High-selectivity cerium-based nano anticorrosive material as well as preparation method and application thereof

Abstract

The invention discloses a high-selectivity cerium-based nano anti-corrosion material as well as a preparation method and application thereof, and belongs to the field of microbial pollution and metal surface anti-corrosion treatment. (1) Zn < 2 + > of the Zn-coated Ce material has lactonase activity, AHLs molecules can be converted, formation of a metal surface biofilm can be inhibited, and microbial corrosion resistance of marine operation equipment can be enhanced; (2) the MIPs take an AHL structural analogue y-heptanolide as a template molecule, so that the prepared composite material has high specificity to the AHLs, efficient capture and quenching of SRB quorum sensing signal molecules can be realized, and formation and evolution of a biological membrane are fundamentally inhibited; and (3) the prepared MIPs are wrapped outside the material, and the hydrophobic structure of the MIPs further prevents the seawater from damaging Zn < 2 + >.

Description

Technical Field

[0001] The present invention relates to the field of microbial contamination and metal surface anti-corrosion treatment, and in particular to a highly selective cerium-based nano-anti-corrosion material, a preparation method thereof, and an application thereof. Background Art

[0002] This study addresses the issue of multiple protective failures in marine engineering equipment in complex corrosive environments. Conventional metal-based anticorrosion coating systems suffer from technical deficiencies such as the indiscriminate release of broad-spectrum biocides, which accelerates coating degradation, and the susceptibility of conventional slow-release components to phase transition and inactivation under high chloride ion penetration. In particular, the biofilm formation mechanism regulated by quorum sensing by corrosive microorganisms such as SRB significantly weakens the effectiveness of conventional antibacterial coatings. Existing technologies struggle to simultaneously address the coupled corrosion issues of physical protective layer degradation, chemical passivation failure, and microbial biofilm proliferation, hindering the long-term protective capabilities of marine equipment.

[0003] Based on the research on the mechanism of microbial corrosion, the present invention proposes a synergistic protection system that combines quorum sensing signal molecule (AHL) molecular imprinting technology with rare earth cerium doped zinc-based materials. 2 + Maintain basic anti-corrosion performance, combined with Ce 3 + / Ce 4 Redox reactions enhance the self-healing properties of the passive film, while AHL-specific recognition sites constructed using molecular imprinting technology block SRB quorum sensing signaling. This system innovatively integrates the dual functions of metal substrate corrosion control and biofilm inhibition. Gradient Ce doping optimizes the electronic structure of the zinc-based material, increasing the densification of the corrosion product layer and reducing the chloride ion permeation rate. Furthermore, AHL molecular imprinting sites reduce the initial SRB attachment density through specific adsorption, thereby prolonging the biofilm maturation period. This synergistic mechanism of "corrosion inhibition, biofilm blocking, and interface stabilization" transcends the single-layer protection model of traditional coatings, achieving a unified approach of dynamic interface microenvironment regulation and long-term, stable protection. Summary of the Invention

[0004] Technical Problem Solved: To address the problem of traditional anti-corrosion materials' poor recognition of bacterial quorum sensing signal molecules (AHLs), particularly their difficulty in accurately capturing or degrading specific AHLs in complex environments, this invention provides a highly selective cerium-based nano-anti-corrosion material, its preparation method, and its application. This addresses the problem of conventional metal-based materials being prone to passivation and aggregation in anti-corrosion applications, resulting in a reduction in active sites and low reuse efficiency.

