CN100589904C - A kind of preparation method of nano copper particle - Google Patents

Abstract

The invention discloses a method for preparing nanometer copper particles. In the method, a dendritic compound with a benzene ring as a core is used as a template and mixed with a copper salt, and the strong coordination effect of multiple amino groups in the dendritic compound is utilized. Cu ²⁺ is complexed inside and outside the cavity of the dendrimers, and then reduced with a reducing agent to transform divalent copper into zero-valent copper. Since the present invention uses the dendritic compound with the benzene ring as the core as the template, it solves the problem that the existing liquid phase reduction method cannot produce nano-copper particles with small particle size and good dispersibility, and realizes the preparation of copper nanoparticles by the liquid phase reduction method. The average particle diameter is 2-5nm, and the uniform spherical nano-copper particles with good dispersibility are obtained. Moreover, the preparation method of the invention is simple, the raw materials are readily available, the cost is low, the conditions are mild, the requirements for equipment are low, the production process is environmentally friendly, the by-products are pollution-free, and large-scale industrial production is possible.

Description

A kind of preparation method of nano copper particle

technical field

The invention relates to a method for preparing nano copper particles, belonging to the technical field of nano metal materials.

Background technique

Due to their special properties in optics, magnetism, heat, electronics, sensors and catalysis, nano-copper particles can be widely used in various fields, such as high-efficiency catalysts, conductive pastes, high-conductivity, high-specific-strength alloys and solid lubricants, etc. At present, there are many methods for preparing nano-copper, such as gas phase evaporation method, plasma method, γ-ray irradiation-hydrothermal crystallization combined method, mechanochemical method, ultrasonic chemical method, electron beam irradiation method, photocatalytic decomposition method, electrolytic method, sol A gel method, reverse microemulsion method, microwave irradiation synthesis method, supercritical extraction method, thermal decomposition method, etc. Some of these preparation methods have high technical requirements and expensive equipment, some have complex processes and are more polluting to the environment, and some require longer reaction time, higher temperature and pressure, and special reaction devices, resulting in higher production costs. In recent years, the liquid phase reduction method is more active in the preparation of nano-copper, but the nano-copper particles obtained by the existing liquid-phase reduction preparation process have a large particle size and a wide particle size distribution, and the resulting product is easy to agglomerate and difficult to be widely used. application.

Contents of the invention

The purpose of the present invention is to provide a method for preparing nano-copper particles that is easy to operate, low-cost and environmentally friendly in view of the defects in the above-mentioned prior art, so as to solve the problem that the liquid-phase reduction method cannot produce nano-copper particles with small particle size and good dispersibility. Copper particles conundrum.

In order to solve the problems of the technologies described above, the technical solution of the present invention is as follows:

The preparation method of the nano-copper particles provided by the invention belongs to the liquid phase reduction method, and the specific steps are as follows:

a) Preparation of template agent: adding polyamide-amine dendrimers with benzene ring as the core into distilled water, stirring at 15-30°C to dissolve completely;

b) Preparation of copper salt solution: adding the copper salt compound into distilled water, stirring at 15-30°C to dissolve it completely;

c) At 15-30°C, add the above-prepared copper salt solution dropwise to the above-prepared templating agent, and continue stirring for 1-2 hours after dropping, wherein the molar ratio of the copper salt to the templating agent is (16 :1)~(4:1);

d) At 15-30°C, quickly add the rehydrating compound-based reducing agent solution that is now prepared into the mixed solution obtained in step c), and stir vigorously for 20-40 minutes, wherein: the molar ratio of the reducing agent to the copper salt is (4 :1)~(2:1);

e) filter, and wash with distilled water and absolute ethanol respectively for 3 times to obtain the target product;

The copper salt compound is copper sulfate;

The complex hydride reducing agent is sodium borohydride.

The polyamide-amine dendritic polymer with benzene ring as the core is preferably its fourth generation product (4G), fifth generation product (5G) or sixth generation product (6G).

In the present invention, a dendritic compound with a benzene ring as the core is used as a template and mixed with a copper salt, and the strong coordination of multiple amino groups present in the dendritic compound is used to make Cu ²⁺ interact with the dendritic compound in the cavity of the dendritic compound. External complexation, and then reduction with a reducing agent to convert divalent copper into zero-valent copper, which can be expressed as DT+Cu ²⁺ --- DT-Cu ²⁺ ; DT-Cu ²⁺ + reducing agent----Cu (0), where DT represents a dendritic compound with a benzene ring as the core. Compared with the prior art, the present invention has the following beneficial effects:

1) The present invention uses the dendritic compound with the benzene ring as the core as the template, so it solves the problem that the existing liquid phase reduction method cannot produce nano-copper particles with small particle size and good dispersibility, and realizes the use of liquid phase The reduction method produces uniform spherical nano-copper particles with an average particle size of 2-5 nm and good dispersibility.

