CN105458295B - A kind of multi-pore micron copper ball and preparation method thereof - Google Patents
A kind of multi-pore micron copper ball and preparation method thereof Download PDFInfo
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- CN105458295B CN105458295B CN201610071062.0A CN201610071062A CN105458295B CN 105458295 B CN105458295 B CN 105458295B CN 201610071062 A CN201610071062 A CN 201610071062A CN 105458295 B CN105458295 B CN 105458295B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
Abstract
The present invention provides a kind of multi-pore micron copper balls and preparation method thereof.The preparation method includes the following steps: for copper source and organic acid complexing agent, organic amine complexing agent to be added in solvent, adds reducing agent hydrazine hydrate after mixing evenly and is reacted, is centrifuged, takes precipitating, be dried in vacuo after washing, obtain multi-pore micron copper ball.The present invention prepares porous copper product using wet chemistry reduction, and using cheap raw material as reactant, reaction condition green is mild, process flow is simple to operation, and generates the good dispersion of Porous Cu microballoon, and monodisperse degree is high, it can be mass-produced, and be applied to efficient catalytic, antibacterial field.
Description
Technical field
The present invention relates to the technical field for belonging to nano metal material, in particular to a kind of multi-pore micron copper ball and its preparation
Method.
Background technique
Porous micro-nano metal is material of the aperture size in micro-nano magnitude, compared to traditional porous metals, aperture size
Smaller, specific surface area is higher, thus has special physical and chemical performance, on catalysis, separation, sensor, vibration reduction and cushioning, surface
Raman enhancing etc. is widely used.
Currently, the preparation method of porous micro-nano metal material mainly has template, sedimentation, powder metallurgic method, de- alloy
Method etc..Template is that the raw material of porous material is filled in the hole of mould material, then leads to using colloid crystal as template
Certain either physically or chemically removing mould material is crossed, to obtain the reversed duplicate of template, i.e. porous material.Template
It is one of the common method of poromerics, wherein the selection of template is mostly important, decides the structure and property of porous material
Can, but the technique of the method is relative complex.De- alloyage is to utilize the chemical activity difference of elements different in alloy, passing through
It learns or more active one or more components is selectively removed in electrochemical method, remaining component passes through the modes such as atom diffusion
Form three-dimensional continuous porous metal material.At present by selective corrosion, oneself has been prepared nanoporous titanium, nanoporous
The materials such as copper and nano porous palladium.One kind is disclosed in the related technology, and nano porous copper is prepared by the de- Cu-Zn alloy of constant potential
Method, disclose again a kind of the whole continuous nano porous copper of Cu-Al alloy preparation is taken off using high temperature in the related technology.But it should
The shortcomings that there are preparation processes is complicated for operation for method, at high cost, and the production cycle is longer, is not suitable for large-scale industrial production.
Currently, it is still simple, at low cost without a kind of preparation process and can be applied to large-scale production about preparing Kufil Jenner
The report of rice material.
Summary of the invention
In view of this, on the one hand providing one kind it is an object of the invention to overcome shortcoming and defect of the existing technology
The preparation method of multi-pore micron copper ball.It is the preparation method simple process, low in cost, environmental-friendly and can be applied to extensive
Production.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of multi-pore micron copper ball includes the following steps: copper source and organic acid complexing agent, organic amine network
Mixture is added in solvent, adds reducing agent hydrazine hydrate after mixing evenly and is reacted, and is centrifuged, takes precipitating, and vacuum is dry after washing
It is dry, obtain multi-pore micron copper ball.
Wherein, copper source is a kind of in Kocide SD, copper nitrate, acetylacetone copper, copper sulphate and copper chloride or at least
Two kinds of mixture.
Wherein, the organic acid complexing agent is one in oleic acid, poly- propionic acid, polyacrylic acid, poly and lauric acid
Kind or at least two mixture.
