replaced with 2H-naphtho[2,3-d][1,2,3]triazole, and the rest remained the same as in Preparation Example 1; Mass spectrometry (MS+H) of 4-(2-(2H-naphtho[2,3-d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid + :426.

[0028] Example 1 Preparation of a phenyl ether-based bimetallic organic framework antifouling material: 1. Raw material components: (1) Phenyl ether organic ligand: 375 mg (1 mmol) of 4-(2-(2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid prepared in Preparation Example 1 was used; (2) Metal salts: Copper nitrate trihydrate (Cu(NO3)2·3H2O) 120.8 mg (0.5 mmol), zinc nitrate hexahydrate (Zn(NO3)2·6H2O) 148.6 mg (0.5 mmol); (Note: The total number of moles of metal ions is 1 mmol, and the Cu:Zn molar ratio is 1:1). (3) Solvents: 15 mL of N,N-dimethylformamide (DMF), 5 mL of ethanol, and 5 mL of deionized water.

[0029] 2. Preparation method: (1) Solution preparation: Dissolve 375 mg of phenyl ether organic ligand in a mixed organic solvent containing 15 mL of N,N-dimethylformamide and 5 mL of ethanol, and sonicate for 10 minutes at a frequency of 40 kHz and a power of 200 W to completely dissolve it, forming a ligand solution; Separately, dissolve 120.8 mg of copper nitrate trihydrate and 148.6 mg of zinc nitrate hexahydrate in 5 mL of deionized water, and stir at a speed of 500 r / min until completely dissolved to form a mixed metal salt solution; (2) Mixing: Under magnetic stirring at a speed of 600 r / min, the mixed metal salt solution is slowly added dropwise to the ligand solution. After the addition is complete, the mixture is stirred at the same speed for 30 minutes to make the solution evenly mixed and obtain a clear or slightly turbid precursor solution. (3) Solvent thermal reaction: The above precursor solution was transferred to a 50mL stainless steel reactor lined with polytetrafluoroethylene, sealed and placed in a forced-air drying oven. The temperature was increased to 120℃ at a rate of 2℃ / min and kept constant for 48 hours. After the reaction was completed, the oven power was turned off and the reactor was allowed to cool naturally to room temperature. (4) Post-processing: Open the reactor and transfer the reaction solution to a centrifuge tube. Centrifuge at 8000 r / min for 5 minutes to collect the solid product at the bottom. Wash the solid product three times with N,N-dimethylformamide (DMF) to remove unreacted organic ligands, and then wash it three times with anhydrous ethanol to replace the high-boiling-point solvent in the channels. Each wash requires ultrasonic dispersion for 5 minutes and centrifugation again. Finally, wash it three times with deionized water. Place the washed solid in a vacuum drying oven and activate it by vacuum drying at a vacuum degree of -0.1 MPa and a temperature of 80℃ for 12 hours. The final product is a powdery solid, which is a phenyl ether-based bimetallic organic framework antifouling material (denoted as Cu / Zn-BTP-MOF-1).

[0030] Example 2 The preparation of a phenyl ether-based bimetallic organic framework antifouling material was carried out according to the preparation method of Example 1, except that the phenyl ether-based organic ligand was replaced with 4-(2-(5,6-dimethyl-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid (403 mg, 1 mmol) obtained in Preparation Example 2, while the rest remained the same as in Example 1. The final product was a phenyl ether-based bimetallic organic framework antifouling material (denoted as Cu / Zn-BTP-MOF-2).

[0031] Example 3 The preparation of a phenyl ether-based bimetallic organic framework antifouling material was carried out according to the preparation method of Example 1, except that the phenyl ether-based organic ligand was replaced with 4-(2-(2H-naphtho[2,3-d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid (425 mg, 1 mmol) obtained in Preparation Example 3, while the rest remained the same as in Example 1. The final product was a phenyl ether-based bimetallic organic framework antifouling material (denoted as Cu / Zn-BTP-MOF-3).

[0032] Example 4 A phenyl ether-based bimetallic organic framework antifouling material was prepared by referring to the preparation method of Example 1, except that the metal salts were replaced with 120.8 mg (0.5 mmol) of copper nitrate trihydrate (Cu(NO3)2·3H2O) and 145.5 mg (0.5 mmol) of cobalt nitrate hexahydrate (Co(NO3)2·6H2O), while the rest remained the same as in Example 1. The final product was a phenyl ether-based bimetallic organic framework antifouling material (denoted as Cu / Co-BTP-MOF).

[0033] Example 5 A phenyl ether-based bimetallic organic framework antifouling material was prepared by referring to the preparation method of Example 1, except that the metal salts were replaced with 120.8 mg (0.5 mmol) of copper nitrate trihydrate (Cu(NO3)2·3H2O) and 145.4 mg (0.5 mmol) of nickel nitrate hexahydrate (Ni(NO3)2·6H2O), while the rest remained the same as in Example 1. The final product was a phenyl ether-based bimetallic organic framework antifouling material (denoted as Cu / Ni-BTP-MOF).

