CN101693297B - Preparation method of copper nanoparticles with different particle diameters - Google Patents
Preparation method of copper nanoparticles with different particle diameters Download PDFInfo
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- CN101693297B CN101693297B CN2009101126684A CN200910112668A CN101693297B CN 101693297 B CN101693297 B CN 101693297B CN 2009101126684 A CN2009101126684 A CN 2009101126684A CN 200910112668 A CN200910112668 A CN 200910112668A CN 101693297 B CN101693297 B CN 101693297B
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Abstract
The invention discloses a preparation method of copper nanoparticles with different particle diameters and relates to a metal nanoparticle. The invention provides a preparation method of copper nanoparticles with different particle diameters, which has simple, economic, environment-friendly process. The preparation method comprises the following steps: adding metal salt of copper chloride or copper acetate, a solvent, a protective agent, a complexing agent and a surfactant in a vessel in sequence, and stirring to obtain a mixture, wherein the protective agent is polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, or the like, the complexing agent is oleic acid, hexadecylamine, oleamide, or the like, and the surfactant is hexadecyl dimethyl ammonium bromide, sodium dodecyl benzene sulfonate or the like; adding a reducing agent in the mixture for reacting, wherein the reducing agent is ascorbic acid, sodium formaldehyde sulphoxylate, sodium borohydride, or the like; cooling the reactant till the temperature is below 40 DEG C, then adding a precipitating agent, mixing, and centrifugally separating; then washing with the organic solvent, centrifugating, and extracting the precipitate; and then drying the precipitate to obtain red powder copper nanoparticles with different particle diameters.
Description
Technical field
The present invention relates to a kind of metal nanoparticle, especially relate to a kind of can be at copper nano-particle of wide region grain-size and pattern and preparation method thereof.
Background technology
Metal nanoparticle not only has skin effect, bulk effect, quantum size effect and macroscopic quantum tunneling effect, and have peculiar electrically, magnetic, optical property and structural property, in catalysis, luminescent material, semi-conducting material and nano-device, fields such as the health care (1.Grouchko that is widely used, M., A.Kamyshny, et al. (2009). " Synthesis ofcopper nanoparticles catalyzed by pre-formed silver nanoparticles. " Journal of NanoparticleResearch 11 (3): 713-716).Some noble metals have obtained comparatively extensive studies as the synthesizing of nano particle of gold, platinum, silver etc. at present, and relatively cheap copper nano-particle is studied less.Copper nano-particle is with its wide application prospect at electronics, spectroscopy, catalysis and aspect such as lubricated, and with cheap relatively price, received increasing concern.The research to copper nano-particle at present is mainly concerned with its preparation method, with and at aspects such as catalyst, lube oil additives.Up to the present, the research of copper nano-particle also is in the comparatively elementary stage, has the following disadvantages:
On preparation process, the preparation of copper nano-particle is than noble metal complexity such as gold, platinum, silver, more difficult control, that has therefore reported demonstrates about preparing in the copper nano-particle documents and materials, the bad control of the pattern of copper nano-particle, in same batch the product, particle size, pattern differ bigger, and the problem of oxidation that reaches in the preparation process after the preparation is serious.
In recent years, a lot of research institutions have attempted the preparation copper powder, have explored the method for a lot of manufactured copper nano particles.This wherein has (2.Zhou such as Mechanical Method, spray drying process, sol-gel process, electrochemical deposition method, microemulsion method, F., R.M.Zhou, et al. (2008). " Influences of surfactant (PVA) concentration and pH on the preparation of coppernanoparticles by electron beam irradiation. " Radiation Physics and Chemistry 77 (2): 169-173).Though above-mentioned several method is simpler, the particle diameter that can not control the product copper nano-particle well distributes.And microemulsion method is because too complicated and be not suitable for the large-scale production copper nano-particle.
Publication number can synthesize the method for particle diameter less than the copper nano particles of 100nm in a large number for the Chinese patent application of CN 101104205A and CN101337277A provides a kind of respectively, but can not regulate and control the size and the pattern of copper nano-particle as required.
Publication number provides a kind of with mantoquita and ammonia solution premix for the korean patent application of 2005-3169, and prepares copper powders may with the aqueous solution of ascorbic acid reduction mantoquita complex compound, prepares the method for the copper particle of 0.3～4 μ m.
Publication number provides a kind of method for the korean patent application of 2004-37824, adds NaOH and hydrazine in copper chloride solution, and reduction makes the copper particle of the about 100nm of particle diameter.