Wherein, in terms of mol/mL, copper source and the organic acid complexing agent mole/volume ratio be 0.01~1.0:1~
20。
Wherein, organic amine complexing agent is ethylenediamine, ethanol amine, triethylamine, trioctylamine, diethylenetriamine and four ethylene
One of five amine or at least two mixtures.
Wherein, in terms of mol/mL, copper source and the organic amine complexing agent mole/volume ratio be 0.01~1.0:1~
20。
It should be noted that in the present invention mole/volume ratio unit is mol/mL, i.e. copper source unit is in terms of mol, organic amine
The unit of complexing agent in terms of mL, obtain mole/volume ratio.If copper source can be 0.01~1.0mol, organic amine complexing agent is 1
~20mL, appear below mole/volume ratio is identical with this.
Wherein, the solvent is water, ethyl alcohol, ethylene glycol, diglycol, Diethylene Glycol, dipropylene glycol
With one of glycerine or at least two mixtures.
Wherein, in terms of mol/mL, copper source and the solvent mole/volume ratio are 0.01~1.0:50~500；
Copper source and the reducing agent hydrazine hydrate mole/volume ratio are 0.01~1.0:1~20.
Wherein, the reaction time is 30~300min, and reaction temperature is 18~22 DEG C；
The condition of the centrifugation is in 3000~8000r/min centrifuge washing 4 times.
Wherein, the solvent of the washing is one of deionized water, dehydrated alcohol and acetone or at least two mixtures；
The vacuum drying condition is to be less than 0.01MPa, 6~12h of drying at room temperature in vacuum degree.
Another aspect of the present invention provides a kind of multi-pore micron copper ball, the multi-pore micron copper ball good dispersion, and monodisperse degree is high,
It can be mass-produced, and be applied to efficient catalytic, antibacterial field.
A kind of multi-pore micron copper ball prepared using above-mentioned preparation method.
Compared with prior art, the present invention has the advantage that with the utility model has the advantages that the present invention is restored using wet chemistry
Multi-pore micron copper ball is prepared, using cheap raw material as reactant, reaction condition green is mild, and process flow is simple to operation,
And the good dispersion of multi-pore micron copper ball is generated, monodisperse degree is high, can be mass-produced, and be applied to efficient catalytic, antibacterial etc.
Field.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) spectrogram of multi-pore micron copper ball prepared by embodiment 1；
Fig. 2 is the field emission scanning electron microscope figure (SEM, × 20000) of multi-pore micron copper ball prepared by embodiment 1；
Fig. 3 is the isothermal nitrogen adsorption curve of multi-pore micron copper ball prepared by embodiment 1.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1
3.2g copper nitrate, the poly- propionic acid of 5mL, 8mL triethylamine are sequentially added in 80mL alcohol solvent, are stirring evenly and then adding into
3mL hydrazine hydrate, after reacting 60min at room temperature, 8000r/min deionized water centrifuge washing 4 times takes and is deposited in vacuum degree and is less than
Drying at room temperature 6h under conditions of 0.01MPa obtains multi-pore micron copper ball.
Multi-pore micron copper ball obtained above is taken, object phase atlas analysis is carried out to it using x-ray diffractometer (XRD), is adopted
With the pattern of field emission scanning electron microscope (SEM) observation particle, the ratio of particle is tested using specific surface area analysis instrument (BET)
Surface area, as a result respectively as shown in Figure 1, Figure 2 and Figure 3.The characteristic peak of metal copper simple substance as can see from Figure 1, without
The characteristic peak of second phase such as any cuprous oxide or copper oxide；As can be seen from Figure 2 the porous structure of copper ball, hole distribution are equal
Even, pore size is 60~80nm, and the uniform particle diameter of copper microballoon, good dispersion, soilless sticking phenomenon.It is available from Fig. 3
The specific surface area of multi-pore micron copper ball is 5.4m2/g。
Embodiment 2
5.5g Kocide SD, 8mL polyacrylic acid, 5mL trioctylamine are sequentially added in 450mL diglycol solvent,
It is stirring evenly and then adding into 5mL hydrazine hydrate, after reacting 100min at room temperature, 6000r/min deionized water centrifuge washing 4 times, it is heavy to take
Form sediment drying at room temperature 8h under conditions of vacuum degree is less than 0.01MPa, obtains multi-pore micron copper ball.
