Marine antifouling coating with active-passive synergistic mechanism and preparation method thereof

Abstract

The invention provides a marine antifouling coating with an active-passive synergistic mechanism and a preparation method thereof.The preparation method comprises the steps that a porous template, ruthenium selenide and absolute ethyl alcohol are mixed and stirred to obtain a mixed solution, and the mixed solution is continuously heated to obtain mixed powder; placing the mixed powder and selenium powder in two crucibles respectively, and placing the crucibles in a tubular furnace for heating and calcining to obtain template-loaded ruthenium selenide; soaking the template-loaded ruthenium selenide in a concentrated alkali solution, heating to remove the porous template, and filtering, washing and drying after etching to obtain porous ruthenium selenide; the preparation method comprises the following steps: dissolving vinyl-terminated polydimethylsiloxane, a photoinitiator and polymercaptopropyl methyl siloxane in cyclohexane to obtain a coating base solution, adding porous ruthenium selenide into the coating base solution, uniformly stirring, carrying out ultrasonic treatment, and carrying out vacuum defoaming to obtain a coating solution; and coating the coating liquid on the surface of a base material, and curing after ultraviolet irradiation to obtain the marine antifouling coating with an active-passive synergistic mechanism.

Description

Technical Field

[0001] The invention belongs to the technical field of marine antifouling, and relates to a marine antifouling coating with an active-passive synergistic mechanism and a preparation method thereof. Background Art

[0002] In the process of human exploration and utilization of marine resources, marine biofouling has always been an unavoidable challenge. This phenomenon not only increases the technical difficulty of marine operations, but also causes huge economic losses. To solve this problem, various antifouling technologies have been continuously developed and improved. Among them, marine antifouling coatings have become one of the most practical solutions due to their wide application and significant cost-effectiveness. For example, the application of antifouling coatings on ships can reduce fuel consumption by 6%-10%, thereby significantly reducing operating costs and carbon dioxide emissions. However, existing antifouling coatings still have obvious limitations: some coatings release metal components such as copper ions during use, posing a potential threat to the marine ecological environment; other coatings perform poorly in static waters and are difficult to adapt to diverse application scenarios; chemical antifouling agents are easily affected by leaching effects, resulting in unstable performance, while natural antifouling agents are restricted by high production costs. Large-scale application. From the perspective of environmental protection and practical application, it is urgent to develop a new generation of antifouling coatings that are both efficient, durable and environmentally friendly. Summary of the invention

[0003] In view of the deficiencies in the prior art, the object of the present invention is to provide a marine antifouling coating with an active-passive synergistic mechanism and a preparation method thereof.

[0004] To achieve this object, the present invention adopts the following technical solutions:

[0005] In a first aspect, the present invention provides a method for preparing a marine antifouling coating having an active-passive synergistic mechanism, the preparation method comprising:

[0006] (I) uniformly mixing a template agent, concentrated hydrochloric acid, n-butanol, tetraethyl orthosilicate and deionized water to obtain a template precursor solution; heating the template precursor solution, cooling it naturally after heating, and then filtering, washing and drying it to obtain an intermediate product; calcining the intermediate product to obtain a porous template;

[0007] (II) the porous template obtained in step (I), ruthenium chloride and anhydrous ethanol are mixed and stirred to obtain a mixed solution, and the mixed solution is continuously heated until the anhydrous ethanol therein is completely evaporated to obtain a mixed powder; the mixed powder and selenium powder are placed in two crucibles respectively and placed in a tubular furnace for heating and calcining to obtain a template-loaded ruthenium selenide in the crucible containing the mixed powder; the template-loaded ruthenium selenide is immersed in a concentrated alkali solution and heated to remove the porous template, and after the etching is completed, it is filtered, washed and dried to obtain a porous ruthenium selenide;

[0008] (III) dissolving vinyl-terminated polydimethylsiloxane, a photoinitiator and polymercaptopropylmethylsiloxane in cyclohexane to obtain a coating base liquid, adding the porous ruthenium selenide obtained in step (II) to the coating base liquid, stirring evenly and then ultrasonicating, followed by vacuum degassing to obtain a coating liquid; coating the coating liquid on the surface of a substrate, curing it after ultraviolet light irradiation, and obtaining the marine antifouling coating with an active-passive synergistic mechanism.

[0009] The marine antifouling coating with active-passive synergistic mechanism proposed in the present invention achieves efficient, environmentally friendly and durable antifouling performance through innovative material design and composite structure. Its core advantage lies in the organic combination of porous ruthenium selenide with dual enzyme activity and low surface energy coating to form a dual protection system. At the passive protection level, the low surface energy coating effectively hinders the initial attachment of marine organisms such as diatoms by reducing the surface free energy of the material. Its low surface energy characteristics can reduce the adsorption of biological macromolecules such as proteins and polysaccharides to form a physical barrier. At the active protection level, porous ruthenium selenide, as a nanozyme, catalyzes hydrogen peroxide to produce reactive oxygen species (ROS) such as hydroxyl free radicals, destroys the cell membrane structure of bacteria and algae, and interferes with their metabolic process, showing efficient sterilization and anti-biological attachment capabilities. In addition, the enzyme-like catalytic activity of porous ruthenium selenide and the low surface energy characteristics of the coating form a synergistic effect, which not only avoids the disadvantages of traditional antifouling coatings that rely on heavy metal release or chemical leaching, but also overcomes the limitations of a single protection mechanism. This technology provides an important technical path for the development of environmentally friendly marine antifouling solutions through the functional design of nanomaterials and the optimization of coating engineering, especially showing significant stability and sustainability in long-term marine environments.

[0010] The marine antifouling coating with active-passive synergistic mechanism proposed in the present invention achieves efficient, environmentally friendly and durable antifouling performance through innovative material design and composite structure construction. Its core advantage lies in the organic combination of porous ruthenium selenide with dual enzyme activity and low surface energy coating to form a dual protection system, which synergistically inhibits marine biofouling from two dimensions: active sterilization and passive barrier. Specifically:

[0011] In terms of active protection mechanism, porous ruthenium selenide is the core active component, and its unique crystal structure and chemical properties give it dual enzyme-like activity. Through the solvothermal method and high-temperature calcination process adopted by the present invention, porous ruthenium selenide nanoparticles form a mesoporous structure, which significantly increases the specific surface area and provides abundant active sites for catalytic reactions. 2 O 2 ), porous ruthenium selenide can mimic the catalytic function of peroxidase (POD) and convert H 2 O 2Decompose into reactive oxygen species (ROS) such as hydroxyl radicals (·OH). Experimental data show that porous ruthenium selenide 2 O 2 The antibacterial rate of Escherichia coli under synergistic effect is as high as 90.41%, which is much higher than that of H 2 O 2 The control group showed that the ROS produced by the catalytic reaction could effectively destroy the bacterial cell membrane structure and interfere with the metabolic process.

[0012] Furthermore, the porous ruthenium selenide also exhibits photoactivated oxidase (OXD) activity under light conditions. Under ultraviolet irradiation, photogenerated electron-hole pairs are generated on the surface of the nanoparticles, driving the reduction of oxygen molecules to generate superoxide radicals (·O 2 - ), and H 2 O 2 The reaction produces singlet oxygen ( 1 O 2 ). This photocatalytic mechanism significantly enhances the efficiency of ROS generation under light conditions, forming a sustained bactericidal effect. The present invention integrates porous ruthenium selenide into the coating system through a UV curing process, so that it can respond to natural light in the marine environment and achieve all-weather active protection.

[0013] In terms of passive protection mechanisms, low surface energy coatings (such as vinyl-terminated polydimethylsiloxane) reduce the surface free energy of the material through chemical modification to form hydrophobic-lipophilic properties. The polysulfide propyl methylsiloxane used in the present invention further enhances the hydrophobicity of the coating, and its surface energy can be reduced to 20~25mJ / m². This low surface energy property achieves physical isolation in two ways: first, it significantly reduces the contact angle hysteresis between seawater and the coating surface, making it difficult for fouling organisms such as bacteria and diatoms to spread and adhere to the surface; second, it hinders the initial adsorption of biomacromolecules (such as proteins and polysaccharides) and cuts off the nutrient supply chain of the fouling biological community.