2) The preparation method of the present invention is simple, the raw materials are readily available, the cost is low, the conditions are mild, the requirements for equipment are low, the production process is environmentally friendly, the by-products are pollution-free, and large-scale industrial production is possible.

Description of drawings

Fig. 1 is the transmission electron micrograph of the nano-copper particle prepared by embodiment 1;

Fig. 2 is the transmission electron micrograph of the nano-copper particle prepared by embodiment 4;

Fig. 3 is the transmission electron micrograph of the nano-copper particle prepared by embodiment 5;

Fig. 4 is the transmission electron micrograph of the nano-copper particle prepared by embodiment 6;

Fig. 5 is the transmission electron micrograph of the nano-copper particle prepared by embodiment 8;

Fig. 6 is the chemical structural formula of the fourth generation product (4G) of the polyamide-amine dendrimers with benzene ring as the nucleus;

Fig. 7 is the chemical structural formula of the fifth generation product (5G) of polyamide-amine dendrimers with benzene ring as the nucleus;

Fig. 8 is the chemical structural formula of the sixth generation product (6G) of the polyamide-amine dendritic polymer with a benzene ring as the core.

Detailed ways

The present invention will be further described below by embodiment, and its purpose is only to understand content of the present invention better but not limit the protection scope of the present invention.

Example 1

The preparation method of the nano-copper particles provided in this embodiment, the specific steps are as follows:

a) Preparation of template agent: add 0.02562 g of the fourth-generation product (4G) of polyamide-amine dendritic polymer with benzene ring as the core into 10 ml of twice-distilled water, stir at 15-30° C. to completely dissolve, Obtain 0.5mmol/L solution;

b) Preparation of copper salt solution: add 0.02g CuSO ₄ ·5H ₂ O into 10ml double distilled water, stir at 15-30°C to dissolve completely, and obtain 8mmol/L solution;

c) At 15-30°C, add the above-prepared copper salt solution dropwise to the above-prepared template agent, after dropping, continue to stir for 1-2 hours, wherein: the molar ratio of copper salt to template agent is 16: 1;

d) Add 0.012g NaBH ₄ into 10ml double-distilled water at 15-30°C, now prepare 32mmol/L sodium borohydride solution, quickly add it into the mixed solution obtained in step c) after preparation, and stir vigorously for 30 minutes, wherein : the molar ratio of reducing agent to copper salt is 4:1;

e) Filtration, washing with distilled water and absolute ethanol three times respectively, to obtain the target product.

As shown in FIG. 1 , the copper nanoparticles prepared in this example are uniform spherical nanoparticles with good dispersion, no agglomeration, and an average particle diameter of 4.9 nm.

Example 2

The preparation method of the nano-copper particles provided in this embodiment, the specific steps are as follows:

a) Preparation of template agent: add 0.02562 g of the fourth-generation product (4G) of polyamide-amine dendritic polymer with benzene ring as the core into 10 ml of twice-distilled water, stir at 15-30° C. to completely dissolve, Obtain 0.5mmol/L solution;

b) Preparation of copper salt solution: add 0.02g CuSO ₄ ·5H ₂ O into 10ml double distilled water, stir at 15-30°C to dissolve completely, and obtain 8mmol/L solution;

c) At 15-30°C, add the above-prepared copper salt solution dropwise to the above-prepared template agent, after dropping, continue to stir for 1-2 hours, wherein: the molar ratio of copper salt to template agent is 16: 1;

d) Add 0.006g of _NaBH4 into 10ml of twice-distilled water at 15-30°C, and now prepare a 16mmol/L sodium borohydride solution. After preparation, quickly add it to the mixed solution obtained in step c), and stir vigorously for 30 minutes. : the molar ratio of reducing agent to copper salt is 2:1;

e) Filtration, washing with distilled water and absolute ethanol three times respectively, to obtain the target product.

The copper nanoparticles prepared in this example are uniform spherical nanoparticles with good dispersibility, no agglomeration, and an average particle diameter of 4.7 nm.