[0034] Comparative Example 1 The preparation of a phenyl ether-based bimetallic organic framework antifouling material was carried out according to the preparation method of Example 1, except that the phenyl ether-based organic ligand was replaced with 4-phenoxyisophthalic acid, while the rest remained the same as in Example 1. The final product was a phenyl ether-based bimetallic organic framework antifouling material (denoted as Cu / Zn-BTP-MOF-D1).

[0035] Comparative Example 2 The preparation of a phenyl ether-based bimetallic organic framework antifouling material was carried out according to the preparation method of Example 1, except that the phenyl ether-based organic ligand was replaced with 4,4'-oxobenzoic acid, while the rest remained the same as in Example 1. The final product was a phenyl ether-based bimetallic organic framework antifouling material (denoted as Cu / Zn-BTP-MOF-D2).

[0036] Comparative Example 3 The preparation of a phenyl ether-based bimetallic organic framework antifouling material was carried out according to the preparation method of Example 1, except that copper nitrate trihydrate was not added, and the rest remained the same as in Example 1. The final product was a phenyl ether-based metal-organic framework antifouling material (denoted as Zn-BTP-MOF). (Note: The amount of zinc nitrate hexahydrate used was 1 mmol).

[0037] Comparative Example 4 The preparation of a phenyl ether-based bimetallic organic framework antifouling material was carried out according to the preparation method of Example 1, except that the metal salts were replaced with 120.8 mg (0.5 mmol) of copper nitrate trihydrate (Cu(NO3)2·3H2O) and 118.1 mg (0.5 mmol) of calcium nitrate tetrahydrate (Ca(NO3)2·4H2O), while the rest remained the same as in Example 1. The final product was a phenyl ether-based bimetallic organic framework antifouling material (denoted as Cu / Ca-BTP-MOF).

[0038] Performance testing: 1. MOF material characterization tests: XRD (X-ray diffraction) was used for testing; The XRD patterns of the MOF materials prepared in Examples 1 to 5 and Comparative Examples 1 to 4 are shown in the figure. Figure 1Examples 1 and 2-5 all exhibited sharp peaks, abundant characteristic peaks in the low-angle region, and relatively consistent peak positions within the 5–50° range, indicating good overall crystallinity of the samples and the formation of similar / isomorphic MOF frameworks under the "BTP-type ligand + Cu and second metal" system. In contrast, the diffraction peak groups corresponding to Comparative Examples 1 and 2 were significantly different from those of the examples, and were generally flatter with fewer characteristic peaks, indicating that the change in ligands led to changes in crystal phase / framework topology or a decrease in crystallinity. Comparative Example 3 still showed several clear diffraction peaks, but the peak shapes differed from those of the bimetallic samples, indicating that it was more likely to form MOFs with different metal nodes / different phases. The curve of Comparative Example 4 (Cu / Ca) showed a clear broad diffuse background and significantly weakened sharp peaks, indicating insufficient crystallization / partial amorphousness, suggesting that the target MOF framework was more difficult to construct stably under the "Cu / Ca substitution" condition.

[0039] 2. Surface wettability test (water contact angle): The MOF powder to be tested was pressed into a tablet, and a contact angle measuring instrument was used to apply 5 μL of deionized water to the sample surface at room temperature using the seat drop method. The droplet morphology was recorded by a CCD camera, and the contact angle between the droplet and the solid surface was measured within 5 seconds after the droplet was applied. The data are shown in Table 1.

[0040] 3. Antifouling activity test: 3.1 Typical marine fouling bacteria were selected: *Vibrio alginolyticus* and *Staphylococcus aureus*. Test method (inhibition zone method): The activated bacterial solution was diluted and spread onto a solid nutrient agar plate. 30 mg of the MOF powder to be tested was weighed and pressed into a 6 mm diameter disc under 10 MPa pressure, and then affixed to the center of the plate. A blank control group was also set up (containing only filter paper discs or solvent-pressed discs without MOF). After incubation at 37℃ for 36 hours, the diameter of the inhibition zone (mm) was measured using calipers. Each sample was tested in triplicate, and the average value was taken. The data are shown in Table 1.

[0041] 3.2 Anti-algae performance test: Test algae species: Chlorella vulgaris. Test method: Algal solution in the logarithmic growth phase was inoculated into Erlenmeyer flasks, and the initial algal cell density was adjusted to be uniform. The MOF material to be tested was added to a final concentration of 100 mg / L. The flasks were then statically cultured in a light incubator (temperature 25±1℃, light intensity 3000 Lux, light-dark ratio 12h:12h) for 72 hours, with shaking three times daily. After the culture, the number of algal cells was counted under a microscope using a hemocytometer, and the algae inhibition rate relative to the blank control group was calculated. The data are shown in Table 1.

