CN-122011414-A - Preparation method and application of bionic cerium-based metal organic framework nano-enzyme for antifouling coating

Abstract

The invention discloses a preparation method and application of bionic cerium-based metal-organic frame nano-enzyme for an anti-fouling coating, and belongs to the technical field of functional materials of anti-fouling coatings. The preparation method comprises the steps of S1, preparing a metal salt solution, S2, preparing an amino acid solution, S3, preparing a complexing solution, S4, performing solvothermal reaction, S5, washing and drying. The bionic cerium-based metal organic framework nano-enzyme for the antifouling coating solves the problems of insufficient catalytic activity, poor specificity, single function and poor antifouling and anticorrosion synergistic effect, and the marine antifouling coating prepared by the nano-enzyme can effectively inhibit bacterial reproduction and microorganism adhesion and has good biocompatibility. The nano-enzyme and the coating thereof have application potential in preparing marine environment antifouling and antiseptic and biological medicine antibacterial materials.

Inventors

• TAKEE KIYOSEI
• WANG JINGYU
• SU RONGXIN
• ZHANG JINLI

Assignees

• 天津大学

Dates

Publication Date

20260512

Application Date

20260212

Claims (10)

1. 1. The preparation method of the bionic cerium-based metal organic frame nano-enzyme for the antifouling coating is characterized in that the bionic cerium-based metal organic frame nano-enzyme is used for preparing an anti-corrosion, antibacterial and algae-inhibiting antifouling coating or medical antibacterial material in a marine environment, and the preparation method comprises the following steps: s1, preparing a metal salt solution: dissolving soluble cerium salt in deionized water to obtain a metal salt solution; s2, preparing an amino acid solution: dissolving amino acid in a polar organic solvent to obtain an amino acid solution; S3, preparing a complexing solution: Slowly dropwise adding the metal salt solution obtained in the step S1 into the amino acid solution obtained in the step S2, controlling the dropwise adding rate to be 0.5-1mL/min, mixing and stirring uniformly to obtain a complex solution, and maintaining the temperature to be 20-50 ℃ in the stirring process; S4, solvothermal reaction: Transferring the complexing solution obtained in the step S3 into a container, heating at 60-120 ℃ to perform solvothermal reaction for 0.1-2h, naturally cooling to room temperature after the reaction is finished, and centrifuging to obtain a precipitate; S5, washing and drying: And (3) washing the precipitate obtained in the step (S4), and placing the washed product in a vacuum drying oven, and drying for 6-24 hours at 40-80 ℃ to obtain the bionic cerium-based metal organic frame nano-enzyme.
2. 2. The method for preparing the bionic cerium-based metal-organic framework nano-enzyme for the antifouling coating according to claim 1, wherein in the step S1, the soluble cerium salt is ammonium cerium nitrate, cerium sulfate or cerium acetate.
3. 3. The method for preparing the bionic cerium-based metal-organic framework nano-enzyme for the antifouling coating according to claim 1, wherein in the step S2, the polar organic solvent is N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, ethanol, N-dimethylacetamide or a mixed solvent system thereof, and the amino acid contains a dicarboxyl structure.
4. 4. The method for preparing the bionic cerium-based metal-organic framework nano-enzyme for the anti-fouling coating according to claim 3, wherein the amino acid containing the dicarboxyl structure is glutamic acid or aspartic acid.
5. 5. The method for preparing the bionic cerium-based metal-organic framework nano-enzyme for the antifouling coating according to claim 1, wherein in the step S1, the concentration of the metal salt solution is 10-100mmol/L, and in the step S2, the concentration of the amino acid solution is 5-100mmol/L.
6. 6. The method for preparing the bionic cerium-based metal-organic framework nano-enzyme for the antifouling coating according to claim 1, wherein in the step S3, the volume ratio of the metal salt solution to the amino acid solution is 1:1-1:5.
7. 7. The preparation method of the bionic cerium-based metal-organic framework nano-enzyme for the anti-fouling coating, as claimed in claim 1, is characterized in that in the step S3, the dropping rate of the metal salt solution is 0.5mL/min, in the step S4, the reaction temperature of the solvothermal reaction is 80-110 ℃, the reaction time is 0.5-1h, and the heating mode is one of oil bath, water bath or oven heating.
8. 8. The method for preparing the bionic cerium-based metal-organic framework nano-enzyme for the anti-fouling coating according to claim 1, wherein in the step S5, the precipitation washing method is to wash the nano-enzyme with one or more of N, N-dimethylformamide, deionized water, ethanol and acetone for 3 times in sequence, and the drying condition is that the nano-enzyme is dried at 60-70 ℃ for 10-12h.
9. 9. The bionic cerium-based metal-organic framework nano-enzyme for an antifouling coating, which is prepared by the preparation method according to any one of claims 1-8.
10. 10. The application of the bionic cerium-based metal-organic framework nano-enzyme for the antifouling coating in preparing an antifouling and anti-corrosive marine environment material and a medical antibacterial material.

