CN112774588B - Preparation method of noble metal @ melamine core-shell nanostructure - Google Patents

Preparation method of noble metal @ melamine core-shell nanostructure Download PDF

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CN112774588B
CN112774588B CN202011509708.1A CN202011509708A CN112774588B CN 112774588 B CN112774588 B CN 112774588B CN 202011509708 A CN202011509708 A CN 202011509708A CN 112774588 B CN112774588 B CN 112774588B
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melamine
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prepolymer
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CN112774588A (en
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蒋绪川
陈伟凡
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Jiangxi Shanna New Material Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The invention relates to a preparation method of Au/Ag @ melamine core-shell structure nanoparticles, which comprises the following steps: (1) Au/Ag surface modification: dispersing a proper amount of Au or Ag nano powder into a solvent, carrying out ultrasonic treatment, then adding a modifier, heating and stirring, centrifuging, collecting a product, washing, and carrying out vacuum drying; (2) preparing a prepolymer: adding melamine into deionized water, adjusting the pH value, heating and stirring until a clear solution is obtained, and continuously preserving heat for 1-5 hours; (3) dispersing a proper amount of modified Au/Ag nano powder into deionized water, and carrying out ultrasonic treatment; (4) and (3) adding a proper amount of the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), adjusting the pH, heating and stirring, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles. The invention can effectively solve the problems of easy agglomeration and poor weather resistance of Au/Ag.

Description

Preparation method of noble metal @ melamine core-shell nanostructure
Technical Field
The invention belongs to the technical field of synthesis of nano composite materials, and particularly relates to a noble metal (such as gold or silver, Au/Ag) @ melamine core-shell structure nano composite material and a hydrothermal preparation method thereof.
Background
Noble metals (e.g., gold, silver) have found widespread use in a variety of fields. This is because gold has high electron density, dielectric properties and catalytic action, can bind to a variety of biomacromolecules, and does not affect the biological activity thereof. Whereas silver has good electrical conductivity. The silver nanoparticles have an extremely important position in the field of microelectronics due to the good conductivity of the silver nanoparticles.
In addition, the nano silver has a strong sterilization effect. Research shows that the smaller the particle size, the stronger the bactericidal performance. After being combined with cell walls/membranes of pathogenic bacteria, the nano silver particles can directly enter thalli and be rapidly combined with sulfydryl (-SH) of oxygen metabolism enzyme, so that the enzyme is inactivated, and respiratory metabolism is blocked to suffocate the bacteria. The unique sterilization mechanism enables the nano silver particles to rapidly kill pathogenic bacteria at low concentration. Nano silver belongs to a non-antibiotic bactericide: the nano silver can kill various pathogenic microorganisms, is stronger than antibiotics, and can quickly and directly kill bacteria by the unique antibacterial mechanism of nano silver particles with the size of 10nm, so that the bacteria lose the reproductive capacity, therefore, the next generation of drug resistance can not be produced, and the repeated attack and long-term treatment caused by the drug resistance can be effectively avoided.
In particular, the nano silver particles have super strong permeability, can quickly permeate into subcutaneous tissues for 2mm sterilization, and have good sterilization effect on deeper tissue infection caused by common bacteria, stubborn bacteria, drug-resistant bacteria and fungi. The nano silver can promote wound healing, promote the repair and regeneration of damaged cells, remove the necrotic tissue, promote tissue regeneration, resist bacteria, diminish inflammation, improve microcirculation of tissues around the wound, effectively activate and promote the growth of tissue cells, accelerate the healing of the wound and reduce the generation of scars.
The nanometer noble metal (such as gold and silver) also has unique application in the aspect of surface fluorescence enhancement. Most of the current researches particularly concern about the preparation of gold and silver nanoparticles which can be used as a noble metal nanoparticle assembly component with excellent surface enhanced fluorescence effect, and focus on the preparation methods of gold and silver nanoparticles with different sizes and appearances, and different structural assemblies are constructed in different assembly modes; a typical example that the precious metal nanoparticle assembly with a multilevel structure and morphology can effectively regulate and control local surface plasmon resonance of the precious metal nanoparticle assembly is described, and the diversified application of the surface enhanced fluorescence effect is shown.