The copper nano-particle particle diameter that above method obtains is too big, and purposes is narrower.
The application of copper nano-particle is scarcely out of swaddling-clothes at present in a word.
Summary of the invention
The objective of the invention is at the adhesion of agent and metallic atom or strong excessively of living of existing table among the existing copper nano-particle preparation method, cross weak shortcoming, provide that a kind of technology is simple, the preparation method of the copper nanoparticles with different particle diameters of economy, environmental protection.
The present invention includes following steps:
1) in container, adds slaine copper chloride or Schweinfurt green successively, solvent, protective agent, complexing agent, surfactant stirs, get mixture, described protective agent is polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) or polyacrylic acid (PAA) etc., and described complexing agent is oleic acid, hexadecylamine or oleyl amine etc., and described surfactant is hexadecyldimethyl benzyl ammonium ammonium bromide (CTAB) or neopelex etc.;
2) in mixture, add reducing agent, reaction, described reducing agent is ascorbic acid (Vitamin C), sodium formaldehyde sulphoxylate (SFS) or sodium borohydride etc.;
3) with step 2) in reactant be cooled to temperature and be lower than 40 ℃;
4) add precipitating reagent again, mix centrifugation;
5) use organic solvent washing again, centrifugal again, taking precipitate;
6) copper nanoparticles with different particle diameters of red powder shape will be got after the drying precipitate.
In step 1), described stirring preferably is warming up to 50 ℃, is incubated 30min again.
In step 1) and 2) in, by mass percentage, the content of each raw material is slaine copper chloride or Schweinfurt green 1%～3%, protective agent 0.1%～3%, and complexing agent 1%～2%, surfactant 10%～20%, reducing agent 2%～6%, surplus is solvent.
In step 2) in, the temperature of described reaction is preferably 70～100 ℃, and the time of reaction is preferably 10～60min.
In step 4), described precipitating reagent is preferably alcohol or formaldehyde etc.; The addition of described precipitating reagent is preferably and adds 10～15mL precipitating reagent in 1g slaine copper chloride or the Schweinfurt green.
In step 5), described organic solvent is preferably acetone, cyclohexane or n-hexane etc.
In step 6), described drying preferably is placed on sediment in the vacuum drying chamber dry, and baking temperature is preferably 50～80 ℃, is preferably 10h drying time.
The gained copper nanoparticles with different particle diameters takes on a red color Powdered, and purity is higher, and the XRD test is shown as the fine copper phase.
Technical scheme of the present invention is to adopt chemical method, in liquid phase, restore nano copper particle, and in course of reaction, by adding the table alive agent strong and weak suitable with the transition metal atoms adhesion, growth of restriction particle and control particle size pattern, overcome the adhesion of agent and metallic atom or strong excessively of living of table in the prior preparation method, cross weak shortcoming, fixed the copper ion in the reaction system preferably, thereby make the easier adjusting of synthesis condition, can be in a kind of preparation method only need by simple fine setting synthetic a series of different-grain diameters in a large number, the pattern particle diameter is controlled, the copper nano-particle that is evenly distributed.Also introduced organic solvent-acetone etc. among the present invention, effectively reduced on the one hand that protective agent forms to synthetic harmful frame structure, on the other hand, can control the boiling point of system, further strengthened the simplification of controlling in the preparation process.
Compare with prior preparation method, the present invention has following outstanding advantage: the preparation method is simple, economy, environmental protection, and can once produce more large batch of product; Product cut size distributes and can control (for example less than 20nm, 20～60nm, 60～100nm, 100～200nm, more than the 200nm), and with the increase of particle diameter, oxidation is more and more slighter.The nano particle of various particle diameters all has its corresponding advantages and application, wherein mainly uses in spectroscopy and microcircuit less than the copper nano-particle of 40nm; The preparation of the copper nano-particle of 40～100nm requires low, can amplify production well, and the copper nano-particle particle diameter of this particle size interval is less than 100nm, again can be because of too not little and oxidized, can be at lubricating additive, and electronics is used in the medical and health industry; Particle diameter is greater than the particle of 100nm, can control better to grow up to various crystalline forms, and in the conducting polymer field certain application prospect be arranged.
Description of drawings
Fig. 1 is the XRD figure of the copper nanoparticles with different particle diameters of embodiment of the invention preparation.In Fig. 1, curve a, b, c, d, e respectively representative diameter be 10nm, 50nm, 100nm, greater than 200nm (pyramid), greater than 200nm (sphere); Abscissa is 2 θ angles; The characteristic peak of Chu Xianing is followed successively by (111), (200), (220) from left to right.