XRD diagram, SEM figure and the isothermal nitrogen adsorption curve of preparation gained Kufil nanometer sheet and the class in embodiment 1
Seemingly, the object for showing the multi-pore micron copper ball is mutually metal copper simple substance, without other impurity；The hole that size is 60~80nm is distributed
Uniformly, microspherulite diameter is uniform, good dispersion, without apparent agglomeration.
Embodiment 3
2.1g acetylacetone copper, 3mL lauric acid, 5mL tetraethylenepentamine are sequentially added in 100mL glycerine solvent, stirred
10mL hydrazine hydrate is added after mixing uniformly, after reacting 180min at room temperature, 5000r/min deionized water centrifuge washing 4 times takes precipitating
Drying at room temperature 10h under conditions of vacuum degree is less than 0.01MPa, obtains multi-pore micron copper ball.
XRD diagram, SEM figure and the isothermal nitrogen adsorption curve of preparation gained Kufil nanometer sheet and the class in embodiment 1
Seemingly, the object for showing the multi-pore micron copper ball is mutually metal copper simple substance, without other impurity；The hole that size is 60~80nm is distributed
Uniformly, microspherulite diameter is uniform, good dispersion, without apparent agglomeration.
Embodiment 4
1.2g copper chloride, 6mL poly, 6mL ethanol amine are sequentially added in 60mL aqueous solvent, are stirring evenly and then adding into
1mL hydrazine hydrate, after reacting 30min at room temperature, 3000r/min deionized water centrifuge washing 4 times takes and is deposited in vacuum degree and is less than
Drying at room temperature 6h under conditions of 0.01MPa obtains multi-pore micron copper ball.
XRD diagram, SEM figure and the isothermal nitrogen adsorption curve of preparation gained Kufil nanometer sheet and the class in embodiment 1
Seemingly, the object for showing the multi-pore micron copper ball is mutually metal copper simple substance, without other impurity；The hole that size is 60~80nm is distributed
Uniformly, microspherulite diameter is uniform, good dispersion, without apparent agglomeration.
Embodiment 5
6.3g copper sulphate, 3mL lauric acid, 5mL ethylenediamine are sequentially added in 300mL dipropylene glycol solvent, stirred
18mL hydrazine hydrate is added after uniformly, after reacting 300min at room temperature, 5000r/min deionized water centrifuge washing 4 times takes and is deposited in
Vacuum degree is less than drying at room temperature 12h under conditions of 0.01MPa, obtains multi-pore micron copper ball.
XRD diagram, SEM figure and the isothermal nitrogen adsorption curve of preparation gained Kufil nanometer sheet and the class in embodiment 1
Seemingly, the object for showing the multi-pore micron copper ball is mutually metal copper simple substance, without other impurity；The hole that size is 60~80nm is distributed
Uniformly, microspherulite diameter is uniform, good dispersion, without apparent agglomeration.
The present invention prepares multi-pore micron copper ball using wet chemistry reduction, using cheap raw material as reactant, reacts item
Part green is mild, and process flow is simple to operation, and generates the good dispersion of multi-pore micron copper ball, and monodisperse degree is high, can advise greatly
Mould production, and it is applied to the fields such as efficient catalytic, antibacterial.
The Applicant declares that the present invention is explained by the above embodiments detailed construction and technique of the invention, but the present invention
It is not limited to above-mentioned detailed construction and technique, that is, does not mean that the present invention must rely on above-mentioned detailed construction and technique could be real
It applies.Person of ordinary skill in the field should be understood that any improvement in the present invention, to the equivalent of each raw material of product of the present invention
Replacement and addition, the selection of concrete mode of auxiliary element etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (13)
1. a kind of preparation method of multi-pore micron copper ball, which comprises the steps of: by copper source, organic acid complexing agent
It is added in solvent with organic amine complexing agent, adds reducing agent hydrazine hydrate after mixing evenly and reacted, be centrifuged, take precipitating, wash
It is dried in vacuo after washing, obtains multi-pore micron copper ball；
The organic acid complexing agent is one of oleic acid, poly- propionic acid, polyacrylic acid, poly and lauric acid or at least two
The mixture of kind.