In view of the nano-size effect of the two, different chemical methods such as liquid phase or gas phase reduction, electrochemical reduction, sol-gel method, atomic deposition, hydrothermal method, etc. have been developed to prepare nano noble metals (e.g., gold, silver). However, gold (Au) or silver (Ag) prepared by the above method has disadvantages, which limit practical applications thereof, such as:
1) the nano powder has poor weather resistance, for example, Ag can generate oxidation reaction after being exposed in the air for a long time;
2) the nano powder is easy to agglomerate;
3) the compatibility requirement is strict when the nano powder is compounded with the organic matrix.
In order to solve the above problems, the preparation of a core-shell structure of noble metals (e.g., gold, silver) is an effective method. In the literature reported so far, inorganic materials are used, such as: SiO 2 2 、TiO 2 The coating of Au/Ag nano powder solves the problems of poor weather resistance and easy agglomeration of Au/Ag, but the problem of compatibility with an organic matrix still exists. In addition, SiO was prepared 2 、TiO 2 The inorganic shell needs high-temperature annealing and other processes, the process is complex, the cost is high, waste liquid is generated, and the method is not suitable for the green industrial production required at present.
The melamine has excellent transparency and performances of heat resistance, wear resistance, acid and alkali resistance and the like, and is an ideal shell material. The surface of Au/Ag is coated with a layer of melamine, so that the Au/Ag alloy has the advantages of an inorganic shell layer, the stress resistance and the strain resistance of the Au/Ag alloy can be improved, and the problem of compatibility of an inorganic material and an organic matrix can be solved. In addition, the preparation method is simple to operate and mild in reaction conditions. The raw materials are cheap and easy to obtain, and the cost is reduced, so that the method is suitable for large-scale production.
Disclosure of Invention
The invention aims to provide Au/Ag @ melamine core-shell structure nanoparticles and a preparation method thereof, and the method can effectively solve the problems of easy agglomeration and poor weather resistance of Au/Ag. In addition, the compatibility problem of the inorganic material and the organic matrix can be improved, so that the application range of the Au/Ag nano powder is expanded.
In order to achieve the above objects and other objects, the present invention is achieved by the following means.
A preparation method of Au/Ag @ melamine core-shell structured nanoparticles comprises the following steps:
(1) Au/Ag surface modification: dispersing a proper amount of Au or Ag nano powder into a solvent, carrying out ultrasonic treatment, then adding a modifier (surfactant), heating and stirring, centrifugally collecting a product, washing, and carrying out vacuum drying;
(2) preparing a prepolymer: adding melamine into deionized water, adjusting the pH value, heating and stirring until a clear solution is obtained, and continuously preserving heat for 1-5 hours;
(3) dispersing a proper amount of modified Au/Ag nano powder into deionized water, and carrying out ultrasonic treatment;
(4) and (3) adding a proper amount of the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), adjusting the pH, heating and stirring, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles.
The Au/Ag in the step (1) is nano-particles obtained according to a method reported in the literature.
In the step (1), the solvent is one or two of alcohols, purified water and toluene. Preferably, the solvent in step (1) is toluene.
The modifier in the step (1) is selected from one or more of polyvinylpyrrolidone PVP, silane coupling agents (KH-570 and KH-550), catechol and ascorbic acid. Preferably, the modifying agent in step (1) is PVP.
The reagent used for adjusting the pH value in the step (2) is one or more of triethanolamine and ammonia reagents. Preferably, the reagent in step (2) is triethanolamine.
And (4) adjusting the pH value by using one or more of acetic acid, hydrochloric acid and sulfuric acid as a reagent. Preferably, the reagent in step (4) is acetic acid
In addition, the addition amount of the modifier in the step (1) is 1-5% of the mass of the Au/Ag nano powder. Preferably, the addition amount of the surface modifier in the step (1) is 2% of the mass of the nano powder.
