CN100569418C - The metal nanoparticle of making method of metal nanoparticles and making thus - Google Patents
The metal nanoparticle of making method of metal nanoparticles and making thus Download PDFInfo
- Publication number
- CN100569418C CN100569418C CNB2007100794970A CN200710079497A CN100569418C CN 100569418 C CN100569418 C CN 100569418C CN B2007100794970 A CNB2007100794970 A CN B2007100794970A CN 200710079497 A CN200710079497 A CN 200710079497A CN 100569418 C CN100569418 C CN 100569418C
- Authority
- CN
- China
- Prior art keywords
- solution
- metal
- group
- dispersion stabilizer
- weight portions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- 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
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
Abstract
The present invention relates to a kind of metal nanoparticle of making method of metal nanoparticles and being made by this method, relate in particular to the manufacturing method of metal nanoparticles that comprises the steps: preparation contains first solution of dispersion stabilizer and polar solvent; Preparation contains second solution of metal precursor and polar solvent; And described second solution is divided at least 2 times joins in described first solution.According to the present invention, manufacturing dimension is evenly and the metal nanoparticle of homogeneous expeditiously can to use a spot of dispersion stabilizer by control reaction.
Description
The cross reference of related application
The application requires the priority of the korean patent application submitted on May 25th, 2006 2006-0047267 number, and its full content is hereby expressly incorporated by reference.
Technical field
The metal nanoparticle that the present invention relates to make method of metal nanoparticles and made by this method relates in particular to high productivity manufacturing dimension evenly and the method for metal nanoparticles of homogeneous and the metal nanoparticle made of method thus.
Background technology
In the manufacturing of metal nanoparticle, chemical autofrettage, machine-building method and electric autofrettage are arranged.Owing to when grinding, be entrained with impurity in the Mechanical Method of use mechanical powder, be difficult to the uniform nano particle of synthesis of high purity and size.As for the electric autofrettage that adopts electrolysis, because the production time is long and the concentration of the particle of manufacturing is low, so production efficiency is low.Wherein, the chemical method of two kinds of main manufacturing metal nanoparticles is arranged, that is, and vapor phase method and colloid method (sol method).But owing to use the vapor phase method of plasma or gas evaporation to need very expensive equipment, employing can be synthesized the colloid method of size homogeneous granules under low cost usually.
A kind of existing method of making metal nanoparticle by colloid method is to dissociate metallic compound and employing reducing agent or surfactant to make the metal nanoparticle of hydrosol form in polar solvent.But in this method, the kind of used dispersion stabilizer is limited.For example, it is reported that the unimolecule dispersion stabilizer that contains citrate only is of a size of several nm or littler and granule density at nano particle and just shows dispersion stabilization when low.Big molecule dispersion stabilizer PVP can stably disperse the nano particle of tens nm in polar solvent, but it must use so that obtain the particle of homogeneous under the concentration of ten weight factors (ten weight factor) or under than the higher concentration of the concentration of silver-colored precursor, that is spheroid.And, have such problem: size that must augmenting response batch (reaction batch) and in every batch the amount of the particle of manufacturing descend.
Summary of the invention
The invention provides a kind of manufacturing method of metal nanoparticles, by this method use polar solvent such as polyalcohol and a spot of dispersion stabilizer can high productivity make size evenly, (isotropic) metallic particles of homogeneous.
In addition, the invention provides the metal nanoparticle of being made by the method that comprises the steps: preparation contains first solution of dispersion stabilizer and polar solvent; Preparation contains second solution of metal precursor and polar solvent; And divide at least twice second solution joined in first solution.
Description of drawings
In conjunction with the following drawings, by the description of hereinafter the specific embodiment, these and/or others of the present invention and advantage will become apparent and be more readily understood.
Fig. 1 is the curve map (virtual graph) that the change in concentration of dispersion stabilizer and metal ion when the solution (second solution) that will contain metal precursor once joins in the solution (first solution) that contains dispersion stabilizer is shown.
Fig. 2 is the curve map that the change in concentration of dispersion stabilizer and metal ion when the solution that will contain metal precursor at twice (second solution) joins in the solution (first solution) that contains dispersion stabilizer is shown.
Fig. 3 is the curve map that the change in concentration of dispersion stabilizer and metal ion when in the solution (first solution) that divides the solution (second solution) will contain metal precursor several times to join to contain dispersion stabilizer is shown.