[0014] Active and passive protection mechanisms do not exist in isolation, but form a synergistic effect through the clever integration of material design. On the one hand, the catalytic activity of porous ruthenium selenide can degrade extracellular polymers (EPS) in the biofilm matrix, weakening the adhesion basis of bacteria and diatoms; on the other hand, the low surface energy coating reduces the initial contact opportunity of fouling organisms through physical barriers, reducing the catalytic load of porous ruthenium selenide. The present invention optimizes the synergistic efficiency of the two by regulating the loading amount of porous ruthenium selenide and the coating thickness.

[0015] As a preferred technical solution of the present invention, in step (I), the preparation process of the template precursor solution includes:

[0016] First, the template, concentrated hydrochloric acid and deionized water are mixed evenly until the template is completely dissolved to obtain a first solution;

[0017] Subsequently, n-butanol is added to the first solution, mixed, stirred and heated to obtain a second solution;

[0018] Finally, tetraethyl orthosilicate is added to the second solution, and the mixture is continuously stirred and heated to obtain a third solution, and the third solution is subjected to ultrasound to obtain the template precursor solution.

[0019] In some optional examples, the template is polyethylene oxide-polypropylene oxide-polyethylene oxide.

[0020] As a preferred technical solution of the present invention, in the first solution, the mass ratio of the template, concentrated hydrochloric acid and deionized water is 1:(1.5~3):(20~30), for example, it can be 1:1.5:20, 1:1.6:21, 1:1.7:22, 1:1.8:23, 1:1.9:24, 1:2:25, 1:2.1:26, 1:2.2:27, 1:2.3:28, 1:2.4:29, 1:2.5:30, 1:2.6:22, 1:2.7:24, 1:2.8:26, 1:2.9:28 or 1:3:30, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0021] In some optional examples, the mass fraction of the concentrated hydrochloric acid is 30-40wt%, for example, it can be 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt% or 40wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0022] In some optional examples, the mass ratio of the template in the first solution to the n-butanol is 1:(1~2), for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0023] In some optional examples, the mixing and stirring time of the first solution and n-butanol is 1 to 2 hours, for example, 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0024] In some optional examples, the heating temperature during the mixing and stirring of the first solution and n-butanol is 30-40°C, for example, it can be 30°C, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h or 40h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0025] In some optional examples, the mass ratio of the template to tetraethyl orthosilicate in the second solution is 1:(2~3), for example, it can be 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 or 1:3.0, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0026] The present invention specifically limits the mass ratio of the template to tetraethoxysilane in the second solution to 1:(2-3), and the template (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer) interacts with the silanol generated by the hydrolysis of tetraethoxysilane in the solution through hydrogen bonding to form an ordered mesostructure. When the ratio of the template to tetraethoxysilane is 1:(2-3), the silicon source provided by tetraethoxysilane can fully wrap the template molecular chain, and will not be excessively cross-linked due to excess, thereby ensuring that the template forms a regular pore structure in the silicon network. At this time, the segment movement of the template is moderately restricted, which is conducive to the formation of uniform mesopores during the subsequent calcination process. The appropriate ratio ensures that the porous template has both a high specific surface area and a regular pore structure. The silicon source provided by tetraethoxysilane just covers the surface of the template and forms moderate cross-linking. The porous template obtained after calcination has a concentrated pore size distribution and a large comparative area, providing sufficient sites for the loading of ruthenium selenide. The loaded porous ruthenium selenide forms mesoporous channels in the coating, promoting the diffusion and transmission of ROS and enhancing the antibacterial efficiency.

[0027] If the relative content of ethyl orthosilicate increases, it will lead to excess silicon source, rapid condensation reaction between silanol groups, forming a disordered dense silicon skeleton, and the template agent will find it difficult to induce the formation of regular pores, which will eventually lead to a wide pore size distribution and even macropore defects. In this case, the specific surface area of ​​the porous template is significantly reduced, the subsequent ruthenium selenide loading is reduced, and the catalytic active sites are insufficient, which directly affects the active bactericidal ability of the coating. At the same time, an overly dense silicon network will increase the difficulty of removing the template agent during calcination, and the residual carbonaceous structure may interfere with the uniformity of the coating.

[0028] On the contrary, if the template agent is excessive, it will occupy too much space and hinder the effective polymerization of the hydrolysis product of ethyl orthosilicate. At this time, the silicon network presents a loose and porous structure due to the lack of sufficient silicon source support, and the mechanical strength is insufficient. It is easy to collapse during the subsequent etching to remove the template agent, resulting in the collapse of the mesoporous structure or the destruction of pore connectivity. This structural defect will reduce the specific surface area of ​​porous ruthenium selenide, reduce the active sites, and reduce the physical barrier function of the coating. In addition, the excess template agent may not be completely decomposed during the calcination process, and the carbon impurities that remain in the material will not only occupy the active space, but also become a potential site for bacterial attachment, weakening the passive antifouling effect of the coating.

[0029] In some optional examples, the mixing and stirring time of the second solution and tetraethyl orthosilicate is 12 to 24 hours, for example, it can be 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0030] In some optional examples, the heating temperature during the mixing and stirring of the second solution and tetraethyl orthosilicate is 30-40°C, for example, it can be 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C or 40°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0031] In some optional examples, the ultrasonic power of the ultrasonic treatment of the third solution is 200~300W, for example, it can be 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W or 300W, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0032] In some optional examples, the ultrasonic treatment time of the third solution is 0.5~1h, for example, it can be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1.0h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0033] As a preferred technical solution of the present invention, in step (I), the heating temperature of the template precursor solution is 90-110°C, for example, it can be 90°C, 92°C, 94°C, 96°C, 98°C, 100°C, 102°C, 104°C, 106°C, 108°C or 110°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0034] In some optional examples, the heating time of the template precursor solution is 20 to 30 hours, for example, it can be 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours or 30 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] In some optional embodiments, the washing process includes: washing the filtered product with deionized water for 3 to 5 times until the pH is neutral, for example, 3 times, 4 times or 5 times, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0036] In some optional embodiments, the drying temperature is 80-100°C, for example, it can be 80°C, 82°C, 84°C, 86°C, 88°C, 90°C, 92°C, 94°C, 96°C, 98°C or 100°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0037] In some optional examples, the drying time is 3 to 5 hours, for example, it can be 3.0 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4.0 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours or 5.0 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0038] As a preferred technical solution of the present invention, in step (I), the heating rate of the intermediate product during calcination is 1-5°C / min, for example, it can be 1.0°C / min, 1.5°C / min, 2.0°C / min, 2.5°C / min, 3.0°C / min, 3.5°C / min, 4.0°C / min, 4.5°C / min or 5.0°C / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0039] In some optional examples, the calcination temperature of the intermediate product is 550-600°C, for example, 550°C, 555°C, 560°C, 565°C, 570°C, 575°C, 580°C, 585°C, 590°C, 595°C or 600°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0040] In some optional examples, the holding time for calcining the intermediate product is 5 to 6 hours, for example, it can be 5.0h, 5.1h, 5.2h, 5.3h, 5.4h, 5.5h, 5.6h, 5.7h, 5.8h, 5.9h or 6.0h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0041] As a preferred technical solution of the present invention, in step (II), the mixed solution is prepared by the following method:

[0042] Ruthenium chloride is dissolved in anhydrous ethanol, and the mixture is mixed evenly to obtain a ruthenium chloride solution. The porous template is added to the ruthenium chloride solution under stirring conditions, and the mixture is mixed evenly to obtain the mixed solution.

[0043] In some optional examples, the ratio of ruthenium chloride to anhydrous ethanol is 1g:(10~20)mL, for example, it can be 1g:10mL, 1g:11mL, 1g:12mL, 1g:13mL, 1g:14mL, 1g:15mL, 1g:16mL, 1g:17mL, 1g:18mL, 1g:19mL or 1g:20mL, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0044] In some optional examples, the mass ratio of the porous template to the ruthenium chloride in the ruthenium chloride solution is (1~2):1, for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0045] The present invention particularly limits the mass ratio of the porous template to the ruthenium chloride in the ruthenium chloride solution to (1-2):1. The porous template plays a spatial confinement role in the ruthenium chloride loading process. When the mass ratio of the two is within the range of (1-2):1, the amount of ruthenium chloride can fully fill the pores of the porous template without excessive accumulation due to excessive amount. At this time, the ruthenium chloride molecules are combined with the silanol groups on the surface of the template through coordination bonds in the ethanol solvent to form a uniform monolayer dispersion state. During the calcination process, the confined growth of ruthenium chloride in the pores of the porous template can inhibit particle agglomeration and form a mesoporous structure with uniform particle size.