In the step (2), the mass concentration of the melamine prepolymer is 5-20%. Preferably, the mass concentration of the melamine prepolymer in the step (2) is 10%.
In the step (2), the pH range is 7-10. Preferably, the pH is 8.
The mass ratio of the modified Au/Ag nano powder in the step (3) to the purified water is 1 (100-500). Preferably, the mass ratio of the modified Au/Ag nano powder in the step (3) to the purified water is 1: 200.
The mass ratio of the prepolymer in the step (4) to the Au/Ag nano powder after surface modification is (0.25-1) to (0.25-1). Preferably, the mass ratio of the prepolymer in the step (4) to the Au/Ag nano powder after surface modification is 0.75: 1.
In the step (4), the pH range is 2-5. Preferably, the pH is 4.
The ultrasonic time is 10-60 min. Preferably, the sonication time is 30 min.
The reaction temperature in the step (1) is 30-100 ℃. Preferably, the reaction temperature is 80 ℃.
The reaction time in the step (1) is 3-24 h. Preferably, the reaction time is 12 h.
The reaction temperature in the step (2) is 50-100 ℃. Preferably, the medium reaction temperature is 75 ℃.
The reaction time in the step (2) is 0.5-2 h. Preferably, the reaction time is 1 h.
In the step (4), the stirring speed is 500-1000 rpm. Preferably, the stirring speed is 800 rpm.
The reaction temperature in the step (4) is 50-100 ℃. Preferably, the reaction temperature is 65 ℃.
The reaction time in the step (4) is 1-4 h. Preferably, the reaction time is 2 h.
Further, after the heating reaction in the step (4) is finished, post-treatment is carried out, wherein the post-treatment comprises centrifugation, washing and vacuum drying. Wherein, the washing is carried out by sequentially adopting deionized water and ethanol, and the vacuum drying temperature is 40 ℃.
The preparation method of the Au/Ag @ melamine core-shell structure nano-particles provided by the invention is simple and feasible, and the prepared core-shell structure not only has the advantages of an inorganic shell layer, but also has strong stress resistance and strain resistance of the flexible shell layer, the compatibility of inorganic powder and an organic matrix is also obviously improved, and the application range is improved.
Drawings
FIG. 1 is a Transmission Electron Micrograph (TEM) of the Au @ melamine core-shell structured nanoparticle of example 1;
FIG. 2 is a scanning drop microscope (SEM) image and TEM image of Ag @ melamine core-shell structured nanoparticles of example 2.
Detailed Description
In the embodiment of the invention, a scanning electron microscope (SEM, Regulus 8100, Hitachi, Japan) is used for observing the appearance of the Au/Ag @ melamine core-shell structure nano-particles; the coating of Au/Ag @ poly-melamine core-shell structured nanoparticles was observed using a transmission electron microscope (TEM, JEM 2100, Japan).
A preparation method of Au/Ag @ melamine core-shell structured nanoparticles comprises the following steps:
(1) Au/Ag surface modification: dispersing a proper amount of Au or Ag nano powder into a solvent, carrying out ultrasonic treatment, then adding a modifier (surfactant), heating and stirring, carrying out reaction at the temperature of 30-100 ℃ for 3-24 h, centrifuging, collecting a product, washing, and carrying out vacuum drying; the Au/Ag is nano-particles obtained according to a method reported in the literature. The solvent is one or two of alcohols, purified water and toluene, the modifier is one or more of polyvinylpyrrolidone PVP, silane coupling agents (KH-570 and KH-550), catechol and ascorbic acid, and the addition amount of the modifier is 1-5% of the mass of the Au/Ag nano powder.