Fig. 4 is the SEM image according to the metal nanoparticle of embodiments of the invention 1 manufacturing.
Fig. 5 is the SEM image according to the metal nanoparticle of embodiments of the invention 2 manufacturings.
Fig. 6 is the SEM image according to the metal nanoparticle of embodiments of the invention 3 manufacturings.
Fig. 7 is the SEM image according to the metal nanoparticle of embodiments of the invention 4 manufacturings.
Fig. 8 is the SEM image according to the metal nanoparticle of embodiments of the invention 5 manufacturings.
The specific embodiment
One aspect of the present invention can provide the manufacturing method of metal nanoparticles, and it comprises:
Prepare first solution, it contains dispersion stabilizer and polar solvent;
Prepare second solution, it contains metal precursor and polar solvent; And
Second solution is divided at least twice to join in first solution.
According to the specific embodiment of the present invention, dispersion stabilizer can be that one or more are selected from the compound in the group of being made up of polyvinylpyrrolidone (PVP), polyacid and derivative thereof.Herein, polyacid can be that one or more are selected from the compound in the group of being made up of polyacrylic acid, poly, polymethyl methacrylate, poly-(acrylic acid-altogether-methacrylic acid), poly-(maleic acid-altogether-acrylic acid) and poly-(acrylamide-altogether-acrylic acid), and derivative can be that one or more are selected from the compound in the group of being made up of sodium salt, sylvite and the ammonium salt of polyacid.
Metal precursor can be that one or more are selected from by AgNO
3, AgBF
4, AgPF
6, Ag
2O, CH
3COOAg, AgCF
3SO
3, AgClO
4, AgCl, Ag
2SO
4, CH
3COCH=COCH
3Ag, Cu (NO
3)
2, CuCl
2, CuSO
4, C
5H
7CuO
2, NiCl
2, Ni (NO
3)
2, NiSO
4And HAuCl
4Slaine in the group of forming.
Be used for preparing the polar solvent of first solution and second solution and can be independently select the solvent of the group that Free water, pure and mild polyalcohol form for one or more.Herein, alcohol can be that one or more are selected from the alcohol in the group of being made up of methyl alcohol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanols, 2-butanols, isobutanol, hexanol and octanol.Polyalcohol can be to be selected from by glycerine, glycol, ethylene glycol, diethylene glycol (DEG), triethylene glycol, butanediol, tetraethylene glycol, propane diols, polyethylene glycol, polypropylene glycol, 1,2-pentanediol and 1, one or more polyalcohols in the group that the 2-hexylene glycol is formed.
According to the present invention, can sneak into polar solvent 200 to 10000 weight portions of first solution based on the dispersion stabilizer of 100 weight portions, can sneak into polar solvent 150 to 100000 weight portions of second solution based on the metal precursor of 100 weight portions.
Can further comprise one or more according to first solution of the present invention and be selected from solid catalyst in the group of forming by Cu (II), Cu (I), Fe (III) and Fe (II).Sneak into the solid catalyst of 1 to 10 weight portion herein, based on the metal precursor of 100 weight portions.
In addition, can further contain one or more according to second solution of the present invention is selected from by dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), NaBH
4, LiBH
4, hydroboration tetrabutylammonium, N
2H
4And composition thereof the reducing agent in the group formed.Sneak into the reducing agent of 1 to 10 weight portion herein, based on the metal precursor of 100 weight portions.
The speed that adds second solution in first solution is the metal precursor of 0.001 to 1 mole of relative 1 mole dispersion stabilizer per minute (adding).
Simultaneously, adding second solution in first solution carries out under 120～190 ℃.
Making method of metal nanoparticles of the present invention may further include:
After adding step, use the mixture of organic solvent washing second solution and first solution; And
Carry out centrifugation by mixture and obtain metal nanoparticle second solution and first solution.
Another aspect of the present invention can provide the metal nanoparticle of being made by this method.
Herein, the content of the dispersion stabilizer that combines with metal nanoparticle can be 2wt%～8wt%.
Below, will be described in detail to method of metal nanoparticles constructed in accordance and by the metal nanoparticle of this method manufacturing in conjunction with the accompanying drawings.