[0046] If the porous template is added in excess, the relative content of ruthenium chloride is insufficient and cannot completely occupy the pore space of the porous template, resulting in some pores not being filled or forming a discontinuous loading layer. This not only reduces the effective loading amount of ruthenium chloride, but also causes the generated ruthenium selenide nanoparticles to aggregate during the subsequent etching process due to lack of sufficient support, causing the mesoporous structure to collapse, ultimately reducing the catalytic active sites and weakening the antibacterial ability.

[0047] On the contrary, if ruthenium chloride is added in excess, the excessive addition of ruthenium chloride will break the balance between the porous template and the reactants. Excessive ruthenium chloride will form multi-layer accumulation on the surface of the porous template, and even block the pores, hindering the volatilization of the ethanol solvent and the escape of gas during the subsequent calcination process. This will cause the generated ruthenium selenide particles to be uneven in size, densification in some areas, and a wider pore size distribution. In addition, excessive ruthenium chloride is prone to side reactions with the porous template during high-temperature calcination to generate amorphous ruthenium selenide compounds or ruthenium oxides. These byproducts not only do not have enzyme-mimicking catalytic activity, but may also introduce impurity phases, reducing the structural stability of the material.

[0048] In some optional instances, the continuous heating temperature of the mixed solution is 50-60°C, for example, it can be 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0049] As a preferred technical solution of the present invention, in step (II), the mass ratio of the mixed powder to the selenium powder is 1:(1-2), for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0050] The present invention specifically limits the mass ratio of the mixed powder to the selenium powder to 1:(1-2). When the mass ratio of the mixed powder to the selenium powder is within the range of 1:(1-2), the supply of selenium powder can ensure the complete conversion of the ruthenium chloride precursor and avoid the side reaction caused by excessive selenium. At this time, the selenium powder, as a selenium source, reacts with the metastable ruthenium chloride in the precursor at high temperature to promote the directional growth of ruthenium selenide. At the same time, the presence of an appropriate amount of selenium powder can inhibit the excessive carbonization of the template during the calcination process and maintain the integrity of the pore structure.

[0051] If the amount of selenium powder is too low, the insufficient supply of selenium powder will cause the chlorine element in the precursor to not be completely replaced by selenium, resulting in the generation of non-target phase ruthenium oxide or mixed valence selenide. These byproducts not only lack catalytic activity, but also block the mesoporous channels. In addition, insufficient selenium powder will aggravate the carbonization degree of the template at high temperature, and the residual carbon may wrap the nanoparticles, reducing the exposure rate of the active sites.

[0052] On the contrary, if the amount of mixed powder is too low, the excess selenium powder will trigger side reactions during the calcination process, resulting in the presence of elemental selenium or mixed-valence selenium oxides on the surface of the formed porous ruthenium selenide nanoparticles. In addition, the excess selenium powder will change the redox potential of the calcination atmosphere, causing the silicon template to undergo an amorphous transformation instead of orderly etching, ultimately leading to the collapse of the mesoporous structure.

[0053] In some optional examples, before heating and calcining, a mixed gas of hydrogen and argon is introduced into the tubular furnace, and the volume ratio of hydrogen to argon in the mixed gas is 1:(15~20), for example, it can be 1:15, 1:15.5, 1:16, 1:16.5, 1:17, 1:17.5, 1:18, 1:18.5, 1:19, 1:19.5 or 1:20, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0054] In some optional examples, the heating rate of the heating calcination is 1~5℃ / min, for example, it can be 1.0℃ / min, 1.5℃ / min, 2.0℃ / min, 2.5℃ / min, 3.0℃ / min, 3.5℃ / min, 4.0℃ / min, 4.5℃ / min or 5.0℃ / min, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0055] In some optional examples, the heating calcination temperature is 550~600℃, for example, it can be 550℃, 555℃, 560℃, 565℃, 570℃, 575℃, 580℃, 585℃, 590℃, 595℃ or 600℃, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0056] In some optional examples, the holding time for the heating and calcining is 2 to 3 hours, for example, it can be 2.0 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3.0 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0057] As a preferred technical solution of the present invention, in step (II), the concentrated alkali solution is a sodium hydroxide solution.

[0058] In some optional examples, the concentration of the sodium hydroxide solution is 2-4 mol / L, for example, it can be 2.0 mol / L, 2.2 mol / L, 2.4 mol / L, 2.6 mol / L, 2.8 mol / L, 3.0 mol / L, 3.2 mol / L, 3.4 mol / L, 3.6 mol / L, 3.8 mol / L or 4.0 mol / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0059] In some optional examples, the heating temperature of the template-loaded ruthenium selenide during immersion in concentrated alkali solution is 60~80°C, for example, it can be 60°C, 62°C, 64°C, 66°C, 68°C, 70°C, 72°C, 74°C, 76°C, 78°C or 80°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0060] In some optional instances, the immersion time of the template-loaded ruthenium selenide is 12 to 24 hours, for example, it can be 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0061] As a preferred technical solution of the present invention, in step (III), the mass ratio of the vinyl-terminated polydimethylsiloxane, the photoinitiator, the polymercaptopropylmethylsiloxane and the cyclohexane is 1:(0.02-0.021):(0.07-0.08):(3-4), for example, it can be 1:0.02:0.07:3, 1:0.0201:0.071:3.1, 1:0.0202:0.072:3.2, 1:0.0203:0.073: 3.3, 1: 0.0204: 0.074: 3.4, 1: 0.0205: 0.075: 3.5, 1: 0.0206: 0.076: 3.6, 1: 0.0207: 0.077: 3.7, 1: 0.0208: 0.078: 3.8, 1: 0.0209: 0.079: 3.9 or 1: 0.021: 0.08:4, but are not limited to the listed values, other unlisted values ​​within the numerical range are also applicable.

[0062] In some optional examples, the photoinitiator is 2-hydroxy-2-methylpropiophenone.

[0063] In some optional examples, the added amount of the porous ruthenium selenide is 0.1~0.5wt% of the total mass of the coating base liquid, for example, it can be 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt% or 0.5wt%, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0064] The present invention specifically limits the amount of porous ruthenium selenide added to 0.1-0.5wt% of the total mass of the coating base liquid. As a nanozyme catalyst, the activity of porous ruthenium selenide depends on the exposure degree of the active site and the diffusion efficiency of the reaction medium. When the addition amount is controlled at 0.1-0.5wt%, the porous ruthenium selenide nanoparticles can be efficiently loaded through the mesoporous structure without causing agglomeration due to excessive accumulation. At this time, the porous ruthenium selenide is in a monodisperse state in the base liquid, and its surface defect sites (such as selenium vacancies) can catalyze hydrogen peroxide to produce hydroxyl radicals, while photogenerated electron-hole pairs can drive oxygen reduction to generate superoxide radicals. This synergistic catalytic effect can effectively degrade bacterial cell membrane lipids and algae chlorophyll, achieving active sterilization.

[0065] If the amount of porous ruthenium selenide added is too low (such as less than 0.1wt%), the loading density of the porous ruthenium selenide nanoparticles is insufficient, resulting in a sharp decrease in the number of active sites, a decrease in the catalytic reaction rate, and a decrease in antibacterial efficiency. In addition, the mesoporous channels of the porous ruthenium selenide nanoparticles at low loadings are easily filled with the polymer matrix, hindering the diffusion and transmission of ROS and weakening its inhibitory effect on biofilm formation. On the contrary, if the amount of porous ruthenium selenide added is too high (such as higher than 0.5wt%), the porous ruthenium selenide nanoparticles will agglomerate due to the steric hindrance effect to form large particle agglomerates, which will not only block the mesoporous structure and reduce the effective catalytic sites, but also destroy the uniformity of the coating. This agglomeration phenomenon will increase the surface roughness of the coating, accelerate the initial attachment of fouling organisms, and may cause cracking of the coating due to local stress concentration, reducing long-term durability.