Description

Preparation method and application of bionic cerium-based metal organic framework nano-enzyme for antifouling coating Technical Field The invention relates to the technical field of antifouling coating functional materials, in particular to a preparation method and application of bionic cerium-based metal-organic framework nano-enzyme for an antifouling coating. Background With the continued development of marine engineering equipment and the shipping industry, biofouling (biofouling) and Microbial Induced Corrosion (MIC) problems in marine environments are increasingly prominent. The biofouling causes the increase of the roughness of the ship body, the increase of the sailing resistance and the increase of the energy consumption, and the microorganism induced corrosion causes the local damage and the structural degradation of the metal material, thereby seriously shortening the service life of the equipment and increasing the maintenance cost. These two processes often promote each other, jointly weaken the protection system of marine facilities, and pose a long-term threat to sustainable marine development. Certain enzymes in nature, such as haloperoxidases and oxidases, can inhibit microbial growth and biofilm formation by catalyzing the production of Reactive Oxygen Species (ROS), exhibiting excellent self-cleaning and protective capabilities. The biocatalysis mechanism provides a bionic thought for ocean protection. However, natural enzymes are poorly stable, easily inactivated, costly and difficult to scale, limiting their practical use in complex marine environments. In contrast, the nanomaterial with enzyme-like activity (i.e., nanoenzyme) becomes a promising candidate system for replacing natural enzymes due to the advantages of high stability, strong environmental adaptability, adjustable structure, low cost and the like. Wherein, cerium-based nano-enzyme (Ce-based nanozymes) can catalyze ROS to generate under mild condition due to reversible Ce 3+/Ce4+ redox cycle, and is widely used in the fields of antibiosis and protection. The existing cerium-based nano enzyme and protective material thereof can realize the antibacterial, antifouling or antiseptic effects to a certain extent, but still have the defects of insufficient catalytic activity, poor enzymatic specificity, unordered structure, uncontrollable coordination, antifouling and antiseptic function cutting and the like. In the field of biological medicine, nano-enzyme is also becoming an increasingly important research direction inspired by natural enzyme capable of exerting antibacterial and antioxidant effects. Whereas most conventional nanoenzymes are amorphous or low crystallinity particles prepared by physical or simple chemical methods, their structural disorder results in insufficient exposure of catalytic active sites, weak substrate binding capacity, and low catalytic conversion numbers and conversion frequencies. In complex physiological environments, the activity of the enzyme is easily interfered by protein adsorption, pH change and ionic strength, so that the catalytic efficiency is far lower than that of natural enzymes or theoretical values, and the effective antibacterial ROS burst amount is difficult to realize. Therefore, a novel bionic cerium-based metal-organic framework nano enzyme system is needed, a metal-ligand environment of a natural enzyme active center can be simulated on a molecular level, electronic structure regulation and control, multienzyme-like synergistic catalysis and excellent biocompatibility are realized, and therefore, efficient catalysis in multiple fields is realized, long-term, green and efficient antifouling and anticorrosion integrated protection can be provided in a complex marine environment, and huge application potential can be shown in preparation of medical materials such as medical antibacterial coatings, wound dressings and the like. This is the core technical problem to be solved by the present invention. Disclosure of Invention Therefore, the invention provides a preparation method and application of bionic cerium-based metal-organic framework nano-enzyme for an antifouling coating, which adopts amino acid as a unique organic ligand and directly coordinates with cerium ions to construct a metal-organic framework so as to solve the problems of unordered catalytic active center structure, poor enzymatic specificity, insufficient biocompatibility, weak synergistic effect of antifouling and anticorrosion functions and the like caused by using traditional organic ligands in the prior art. In order to achieve the above object, the present invention provides the following technical solutions: according to a first aspect of the present invention, there is provided a method for preparing a bionic cerium-based metal-organic framework nano-enzyme for an antifouling coating, the bionic cerium-based metal-organic framework nano-enzyme being used for preparing an anti-corrosion, anti-bacterial and an