Example 3

The preparation method of the nano-copper particles provided in this embodiment, the specific steps are as follows:

a) Preparation of template agent: add 0.02562 g of the fourth-generation product (4G) of polyamide-amine dendritic polymer with benzene ring as the core into 10 ml of twice-distilled water, stir at 15-30° C. to completely dissolve, Obtain 0.5mmol/L solution;

b) Preparation of copper salt solution: add 0.01g CuSO ₄ ·5H ₂ O into 10ml double distilled water, stir at 15-30°C to dissolve completely, and obtain a 4mmol/L solution;

c) At 15-30°C, add the copper salt solution prepared above dropwise to the template agent prepared above, after dropping, continue to stir for 1-2 hours, wherein: the molar ratio of copper salt to template agent is 8: 1;

d) Add 0.006g of _NaBH4 into 10ml of twice-distilled water at 15-30°C, and now prepare a 16mmol/L sodium borohydride solution. After preparation, quickly add it to the mixed solution obtained in step c), and stir vigorously for 30 minutes. : the molar ratio of reducing agent to copper salt is 4:1;

e) Filtration, washing with distilled water and absolute ethanol three times respectively, to obtain the target product.

The copper nanoparticles prepared in this example are uniform spherical nanoparticles with good dispersibility, no agglomeration, and an average particle diameter of 4.3 nm.

Example 4

The preparation method of the nano-copper particles provided in this embodiment, the specific steps are as follows:

a) Preparation of template agent: add 0.02562 g of the fourth-generation product (4G) of polyamide-amine dendritic polymer with benzene ring as the core into 10 ml of twice-distilled water, stir at 15-30° C. to completely dissolve, Obtain 0.5mmol/L solution;

b) Preparation of copper salt solution: add 0.005g CuSO ₄ ·5H ₂ O into 10ml double distilled water, stir at 15-30°C to dissolve completely, and obtain a 2mmol/L solution;

c) At 15-30°C, add the copper salt solution prepared above dropwise to the template agent prepared above, after dropping, continue to stir for 1-2 hours, wherein: the molar ratio of copper salt to template agent is 4: 1;

d) Add 0.003g NaBH ₄ into 10ml double-distilled water at 15-30°C, now prepare 8mmol/L sodium borohydride solution, quickly add it into the mixed solution obtained in step c) after preparation, and stir vigorously for 30 minutes, wherein : the molar ratio of reducing agent to copper salt is 4:1;

e) Filtration, washing with distilled water and absolute ethanol three times respectively, to obtain the target product.

As shown in FIG. 2 , the copper nanoparticles prepared in this embodiment are uniform spherical nanoparticles with good dispersion, no agglomeration, and an average particle diameter of 3.9 nm.

Example 5

The preparation method of the nano-copper particles provided in this embodiment, the specific steps are as follows:

a) Prepare template agent: add 0.02562 g of the fifth-generation product (5G) of polyamide-amine dendrimers with benzene ring as the core into 10 ml of twice-distilled water, stir at 15-30° C. to dissolve completely, Obtain 0.5mmol/L solution;

b) Preparation of copper salt solution: add 0.02g CuSO ₄ ·5H ₂ O into 10ml double distilled water, stir at 15-30°C to dissolve completely, and obtain 8mmol/L solution;

c) At 15-30°C, add the above-prepared copper salt solution dropwise to the above-prepared template agent, after dropping, continue to stir for 1-2 hours, wherein: the molar ratio of copper salt to template agent is 16: 1;

d) Add 0.012g NaBH ₄ into 10ml double-distilled water at 15-30°C, now prepare 32mmol/L sodium borohydride solution, quickly add it into the mixed solution obtained in step c) after preparation, and stir vigorously for 30 minutes, wherein : the molar ratio of reducing agent to copper salt is 4:1;

e) Filtration, washing with distilled water and absolute ethanol three times respectively, to obtain the target product.

As shown in FIG. 3 , the copper nanoparticles prepared in this embodiment are uniform spherical nanoparticles with good dispersion, no agglomeration, and an average particle diameter of 3.4 nm.

Example 6

The preparation method of the nano-copper particles provided in this embodiment, the specific steps are as follows:

a) Prepare template agent: add 0.02562 g of the fifth-generation product (5G) of polyamide-amine dendrimers with benzene ring as the core into 10 ml of twice-distilled water, stir at 15-30° C. to dissolve completely, Obtain 0.5mmol/L solution;

b) Preparation of copper salt solution: add 0.01g CuSO ₄ ·5H ₂ O into 10ml double distilled water, stir at 15-30°C to dissolve completely, and obtain a 4mmol/L solution;

c) At 15-30°C, add the copper salt solution prepared above dropwise to the template agent prepared above, after dropping, continue to stir for 1-2 hours, wherein: the molar ratio of copper salt to template agent is 8: 1;

d) Add 0.003g NaBH ₄ into 10ml double-distilled water at 15-30°C, now prepare 8mmol/L sodium borohydride solution, quickly add it into the mixed solution obtained in step c) after preparation, and stir vigorously for 30 minutes, wherein : the molar ratio of reducing agent to copper salt is 2:1;

e) Filtration, washing with distilled water and absolute ethanol three times respectively, to obtain the target product.