Fig. 2 is the transmission electron microscope picture of the copper nanoparticles with different particle diameters of embodiment of the invention preparation.In Fig. 2, a is particle diameter 10nm, scale 10nm; B is particle diameter 50nm, scale 50nm; C is particle diameter 100nm, scale 100nm; D is that particle diameter is greater than 200nm (pyramid), scale 200nm.
Fig. 3 is the electron scanning micrograph of the large-tonnage product of the copper nanoparticles with different particle diameters of embodiment of the invention preparation.In Fig. 3, a is particle diameter 100nm, b be particle diameter greater than 200nm (sphere), c be particle diameter greater than 200nm (pyramid), scale is 2 μ m.
The specific embodiment
Embodiment 1: get Schweinfurt green 0.0025mol and add in the 10mL ethylene glycol, get the 1mL oleyl amine and be dissolved in the 10mL acetone, two solution mix, strong agitation.0.25gPVP is scattered in 8g ethylene glycol (saturated NaOH), is poured in the mixed liquor of preceding two solution, be heated to boiling.The 1.00g ascorbic acid is scattered in the 12g ethylene glycol (saturated NaOH), ascorbic acid solution is fallen in the mixed system of front again, solution becomes colorless rapidly from blueness, and is yellow then, redness.Remain on boiling point, continue to stir 10min, drop to room temperature.Extract oil-soluble nano particle with cyclohexane, precipitation is got in centrifugation, adds acetone and alcohol blend, and ultrasonic wave disperses, low-speed centrifugal 5min, and precipitation is that particle diameter is 30～50nm copper nano-particle, gets the troubled liquor on upper strata.High speed centrifugation is isolated powder, is the copper nano-particle (as Fig. 2 a shown in) of diameter less than 10nm.
Embodiment 2: Schweinfurt green 0.0025mol adds in the 10mL ethylene glycol, gets the 1mL oleyl amine and is dissolved in the 10mL acetone, and two solution mix, strong agitation.0.2gPVP is scattered in 8g ethylene glycol (saturated NaOH), is poured in the mixed liquor of preceding two solution, be heated to boiling.The 1.00g ascorbic acid is scattered in the 12g ethylene glycol (saturated NaOH), ascorbic acid solution is fallen in the mixed system of front again, solution becomes colorless rapidly from blueness, and is yellow then, redness.Remain on boiling point, continue to stir 10min, drop to room temperature.Extract oil-soluble nano particle with cyclohexane, precipitation is got in centrifugation, washs 3～5 times with acetone and alcohol, and ultrasonic wave disperses, the centrifugal 5min of 6000 commentaries on classics/min, and precipitation is that particle diameter is 50nm copper nano-particle (shown in Fig. 2 b).
Embodiment 3: copper chloride 0.0025mol and 6mL glycerine add in the 10mL ethylene glycol simultaneously, get 2g oleic acid and are dissolved in the 10mL acetone, mix two solution, strong agitation.1.5gPVP is scattered in the 8g ethylene glycol, and two kinds of liquid mix, and are heated to boiling.The 1.00g ascorbic acid is scattered in 12mL ethylene glycol (saturated NaOH), ascorbic acid solution is fallen in aforesaid system, keep boiling 40min, obtain reddish yellow solution.Washing, centrifugal, obtain yellow powder, i.e. the spherical copper nano-particle of diameter 200nm (shown in Fig. 2 c, Fig. 2 d, Fig. 3 a and Fig. 3 b).
Embodiment 4: change the glycerine among the embodiment 3 into the 6mL triethanolamine, all the other are constant, then obtain the pyramid of particle diameter 200nm or by the pyramidal copper nano-particle of rescinded angle (shown in Fig. 3 c).
The XRD figure spectrum of product shows all be fine copper phase (as shown in Figure 1).