(2) Preparing a prepolymer: adding melamine into deionized water, adjusting the pH value to 7-10, heating and stirring until a clear solution is obtained, reacting at the temperature of 50-100 ℃ for 0.5-2 hours, and continuously preserving heat for 1-5 hours; the mass concentration of the melamine prepolymer is 5-20%, the total solution amount can be adjusted by adjusting the amount of dehydrated water, and the reagent for adjusting the pH is one or more of triethanolamine and ammonia reagents.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1 (100-500), and carrying out ultrasonic treatment for 10-60 min;
(4) and (3) adding a proper amount of the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), wherein the mass ratio of the prepolymer to the Au/Ag nano powder after surface modification is (0.25-1) to (0.25-1), adjusting the pH to 2-5, heating and stirring at the stirring speed of 500-1000 rpm, the reaction temperature of 50-100 ℃, the reaction time of 1-4 h, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles. The reagent for adjusting pH is one or more of acetic acid, hydrochloric acid and sulfuric acid, preferably acetic acid.
The invention is further illustrated by the following examples, which are not intended to be limiting and the scope of protection is indicated in the claims.
Example 1
(1) Surface modification of Au nanoparticles:
a50 mL three-necked flask was charged with 1.0g of Au and 80mL of toluene, and sonicated for 30 min. 0.025g of PVP was then added to the system, heated to 80 ℃ and stirred for 12 h. The product was collected by centrifugation, washed with absolute ethanol and dried under vacuum at 40 ℃.
(2) Preparation of a prepolymer:
to a 50mL beaker, 1.4g of melamine, 2.7g of an aqueous formaldehyde solution, and 11g of purified water were added, and the pH was adjusted to 8 with triethanolamine. And putting the beaker into a water bath, heating to 80 ℃, and stirring for reacting for 1h until a clear and transparent solution is obtained.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1:200, and carrying out ultrasonic treatment for 30 min;
(4) and (3) adding the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), adjusting the mass ratio of the prepolymer to the surface-modified Au/Ag nano powder to be 0.75:1, adjusting the pH to be 4 by hydrochloric acid, heating and stirring at the stirring speed of 800rpm and the reaction temperature of 65 ℃ for 2 hours, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles.
Fig. 1 is a TEM image of the Au @ melamine core-shell structured nanoparticle in example 1, and it can be seen that the prepared composite structured nanoparticle has a clear core-shell structure and a particle size distribution in the range of 100 to 200 nm.
Example 2
(1) Surface modification of Ag nanoparticles:
a50 mL three-necked flask was charged with 1.0g of Ag and 8.0mL of toluene, and sonicated for 30 min. 0.05g PVP was then added to the system, heated to 80 ℃ and stirred for 12 h. The product was collected by centrifugation, washed with absolute ethanol and dried under vacuum at 40 ℃.
(2) Preparation of a prepolymer:
to a 50mL beaker, 1.4g of melamine, 3.6g of an aqueous formaldehyde solution, and 8.0g of purified water were added, and the pH was adjusted to 8.5 with 0.1M triethanolamine. The beaker is put into a water bath to be heated to 80 ℃, and the reaction is stirred for 0.5h until a clear and transparent solution is obtained.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1:200, and carrying out ultrasonic treatment for 30 min;
(4) and (3) adding the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), adjusting the mass ratio of the prepolymer to the surface-modified Au/Ag nano powder to be 0.75:1, adjusting the pH to be 4 by hydrochloric acid, heating and stirring at the stirring speed of 800rpm and the reaction temperature of 65 ℃ for 2 hours, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles.
Fig. 2 is a TEM image of Ag @ melamine core-shell structured nanoparticles in the example, and it can be seen that melamine is uniformly coated on the surface of Ag particles.
Example 3
(1) Surface modification of Ag nanoparticles:
a50 mL three-necked flask was charged with 1.0g of Ag and 10.0mL of water, and sonicated for 30 min. 0.05g of ascorbic acid was subsequently added to the system, heated to 80 ℃ and stirred for 12 h. The product was collected by centrifugation, washed with purified water and dried under vacuum at 40 ℃.
