CN108971513B - Nano copper particle and low-cost green and environment-friendly preparation method thereof - Google Patents
Nano copper particle and low-cost green and environment-friendly preparation method thereof Download PDFInfo
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- CN108971513B CN108971513B CN201811177749.8A CN201811177749A CN108971513B CN 108971513 B CN108971513 B CN 108971513B CN 201811177749 A CN201811177749 A CN 201811177749A CN 108971513 B CN108971513 B CN 108971513B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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Abstract
The invention discloses a method for preparing nano-scale elemental copper particles by a water phase method. The method adopts a monovalent copper compound as a copper source, and ingeniously utilizes a water-soluble amino high molecular compound as a dispersing agent, a complexing agent and a reducing agent. Under the condition of stirring, solid monovalent copper ions and the macromolecular amino compound are subjected to complexation reduction and enter a water phase to obtain a stable water solution of nano-scale copper particles; and slowly adding the aqueous solution into the organic solvent, and separating the nano-copper particles from the aqueous phase in a precipitation form to finally obtain the solid nano-copper particles. The method is a water phase reaction, the process is simple, the prepared nano-copper particles are in a single crystal state, the particle size of the nano-copper particles is 50-200nm, and the average particle size is 80-120 nm; the prepared nano copper particles can be dispersed in water and can also be dispersed in a weak polar solvent.
Description
Technical Field
The invention belongs to the field of new metal nano materials, relates to a preparation method of nano copper powder, and particularly relates to a low-cost green environment-friendly preparation method of nano copper particles subjected to water-phase reduction by using a water-soluble high-molecular compound as a dispersing agent, a complexing agent and a reducing agent.
Background
The nanometer copper powder has the characteristics of small size, large specific surface area, small resistance, quantum size effect, macroscopic quantum tunneling effect and the like, thereby showing many special properties completely different from bulk metal copper, such as reduced melting point, increased surface energy, improved catalytic activity, greatly increased elongation, reduced conductivity and the like. The method is widely applied to the fields of optics, electronics, catalysis, antibiosis, lubrication, polymer filling modification and the like.
The preparation method of the nano copper powder is mainly divided into a physical method and a chemical method. Among them, physical methods include physical vapor deposition, high-energy ball milling, and high-temperature plasma methods, and chemical methods include chemical vapor deposition, chemical precipitation, sol-gel method, hydrothermal method, electrolytic method, and liquid-phase reduction method.
The liquid phase reduction method is the most commonly used preparation method for preparing the nano-copper in laboratories and industries at present. Selecting proper soluble copper salt precursor and proper reducing agent such as hydrazine hydrate, sodium borohydride, ascorbic acid and the like to react in liquid phase, wherein the divalent copper ion is Cu2+Reduced and nucleated to grow into nanometer copper powder. The method can control the nucleation and growth processes by changing reaction parameters such as the type of a reducing agent, the concentration of a precursor, the reaction temperature and time, particularly the type and the dosage of a surfactant and the like, thereby controlling the size and the shape of particles. The method has low requirement on equipment, and the used raw materials are cheap inorganic salts, so that the method is easy to expand to industrial production; however, the preparation method has high heating temperature, needs toxic reducing agents such as hydrazine hydrate and the like and organic solvents, has complicated operation steps, and obtains powder with uneven granularity, difficult dispersion and lower yield. In summary, based on the liquid phase reduction method, a more practical, low-cost, green and environment-friendly method is urgently needed to be developed to prepare the nano-copper particles with uniform particle size and easy dispersion.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a nano-copper particle and a low-cost green and environment-friendly preparation method thereof, and solve the problems of easy agglomeration, poor stability, high viscosity, complex post-treatment process and the like in the existing liquid phase reduction method. The invention adopts water-soluble polymer as dispersant, complexing agent and reducing agent, which reacts with monovalent copper ions under the condition of water phase to generate nano-copper particle water solution, and then the nano-copper particles are separated from the solution by organic solvent to obtain the nano-copper particles. The specific technical scheme is as follows:
(1) dissolving a proper amount of water-soluble amino high molecular compound containing primary amine, secondary amine or tertiary amine functional groups in the molecule into water to prepare high molecular aqueous solution with proper concentration;
(2) weighing a proper amount of monovalent copper compound, adding the monovalent copper compound into the polymer aqueous solution obtained in the step (1) under magnetic stirring, heating the suspension to 30-80 ℃, and carrying out complex reduction reaction on the solid monovalent copper ion compound and the amino polymer compound; reacting for 3-6 hours to obtain a stable aqueous solution of the copper amino polymer complex;
(3) slowly adding the aqueous solution of the copper amino polymer complex obtained in the step (2) into a proper ketone organic solvent or ketone/hydrocarbon mixed solvent, stirring vigorously, generating a large amount of brown precipitates immediately, and obtaining a dispersion liquid of the nano copper powder after the reaction is finished;
(4) and (4) carrying out centrifugal separation, washing and vacuum drying on the dispersion liquid prepared in the step (3) to obtain a nano copper particle product.