For the size even metal nano particle of making under the high concentration, the selection of metal precursor, dispersion stabilizer, solvent and additional reducing agent all is very important.The growth to nucleation and nano particle of the combination of these components, reaction temperature and reaction time has certain influence.
According to the pattern of nucleation and growth, the nucleus that has less than the critical value size that generates in the starting stage is unsettled and is dissolved in the solvent once again; But size is stable greater than the nucleus of critical value, and nucleation takes place thus.Critical value is normally determined according to the amount of precursor and dispersant.According to this theory, a large amount of precursors makes along with reaction is carried out forming the size homogeneous granules in the starting stage; Because the concentration of precursor reduces, so that the degree of size distribution becomes is increasing people such as (, the Nature 2005) Alivisatos.Therefore, for the manufacturing dimension homogeneous granules, think that the ratio of in reaction precursor concentration and precursor and dispersion stabilizer is important.
In addition, people's such as Xia the research about synthetic silver nano-grain has shown that initial nucleation has very big influence to the coating of particles of final manufacturing.That is, has only the nano particle that when initial nucleation stage has the shape of approximate spheroid, can form spheroid form when nano particle.At this moment, as can be seen, the molar ratio of the silver-colored relatively precursor of dispersion stabilizer polyvinylpyrrolidone (PVP) must be greater than 10 factors (10 times), by use factor greater than 15 PVP final form heterogeneous particle (Xia et al, theChem.Eur.J.2005).
As previously described, in order to make spherical and size even metal nano particle, require to use a large amount of dispersion stabilizers, this causes the increase of the size of reaction batch, thereby the productive rate of the synthetic particle of each reaction batch reduces.
Therefore, the present inventor attempts providing that a kind of manufacturing dimension is evenly and the method for metal nanoparticles of homogeneous expeditiously by control reaction in the mixing of dispersant and metal precursor.
The present invention can provide the manufacturing method of metal nanoparticles, and it comprises:
Prepare first solution, it contains dispersion stabilizer and polar solvent;
Prepare second solution, it contains metal precursor and polar solvent; And
Second solution is divided at least twice to join in first solution.
As shown in Figure 1, when second solution that will contain metal precursor joins in first solution that contains dispersion stabilizer once, along with the carrying out of reaction, the amount that forms the dispersion stabilizer of complex compound with metal ion will diminish, and the amount of self-existent dispersion stabilizer will become big.As a result, remaining dispersion stabilizer is dropped after nano particle is stable.
But as shown in Figure 2, when second solution that will contain metal precursor is divided into when joining in first solution twice, dispersion stabilizer becomes 2 times with respect to the real equivalent ratio of metal precursor, and this helps forming the particle of homogeneous.As shown in FIG. 3, when second solution being divided into when joining in first solution several times, dispersion stabilizer is with respect to the real equivalent ratio convergence infinity of metal precursor.Therefore, according to the present invention, even the amount of the dispersion stabilizer that adds reduces, dispersion stabilizer can remain on more than ten factors (more than ten times with respect to the real equivalent ratio of metal precursor, and can obtain the metal nanoparticle of homogeneous expeditiously over the factor of ten).
According to the specific embodiment of the present invention, dispersion stabilizer can be to be selected from one or more of the group be made up of polyvinylpyrrolidone (PVP), polyacid and derivative thereof.Herein, polyacid can be that to have carboxyl and the degree of polymerization on main chain or side chain be 10 to 100000 polymer or derivatives thereof.The example of polyacid can comprise polyacrylic acid, poly, polymethyl methacrylate, poly-(acrylic acid-altogether-methacrylic acid), poly-(maleic acid-altogether-acrylic acid), poly-(acrylamide-altogether-acrylic acid) etc., but is not limited thereto.
The derivative of polyacid is meant the compound that the hydrogen atom in the carboxyl of polyacid is wherein replaced by other atom or molecule, and the derivative of polyacid can be sodium salt, sylvite and the ammonium salt of polyacid.
In the present invention, the metal that forms metal nanoparticle does not have specific limited, and can comprise gold, silver, copper, nickel, palladium etc.As for the metal precursor that the metal ion that can be reduced into metal nanoparticle is provided, can use the salt of these metals.These slaines can be to be selected from by AgNO
3, AgBF
4, AgPF
6, Ag
2O, CH
3COOAg, AgCF
3SO
3, AgClO
4, AgCl, Ag
2SO
4, CH
3COCH=COCH
3Ag, Cu (NO
3)
2, CuCl
2, CuSO
4, C
5H
7CuO
2, NiCl
2, Ni (NO
3)
2, NiSO
4And HAuCl
4One or more of the group of forming, but be not limited thereto.