As shown in FIG. 4 , the copper nanoparticles prepared in this embodiment are uniform spherical nanoparticles with good dispersion, no agglomeration, and an average particle diameter of 3.2 nm.

Example 7

The preparation method of the nano-copper particles provided in this embodiment, the specific steps are as follows:

a) Preparation of template agent: Add 0.02562 g of the sixth generation product (6G) of polyamide-amine dendrimers with benzene ring as the core into 10 ml of twice distilled water, stir at 15-30° C. to dissolve completely, Obtain 0.5mmol/L solution;

b) Preparation of copper salt solution: add 0.02g CuSO ₄ ·5H ₂ O into 10ml double distilled water, stir at 15-30°C to dissolve completely, and obtain 8mmol/L solution;

c) At 15-30°C, add the above-prepared copper salt solution dropwise to the above-prepared template agent, after dropping, continue to stir for 1-2 hours, wherein: the molar ratio of copper salt to template agent is 16: 1;

d) Add 0.012g NaBH ₄ into 10ml double-distilled water at 15-30°C, now prepare 32mmol/L sodium borohydride solution, quickly add it into the mixed solution obtained in step c) after preparation, and stir vigorously for 30 minutes, wherein : the molar ratio of reducing agent to copper salt is 4:1;

e) Filtration, washing with distilled water and absolute ethanol three times respectively, to obtain the target product.

The copper nanoparticles prepared in this example are uniform spherical nanoparticles with good dispersibility, no agglomeration, and an average particle diameter of 2.9 nm.

Example 8

The preparation method of the nano-copper particles provided in this embodiment, the specific steps are as follows:

a) Prepare template agent: add 0.02562 g of the fifth-generation product (5G) of polyamide-amine dendrimers with benzene ring as the core into 10 ml of twice-distilled water, stir at 15-30° C. to dissolve completely, Obtain 0.5mmol/L solution;

b) Preparation of copper salt solution: add 0.01g CuSO ₄ ·5H ₂ O into 10ml double distilled water, stir at 15-30°C to dissolve completely, and obtain a 4mmol/L solution;

c) At 15-30°C, add the copper salt solution prepared above dropwise to the template agent prepared above, after dropping, continue to stir for 1-2 hours, wherein: the molar ratio of copper salt to template agent is 8: 1;

d) Add 0.006g of _NaBH4 into 10ml of twice-distilled water at 15-30°C, and now prepare a 16mmol/L sodium borohydride solution. After preparation, quickly add it to the mixed solution obtained in step c), and stir vigorously for 30 minutes. : the molar ratio of reducing agent to copper salt is 4:1;

e) Filtration, washing with distilled water and absolute ethanol three times respectively, to obtain the target product.

As shown in FIG. 5 , the copper nanoparticles prepared in this embodiment are uniform spherical nanoparticles with good dispersion, no agglomeration, and an average particle diameter of 2.6 nm.

The chemical structural formulas of the fourth-generation product (4G), the fifth-generation product (5G) and the sixth-generation product (6G) of the polyamide-amine dendritic polymer with a benzene ring as the nucleus described in this description are shown in Figure 6, Figure 7 and Figure 8.

Claims (2)

1. the preparation method of a nano copper particle is characterized in that, described method comprises following concrete steps:

A) preparation template agent: the polyamide-amide class dendritic that will be nuclear with the phenyl ring adds in the distilled water, 15～30 ℃ of stirrings it is dissolved fully;

B) preparation copper salt solution: compound nantokite is added in the distilled water, it is dissolved fully 15～30 ℃ of stirrings;

C) at 15～30 ℃, the copper salt solution of above-mentioned preparation dropwise is added drop-wise in the template agent of above-mentioned preparation, drip and finish, continue to stir 1～2 hour, wherein: the mol ratio of mantoquita and template agent is (16: 1)～(4: 1);

D) at 15～30 ℃, the multiple hydrogen compound class reductant solution of now joining is added in the mixed solution of step c) gained fast, vigorous stirring 20～40 minutes, wherein: the mol ratio of reducing agent and mantoquita is (4: 1)～(2: 1);

E) filter, wash each respectively 3 times, promptly get target product with distilled water and absolute ethyl alcohol;

Described compound nantokite is a copper sulphate, and described multiple hydrogen compound class reducing agent is a sodium borohydride.

2. the preparation method of nano copper particle according to claim 1 is characterized in that, described with the phenyl ring be nuclear polyamide-amide class dendritic be its 4th generation product, the 5th generation product or the 6th generation product.

Images