CN100589904C - Preparation of nano copper particle - Google Patents
Preparation of nano copper particle Download PDFInfo
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- CN100589904C CN100589904C CN200810037326A CN200810037326A CN100589904C CN 100589904 C CN100589904 C CN 100589904C CN 200810037326 A CN200810037326 A CN 200810037326A CN 200810037326 A CN200810037326 A CN 200810037326A CN 100589904 C CN100589904 C CN 100589904C
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Abstract
The invention discloses a preparation method for nanometer copper grain, comprising the following steps: mixing and stirring a dentritic compound with a benzene ring core used as template agent and copper salt, using the strong coordination of a plurality of amino existing in the dentritic compound to make Cu<2+> complex in the inner part and the outer part of the cavity of the dentritic compound,and using reducing agent for reduction to convert bivalent copper to zero valent copper. The dentritic compound with a benzene ring core is adopted as the template agent, accordingly solving the problem of inability to obtain nanometer copper grain with small diameter and good dispersion in the prior liquidoid reduction method, obtaining even spherical nanometer copper grain with the average diameter between two and five nm and good dispersion by liquidoid reduction method. In addition, the preparation method for nanometer copper grain has the advantages of simple preparation method, easily available raw material, low cost, temperate conditions, low requirements for equipment, environmental friendly production process, and pollution-free by-product, thus being suitable for mass industrialproduction.
Description
Technical field
The present invention relates to a kind of preparation method of nano copper particle, belong to the nano metal material technical field.
Background technology
Because nano copper particle has property aspect optics, magnetics, calorifics, electronics, sensor and the catalysis, therefore it can be widely used in various fields, for example at aspects such as effective catalyst, electrocondution slurry, high conductivity, high specific strength alloy and kollags.The method for preparing at present nanometer copper is a lot, for example gas evaporation method, plasma method, gamma-ray irradiation one hydrothermal crystallization combination method, mechanochemical reaction, sonochemistry method, electron beam irradiation method, photocatalysis Decomposition method, electrolysis, sol-gel method, reverse microemulsion process, microwave irradiation synthetic method, supercritical extraction, thermal decomposition method etc.Some specification requirement height of these preparation methods, apparatus expensive, some complex process, environmental pollution are bigger, and some needs long reaction time, higher temperature and pressure and special reaction unit, causes production cost higher.In recent years, what the method for preparing nanometer copper was comparatively active is liquid phase reduction, but the nano copper particle particle diameter of existing liquid phase reduction preparation technology gained is bigger, the particle diameter wider distribution, and products therefrom is easily reunited, and is difficult to extensive use.
Summary of the invention
The objective of the invention is at above-mentioned existing in prior technology defective, the preparation method of the nano copper particle of a kind of easy and simple to handle, low cost and environmental protection is provided, solve liquid phase reduction and can not make that particle diameter is little, the difficult problem of the nano copper particle of good dispersion.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows:
The preparation method of nano copper particle provided by the invention belongs to liquid phase reduction, and concrete steps are as follows:
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;
Described multiple hydrogen compound class reducing agent is a sodium borohydride.
Described is preferred its 4th generation product (4G), the 5th generation product (5G) or the 6th generation product (6G) of the polyamide-amide class dendritic of nuclear with the phenyl ring.
The present invention is earlier that the dendrimer of nuclear is that the template agent mixes stirring with mantoquita with the phenyl ring, utilizes the strong coordination of a plurality of amino that exist in the dendrimer, makes Cu
2+In the cavity inside and the outside complexing of dendrimer, with the reducing agent reduction, make cupric change zerovalent copper into then, can be expressed as DT+Cu
2+---DT-Cu
2+DT-Cu
2++ reducing agent----Cu (0), wherein DT represents with the phenyl ring to be the dendrimer of nuclear.Compared with prior art, the present invention has following beneficial effect:
1) the present invention is that the dendrimer of examining is the template agent owing to using with the phenyl ring, therefore solved existing liquid phase reduction and can not make that particle diameter is little, the difficult problem of the nano copper particle of good dispersion, realized making the even spherical nano copper particle of average grain diameter at 2～5nm, good dispersion with liquid phase reduction.
2) preparation method of the present invention is simple, raw material is easy to get, with low cost, mild condition, the low and production process environmental protection to the requirement of equipment, accessory substance are nuisanceless, but large-scale industrial production.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the prepared nano copper particle of embodiment 1;
Fig. 2 is the transmission electron microscope photo of the prepared nano copper particle of embodiment 4;
Fig. 3 is the transmission electron microscope photo of the prepared nano copper particle of embodiment 5;
Fig. 4 is the transmission electron microscope photo of the prepared nano copper particle of embodiment 6;
Fig. 5 is the transmission electron microscope photo of the prepared nano copper particle of embodiment 8;
Fig. 6 is for the phenyl ring being the chemical structural formula of the 4th generation product (4G) of the polyamide-amide class dendritic of nuclear;
Fig. 7 is for the phenyl ring being the chemical structural formula of the 5th generation product (5G) of the polyamide-amide class dendritic of nuclear;
Fig. 8 is for the phenyl ring being the chemical structural formula of the 6th generation product (6G) of the polyamide-amide class dendritic of nuclear.