[0005] Technical solution: A method for preparing a highly selective cerium-based nano-anticorrosive material, comprising the following steps: (1) Preparation of Zn@Ce carrier: a. Dissolving a metallic zinc source, a cerium source and an organic ligand in methanol at a molar ratio of Zn:Ce:organic ligand of 1:(0.05-0.3):(3-8) to form a solution; b. Mixing the metal salt solution and the organic ligand solution at room temperature, stirring at 50-500 rpm for 1-6 hours, and then centrifuging at 3000-6000 rpm for 10-30 minutes to collect the precipitate; c. Washing the precipitate with methanol 2-5 times, and vacuum drying at 50-100°C for 6-24 hours; d. In a nitrogen or inert gas atmosphere, heating to 600-900°C at 2-10°C / min, and calcining for 1-5 hours to obtain a Zn@Ce carrier; (2) Molecular imprinting polymerization The method comprises the following steps: a. adding a Zn@Ce carrier, a template molecule, and a functional monomer to a mixed solvent of methanol and acetonitrile in a carrier: template molecule: functional monomer mass ratio of 1: (0.5-3): (5-20) to form a prepolymerization system; b. introducing nitrogen into the prepolymerization system for deoxygenation treatment for 10-30 minutes; c. adding a crosslinker, an initiator, and methanol, wherein the molar ratio of the crosslinker to the functional monomer is (1-5): 1, the mass of the initiator is 1-10% of the crosslinker, and the volume of methanol is 20%-50% of the volume of the mixed solvent in step (2) a, and stirring the reaction at 20-50° C. for 8-24 hours; d. washing and removing the template molecule with ethyl acetate in an amount of 1-5 times the volume of the reaction system, centrifuging, and vacuum drying at 40-80° C. for 12-48 hours to obtain a Zn@Ce-MIPs composite material.

[0006] The metallic zinc source is zinc nitrate hexahydrate or zinc chloride, the cerium source is cerium nitrate hexahydrate or ammonium cerium sulfate, the organic ligand is 2-methylimidazole or 1,3,5-benzenetricarboxylic acid, the template molecule is γ-heptanolide, δ-decalactone and homologues thereof, the functional monomer is selected from at least two combinations of 2-acrylamide-2-methylpropanesulfonic acid, 4-vinylpyridine or hydroxyethyl methacrylate, with a molar ratio of 1:1-1:3, the crosslinking agent is ethylene glycol dimethacrylate or pentaerythritol triacrylate, and the molar ratio of the crosslinking agent to the functional monomer is further limited to (2-3.5):1, and the initiator is dopamine or azobisisobutyronitrile, and the amount used is 3%-8% of the mass of the crosslinking agent.

[0007] In step (1) b: the centrifugation parameter is 4000-5000 rpm, and the centrifugation is 15-25 minutes.

[0008] In step (1) d: the calcination condition is to increase the temperature to 700° C. at 5° C. / min under a nitrogen atmosphere and maintain the temperature for 2-4 hours.

[0009] In step (2) a: the volume ratio of the mixed solvent of methanol and acetonitrile is 1:1±0.1.

[0010] In step (2) c: the molar ratio of the cross-linking agent to the functional monomer is 2:1-4:1.

[0011] In step (2) d: the amount of ethyl acetate used is 2-3 times the volume of the reaction system, and the number of washing times is 3-5 times.

[0012] The highly selective cerium-based nano-anticorrosive material (Zn@Ce-MIPs composite material) prepared by the above method.

[0013] Application of the above composite materials in anti-corrosion and antibacterial coatings for marine equipment.

[0014] A coating, the active ingredient of which contains the Zn@Ce-MIPs composite material.

[0015] Beneficial effects: The present invention prepares a Zn@Ce-MIPs material, which has the following beneficial effects: (1) Zn 2+ It has lactone enzyme activity, can transform AHLs molecules, inhibit the formation of biofilm on metal surfaces, and can enhance the resistance of marine equipment to microbial corrosion; (2) MIPs uses y-heptanolide, an AHL structural analogue, as a template molecule, so that the prepared composite material has high specificity for AHLs, can achieve efficient capture and quenching of SRB quorum sensing signal molecules, and fundamentally inhibit the formation and evolution of biofilm; (3) The prepared MIPs are wrapped outside the material, and its hydrophobic structure further prevents seawater from attacking Zn 2+ destruction. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Preparation flow chart of Zn@Ce-MIPs composite materials.

[0017] Figure 2 Conversion effect of composite materials on γ-heptanolactone under different preparation conditions.

[0018] Figure 3 This is a scanning electron micrograph of the prepared cerium-doped metal zinc-based material combined with AHL molecular imprinting. DETAILED DESCRIPTION

[0019] Embodiment 1:

[0020] The preparation steps of Zn@Ce-MIPs composite materials are as follows:

[0021] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0022] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.49 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0023] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0024] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0025] (5) Disperse 100 mg Zn@Ce, 1 mmol γ-heptanolactone, 2 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 2 mmol 4-vinylpyridine in 40 mL methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h;

[0026] (6) Deoxygenate with N2 for 15 min, add 4 mmol of ethylene glycol dimethacrylate, 30 mg of dopamine, and 10 mL of methanol, and polymerize with stirring at 60°C for 12 h;

[0027] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0028] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0029] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 86.4%.