[0042] Table 1 The overall results in Table 1 show that the MOF materials constructed using phenyl ether-based benzotriazole ligands and introducing bimetallic nodes exhibit a consistent and significant improvement trend in surface hydrophobicity, antibacterial properties, and algae-inhibiting properties. The water contact angle of the example samples is generally higher than that of the comparative samples, indicating enhanced surface hydrophobicity, which is beneficial for inhibiting the initial attachment of marine organisms. Simultaneously, its inhibitory ability against *Vibrio alginolyticus* and *Staphylococcus aureus* is significantly stronger than that of the comparative samples, and it maintains a stable antibacterial effect against different bacterial species, demonstrating the broadened antibacterial spectrum brought about by bimetallic synergy. In the antialgae test, the example samples also showed a more significant inhibitory effect on algal growth, corroborating the improvement trend in hydrophobicity and antibacterial properties. Overall, the data in Table 1 show good synergy among different performance indicators, indicating that the synergistic design of the phenyl ether-based ligand structure and bimetallic nodes can systematically improve the comprehensive antifouling performance of MOF materials.

[0043] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A phenyl ether-based bimetallic organic framework antifouling material, characterized in that, The material has a three-dimensional porous network structure and is formed by the self-assembly of a phenyl ether-based organic ligand and two different metal ions through coordination bonds. The two different metal ions are selected from copper ions (Cu). 2+ Zinc ions (Zn) 2+ Cobalt ions (Co) 2+ Nickel ions Ni 2+ Any two of them; The phenyl ether organic ligand is a compound represented by Formula 1; Formula 1 ; In Formula 1, R1 and R2, which may be the same or different, are selected from any one of hydrogen and alkyl groups having 1-5 carbon atoms; Or R1 and R2 in Formula 1 may fuse to form a six-membered aromatic ring; The phenyl ether-based organic ligand is a benzotriazole-bridged isophthalic acid derivative.

2. The phenyl ether-based bimetallic organic framework antifouling material according to claim 1, characterized in that, The two different metal ions are any one of copper-zinc (Cu-Zn), copper-cobalt (Cu-Co), or copper-nickel (Cu-Ni), and the molar ratio of the two metal ions is from 1:0.1 to 1:

10.

3. The phenyl ether-based bimetallic organic framework antifouling material according to claim 1, characterized in that, The benzotriazole-bridged isophthalic acid derivative is any one of 4-(2-(2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid, 4-(2-(5,6-dimethyl-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid, and 4-(2-(2H-naphtho[2,3-d][1,2,3]triazol-2-yl)phenoxy)isophthalic acid.

4. The phenyl ether-based bimetallic organic framework antifouling material according to claim 1, characterized in that, The antifouling material has a water contact angle greater than 90°.

5. A method for preparing a phenyl ether-based bimetallic organic framework antifouling material as described in any one of claims 1-4, characterized in that, Includes the following steps: (1) Solution preparation: Dissolve the phenyl ether organic ligand in an organic solvent to form a ligand solution, and dissolve two different metal salts in solvent A to form a mixed metal salt solution; (2) Mixing: The ligand solution and the mixed metal salt solution are mixed evenly to obtain a precursor solution; (3) Solvothermal reaction: The precursor solution is placed in a closed reaction vessel and a solvothermal reaction is carried out. After the reaction is completed, it is cooled to room temperature. (4) Post-processing: The reaction product is centrifuged and washed alternately with organic solvent and deionized water. After vacuum drying and activation, the phenyl ether-based bimetallic organic framework antifouling material is obtained.

6. The method for preparing a phenyl ether-based bimetallic organic framework antifouling material according to claim 5, characterized in that, The metal salt mentioned in step (1) is a metal nitrate, chloride, acetate, or sulfate.

7. The method for preparing a phenyl ether-based bimetallic organic framework antifouling material according to claim 5, characterized in that, The organic solvent is selected from one or more of N,N-dimethylformamide, N,N-diethylformamide, ethanol, methanol or acetone; Solvent A is deionized water.

8. The method for preparing a phenyl ether-based bimetallic organic framework antifouling material according to claim 5, characterized in that, In step (3), the temperature of the solvothermal reaction is 80°C to 160°C, and the reaction time is 12 hours to 72 hours. In step (2), the ratio of the total number of moles of metal ions to the number of moles of ligands in the mixed precursor solution is 1:0.5 to 1:

3.

9. A marine antifouling coating, characterized in that, The antifouling agent comprises a phenyl ether-based bimetallic organic framework antifouling material as described in any one of claims 1-4, as well as a film-forming resin, solvent, and additives.

10. A marine antifouling coating according to claim 9, characterized in that, The amount of the phenyl ether-based bimetallic organic framework antifouling material added to the coating is 1% to 20% by weight.

Images