The polar solvent that is used to prepare first solution and second solution is not particularly limited, if in this area normally used solvent, can comprise water, alcohol, polyalcohol and composition thereof.This polar solvent plays the effect that the metal ion reduction is formed the reducing agent of metallic particles.
Herein, the example of alcohol can comprise methyl alcohol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanols, 2-butanols, isobutanol, hexanol and octanol etc., but is not limited thereto.
Polyalcohol is meant low-molecular-weight water-soluble polymer and the glycol with a plurality of oh groups.The example of polyalcohol can comprise glycerine, glycol, ethylene glycol, diethylene glycol (DEG), triethylene glycol, butanediol, tetraethylene glycol, propane diols, polyethylene glycol, polypropylene glycol, 1,2-pentanediol and 1, and 2-hexylene glycol etc., but be not limited thereto.
According to the present invention, when preparation first solution, can sneak into the polar solvent of 200 to 10000 weight portions based on the dispersion stabilizer of 100 weight portions.When use is lower than the polar solvent of 200 weight portions, can not realize the dissolving fully of dispersion stabilizer; And when the polar solvent that uses greater than 10000 weight portions, the reactant volume has to increase, thereby has reduced productivity ratio.
In addition, when preparation second solution, can sneak into the polar solvent of 150 to 100000 weight portions based on the metal precursor of 100 weight portions.When employed polar solvent during, can not realize the dissolving fully of metal precursor less than 150 weight portions; And when employed polar solvent during greater than 100000 weight portions, reaction volume has to increase, thereby has reduced productivity ratio.
In addition, in order to control nucleation and reaction speed, first solution and second solution can further contain additive, such as catalyst or reducing agent.
Can further contain the solid catalyst that one or more are selected from the group of being made up of Cu (II), Cu (I), Fe (III), Fe (II) according to first solution of the present invention.The solid catalyst that can add 1 to 10 weight portion herein, based on the metal precursor of 100 weight portions.
Can further contain one or more according to second solution of the present invention is selected from by dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), NaBH
4, LiBH
4, hydroboration tetrabutylammonium, N
2H
4And composition thereof the reducing agent of the group formed.Sneak into the reducing agent of 1 to 10 weight portion herein, based on the metal precursor of 100 weight portions.
After preparing first solution and second solution by this method, second solution is divided at least twice joins in first solution.When joining second solution in first solution, can adopt any common adding method.Preferably, can under agitation second solvent be joined in first solution continuously by the charger of metal precursor.At this moment, speed in first solution that second solution is joined is the metal precursor of 0.001 to 1 mole of relative 1 mole dispersion stabilizer per minute.This is because the adding speed of this scope is effective to the formation of the nano particle of nucleation and homogeneous.
And, the step that second solution joins in first solution is carried out under 120～190 ℃.With temperature from the boiling point of polar solvent or above more low temperature is elevated to described scope make reduction reaction take place.Simultaneously, on one side when the mixed solution that contains first solution and second solution was stirred an edge height temperature, temperature was elevated to temperature range recited above with constant speed, so that form the uniform nano particle of size, this helps controlling the size of particle.If the adding reducing agent is then compared when not adding reducing agent, reaction can be carried out under lower temperature.
When first solution and second solution being mixed and metallic particles when beginning to form by this way, the color of mixed solution begins to become redness, and when metal nanoparticle began to grow into nano-scale, mixed solution became dirty-green then.Because the size of the metallic particles of growing is measured by the change at the peak of metal in UV-Vis spectrum, when forming the particle of desired size, can stop reaction by the observation change color.
The reaction time that forms nano particle can be adjusted by the having or not of mixed proportion, temperature conditions and reducing agent of component, for example was 1 to 60 minute.When greater than 60 minutes, the size of formed particle is too big.
After the metal nanoparticle of making as previously described, can obtain nano particle from reaction solution by the normally used method in this area.