[0030] Example 2: (δ-decalactone as template)

[0031] The preparation steps of Zn@Ce-MIPs composite materials are as follows:

[0032] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0033] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.49 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0034] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0035] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0036] (5) Disperse 100 mg Zn@Ce, 1 mmol δ-decalactone, 2 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 2 mmol 4-vinylpyridine in 40 mL of a methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h;

[0037] (6) Deoxygenate with N2 for 15 min, add 4 mmol of ethylene glycol dimethacrylate, 30 mg of dopamine, and 10 mL of methanol, and polymerize with stirring at 60°C for 12 h;

[0038] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0039] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0040] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 48.7%.

[0041] Example 3: (Monomer Ratio Optimization)

[0042] The preparation steps of Zn@Ce-MIPs composite materials are as follows:

[0043] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0044] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.49 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0045] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0046] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0047] (5) Disperse 100 mg Zn@Ce, 1 mmol γ-heptanolactone, 3 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 1 mmol 4-vinylpyridine in 40 mL methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h.

[0048] (6) Deoxygenate with N2 for 15 min, add 4 mmol of ethylene glycol dimethacrylate, 30 mg of dopamine, and 10 mL of methanol, and polymerize with stirring at 60°C for 12 h;

[0049] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0050] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0051] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 90.2%.

[0052] Example 4: (Solvent Polarity Adjustment)

[0053] The preparation steps of Zn@Ce-MIPs composite materials are as follows:

[0054] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0055] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.49 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0056] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0057] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0058] (5) Disperse 100 mg Zn@Ce, 1 mmol γ-heptanolactone, 2 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 2 mmol 4-vinylpyridine in 40 mL methanol / acetone (3:1) mixture and stir at 40 °C in the dark for 12 h;

[0059] (6) Deoxygenate with N2 for 15 min, add 4 mmol of ethylene glycol dimethacrylate, 30 mg of dopamine, and 10 mL of methanol, and polymerize with stirring at 60°C for 12 h;

[0060] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0061] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0062] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 77.3%.

[0063] Example 5: (Gradient thermal polymerization)

[0064] The preparation steps of Zn@Ce-MIPs composite materials are as follows:

[0065] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0066] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.49 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0067] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0068] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0069] (5) Disperse 100 mg Zn@Ce, 1 mmol γ-heptanolactone, 2 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 2 mmol 4-vinylpyridine in 40 mL methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h;

[0070] (6) After deoxygenation with N2 for 15 min, 4 mmol of ethylene glycol dimethacrylate, 30 mg of dopamine, and 10 mL of methanol were added and the mixture was reacted at 45 °C for 4 h, and then the mixture was heated to 70 °C for 8 h for polymerization.

[0071] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0072] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0073] The prepared Zn@Ce-NIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 93.1%.

[0074] Example 6: (Optimization of Cerium Doping Ratio)

[0075] The preparation steps of Zn@Ce-MIPs composite materials are as follows:

[0076] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0077] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 3.04 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0078] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0079] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0080] (5) Disperse 100 mg Zn@Ce, 1 mmol γ-heptanolactone, 2 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 2 mmol 4-vinylpyridine in 40 mL methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h;

[0081] (6) Deoxygenate with N2 for 15 min, add 4 mmol of ethylene glycol dimethacrylate, 30 mg of dopamine, and 10 mL of methanol, and polymerize with stirring at 60°C for 12 h;

[0082] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0083] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0084] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 91.2%.

[0085] Control Example 1: (no template)

[0086] The preparation steps of Zn@Ce-MIPs composite materials are as follows:

[0087] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0088] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.49 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0089] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0090] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0091] (5) Disperse 100 mg Zn@Ce, 2 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 2 mmol 4-vinylpyridine in 40 mL of a methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h.

[0092] (6) Deoxygenate with N2 for 15 min, add 4 mmol of ethylene glycol dimethacrylate, 30 mg of dopamine, and 10 mL of methanol, and stir and polymerize for 12 h;

[0093] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0094] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0095] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 12.6%.