The water-soluble amino high molecular compound in the step (1) is one or more of polyethyleneimine, polyvinylamine and derivatives thereof. The mass percentage concentration of the water-soluble amino macromolecular compound aqueous solution is 3-20%, preferably 5-10%.
And (3) in the step (2), the monovalent copper compound is one or more of cuprous chloride, cuprous bromide and cuprous oxide.
The mass ratio of the monovalent copper compound to the amino macromolecular compound in the step (2) is 1: 2-1: 20, preferably 1: 4-1: 10.
the magnetic stirring speed in the step (2) is 500-1500r/min, the reaction temperature is 30-80 ℃, and the reaction time is 3-6 h.
The organic solvent suitable in the step (3) is a ketone organic solvent or a ketone/hydrocarbon mixed solvent; preferably, the organic solvent is one or more of acetone, methyl ethyl ketone, n-hexane/acetone and n-hexane/methyl ethyl ketone.
The speed of the vigorous stirring in the step (3) is 1000-1500 r/min.
And (4) selecting anhydrous ethanol and/or deionized water as the detergent in the step (4), and washing for 3-4 times.
The temperature of vacuum drying in the step (4) is 50-80 ℃, and the time is 3-6 h.
The particle size of the nano copper powder obtained in the step (4) is 50-200nm, most of the nano copper powder is 80-120nm, the average particle size is 100nm, and the yield is over 95 percent; the nano-copper particles can be dispersed in water and a weak polar solvent.
The invention has the beneficial effects that:
(1) the nano copper powder prepared by the method has extremely high dispersity, does not have the phenomenon of particle agglomeration, and has important practical value for research and development and industrialization of novel nano powder.
(2) The nano copper powder prepared by the method has good oxidation resistance, uniform particle size distribution, average particle size of 100nm, yield of over 95 percent and most of the nano copper powder distributed in 80-120nm, and can be dispersed in water and weak solvents.
(3) The preparation method provided by the invention has the advantages of simple process, aqueous phase reaction, low heating temperature, low energy consumption, economy, high efficiency, greenness, environmental protection and suitability for mass production.
Drawings
FIG. 1 is a scanning electron micrograph of the copper nanoparticles prepared in example 1 of the present invention. FIG. 2 is an XRD pattern of the nano-copper powder prepared in example 1 of the present invention.
Detailed Description
The preparation of the process of the invention is illustrated in detail below by means of several examples. It should be noted that the following examples are only illustrative of the preparation process of the present invention, and are not intended to limit the scope of the present invention.
Example 1
Weighing 1g of cuprous chloride, adding the cuprous chloride into 80g of a prepared polyethyleneimine aqueous solution with the concentration of 8%, heating the aqueous solution to 45 ℃ under the condition of stirring, and gradually changing the solution from a white turbid solution to a colorless transparent liquid and then to a reddish brown transparent liquid along with the prolonging of the reaction time. Stopping the reaction after 4 hours, slowly adding the solution into acetone and stirring vigorously, and immediately generating a large amount of brown precipitate to obtain the nano copper dispersion liquid with the particle size of about 100 nanometers. And (3) carrying out centrifugal separation on the obtained nano copper powder dispersion liquid to obtain copper colloid, alternately washing the copper colloid twice by using absolute ethyl alcohol and deionized water respectively, and carrying out vacuum drying to obtain the nano copper powder with the particle size of about 100 nm.
Example 2
0.7g of freshly prepared cuprous oxide is weighed, added to 80g of a prepared polyvinylamine aqueous solution with the concentration of 6%, the temperature of the aqueous solution is raised to 60 ℃ under the condition of stirring, and the solution gradually changes from red turbid liquid to colorless transparent liquid and then to reddish brown transparent liquid along with the extension of the reaction time. And stopping the reaction after 4 hours, slowly adding the solution into methyl ethyl ketone, and violently stirring to immediately generate a large amount of brown precipitates to obtain the nano copper particle dispersion liquid with the particle size of about 80 nanometers. And (3) carrying out centrifugal separation on the obtained nano copper powder dispersion liquid to obtain copper colloid, alternately washing the copper colloid twice by using absolute ethyl alcohol and deionized water respectively, and carrying out vacuum drying to obtain the nano copper powder with the particle size of about 80 nm.