The specific embodiment
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention.
Embodiment 1
The preparation method of the nano copper particle that present embodiment provides, concrete steps are as follows:
A) preparation template agent: the 4th generation product (4G) 0.02562g that will be the polyamide-amide class dendritic of nuclear with the phenyl ring adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 0.5mmol/L solution;
B) preparation copper salt solution: with 0.02g CuSO
45H
2O adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 8mmol/L solution;
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;
D) at 15～30 ℃, with 0.012gNaBH
4Add in the 10ml redistilled water, the sodium borohydride solution of now joining 32mmol/L prepares the back and adds fast in the mixed solution of step c) gained, vigorous stirring 30 minutes, and wherein: the mol ratio of reducing agent and mantoquita is 4: 1;
E) filter, wash each respectively 3 times, promptly get target product with distilled water and absolute ethyl alcohol.
As shown in Figure 1, the prepared nano copper particle of present embodiment be good dispersion, do not have to reunite, average grain diameter is in the even spherical nanoparticles of 4.9nm.
Embodiment 2
The preparation method of the nano copper particle that present embodiment provides, concrete steps are as follows:
A) preparation template agent: the 4th generation product (4G) 0.02562g that will be the polyamide-amide class dendritic of nuclear with the phenyl ring adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 0.5mmol/L solution;
B) preparation copper salt solution: with 0.02g CuSO
45H
2O adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 8mmol/L solution;
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;
D) at 15～30 ℃, with 0.006gNaBH
4Add in the 10ml redistilled water, the sodium borohydride solution of now joining 16mmol/L prepares the back and adds fast in the mixed solution of step c) gained, vigorous stirring 30 minutes, and wherein: the mol ratio of reducing agent and mantoquita is 2: 1;
E) filter, wash each respectively 3 times, promptly get target product with distilled water and absolute ethyl alcohol.
The prepared nano copper particle of present embodiment is good dispersion, do not have to reunite, average grain diameter is in the even spherical nanoparticles of 4.7nm.
Embodiment 3
The preparation method of the nano copper particle that present embodiment provides, concrete steps are as follows:
A) preparation template agent: the 4th generation product (4G) 0.02562g that will be the polyamide-amide class dendritic of nuclear with the phenyl ring adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 0.5mmol/L solution;
B) preparation copper salt solution: with 0.01g CuSO
45H
2O adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 4mmol/L solution;
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 8: 1;
D) at 15～30 ℃, with 0.006gNaBH
4Add in the 10ml redistilled water, the sodium borohydride solution of now joining 16mmol/L prepares the back and adds fast in the mixed solution of step c) gained, vigorous stirring 30 minutes, and wherein: the mol ratio of reducing agent and mantoquita is 4: 1;
E) filter, wash each respectively 3 times, promptly get target product with distilled water and absolute ethyl alcohol.
The prepared nano copper particle of present embodiment is good dispersion, do not have to reunite, average grain diameter is in the even spherical nanoparticles of 4.3nm.
Embodiment 4
The preparation method of the nano copper particle that present embodiment provides, concrete steps are as follows:
A) preparation template agent: the 4th generation product (4G) 0.02562g that will be the polyamide-amide class dendritic of nuclear with the phenyl ring adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 0.5mmol/L solution;
B) preparation copper salt solution: with 0.005g CuSO
45H
2O adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 2mmol/L solution;
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 4: 1;
D) at 15～30 ℃, with 0.003gNaBH
4Add in the 10ml redistilled water, the sodium borohydride solution of now joining 8mmol/L prepares the back and adds fast in the mixed solution of step c) gained, vigorous stirring 30 minutes, and wherein: the mol ratio of reducing agent and mantoquita is 4: 1;
E) filter, wash each respectively 3 times, promptly get target product with distilled water and absolute ethyl alcohol.
As shown in Figure 2, the prepared nano copper particle of present embodiment be good dispersion, do not have to reunite, average grain diameter is in the even spherical nanoparticles of 3.9nm.
Embodiment 5
The preparation method of the nano copper particle that present embodiment provides, concrete steps are as follows:
A) preparation template agent: the 5th generation product (5G) 0.02562g that will be the polyamide-amide class dendritic of nuclear with the phenyl ring adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 0.5mmol/L solution;
B) preparation copper salt solution: with 0.02g CuSO
45H
2O adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 8mmol/L solution;
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;
D) at 15～30 ℃, with 0.012gNaBH
4Add in the 10ml redistilled water, the sodium borohydride solution of now joining 32mmol/L prepares the back and adds fast in the mixed solution of step c) gained, vigorous stirring 30 minutes, and wherein: the mol ratio of reducing agent and mantoquita is 4: 1;
E) filter, wash each respectively 3 times, promptly get target product with distilled water and absolute ethyl alcohol.