[0096] Control Example 2: (Non-imprinted polymer NIPs)

[0097] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0098] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.49 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0099] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0100] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0101] (5) Disperse 100 mg Zn@Ce, 1 mmol γ-heptanolactone, 2 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 2 mmol 4-vinylpyridine in 40 mL methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h;

[0102] (6) Only water washing is used to remove the template;

[0103] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0104] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0105] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 27.6%.

[0106] Comparative Example 3: (Random Copolymer)

[0107] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0108] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.49 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0109] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0110] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0111] (5) Disperse 100 mg Zn@Ce, 1 mmol γ-heptanolide, and 4 mmol methacrylic acid in 40 mL of a methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h.

[0112] (6) Deoxygenate with N2 for 15 min, add 4 mmol of ethylene glycol dimethacrylate, 30 mg of dopamine, and 10 mL of methanol, and polymerize at 60°C for 12 h;

[0113] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0114] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0115] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 21.4%.

[0116] Comparative Example 4: (without crosslinking agent)

[0117] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0118] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.49 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0119] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0120] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0121] (5) Disperse 100 mg Zn@Ce, 1 mmol γ-heptanolactone, 2 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 2 mmol 4-vinylpyridine in 40 mL methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h;

[0122] (6) Deoxygenate with N2 for 15 min, add 30 mg of dopamine and 10 mL of methanol, and stir at 60 °C for 12 h;

[0123] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0124] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0125] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 8.4%.

[0126] Comparative Example 5: (Thermal polymerization without stirring)

[0127] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0128] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.49 g of cerium nitrate hexahydrate in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0129] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0130] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0131] (5) Disperse 100 mg Zn@Ce, 1 mmol γ-heptanolactone, 2 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 2 mmol 4-vinylpyridine in 40 mL methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h;

[0132] (6) Deoxygenate with N2 for 15 min, add 4 mmol of ethylene glycol dimethacrylate, 30 mg of dopamine, and 10 mL of methanol, and polymerize with stirring at 60°C for 12 h;

[0133] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0134] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0135] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 64.2%.

[0136] Comparative Example 6: (Changing the doped rare earth element)

[0137] The preparation steps of Zn@Ce-MIPs composite materials are as follows:

[0138] (1) Dissolve 5.5 g of 2-methylimidazole in 300 mL of methanol to form solution A;

[0139] (2) Dissolve 4.76 g of zinc nitrate hexahydrate and 1.48 g of lanthanum nitrate hexahydrate (La(NO3)3·6H2O) in 200 mL and 100 mL of methanol, respectively, and mix to obtain solution B;

[0140] (3) Mix solutions A and B at room temperature, stir at 100 rpm for 2 hours, and centrifuge at 4000 rpm for 20 minutes to collect the precipitate;

[0141] (4) After washing with methanol three times, the mixture was dried at 60°C and pyrolyzed at 700°C at a rate of 5°C / min in a nitrogen atmosphere for 2 hours to obtain Zn@Ce material;

[0142] (5) Disperse 100 mg Zn@Ce, 1 mmol γ-heptanolactone, 2 mmol 2-acrylamido-2-methylpropanesulfonic acid, and 2 mmol 4-vinylpyridine in 40 mL methanol / acetonitrile (1:1) mixture and stir at 40 °C in the dark for 12 h;

[0143] (6) Deoxygenate with N2 for 15 min, add 4 mmol of ethylene glycol dimethacrylate, 30 mg of dopamine, and 10 mL of methanol, and polymerize with stirring at 60°C for 12 h;

[0144] (7) Collect the solid by centrifugation and wash it with ethyl acetate three times to remove the template;

[0145] (8) After washing with water and vacuum drying, Zn@Ce@MIPs were obtained.

[0146] The prepared Zn@Ce-MIPs were used to degrade γ-heptanolactone at a concentration of 0.02 mL / mL, with a conversion rate of 68.5%.

[0147] The conversion effect of composite materials on γ-heptalactone under different preparation conditions is as follows Figure 2 As shown, the composite material prepared in Example 5 has the best conversion effect of 93.1%. In the control experiment, the composite material prepared in Control Example 6 has the best conversion effect of 68.5%. Overall, the combination of Zn and Ce greatly enhances the conversion rate of γ-heptanolactone, and the combination with MIPs further enhances its conversion rate.