Therefore, manufacturing method of metal nanoparticles of the present invention may further include:
After the step that second solution is joined in first solution, use the organic solvent washing reactant mixture; And
By with the centrifugal acquisition metal nanoparticle of reactant mixture.
In washing step, can use methyl alcohol, ethanol, MDF or its mixture as organic solvent.
And, make method of metal nanoparticles of the present invention and can comprise the dry metal nanoparticle that is obtained.Metal nanoparticle made according to the method for the present invention can be disperseed equably by dispersion stabilizer, thus growth and not condensing equably, and can obtain with the form of the nano particle of homogeneous.Herein, the content of the dispersion stabilizer that combines with metal nanoparticle can be the 2wt%～8wt% of the metal nanoparticle gross weight of manufacturing.
The present invention is described further below by embodiment.The following examples are intended to further specify the present invention rather than limit scope of the present invention.
Embodiment 1
After the polyvinylpyrrolidone (PVP) with the ethylene glycol of 300 weight portions and 100 weight portions mixes, the solution (first solution) of this preparation is heated to 170 ℃.AgNO with 100 weight portions
3Mix to prepare second solution with the ethylene glycol of 250 weight portions.Is that 0.4 speed join second solution in first solution with the per minute silver ion with respect to the mol ratio of PVP total amount by fluid control, makes formed solution reaction 20 minutes.Solution become emerald green after, with acetone/methanol mixture washing and centrifugal to obtain silver nano-grain.
Embodiment 2
Except reaction temperature is that 150 ℃, adding speed are per minute 0.2 mol ratio and reaction time to be 30 minutes, obtain silver nano-grain by the method identical with embodiment 1.
Embodiment 3
After the polyvinylpyrrolidone (PVP) with the ethylene glycol of 400 weight portions and 100 weight portions mixes, the solution (first solution) of this preparation is heated to 150 ℃.AgNO with 100 weight portions
3Mix to prepare second solution with the ethylene glycol of 300 weight portions.Is that 0.07 adding speed join second solution in first solution with the per minute silver ion with respect to the mol ratio of PVP total amount by fluid control, makes formed solution reaction 60 minutes.Solution become emerald green after, with the washing of acetone/methanol mixture and centrifugation to obtain silver nano-grain.
Embodiment 4
After the Cu (II) with the polyvinylpyrrolidone (PVP) of the ethylene glycol of 400 weight portions, 100 weight portions and 6 weight portions mixes, the solution (first solution) of this preparation is heated to 160 ℃.AgNO with 100 weight portions
3, the DMF of 100 weight portions and 100 weight portions ethylene glycol mix to prepare second solution.Is that 0.2 adding speed join second solution in first solution with the per minute silver ion with respect to the mol ratio of PVP total amount by fluid control, makes formed solution reaction 60 minutes.Solution become emerald green after, with the washing of acetone/methanol mixture and centrifugation to obtain silver nano-grain.
By being that all the other conditions and embodiment 4 identical methods 15 minutes obtain silver nano-grain except not use Cu (II) catalyst, reaction temperature be 150 ℃, adding speed as per minute 0.2 mol ratio and reaction time.
Fig. 4～Fig. 8 is the SEM image according to the metal nanoparticle of embodiments of the invention 1 to 5 manufacturing.With reference to figure 4～Fig. 8, the silver nano-grain of average 20 to 60nm homogeneous constructed in accordance.And as in embodiment 4, under the situation that adds metallic catalyst and reducing agent, nucleation takes place fast, can generate the nano particle of the uniform-dimension with about 10nm.Simultaneously, as in embodiment 5, under PVP with respect to the mol ratio of silver ion is bigger situation, although the reaction time is short, the gross production rate height.
Should be appreciated that, under the situation of the scope that does not deviate from the disclosed theme of the present invention, can the various details of the disclosed theme of the present invention be changed.And the description of front is only in order to be described, rather than restriction.
Industrial applicability
According to the present invention, provide a kind of by control reaction, a small amount of stably dispersing of use Agent is the equal method of the metal nanoparticle of even homogeneous of manufacturing dimension expeditiously, and the method is suitable For synthesizing of the metal nanoparticle that makes in colloidal dispersion.