2. preparation method according to claim 1, which is characterized in that copper source is Kocide SD, copper nitrate, levulinic
In ketone copper, copper sulphate and copper chloride it is a kind of or at least two mixture.
3. preparation method according to claim 1, which is characterized in that in terms of mol/mL, copper source and the organic acid
Complexing agent mole/volume ratio is 0.01 ~ 1.0:1 ~ 20.
4. preparation method according to claim 1, which is characterized in that organic amine complexing agent be ethylenediamine, ethanol amine,
One of triethylamine, trioctylamine, diethylenetriamine and tetraethylenepentamine or at least two mixtures.
5. preparation method according to claim 1, which is characterized in that in terms of mol/mL, copper source and the organic amine
Complexing agent mole/volume ratio is 0.01 ~ 1.0:1 ~ 20.
6. preparation method according to claim 1, which is characterized in that the solvent is water, ethyl alcohol, ethylene glycol, a contracting two
One of ethylene glycol, Diethylene Glycol, dipropylene glycol and glycerine or at least two mixtures.
7. preparation method according to claim 1, which is characterized in that in terms of mol/mL, copper source is rubbed with the solvent
That/volume ratio is 0.01 ~ 1.0:50 ~ 500.
8. preparation method according to claim 1, which is characterized in that in terms of mol/mL, copper source and the reducing agent
Hydrazine hydrate mole/volume ratio is 0.01 ~ 1.0:1 ~ 20.
9. preparation method according to claim 1, which is characterized in that the reaction time is 30 ~ 300min, reaction temperature
It is 18 ~ 22 DEG C.
10. preparation method according to claim 1, which is characterized in that the condition of the centrifugation is in 3000 ~ 8000
R/min centrifuge washing 4 times.
11. preparation method according to claim 1, which is characterized in that the solvent of the washing is deionized water, anhydrous second
One of pure and mild acetone or at least two mixtures.
12. preparation method according to claim 1, which is characterized in that the vacuum drying condition is in vacuum degree
Less than 6 ~ 12h of drying at room temperature under conditions of 0.01MPa.
13. a kind of multi-pore micron copper ball prepared using preparation method described in claim 1.
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| CN105710383A (en) * | 2016-04-30 | 2016-06-29 | 安徽农业大学 | Method for preparing Cu powder by reducing CuO by adopting glycerinum |
| CN109722087A (en) * | 2018-12-29 | 2019-05-07 | 中国有色桂林矿产地质研究院有限公司 | A kind of copper-based composite antibacterial coating material of argentiferous and preparation method thereof |
| CN110153443A (en) * | 2019-07-11 | 2019-08-23 | 中国科学院深圳先进技术研究院 | A kind of copper nanometer sheet and its preparation method and application |
| CN110560702A (en) * | 2019-09-16 | 2019-12-13 | 上海交通大学 | method for preparing micron-sized single crystal copper powder at room temperature |
| CN114082938B (en) * | 2022-01-11 | 2023-08-25 | 苏州艾美特企业管理有限公司 | Metal particle and preparation method and application thereof |
| CN115011956A (en) * | 2022-06-28 | 2022-09-06 | 南通赛可特电子有限公司 | Organic copper surface protective agent and preparation method thereof |
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| CN101332514B (en) * | 2008-07-30 | 2011-02-02 | 中南大学 | Preparation method of porous copper powder |
| CN102513542B (en) * | 2011-11-21 | 2014-03-26 | 南京师范大学 | Method for preparing porous Pd nanospheres with liquid phase reduction method and prepared nanospheres |
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