[0148] The above describes the embodiments of the present invention in detail with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. After knowing the contents described in the present invention, ordinary technicians in this technical field can make several equivalent changes and substitutions without departing from the principles of the present invention. These equivalent changes and substitutions should also be regarded as falling within the scope of protection of the present invention.

Claims

1. A method for preparing a highly selective cerium-based nano-anticorrosive material, characterized in that The following steps are involved: (1) Preparation of Zn@Ce carrier: a. The metallic zinc source, the cerium source and the organic ligand are dissolved in methanol to form a solution at a molar ratio of Zn:Ce: organic ligand of 1:(0.05-0.3):(3-8); b. The metal salt solution and the organic ligand solution were mixed at room temperature, stirred at 50-500 rpm for 1-6 hours, and then centrifuged at 3000-6000 rpm for 10-30 minutes to collect the precipitate; c. Wash the precipitate with methanol 2-5 times and dry it in vacuum at 50-100°C for 6-24 hours; d. In a nitrogen or inert gas atmosphere, the temperature is raised to 600-900°C at 2-10°C / min and calcined for 1-5 hours to obtain a Zn@Ce carrier; (2) Molecular imprinting polymerization: a. The Zn@Ce carrier, template molecule, functional monomer were added to a mixed solvent of methanol and acetonitrile in a carrier: template molecule: functional monomer mass ratio of 1: (0.5-3): (5-20) to form a prepolymerization system; b. Nitrogen was introduced into the prepolymerization system for deoxygenation for 10-30 minutes; c. Add a crosslinker, an initiator and methanol, wherein the molar ratio of the crosslinker to the functional monomer is (1-5): 1, the mass of the initiator is 1-10% of the crosslinker, the volume of methanol is 20% -50% of the volume of the mixed solvent in step (2) a, and the reaction is stirred at 20-50 ° C for 8-24 hours; d. The template molecules were removed by washing with ethyl acetate (1-5 times the volume of the reaction system), centrifuged, and vacuum dried at 40-80°C for 12-48 hours to obtain a Zn@Ce-MIPs composite material.

2. The method according to claim 1, characterized in that The metallic zinc source is zinc nitrate hexahydrate or zinc chloride, the cerium source is cerium nitrate hexahydrate or ammonium cerium sulfate, the organic ligand is 2-methylimidazole or 1,3,5-benzenetricarboxylic acid, the template molecule is γ-heptanolide, δ-decalactone and homologues thereof, the functional monomer is selected from at least two combinations of 2-acrylamide-2-methylpropanesulfonic acid, 4-vinylpyridine or hydroxyethyl methacrylate, with a molar ratio of 1:1-1:3, the crosslinking agent is ethylene glycol dimethacrylate or pentaerythritol triacrylate, and the molar ratio of the crosslinking agent to the functional monomer is further limited to (2-3.5):1, and the initiator is dopamine or azobisisobutyronitrile, and the amount used is 3%-8% of the mass of the crosslinking agent.

3. The method according to claim 1, characterized in that In step (1) b: the centrifugation parameter is 4000-5000 rpm, and the centrifugation is 15-25 minutes.

4. The method according to claim 1, wherein In step (1) d: the calcination condition is to increase the temperature to 700° C. at 5° C. / min under a nitrogen atmosphere and maintain the temperature for 2-4 hours.

5. The method according to claim 1, wherein In step (2) a: the volume ratio of the mixed solvent of methanol and acetonitrile is 1:1±0.

1.

6. The method according to claim 1, wherein In step (2) c: the molar ratio of the cross-linking agent to the functional monomer is 2:1-4:

1.

7. The method according to claim 1, characterized in that In step (2) d: the amount of ethyl acetate used is 2-3 times the volume of the reaction system, and the number of washing times is 3-5 times.

8. Highly selective cerium-based nano-anticorrosive material prepared by the method according to any one of claims 1 to 7: Zn@Ce-MIPs composite material.

9. Use of the composite material according to claim 8 in anti-corrosion and antibacterial coatings for marine equipment.

10. A coating, characterized in that: The active ingredient contains the Zn@Ce-MIPs composite material according to claim 8.

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