[0066] In addition, the appropriate amount of porous ruthenium selenide added achieves the optimal synergy of active protection and passive barrier. When the addition amount is 0.3wt%, the loading amount of porous ruthenium selenide can form a dense but not excessive catalytic layer, and its mesoporous structure allows H 2 O 2 Penetrate to the particle surface and quickly diffuse ROS, the antibacterial rate against Escherichia coli can reach more than 90%, and the anti-attachment rate against diatoms exceeds 92%. At this time, the low surface energy coating (surface energy of about 22mJ / m²) provides a physical barrier to prevent protein adsorption and extension of diatom byssus, while the nanoenzyme activity further destroys the metabolic function of attached microorganisms, forming a double protection. If the amount of porous ruthenium selenide added is too low, the catalytic activity will decrease significantly, the coating will only rely on the low surface energy characteristics, the anti-diatom rate will decrease, and the performance will decay faster due to the accumulation of biofilm after long-term immersion. If the amount of porous ruthenium selenide added is too high, the porous ruthenium selenide nanoparticles will agglomerate, resulting in microcracks on the coating surface, reduced hydrophobicity, and increased diatom attachment area. At the same time, excessive generation of ROS may cause local oxidative corrosion, which will accelerate the damage of the metal substrate.

[0067] In some optional instances, the stirring time of the porous ruthenium selenide and the coating base liquid is 20 to 30 minutes, for example, it can be 20 minutes, 21 minutes, 22 minutes, 23 minutes, 24 minutes, 25 minutes, 26 minutes, 27 minutes, 28 minutes, 29 minutes or 30 minutes, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0068] In some optional instances, the stirring speed of the porous ruthenium selenide and the coating base liquid is 300~500rpm, for example, it can be 300rpm, 320rpm, 340rpm, 360rpm, 380rpm, 400rpm, 420rpm, 440rpm, 460rpm, 480rpm or 500rpm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0069] In some optional instances, the ultrasonic power is 400~600W, for example, it can be 400W, 420W, 440W, 460W, 480W, 500W, 520W, 540W, 560W, 580W or 600W, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0070] In some optional instances, the ultrasound time is 30 to 40 minutes, for example, it can be 30 minutes, 31 minutes, 32 minutes, 33 minutes, 34 minutes, 35 minutes, 36 minutes, 37 minutes, 38 minutes, 39 minutes or 40 minutes, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0071] In some optional examples, the vacuum degassing time is 10 to 20 minutes, for example, it can be 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes or 20 minutes, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0072] In some optional examples, the coating thickness of the coating liquid is 1 to 20 μm, for example, it can be 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm or 20 μm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0073] In some optional examples, the coating liquid is applied by spin coating, spray coating or blade coating.

[0074] In some optional embodiments, the ultraviolet light irradiation time is 10 to 30 minutes, for example, it can be 10 minutes, 12 minutes, 14 minutes, 16 minutes, 18 minutes, 20 minutes, 22 minutes, 24 minutes, 26 minutes, 28 minutes or 30 minutes, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0075] In a second aspect, the present invention provides a marine antifouling coating having an active-passive synergistic mechanism prepared by the preparation method described in the first aspect.

[0076] Compared with the prior art, the present invention has the following beneficial effects:

[0077] The marine antifouling coating with active-passive synergistic mechanism proposed in the present invention achieves efficient, environmentally friendly and durable antifouling performance through innovative material design and composite structure. Its core advantage lies in the organic combination of porous ruthenium selenide with dual enzyme activity and low surface energy coating to form a dual protection system. At the passive protection level, the low surface energy coating effectively hinders the initial attachment of marine organisms such as diatoms by reducing the surface free energy of the material. Its low surface energy characteristics can reduce the adsorption of biological macromolecules such as proteins and polysaccharides to form a physical barrier. At the active protection level, porous ruthenium selenide, as a nanozyme, catalyzes hydrogen peroxide to produce reactive oxygen species (ROS) such as hydroxyl free radicals, destroys the cell membrane structure of bacteria and algae, and interferes with their metabolic process, showing efficient sterilization and anti-biological attachment capabilities. In addition, the enzyme-like catalytic activity of porous ruthenium selenide and the low surface energy characteristics of the coating form a synergistic effect, which not only avoids the disadvantages of traditional antifouling coatings that rely on heavy metal release or chemical leaching, but also overcomes the limitations of a single protection mechanism. This technology provides an important technical path for the development of environmentally friendly marine antifouling solutions through the functional design of nanomaterials and the optimization of coating engineering, especially showing significant stability and sustainability in long-term marine environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0078] Figure 1 This is a transmission electron microscope (TEM) image of the porous ruthenium selenide prepared in Example 1 of the present invention;

[0079] Figure 2 This is an energy dispersive spectrometer (EDS) elemental spectrum of the porous ruthenium selenide prepared in Example 1 of the present invention;

[0080] Figure 3 This is an X-ray diffraction (XRD) pattern of the porous ruthenium selenide prepared in Example 1 of the present invention;

[0081] Figure 4 This is a pore size distribution diagram of the porous ruthenium selenide prepared in Example 1 of the present invention;

[0082] Figure 5 This is an antibacterial test diagram of the porous ruthenium selenide prepared in Example 1 of the present invention;

[0083] Figure 6 The anti-diatom optical microscope images of the glass sheet, the marine antifouling coating prepared in Example 1 of the present invention and the comparative example;

[0084] Figure 7 Actual surface photos of the marine antifouling coatings prepared for the blank group, experimental group, control group 1 and control group 2 after being immersed in seawater for 180 days (location: Bohai Sea, China). DETAILED DESCRIPTION

[0085] The technical solution of the present invention is described in detail below in conjunction with specific embodiments and their accompanying drawings. The embodiments recorded herein are specific embodiments of the present invention, which are used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary and should not be construed as limitations on the embodiments of the present invention and the scope of protection of the present invention. In addition to the embodiments recorded herein, those skilled in the art can also adopt other obvious technical solutions based on the contents disclosed in the claims of this application and its specification, including technical solutions that adopt any obvious replacements and modifications to the embodiments recorded herein.

[0086] Example 1

[0087] This embodiment provides a method for preparing a marine antifouling coating having an active-passive synergistic mechanism, the preparation method comprising:

[0088] (1) Polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), concentrated hydrochloric acid and deionized water are mixed uniformly in a mass ratio of 1:1.5:20 until P123 is completely dissolved to obtain a first solution, wherein the mass fraction of concentrated hydrochloric acid is 30wt%; n-butanol is added to the first solution, the mass ratio of P123 to n-butanol in the first solution is 1:1, and the mixture is mixed and stirred at 30°C for 2h to obtain a second solution; tetraethyl orthosilicate is added to the second solution, the mass ratio of P123 to tetraethyl orthosilicate in the second solution is 1:2, and the mixture is mixed and stirred at 30°C for 24h to obtain a third solution, and the third solution is ultrasonically treated with an ultrasonic power of 200W for 1h to obtain a template precursor solution;

[0089] The template precursor solution was heated to 90°C and kept warm for 30 hours, cooled naturally after heating, and then filtered. After filtering, the filtered product was washed 3 times with deionized water until the pH was neutral, and finally dried at 80°C for 5 hours to obtain an intermediate product; the intermediate product was calcined at a heating rate of 1°C / min, the calcination temperature was 550°C, and the insulation time was 6 hours. After the calcination, a porous template was obtained;

[0090] (2) dissolving ruthenium chloride in anhydrous ethanol, wherein the ratio of ruthenium chloride to anhydrous ethanol is 1 g:10 mL, and mixing them uniformly to obtain a ruthenium chloride solution. Under stirring conditions, the porous template obtained in step (1) is added to the ruthenium chloride solution, wherein the mass ratio of the porous template to the ruthenium chloride in the ruthenium chloride solution is 1:1. After mixing them uniformly, a mixed solution is obtained. The mixed solution is heated to 50° C. and continuously stirred until the anhydrous ethanol therein is completely evaporated to obtain a mixed powder.