Example 3
Adding 2g of freshly prepared cuprous chloride into 80g of a 10% polyethyleneimine aqueous solution prepared in advance, heating the aqueous solution to 70 ℃ under the condition of stirring, stopping the reaction after 4 hours, slowly adding the solution into a n-hexane/acetone mixed solvent, and immediately generating a large amount of brown precipitate to obtain the nano copper particle dispersion liquid with the particle size of about 120 nanometers. And (3) carrying out centrifugal separation on the obtained nano copper powder dispersion liquid to obtain copper colloid, alternately washing the copper colloid twice by using absolute ethyl alcohol and deionized water respectively, and carrying out vacuum drying to obtain the nano copper powder with the particle size of about 120 nm.
Example 4
Adding 0.4g of freshly prepared cuprous oxide into 80g of a 5% polyvinyl amine aqueous solution prepared in advance, heating the aqueous solution to 45 ℃ under the condition of stirring, stopping the reaction after 4 hours, slowly adding the solution into a n-hexane/methyl ethyl ketone mixed solvent, and immediately generating a large amount of brown precipitate to obtain the nano-copper particle dispersion liquid with the particle size of about 60 nanometers. And (3) carrying out centrifugal separation on the obtained nano copper powder dispersion liquid to obtain copper colloid, alternately washing the copper colloid twice by using absolute ethyl alcohol and deionized water respectively, and carrying out vacuum drying to obtain the nano copper powder with the particle size of about 60 nm.
Claims (15)
1. A low-cost green environment-friendly preparation method of nano-copper particles is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving a proper amount of water-soluble macromolecular compound containing primary amine, secondary amine or tertiary amine functional group in the molecule into water to prepare macromolecular compound aqueous solution with proper concentration;
(2) weighing a proper amount of monovalent copper compound, and adding the monovalent copper compound into the macromolecular compound aqueous solution obtained in the step (1) under magnetic stirring to obtain a suspension; heating the suspension to 30-80 ℃, carrying out complex reduction reaction on the solid monovalent copper ion compound and the high molecular compound, and reacting for 3-6 hours to obtain a stable aqueous solution of the copper amino high molecular complex;
(3) slowly adding the aqueous solution of the copper amino polymer complex obtained in the step (2) into a proper ketone organic solvent or ketone/hydrocarbon mixed solvent, stirring vigorously, generating a large amount of brown precipitates immediately, and obtaining a dispersion liquid of the nano copper powder after the reaction is finished;
(4) and (4) carrying out centrifugal separation on the dispersion liquid obtained in the step (3), washing and drying in vacuum to obtain the nano-copper particle product.
2. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1, characterized in that: the water-soluble polymer compound in the step (1) is an amino polymer compound.
3. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1, characterized in that: the water-soluble high molecular compound in the step (1) is used as a dispersant, a complexing agent and a reducing agent of a reaction system.
4. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1 or 2, characterized in that: the water-soluble high molecular compound in the step (1) is one or more of polyethyleneimine, polyvinylamine and derivatives thereof.
5. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1, characterized in that: the mass percentage concentration of the macromolecular compound aqueous solution in the step (1) is 3-20%.
6. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1 or 5, characterized in that: the mass percentage concentration of the macromolecular compound aqueous solution in the step (1) is 5-10%.
7. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1, characterized in that: and (3) in the step (2), the monovalent copper compound is one or more of cuprous chloride, cuprous bromide and cuprous oxide.
8. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1, characterized in that: the mass ratio of the monovalent copper compound to the high molecular compound in the step (2) is 1: 20-1: 2.
9. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1 or 8, characterized in that: the mass ratio of the monovalent copper compound to the high molecular compound in the step (2) is 1: 10-1: 4.
10. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1, characterized in that: the magnetic stirring speed in the step (2) is 500-1500r/min, the reaction temperature is 30-80 ℃, and the reaction time is 3-6 h.
11. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1, characterized in that: the organic solvent in step (3) is a ketone organic solvent or a mixed solvent of ketones and hydrocarbons.
12. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1 or 11, characterized in that: the organic solvent in the step (3) is one or more of acetone, methyl ethyl ketone, n-hexane/acetone and n-hexane/methyl ethyl ketone.
13. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1, characterized in that: the speed of the vigorous stirring in the step (3) is 1000-1500 r/min.
14. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1, characterized in that: in the step (4), the detergent is selected from absolute ethyl alcohol and/or deionized water, and is washed for 3-4 times; the temperature of vacuum drying in the step (4) is 50-80 ℃, and the time is 3-6 h.
15. The low-cost green and environment-friendly preparation method of the nano-copper particles as claimed in claim 1, characterized in that: the yield of the nano copper particles is more than 95%.
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| CN109732099B (en) * | 2019-03-08 | 2022-04-05 | 辽宁大学 | Preparation method of antioxidant micron copper |
| CN111943251B (en) * | 2020-08-20 | 2021-07-02 | 苏州维格纳信息科技有限公司 | Method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material |
| CN112916864B (en) * | 2021-01-21 | 2023-07-21 | 范期奎 | Aqueous phase copper nanocrystalline and preparation method and application thereof |
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