Claims (4)
1. the preparation method of a copper nanoparticles with different particle diameters is characterized in that may further comprise the steps:
1) in container, adds slaine copper chloride or Schweinfurt green successively, solvent, protective agent, complexing agent, surfactant stirs, get mixture, described protective agent is polyvinylpyrrolidone, polyvinyl alcohol or polyacrylic acid, and described complexing agent is oleic acid, hexadecylamine or oleyl amine, and described surfactant is hexadecyldimethyl benzyl ammonium ammonium bromide or neopelex;
2) in mixture, add reducing agent, reaction, described reducing agent is ascorbic acid, sodium formaldehyde sulphoxylate or sodium borohydride, and the temperature of described reaction is 70～100 ℃, and the time of reaction is 10～60min;
3) with step 2) in reactant be cooled to temperature and be lower than 40 ℃;
4) add precipitating reagent again, mix, centrifugation, described precipitating reagent is alcohol or formaldehyde, the addition of described precipitating reagent is to add 10～15mL precipitating reagent in 1g slaine copper chloride or the Schweinfurt green;
5) use organic solvent washing again, centrifugal again, taking precipitate;
6) copper nanoparticles with different particle diameters will be got after the drying precipitate;
In step 1) and 2) in, by mass percentage, the content of each raw material is slaine copper chloride or Schweinfurt green 1%～3%, protective agent 0.1%～3%, and complexing agent 1%～2%, surfactant 10%～20%, reducing agent 2%～6%, surplus is solvent.
2. the preparation method of a kind of copper nanoparticles with different particle diameters as claimed in claim 1 is characterized in that in step 1), and described stirring is to be warming up to 50 ℃, is incubated 30min again.
3. the preparation method of a kind of copper nanoparticles with different particle diameters as claimed in claim 1 is characterized in that in step 5), and described organic solvent is acetone, cyclohexane or n-hexane.
4. the preparation method of a kind of copper nanoparticles with different particle diameters as claimed in claim 1 is characterized in that in step 6), and the temperature of described drying is 50～80 ℃, and be 10h drying time.
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| CN102114545B (en) * | 2011-03-01 | 2013-01-30 | 宁波大学 | Method for preparing copper nanometer granules |
| CN102274979B (en) * | 2011-09-20 | 2013-04-24 | 南京林业大学 | Method for preparing nano copper powder in micromolecular viscous medium |
| CN102371358A (en) * | 2011-11-18 | 2012-03-14 | 复旦大学 | Aqueous-phase preparation method for re-dispersible nano-copper particles |
| CN102601383A (en) * | 2012-03-30 | 2012-07-25 | 电子科技大学 | Method for preparing ultrafine copper powder at room temperature |
| CN102837004B (en) * | 2012-09-25 | 2015-02-04 | 吉林大学 | Preparation method of polyhedral copper nanoparticle |
| US9700940B2 (en) * | 2012-09-27 | 2017-07-11 | Lockheed Martin Corporation | Metal nanoparticles formed around a nucleus and scalable processes for producing same |
| CN103056383B (en) * | 2013-01-04 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Preparation method for high-performance conducting copper slurry |
| CN103194616B (en) * | 2013-04-08 | 2014-07-30 | 吉林大学 | Method for preparing copper nanocrystalline |
| CN103722179B (en) * | 2013-12-19 | 2015-11-04 | 中国科学院深圳先进技术研究院 | For the preparation method of the nano copper slurry of electrically conductive ink |
| CN104057100B (en) * | 2014-06-21 | 2016-02-24 | 吉林大学 | A kind of method of copper nano particles of purifying |
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| US10208211B2 (en) * | 2015-09-18 | 2019-02-19 | Cn Innovations Limited | Conductive pastes using bimodal particle size distribution |
| CL2015003794A1 (en) * | 2015-12-30 | 2016-07-29 | Univ Chile | Method of obtaining copper nanoparticles and use of said particles |
| CN107186222A (en) * | 2017-05-11 | 2017-09-22 | 佛山实瑞先导材料研究院（普通合伙） | A kind of method that supersonic liquid phase reduction prepares Nanometer Copper |
| CN108672717A (en) * | 2018-05-25 | 2018-10-19 | 苏州大学 | The method of one-step synthesis cluster type palladium copper nano-particle and the application of cluster type palladium copper nano-particle |
| CN109079154B (en) * | 2018-09-07 | 2022-03-01 | 长春永固科技有限公司 | Nano silver and synthetic method thereof |
| CN110744068B (en) * | 2019-10-21 | 2021-01-26 | 河南大学 | Oil-soluble nano copper and preparation method thereof |
| CN112940459B (en) * | 2021-02-24 | 2023-04-11 | 苏州克里斯图材料科技有限公司 | Nanocrystalline composite liquid crystal material and preparation method thereof |
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| CN101104205A (en) * | 2006-07-10 | 2008-01-16 | 三星电机株式会社 | Method for manufacturing copper nano granule and copper nano granule produced thereby |
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| CN101104205A (en) * | 2006-07-10 | 2008-01-16 | 三星电机株式会社 | Method for manufacturing copper nano granule and copper nano granule produced thereby |
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