[0091] The mixed powder and selenium powder are placed in two crucibles respectively, the mass ratio of the mixed powder to the selenium powder is 1:1, a mixed gas of hydrogen and argon with a volume ratio of 1:15 is introduced into the tubular furnace, and the two crucibles are placed in the tubular furnace, wherein the crucible containing the selenium powder is placed near the air inlet of the tubular furnace, and the mixed powder and selenium powder are heated to 550°C at a heating rate of 1°C / min and kept warm for 3 hours to complete calcination, and after the calcination is completed, a template-loaded ruthenium selenide is obtained in the crucible containing the mixed powder;

[0092] The template-loaded ruthenium selenide is immersed in a 2 mol / L sodium hydroxide solution at 80° C. for 12 h to remove the porous template, and after etching, the porous template is filtered, washed and dried to obtain porous ruthenium selenide;

[0093] (3) Dissolving vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methylpropiophenone and polymercaptopropylmethylsiloxane in cyclohexane to obtain a coating base liquid, wherein the mass ratio of vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methylpropiophenone, polymercaptopropylmethylsiloxane and cyclohexane is 1:0.02:0.07:3; adding the porous ruthenium selenide obtained in step (2) to the coating base liquid, wherein the amount of the porous ruthenium selenide added is 0.1wt% of the total mass of the coating base liquid; stirring the mixture at a speed of 300 rpm for 30 minutes, and then ultrasonicating the mixture at an ultrasonic power of 400 W for 40 minutes, and then vacuum degassing the mixture for 10 minutes to obtain a coating liquid; applying the coating liquid on the surface of the substrate to a coating thickness of 1 μm, and curing the coating after irradiating the substrate with ultraviolet light of a wavelength of 365 nm for 10 minutes to obtain the marine antifouling coating with the active-passive synergistic mechanism.

[0094] Figure 1 This is a transmission electron microscope (TEM) image of the porous ruthenium selenide prepared in this example. Figure 1 The stacking arrangement of porous ruthenium selenide is shown, together forming a porous nanostructure.

[0095] Figure 2 This is the energy dispersive spectrometer (EDS) elemental spectrum of the porous ruthenium selenide prepared in this example. Figure 2 The obvious spatial copolymerization of Ru and Se elements is shown.

[0096] Figure 3 is the X-ray diffraction (XRD) pattern of the porous ruthenium selenide prepared in this example, Figure 3 It shows multiple sharp and obvious diffraction peaks, indicating that it has a high degree of crystallinity. These diffraction peaks are consistent with RuSe 2 The standard XRD pattern of RuSe (JCPDS No.: 80-0670) has a strong correlation, which confirms that the impurity content in the synthesized porous ruthenium selenide is extremely low, and the strongest peak at 2θ value of 50.9° belongs to RuSe 2 The (311) plane is the main diffraction peak of the porous ruthenium selenide. The second peaks are at 33.5° (210), 29.9° (200), 37.0° (211), 43.2° (220), and 84.8° (511). The appearance of these diffraction peaks clearly confirms the highly ordered crystalline nature of porous ruthenium selenide.

[0097] Figure 4 This is the pore size distribution diagram of the porous ruthenium selenide prepared in this example. It can be seen from the figure that the pore size of the porous ruthenium selenide is about 3~5nm, which belongs to mesoporous nanomaterials (2~50nm). Its BET specific surface area is 64.07m 2 / g, the BJH adsorption pore size is 5.02nm, and the BJH desorption pore size is 4.39nm.

[0098] Example 2

[0099] This embodiment provides a method for preparing a marine antifouling coating having an active-passive synergistic mechanism, the preparation method comprising:

[0100] (1) Polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), concentrated hydrochloric acid and deionized water are mixed uniformly in a mass ratio of 1:1.8:22 until P123 is completely dissolved to obtain a first solution, wherein the mass fraction of concentrated hydrochloric acid is 32wt%; n-butanol is added to the first solution, wherein the mass ratio of P123 to n-butanol in the first solution is 1:1.2, and the mixture is mixed and stirred at 32°C for 1.8h to obtain a second solution; tetraethyl orthosilicate is added to the second solution, wherein the mass ratio of P123 to tetraethyl orthosilicate in the second solution is 1:2.2, and the mixture is mixed and stirred at 32°C for 21h to obtain a third solution, and the third solution is ultrasonically treated with an ultrasonic power of 220W for 0.9h to obtain a template precursor solution;

[0101] The template precursor solution was heated to 95°C and kept warm for 28 hours, cooled naturally after heating, and then filtered. After filtering, the filtered product was washed 3 times with deionized water until the pH was neutral, and finally dried at 85°C for 4.5 hours to obtain an intermediate product; the intermediate product was calcined at a heating rate of 2°C / min, the calcination temperature was 560°C, and the insulation time was 5.8 hours. After the calcination, a porous template was obtained;

[0102] (2) dissolving ruthenium chloride in anhydrous ethanol, wherein the ratio of ruthenium chloride to anhydrous ethanol is 1 g:12 mL, and mixing them uniformly to obtain a ruthenium chloride solution. Under stirring conditions, the porous template obtained in step (1) is added to the ruthenium chloride solution, wherein the mass ratio of the porous template to the ruthenium chloride in the ruthenium chloride solution is 1.2:1. After mixing them uniformly, a mixed solution is obtained. The mixed solution is heated to 52° C. and continuously stirred until the anhydrous ethanol therein is completely evaporated to obtain a mixed powder.

[0103] The mixed powder and selenium powder are placed in two crucibles respectively, the mass ratio of the mixed powder to the selenium powder is 1:1.2, a mixed gas of hydrogen and argon with a volume ratio of 1:16 is introduced into the tubular furnace, and the two crucibles are placed in the tubular furnace, wherein the crucible containing the selenium powder is placed near the air inlet of the tubular furnace, and the mixed powder and selenium powder are heated to 560°C at a heating rate of 2°C / min and kept warm for 2.5h to complete calcination, and after the calcination is completed, a template-loaded ruthenium selenide is obtained in the crucible containing the mixed powder;

[0104] The template-loaded ruthenium selenide is immersed in a 2.5 mol / L sodium hydroxide solution at 75°C for 15 hours to remove the porous template, and after etching, the porous ruthenium selenide is obtained by filtering, washing and drying.

[0105] (3) Dissolving vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methylpropiophenone and polymercaptopropylmethylsiloxane in cyclohexane to obtain a coating base liquid, wherein the mass ratio of vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methylpropiophenone, polymercaptopropylmethylsiloxane and cyclohexane is 1:0.0203:0.073:3.2; adding the porous ruthenium selenide obtained in step (2) to the coating base liquid, wherein the amount of the porous ruthenium selenide added is 0.2wt% of the total mass of the coating base liquid; stirring the mixture at a speed of 350 rpm for 28 minutes, and then ultrasonicating the mixture at an ultrasonic power of 450 W for 38 minutes, and then vacuum degassing the mixture for 12 minutes to obtain a coating liquid; applying the coating liquid to the surface of the substrate to a coating thickness of 5 μm, and curing the coating after irradiating the substrate with ultraviolet light of a wavelength of 365 nm for 15 minutes to obtain the marine antifouling coating having an active-passive synergistic mechanism.

[0106] Example 3

[0107] This embodiment provides a method for preparing a marine antifouling coating having an active-passive synergistic mechanism, the preparation method comprising:

[0108] (1) Polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), concentrated hydrochloric acid and deionized water are mixed uniformly in a mass ratio of 1:2:25 until P123 is completely dissolved to obtain a first solution, wherein the mass fraction of concentrated hydrochloric acid is 35wt%; n-butanol is added to the first solution, the mass ratio of P123 to n-butanol in the first solution is 1:1.5, and the mixture is mixed and stirred at 35°C for 1.5 hours to obtain a second solution; tetraethyl orthosilicate is added to the second solution, the mass ratio of P123 to tetraethyl orthosilicate in the second solution is 1:2.5, and the mixture is mixed and stirred at 35°C for 18 hours to obtain a third solution, and the third solution is ultrasonically treated with an ultrasonic power of 250 W for 0.8 hours to obtain a template precursor solution;

[0109] The template precursor solution was heated to 100°C and kept warm for 25 hours, cooled naturally after heating, and then filtered. After filtering, the filtered product was washed 4 times with deionized water until the pH was neutral, and finally dried at 90°C for 4 hours to obtain an intermediate product; the intermediate product was calcined at a heating rate of 3°C / min, the calcination temperature was 580°C, and the insulation time was 5.5 hours. After the calcination, a porous template was obtained;

[0110] (2) dissolving ruthenium chloride in anhydrous ethanol, wherein the ratio of ruthenium chloride to anhydrous ethanol is 1 g:15 mL, and mixing them uniformly to obtain a ruthenium chloride solution. Under stirring conditions, the porous template obtained in step (1) is added to the ruthenium chloride solution, wherein the mass ratio of the porous template to the ruthenium chloride in the ruthenium chloride solution is 1.5:1. After mixing them uniformly, a mixed solution is obtained. The mixed solution is heated to 55° C. and continuously stirred until the anhydrous ethanol therein is completely evaporated to obtain a mixed powder.