(2) Preparation of a prepolymer:
to a 50mL beaker, 1.4g of melamine, 3.6g of an aqueous formaldehyde solution, and 8.0g of purified water were added, and the pH was adjusted to 8.5 with 0.1M triethanolamine. The beaker is put into a water bath to be heated to 80 ℃, and the reaction is stirred for 0.5h until a clear and transparent solution is obtained.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1:100, and carrying out ultrasonic treatment for 30 min;
(4) and (3) adding the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), adjusting the mass ratio of the prepolymer to the surface-modified Au/Ag nano powder to be 0.25:1, adjusting the pH to be 4 by hydrochloric acid, heating and stirring at the stirring speed of 800rpm and the reaction temperature of 65 ℃ for 2 hours, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles.
Example 4
(1) Surface modification of Ag nanoparticles:
a50 mL three-necked flask was charged with 1.0g of Ag and 8.0mL of toluene, and sonicated for 30 min. 0.05g of catechol was subsequently added to the system, heated to 80 ℃ and stirred for 12 h. The product was collected by centrifugation, washed with absolute ethanol and dried under vacuum at 40 ℃.
(2) Preparation of a prepolymer:
to a 50mL beaker, 1.4g of melamine, 3.6g of an aqueous formaldehyde solution, and 8.0g of purified water were added, and the pH was adjusted to 8.5 with 0.1M triethanolamine. The beaker is put into a water bath to be heated to 80 ℃, and the reaction is stirred for 0.5h until a clear and transparent solution is obtained.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1:500, and carrying out ultrasonic treatment for 30 min;
(4) and (3) adding the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), wherein the mass ratio of the prepolymer to the surface-modified Au/Ag nano powder is 1:0.25, adjusting the pH to 4 by hydrochloric acid, heating and stirring at the stirring speed of 800rpm and the reaction temperature of 65 ℃ for 2 hours, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles.
Example 5
(1) Surface modification of Ag nanoparticles:
a50 mL three-necked flask was charged with 1.0g of Ag and 8.0mL of toluene, and sonicated for 30 min. 0.05g PVP was then added to the system, heated to 30 ℃ and stirred for 24 h. The product was collected by centrifugation, washed with absolute ethanol and dried under vacuum at 40 ℃.
(2) Preparation of a prepolymer:
to a 50mL beaker, 1.4g of melamine, 3.6g of an aqueous formaldehyde solution, and 8.0g of purified water were added, and the pH was adjusted to 8.5 with 0.1M triethanolamine. And putting the beaker into a water bath, heating to 50 ℃, and stirring for reacting for 2 hours until a clear and transparent solution is obtained.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1:200, and carrying out ultrasonic treatment for 10 min;
(4) and (3) adding the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), adjusting the mass ratio of the prepolymer to the surface-modified Au/Ag nano powder to be 0.75:1, adjusting the pH to be 4 by hydrochloric acid, heating and stirring at the stirring speed of 800rpm and the reaction temperature of 65 ℃ for 2 hours, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles.
Example 6
(1) Surface modification of Ag nanoparticles:
a50 mL three-necked flask was charged with 1.0g of Ag and 8.0mL of toluene, and sonicated for 30 min. 0.01g PVP was then added to the system, heated to 80 ℃ and stirred for 12 h. The product was collected by centrifugation, washed with absolute ethanol and dried under vacuum at 40 ℃.
(2) Preparation of a prepolymer:
to a 50mL beaker, 1.4g of melamine, 3.6g of an aqueous formaldehyde solution, and 8.0g of purified water were added, and the pH was adjusted to 8.5 with 0.1M triethanolamine. And putting the beaker into a water bath, heating to 75 ℃, and stirring for reacting for 1h until a clear and transparent solution is obtained.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1:200, and carrying out ultrasonic treatment for 30 min;
(4) and (3) adding the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), adjusting the mass ratio of the prepolymer to the surface-modified Au/Ag nano powder to be 0.75:1, adjusting the pH to be 4 by hydrochloric acid, heating and stirring at the stirring speed of 800rpm and the reaction temperature of 65 ℃ for 2 hours, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles.