As shown in Figure 3, the prepared nano copper particle of present embodiment be good dispersion, do not have to reunite, average grain diameter is in the even spherical nanoparticles of 3.4nm.
Embodiment 6
The preparation method of the nano copper particle that present embodiment provides, concrete steps are as follows:
A) preparation template agent: the 5th generation product (5G) 0.02562g that will be the polyamide-amide class dendritic of nuclear with the phenyl ring adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 0.5mmol/L solution;
B) preparation copper salt solution: with 0.01g CuSO
45H
2O adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 4mmol/L solution;
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 8: 1;
D) at 15～30 ℃, with 0.003gNaBH
4Add in the 10ml redistilled water, the sodium borohydride solution of now joining 8mmol/L prepares the back and adds fast in the mixed solution of step c) gained, vigorous stirring 30 minutes, and wherein: the mol ratio of reducing agent and mantoquita is 2: 1;
E) filter, wash each respectively 3 times, promptly get target product with distilled water and absolute ethyl alcohol.
As shown in Figure 4, the prepared nano copper particle of present embodiment be good dispersion, do not have to reunite, average grain diameter is in the even spherical nanoparticles of 3.2nm.
Embodiment 7
The preparation method of the nano copper particle that present embodiment provides, concrete steps are as follows:
A) preparation template agent: the 6th generation product (6G) 0.02562g that will be the polyamide-amide class dendritic of nuclear with the phenyl ring adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 0.5mmol/L solution;
B) preparation copper salt solution: with 0.02g CuSO
45H
2O adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 8mmol/L solution;
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;
D) at 15～30 ℃, with 0.012gNaBH
4Add in the 10ml redistilled water, the sodium borohydride solution of now joining 32mmol/L prepares the back and adds fast in the mixed solution of step c) gained, vigorous stirring 30 minutes, and wherein: the mol ratio of reducing agent and mantoquita is 4: 1;
E) filter, wash each respectively 3 times, promptly get target product with distilled water and absolute ethyl alcohol.
The prepared nano copper particle of present embodiment is good dispersion, do not have to reunite, average grain diameter is in the even spherical nanoparticles of 2.9nm.
Embodiment 8
The preparation method of the nano copper particle that present embodiment provides, concrete steps are as follows:
A) preparation template agent: the 5th generation product (5G) 0.02562g that will be the polyamide-amide class dendritic of nuclear with the phenyl ring adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 0.5mmol/L solution;
B) preparation copper salt solution: with 0.01g CuSO
45H
2O adds in the 10ml redistilled water, 15～30 ℃ of stirrings it is dissolved fully, obtains 4mmol/L solution;
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 8: 1;
D) at 15～30 ℃, with 0.006gNaBH
4Add in the 10ml redistilled water, the sodium borohydride solution of now joining 16mmol/L prepares the back and adds fast in the mixed solution of step c) gained, vigorous stirring 30 minutes, and wherein: the mol ratio of reducing agent and mantoquita is 4: 1;
E) filter, wash each respectively 3 times, promptly get target product with distilled water and absolute ethyl alcohol.
As shown in Figure 5, the prepared nano copper particle of present embodiment be good dispersion, do not have to reunite, average grain diameter is in the even spherical nanoparticles of 2.6nm.
Described in this specification is that Fig. 6, Fig. 7 and shown in Figure 8 seen respectively in the chemical structural formula of the 4th generation product (4G), the 5th generation product (5G) and the 6th generation product (6G) of the polyamide-amide class dendritic of nuclear with the phenyl ring.
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.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514486B (en) * | 2009-02-27 | 2011-09-21 | 华东师范大学 | Cu dendritic single crystalline nano material and preparation method thereof |
| CN101708866B (en) * | 2009-11-17 | 2012-06-06 | 上海师范大学 | Preparation method of superparamagnetic water-soluble manganous ferrite nano-particle |
| CN102218544B (en) * | 2011-05-27 | 2013-05-01 | 中国科学院理化技术研究所 | Preparation method and application of metal nanoparticles |
| CN103071530B (en) * | 2011-05-27 | 2014-11-12 | 中国科学院理化技术研究所 | Application of metal nanoparticles |
| CN104874416B (en) * | 2015-05-13 | 2017-08-25 | 山西大学 | A kind of maleic anhydride hydrogenation prepares succinic anhydride catalyst and preparation method thereof |
| CN108188410B (en) * | 2018-01-26 | 2019-03-15 | 东华理工大学 | The minimizing technology of sexavalence uranium ion in a kind of aqueous solution |
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