[0111] The mixed powder and selenium powder are placed in two crucibles respectively, the mass ratio of the mixed powder to the selenium powder is 1:1.5, a mixed gas of hydrogen and argon with a volume ratio of 1:18 is introduced into the tubular furnace, and the two crucibles are placed in the tubular furnace, wherein the crucible containing the selenium powder is placed near the air inlet of the tubular furnace, and the mixed powder and selenium powder are heated to 580°C at a heating rate of 3°C / min and kept warm for 2.5h to complete calcination, and after the calcination is completed, a template-loaded ruthenium selenide is obtained in the crucible containing the mixed powder;

[0112] The template-loaded ruthenium selenide is immersed in a 3 mol / L sodium hydroxide solution at 70° C. for 18 h to remove the porous template, and after etching, the porous ruthenium selenide is obtained by filtering, washing and drying.

[0113] (3) Dissolving vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methylpropiophenone and polymercaptopropylmethylsiloxane in cyclohexane to obtain a coating base liquid, wherein the mass ratio of vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methylpropiophenone, polymercaptopropylmethylsiloxane and cyclohexane is 1:0.0205:0.075:3.5; adding the porous ruthenium selenide obtained in step (2) to the coating base liquid, wherein the amount of the porous ruthenium selenide added is 0.3wt% of the total mass of the coating base liquid; stirring the mixture at a speed of 400 rpm for 25 minutes, and then ultrasonicating the mixture at an ultrasonic power of 500 W for 35 minutes, and then vacuum degassing the mixture for 15 minutes to obtain a coating liquid; applying the coating liquid on the surface of the substrate to a coating thickness of 10 μm, and curing the coating after irradiating the substrate with ultraviolet light of a wavelength of 365 nm for 20 minutes to obtain the marine antifouling coating with the active-passive synergistic mechanism.

[0114] Example 4

[0115] This embodiment provides a method for preparing a marine antifouling coating having an active-passive synergistic mechanism, the preparation method comprising:

[0116] (1) Polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), concentrated hydrochloric acid and deionized water are mixed uniformly in a mass ratio of 1:2.5:28 until P123 is completely dissolved to obtain a first solution, wherein the mass fraction of concentrated hydrochloric acid is 38wt%; n-butanol is added to the first solution, the mass ratio of P123 to n-butanol in the first solution is 1:1.8, and the mixture is mixed and stirred at 38°C for 1.2h to obtain a second solution; tetraethyl orthosilicate is added to the second solution, the mass ratio of P123 to tetraethyl orthosilicate in the second solution is 1:2.8, and the mixture is mixed and stirred at 38°C for 15h to obtain a third solution, and the third solution is ultrasonically treated with an ultrasonic power of 280W for 0.6h to obtain a template precursor solution;

[0117] The template precursor solution was heated to 105°C and kept warm for 22 hours, cooled naturally after heating, and then filtered. After filtering, the filtered product was washed 4 times with deionized water until the pH was neutral, and finally dried at 95°C for 3.5 hours to obtain an intermediate product; the intermediate product was calcined at a heating rate of 4°C / min, the calcination temperature was 590°C, and the insulation time was 5.2 hours. After the calcination, a porous template was obtained;

[0118] (2) dissolving ruthenium chloride in anhydrous ethanol, wherein the ratio of ruthenium chloride to anhydrous ethanol is 1 g:18 mL, and mixing them uniformly to obtain a ruthenium chloride solution. Under stirring conditions, the porous template obtained in step (1) is added to the ruthenium chloride solution, wherein the mass ratio of the porous template to the ruthenium chloride in the ruthenium chloride solution is 1.8:1. After mixing them uniformly, a mixed solution is obtained. The mixed solution is heated to 58° C. and continuously stirred until the anhydrous ethanol therein is completely evaporated to obtain a mixed powder.

[0119] The mixed powder and selenium powder are placed in two crucibles respectively, the mass ratio of the mixed powder to the selenium powder is 1:1.8, a mixed gas of hydrogen and argon with a volume ratio of 1:19 is introduced into the tubular furnace, and the two crucibles are placed in the tubular furnace, wherein the crucible containing the selenium powder is placed near the air inlet of the tubular furnace, and the mixed powder and selenium powder are heated to 590°C at a heating rate of 4°C / min and kept warm for 2.2h to complete calcination, and after the calcination is completed, a template-loaded ruthenium selenide is obtained in the crucible containing the mixed powder;

[0120] The template-loaded ruthenium selenide was immersed in a 3.5 mol / L sodium hydroxide solution at 65° C. for 21 h to remove the porous template, and after etching, the porous ruthenium selenide was obtained by filtering, washing and drying.

[0121] (3) Dissolving vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methylpropiophenone and polymercaptopropylmethylsiloxane in cyclohexane to obtain a coating base liquid, wherein the mass ratio of vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methylpropiophenone, polymercaptopropylmethylsiloxane and cyclohexane is 1:0.0208:0.078:3.8; adding the porous ruthenium selenide obtained in step (2) to the coating base liquid, wherein the amount of the porous ruthenium selenide added is 0.4wt% of the total mass of the coating base liquid; stirring the mixture at a speed of 450rpm for 22min, ultrasonicating the mixture at an ultrasonic power of 550W for 32min, and vacuum degassing the mixture for 18min to obtain a coating liquid; applying the coating liquid to the surface of the substrate to obtain a coating with a thickness of 15μm; and curing the coating after irradiating the substrate with ultraviolet light of a wavelength of 365nm for 25min to obtain the marine antifouling coating with the active-passive synergistic mechanism.

[0122] Example 5

[0123] This embodiment provides a method for preparing a marine antifouling coating having an active-passive synergistic mechanism, the preparation method comprising:

[0124] (1) Polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), concentrated hydrochloric acid and deionized water are mixed uniformly in a mass ratio of 1:3:30 until P123 is completely dissolved to obtain a first solution, wherein the mass fraction of concentrated hydrochloric acid is 40wt%; n-butanol is added to the first solution, the mass ratio of P123 to n-butanol in the first solution is 1:2, and the mixture is mixed and stirred at 40°C for 1 hour to obtain a second solution; tetraethyl orthosilicate is added to the second solution, the mass ratio of P123 to tetraethyl orthosilicate in the second solution is 1:3, and the mixture is mixed and stirred at 40°C for 12 hours to obtain a third solution, and the third solution is ultrasonically treated with an ultrasonic power of 300 W for 0.5 hours to obtain a template precursor solution;

[0125] The template precursor solution was heated to 110°C and kept warm for 20 hours, cooled naturally after heating, and then filtered. After filtering, the filtered product was washed 5 times with deionized water until the pH was neutral, and finally dried at 100°C for 3 hours to obtain an intermediate product; the intermediate product was calcined at a heating rate of 5°C / min, the calcination temperature was 600°C, and the insulation time was 5 hours. After the calcination, a porous template was obtained;

[0126] (2) dissolving ruthenium chloride in anhydrous ethanol, wherein the ratio of ruthenium chloride to anhydrous ethanol is 1 g:20 mL, and mixing them uniformly to obtain a ruthenium chloride solution. Under stirring conditions, the porous template obtained in step (1) is added to the ruthenium chloride solution, wherein the mass ratio of the porous template to the ruthenium chloride in the ruthenium chloride solution is 2:1. After mixing them uniformly, a mixed solution is obtained. The mixed solution is heated to 60° C. and continuously stirred until the anhydrous ethanol therein is completely evaporated to obtain a mixed powder.