Example 7
(1) Surface modification of Ag nanoparticles:
a50 mL three-necked flask was charged with 1.0g of Ag and 10.0mL of ethanol, and sonicated for 30 min. 0.05g KH-570 was then added to the system, heated to 80 ℃ and stirred for 12 h. The product was collected by centrifugation, washed with absolute ethanol and dried under vacuum at 40 ℃.
(2) Preparation of a prepolymer:
to a 50mL beaker, 1.4g of melamine, 3.6g of an aqueous formaldehyde solution, and 8.0g of purified water were added, and the pH was adjusted to 8.5 with 0.1M triethanolamine. The beaker is put into a water bath to be heated to 80 ℃, and the reaction is stirred for 0.5h until a clear and transparent solution is obtained.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1:100, and carrying out ultrasonic treatment for 60 min;
(4) adding the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), wherein the mass ratio of the prepolymer to the Au/Ag nano powder subjected to surface modification is 1:1, adjusting the pH value to 5 with acetic acid, heating and stirring at the stirring speed of 500rpm, the reaction temperature of 100 ℃ for 1h, and carrying out post-treatment to obtain the Au/Ag @ melamine core-shell structure nanoparticles.
Example 8
(1) Surface modification of Ag nanoparticles:
a50 mL three-necked flask was charged with 1.0g of Ag and 10.0mL of ethanol, and sonicated for 30 min. 0.05g KH-570 was then added to the system, heated to 100 ℃ and stirred for 3 h. The product was collected by centrifugation, washed with absolute ethanol and dried under vacuum at 40 ℃.
(2) Preparation of a prepolymer:
to a 50mL beaker, 1.4g of melamine, 3.6g of an aqueous formaldehyde solution, and 8.0g of purified water were added, and the pH was adjusted to 8.5 with 0.1M triethanolamine. Putting the beaker into a water bath, heating to 50 ℃, and stirring for reacting for 2 hours until a clear and transparent solution is obtained.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1:200, and carrying out ultrasonic treatment for 60 min;
(4) and (3) adding the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), wherein the mass ratio of the prepolymer to the Au/Ag nano powder subjected to surface modification is 1: regulating the pH value to 5 by using sulfuric acid, heating and stirring at the stirring speed of 1000rpm, the reaction temperature of 50 ℃ for 4h, and carrying out post-treatment to obtain the Au/Ag @ melamine core-shell structure nanoparticles.
Example 9
(1) Surface modification of Ag nanoparticles:
a50 mL three-necked flask was charged with 1.0g of Ag and 10.0mL of water, and sonicated for 30 min. 0.05g of ascorbic acid was subsequently added to the system, heated to 80 ℃ and stirred for 12 h. The product was collected by centrifugation, washed with purified water and dried under vacuum at 40 ℃.
(2) Preparation of a prepolymer:
to a 50mL beaker, 1.4g of melamine, 3.6g of an aqueous formaldehyde solution, and 23.0g of purified water were added, and the pH was adjusted to 8.5 with 0.1M triethanolamine. The beaker is put into a water bath to be heated to 80 ℃, and the reaction is stirred for 0.5h until a clear and transparent solution is obtained.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1:100, and carrying out ultrasonic treatment for 30 min;
(4) and (3) adding the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), adjusting the mass ratio of the prepolymer to the surface-modified Au/Ag nano powder to be 0.25:1, adjusting the pH to be 4 by hydrochloric acid, heating and stirring at the stirring speed of 800rpm and the reaction temperature of 65 ℃ for 2 hours, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles.
Example 10
(1) Surface modification of Ag nanoparticles:
a50 mL three-necked flask was charged with 1.0g of Ag and 10.0mL of water, and sonicated for 30 min. 0.05g of ascorbic acid was subsequently added to the system, heated to 80 ℃ and stirred for 12 h. The product was collected by centrifugation, washed with purified water and dried under vacuum at 40 ℃.