[0127] The mixed powder and selenium powder are placed in two crucibles respectively, the mass ratio of the mixed powder to the selenium powder is 1:2, a mixed gas of hydrogen and argon with a volume ratio of 1:20 is introduced into the tubular furnace, and the two crucibles are placed in the tubular furnace, wherein the crucible containing the selenium powder is placed near the air inlet of the tubular furnace, and the mixed powder and selenium powder are heated to 600°C at a heating rate of 5°C / min and kept warm for 2h to complete calcination, and after the calcination is completed, a template-loaded ruthenium selenide is obtained in the crucible containing the mixed powder;

[0128] The template-loaded ruthenium selenide is immersed in a 4 mol / L sodium hydroxide solution at 60° C. for 24 hours to remove the porous template, and after etching, the porous ruthenium selenide is obtained by filtering, washing and drying.

[0129] (3) Dissolving vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methylpropiophenone and polymercaptopropylmethylsiloxane in cyclohexane to obtain a coating base liquid, wherein the mass ratio of vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methylpropiophenone, polymercaptopropylmethylsiloxane and cyclohexane is 1:0.021:0.08:4; adding the porous ruthenium selenide obtained in step (2) to the coating base liquid, wherein the amount of the porous ruthenium selenide added is 0.5wt% of the total mass of the coating base liquid; stirring the mixture at a speed of 500 rpm for 20 minutes, ultrasonicating the mixture at an ultrasonic power of 600 W for 30 minutes, and vacuum degassing the mixture for 20 minutes to obtain a coating liquid; applying the coating liquid on the surface of the substrate to a coating thickness of 20 μm; and curing the coating liquid after irradiating the substrate with ultraviolet light of a wavelength of 365 nm for 30 minutes to obtain the marine antifouling coating having an active-passive synergistic mechanism.

[0130] Example 6

[0131] This embodiment provides a method for preparing a marine antifouling coating with an active-passive synergistic mechanism. The difference from Example 1 is that in step (1), the mass ratio of P123 to ethyl orthosilicate in the second solution is adjusted to 1:1.5, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0132] Example 7

[0133] This embodiment provides a method for preparing a marine antifouling coating with an active-passive synergistic mechanism. The difference from Example 1 is that in step (1), the mass ratio of P123 to ethyl orthosilicate in the second solution is adjusted to 1:3.5, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0134] Example 8

[0135] This embodiment provides a method for preparing a marine antifouling coating having an active-passive synergistic mechanism, which differs from Embodiment 1 in that, in step (2), the mass ratio of the porous template to the ruthenium chloride in the ruthenium chloride solution is adjusted to 0.5:1, and the other operating steps and process parameters are exactly the same as those in Embodiment 1.

[0136] Example 9

[0137] This embodiment provides a method for preparing a marine antifouling coating having an active-passive synergistic mechanism, which differs from Embodiment 1 in that, in step (2), the mass ratio of the porous template to the ruthenium chloride in the ruthenium chloride solution is adjusted to 2.5:1, and the other operating steps and process parameters are exactly the same as those in Embodiment 1.

[0138] Example 10

[0139] This embodiment provides a method for preparing a marine antifouling coating with an active-passive synergistic mechanism. The difference from Example 1 is that in step (2), the mass ratio of the mixed powder to the selenium powder is adjusted to 1:0.5, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0140] Embodiment 11

[0141] This embodiment provides a method for preparing a marine antifouling coating with an active-passive synergistic mechanism. The difference from Example 1 is that in step (2), the mass ratio of the mixed powder to the selenium powder is adjusted to 1:2.5, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0142] Example 12

[0143] This embodiment provides a method for preparing a marine antifouling coating with an active-passive synergistic mechanism. The difference from Example 1 is that in step (3), the amount of porous ruthenium selenide added is 0.05wt% of the total mass of the coating base liquid, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0144] Example 13

[0145] This embodiment provides a method for preparing a marine antifouling coating with an active-passive synergistic mechanism. The difference from Example 1 is that in step (3), the amount of porous ruthenium selenide added is 0.6wt% of the total mass of the coating base liquid, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0146] Comparative Example

[0147] This embodiment provides a method for preparing a marine antifouling coating. The difference from Embodiment 1 is that step (1) and step (2) are omitted, porous ruthenium selenide is not added to the coating base liquid prepared in step (3), and the coating base liquid is directly used for coating. The other operating steps and process parameters are exactly the same as those in Embodiment 1.

[0148] The various properties of the porous ruthenium selenide and the marine antifouling coating prepared in Examples 1-13 and the comparative example were tested, and the specific steps are as follows:

[0149] (1) Antibacterial test

[0150] The formation of marine biofouling is a multivariate process, in which bacterial attachment to material surfaces and biofilm proliferation is a critical intermediate stage. Therefore, the use of nanozymes with antimicrobial functions is a promising antifouling strategy because they can effectively prevent bacterial colonization and thus block the development of subsequent biofouling. Therefore, antimicrobial testing is an essential component for evaluating the marine antifouling properties of materials.

[0151] The antibacterial rate of the porous ruthenium selenide prepared in Example 1-13 was tested. The antibacterial test used Escherichia coli (E. coli) as the target microorganism, and the standard plate count method was used to evaluate the antibacterial performance of the porous ruthenium selenide. First, phosphate buffered saline (PBS) was used to prepare a 1×10 6 Then, porous ruthenium selenide and appropriate amount of H 2 O 2 (final concentration is 0.3mM) and shake culture for 3h. After the culture, the colony count of the blank group is recorded as U 1 The colony counts of the control group and the experimental group were recorded as U 2 The antibacterial rate of porous ruthenium selenide is calculated as follows:

[0152]

[0153] Among them, U 2 is the colony count of the experimental group and the control group, U 1 is the colony count of the blank group, and A is the antibacterial rate (%) of different groups.

[0154] Considering the peroxidase-like activity of porous RuSe, H was introduced during the test. 2 O 2 In order to exclude H 2 O 2 The present invention also adds a H 2 O 2 The colony after culture is shown in the following figure. Figure 5 As shown in the figure, the comparative analysis of the antibacterial effects showed that the "porous ruthenium selenide" and "H 2 O 2 The antibacterial rates of the "porous ruthenium selenide + H 2 O 2 The antibacterial rate of the group was significantly higher, reaching 90.41% (Example 1). This result shows that porous ruthenium selenide and H 2 O 2 After binding, its peroxidase-mimicking catalytic activity can be activated, thereby greatly improving the antibacterial properties of the material.

[0155] Using "porous ruthenium selenide + H2 O 2 The antibacterial rate of the porous ruthenium selenide prepared in Examples 1-13 was tested by combining the above-mentioned compounds. The test results are shown in Table 1.

[0156] (2) Anti-diatom test

[0157] The anti-diatom test was carried out in the form of a coating. The coated sample and the blank sample (glass slide) were immersed in a beaker filled with a diatom solution (diatom species: Nitzschiaclosteriumf.minutissima) and cultured for 7 days. The diatom culture was carried out in F / 2 medium and the culture temperature was controlled at 21 ± 2°C. The incubator provided 2000 lux of light with a light-dark cycle of 12 h / 2 h. After the incubation period, the sample at the bottom of the beaker was removed, the sample surface was cleaned with distilled water, and the diatom attachment on the surface was observed with an optical microscope:

[0158]

[0159] Among them, N 2 is the number of diatoms on the coating surface, N 1 is the number of diatoms on the surface of the glass sheet, and r is the anti-diatom rate of the coating (%).

[0160] The anti-diatom rates of the marine antifouling coatings prepared in Examples 1-13 and the comparative example were tested, and the test results are shown in Table 1.

[0161] (3) Diatom attachment test

[0162] Similar to the antibacterial test, the ability to resist diatom adhesion is also an important indicator in the marine antifouling test. The marine antifouling coatings prepared in Example 1 and the comparative example were immersed in a suspension of diatom exponential growth and cultured for one week. After the culture period, an optical microscope was used to observe and quantify the diatom adhesion on the sample surface. Figure 6 It can be seen that compared with the glass sheet, the number of diatoms on the surface of the marine antifouling coating prepared in Example 1 and the comparative example is significantly reduced, and the number of diatoms on the surface of the marine antifouling coating prepared in Example 1 is the least compared with the comparative example. These findings indicate that the inherent low surface energy characteristics of the marine antifouling coating greatly promote its anti-diatom adsorption performance, and the addition of porous ruthenium selenide further improves the anti-diatom efficiency of the marine antifouling coating. One mechanistic explanation for this enhancement is that porous ruthenium selenide catalyzes the generation of reactive oxygen species (ROS), thereby causing oxidative stress and subsequent cell damage in the diatom body.

[0163] (4) Marine field testing

[0164] The coating was spin-coated on an epoxy resin plate of 50 mm × 50 mm in size and cured to obtain a marine test sample. The sample was then fixed on a stainless steel chain and immersed in Bohai Sea water together with the sample. The sample was taken out of the sea water regularly to observe the fouling area of ​​the sample.

[0165] For comparison, the present invention prepared three groups of samples: epoxy resin board (blank group), marine antifouling coating prepared in Example 1 (experimental group), marine antifouling coating prepared in comparative example (control group 1) and Jotun coating (commercial product, control group 2). The test results are shown in Figure 2. Figure 7 As shown in the figure, the dirt coverage area on the sample surface was statistically analyzed using ImageJ software. The blank group had the largest dirt area, with a dirt coverage rate of 91.29%. In contrast, the experimental group had the smallest dirt coverage area, only 5.07%, the control group 2 had a dirt coverage area of ​​17.14%, and the control group 1 had a dirt coverage area of ​​23.42%.

[0166] Table 1

[0167] Antibacterial rate% Anti-diatom rate% Example 1 90.41 98.42 Example 2 91.26 98.53 Example 3 93.65 99.61 Example 4 92.74 98.74 Example 5 91.87 97.58 Example 6 82.45 93.15 Example 7 81.76 92.47 Example 8 79.32 90.83 Example 9 76.89 89.45 Example 10 74.56 87.92 Embodiment 11 73.28 86.71 Example 12 70.15 84.38 Example 13 68.92 83.15 Comparative Example 30.55 65.28

[0168] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a marine antifouling coating having an active-passive synergistic mechanism, characterized in that: The preparation method comprises: (I) uniformly mixing a template agent, concentrated hydrochloric acid, n-butanol, tetraethyl orthosilicate and deionized water to obtain a template precursor solution; heating the template precursor solution, cooling it naturally after heating, and then filtering, washing and drying it to obtain an intermediate product; calcining the intermediate product to obtain a porous template; (II) the porous template obtained in step (I), ruthenium chloride and anhydrous ethanol are mixed and stirred to obtain a mixed solution, and the mixed solution is continuously heated until the anhydrous ethanol therein is completely evaporated to obtain a mixed powder; the mixed powder and selenium powder are placed in two crucibles respectively and placed in a tubular furnace for heating and calcining to obtain a template-loaded ruthenium selenide in the crucible containing the mixed powder; the template-loaded ruthenium selenide is immersed in a concentrated alkali solution and heated to remove the porous template, and after the etching is completed, it is filtered, washed and dried to obtain a porous ruthenium selenide; (III) dissolving vinyl-terminated polydimethylsiloxane, a photoinitiator and polymercaptopropylmethylsiloxane in cyclohexane to obtain a coating base liquid, adding the porous ruthenium selenide obtained in step (II) to the coating base liquid, stirring evenly and then ultrasonicating, followed by vacuum degassing to obtain a coating liquid; coating the coating liquid on the surface of a substrate, curing it after ultraviolet light irradiation, and obtaining the marine antifouling coating with an active-passive synergistic mechanism.

2. The preparation method according to claim 1, characterized in that: In step (I), the preparation process of the template precursor solution includes: First, the template, concentrated hydrochloric acid and deionized water are mixed evenly until the template is completely dissolved to obtain a first solution; Subsequently, n-butanol is added to the first solution, mixed, stirred and heated to obtain a second solution; Finally, adding tetraethyl orthosilicate to the second solution, continuing to mix, stir and heat to obtain a third solution, and subjecting the third solution to ultrasound to obtain the template precursor solution; The template agent is polyethylene oxide-polypropylene oxide-polyethylene oxide.

3. The preparation method according to claim 2, characterized in that: In the first solution, the mass ratio of the template, concentrated hydrochloric acid and deionized water is 1:(1.5-3):(20-30); The mass fraction of the concentrated hydrochloric acid is 30-40wt%; The mass ratio of the template in the first solution to the n-butanol is 1:(1-2); The mixing and stirring time of the first solution and n-butanol is 1 to 2 hours; The heating temperature during the mixing and stirring of the first solution and n-butanol is 30-40° C.; The mass ratio of the template agent to tetraethyl orthosilicate in the second solution is 1:(2-3); The mixing time of the second solution and ethyl orthosilicate is 12 to 24 hours; The heating temperature during the mixing and stirring of the second solution and ethyl orthosilicate is 30-40° C.; The ultrasonic power of the ultrasonic treatment of the third solution is 200-300W; The ultrasonic treatment time of the third solution is 0.5-1h.

4. The preparation method according to claim 1, characterized in that: In step (I), the heating temperature of the template precursor solution is 90-110°C; The heating time of the template precursor solution is 20 to 30 hours; The washing process comprises: washing the filtered product with deionized water for 3 to 5 times until the pH is neutral; The drying temperature is 80-100°C; The drying time is 3 to 5 hours.

5. The preparation method according to claim 1, characterized in that: In step (I), the heating rate of the intermediate product during calcination is 1-5°C / min; The calcination temperature of the intermediate product is 550-600°C; The holding time for calcining the intermediate product is 5 to 6 hours.

6. The preparation method according to claim 1, characterized in that: In step (II), the mixed solution is prepared by the following method: Dissolving ruthenium chloride in anhydrous ethanol, mixing evenly to obtain a ruthenium chloride solution, adding the porous template to the ruthenium chloride solution under stirring conditions, and mixing evenly to obtain the mixed solution; The ratio of ruthenium chloride to anhydrous ethanol is 1 g: (10-20) mL; The mass ratio of the porous template to the ruthenium chloride in the ruthenium chloride solution is (1-2):1; The temperature of the continuous heating of the mixed solution is 50-60°C.

7. The preparation method according to claim 1, characterized in that: In step (II), the mass ratio of the mixed powder to selenium powder is 1:(1-2); Before heating and calcining, a mixed gas of hydrogen and argon is introduced into the tubular furnace, wherein the volume ratio of hydrogen to argon in the mixed gas is 1:(15-20); The heating rate of the heating calcination is 1-5°C / min; The heating and calcining temperature is 550-600°C; The holding time of the heating calcination is 2 to 3 hours.

8. The preparation method according to claim 1, characterized in that: In step (II), the concentrated alkali solution is a sodium hydroxide solution; The concentration of the sodium hydroxide solution is 2-4 mol / L; The heating temperature of the template-loaded ruthenium selenide during immersion in concentrated alkali solution is 60-80°C; The immersion time of the template-loaded ruthenium selenide is 12 to 24 hours.

9. The preparation method according to claim 1, characterized in that: In step (III), the mass ratio of the vinyl-terminated polydimethylsiloxane, the photoinitiator, the polymercaptopropylmethylsiloxane and the cyclohexane is 1:(0.02-0.021):(0.07-0.08):(3-4); The photoinitiator is 2-hydroxy-2-methylpropiophenone; The amount of porous ruthenium selenide added is 0.1-0.5wt% of the total mass of the coating base liquid; The stirring time of the porous ruthenium selenide and the coating base liquid is 20 to 30 minutes; The stirring speed of the porous ruthenium selenide and the coating base liquid is 300-500 rpm; The power of the ultrasound is 400-600W; The ultrasound time is 30 to 40 minutes; The vacuum degassing time is 10 to 20 minutes; The coating thickness of the coating liquid is 1 to 20 μm; The coating liquid is applied by spin coating, spray coating or scraping coating; The ultraviolet light irradiation time is 10 to 30 minutes.

10. A marine antifouling coating having an active-passive synergistic mechanism prepared by the preparation method according to any one of claims 1 to 9.

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