(2) Preparation of a prepolymer:
to a 50mL beaker, 1.4g of melamine, 2.7g of aqueous formaldehyde, and 2.9g of purified water were added, and the pH was adjusted to 8.5 with 0.1M triethanolamine. The beaker is put into a water bath to be heated to 80 ℃, and the reaction is stirred for 0.5h until a clear and transparent solution is obtained.
(3) Dispersing a proper amount of modified Au/Ag nano powder into deionized water, wherein the mass ratio of the modified Au/Ag nano powder to the purified water is 1:100, and carrying out ultrasonic treatment for 30 min;
(4) and (3) adding the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), adjusting the mass ratio of the prepolymer to the surface-modified Au/Ag nano powder to be 0.25:1, adjusting the pH to be 4 by hydrochloric acid, heating and stirring at the stirring speed of 800rpm and the reaction temperature of 65 ℃ for 2 hours, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (9)

1. A preparation method of Au/Ag @ melamine core-shell structure nanoparticles is characterized by comprising the following steps:
(1) Au/Ag surface modification: dispersing a proper amount of Au or Ag nano powder into a solvent, carrying out ultrasonic treatment, then adding a modifier, heating and stirring, centrifuging, collecting a product, washing, and carrying out vacuum drying; the modifier in the step (1) is selected from one or more of polyvinylpyrrolidone PVP, a silane coupling agent, catechol and ascorbic acid;
(2) preparing a prepolymer: adding melamine into deionized water, adjusting the pH value, heating and stirring until a clear solution is obtained, and continuously preserving heat for 1-5 hours;
(3) dispersing a proper amount of modified Au/Ag nano powder into deionized water, and carrying out ultrasonic treatment;
(4) and (3) adding a proper amount of the prepolymer aqueous solution prepared in the step (2) into the dispersion liquid of the modified Au/Ag nano powder in the step (3), adjusting the pH, heating and stirring, and performing post-treatment to obtain the Au/Ag @ melamine core-shell structure nano particles.
2. The method for preparing Au/Ag @ melamine core-shell structured nanoparticles according to claim 1, wherein the method comprises the following steps: the reagent used for adjusting the pH value in the step (2) is one or more of triethanolamine and ammonia reagents.
3. The method for preparing Au/Ag @ melamine core-shell structured nanoparticles according to claim 1, wherein the method comprises the following steps: and (4) adjusting the pH value by using one or more of acetic acid, hydrochloric acid and sulfuric acid as a reagent.
4. The method for preparing Au/Ag @ melamine core-shell structured nanoparticles according to claim 1, wherein the method comprises the following steps: in the step (1), the solvent is one or two of alcohols, purified water and toluene.
5. The method for preparing Au/Ag @ melamine core-shell structured nanoparticles according to claim 1, wherein the method comprises the following steps: in the step (1), the addition amount of the modifier is 1-5% of the mass of the Au/Ag nano powder.
6. The method for preparing Au/Ag @ melamine core-shell structured nanoparticles according to claim 1, wherein the method comprises the following steps: in the step (2), the mass concentration of the melamine prepolymer is 5-20%.
7. The method for preparing Au/Ag @ melamine core-shell structured nanoparticles according to claim 1, wherein the method comprises the following steps: in the step (2), the pH range is 7-10.
8. The method for preparing Au/Ag @ melamine core-shell structured nanoparticles according to claim 1, wherein the method comprises the following steps: the mass ratio of the modified Au/Ag nano powder in the step (3) to the purified water is 1 (100-500).
9. The method for preparing Au/Ag @ melamine core-shell structured nanoparticles according to claim 1, wherein the method comprises the following steps: the mass ratio of the prepolymer in the step (4) to the Au/Ag nano powder after surface modification is (0.25-1) to (0.25-1).
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