Claims (15)
1. make method of metal nanoparticles for one kind, it comprises:
Prepare first solution, it contains dispersion stabilizer and polar solvent;
Prepare second solution, it contains metal precursor and polar solvent; And
Described second solution is divided at least 2 times to join in described first solution;
Wherein, described dispersion stabilizer is that one or more are selected from the compound in the group of being made up of polyvinylpyrrolidone, polyacid and derivative thereof; Described metal precursor is to be selected from by AgNO
3, AgBF
4, AgPF
6, Ag
2O, CH
3COOAg, AgCF
3SO
3, AgClO
4, AgCl, Ag
2SO
4, CH
3COCH=COCH
3Ag, Cu (NO
3)
2, CuCl
2, CuSO
4, C
5H
7CuO
2, NiCl
2, Ni (NO
3)
2, NiSO
4And HAuCl
4Compound in the group of forming; The described polar solvent that is used for preparing described first solution and described second solution selects the solvent of the group that Free water, pure and mild polyalcohol form independently for one or more.
2. method according to claim 1, wherein, described polyacid is that one or more are selected from the compound in the group of being made up of polyacrylic acid, poly, polymethyl methacrylate, poly-(acrylic acid-altogether-methacrylic acid), poly-(maleic acid-altogether-acrylic acid) and poly-(acrylamide-altogether-acrylic acid); Described derivative is that one or more are selected from the compound in the group of being made up of sodium salt, sylvite and the ammonium salt of described polyacid.
3. method according to claim 1, wherein, described alcohol is that one or more are selected from the alcohol in the group of being made up of methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, isobutanol, hexanol and octanol.
4. method according to claim 1, wherein, described polyalcohol is that one or more are selected from by glycerine, glycol, ethylene glycol, diethylene glycol (DEG), triethylene glycol, butanediol, tetraethylene glycol, propane diols, polyethylene glycol, polypropylene glycol, 1,2-pentanediol and 1, the polyalcohol in the group that the 2-hexylene glycol is formed.
5. method according to claim 1 wherein, is sneaked into described polar solvent 200 to 10000 weight portions of described first solution based on the described dispersion stabilizer of 100 weight portions.
6. method according to claim 1 wherein, is sneaked into described polar solvent 150 to 100000 weight portions of described second solution based on the described metal precursor of 100 weight portions.
7. method according to claim 1, wherein, described first solution further comprises one or more and is selected from solid catalyst in the group of being made up of Cu (II), Cu (I), Fe (III), Fe (II).
8. method according to claim 7 wherein, is sneaked into the described solid catalyst of 1 to 10 weight portion based on the described metal precursor of 100 weight portions.
9. method according to claim 1, wherein, described second solution further comprises one or more and is selected from by dimethyl formamide, dimethyl sulfoxide (DMSO), NaBH
4, LiBH
4, hydroboration tetrabutylammonium, N
2H
4And composition thereof the reducing agent in the group formed.
10. method according to claim 9 wherein, is sneaked into the described reducing agent of 1 to 10 weight portion based on the described metal precursor of 100 weight portions.
11. method according to claim 1, wherein, the adding speed of described second solution is the described metal precursor of 0.001 to 1 mole of relative 1 mole described dispersion stabilizer per minute.
12. method according to claim 1, wherein, described adding step is carried out under 120 to 190 ℃.
13. method according to claim 1, wherein said manufacturing method of metal nanoparticles further comprises:
After the step that described second solution is joined in described first solution, with the described mixture of organic solvent washing; And
By with the described metal nanoparticle of the centrifugal acquisition of described mixture.
14. metal nanoparticle according to any method manufacturing described in claim 1 and 13.
15. metal nanoparticle according to claim 14 contains the described dispersion stabilizer of 2wt% to 8wt% in described metal nanoparticle.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060047267A KR100790948B1 (en) | 2006-05-25 | 2006-05-25 | Method for preparing metal nanoparticles and metal nanoparticles prepared using the same |
| KR1020060047267 | 2006-05-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101077530A CN101077530A (en) | 2007-11-28 |
| CN100569418C true CN100569418C (en) | 2009-12-16 |
Family
ID=38749898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100794970A Expired - Fee Related CN100569418C (en) | 2006-05-25 | 2007-04-11 | The metal nanoparticle of making method of metal nanoparticles and making thus |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20070275259A1 (en) |
| JP (1) | JP2007314869A (en) |
| KR (1) | KR100790948B1 (en) |
| CN (1) | CN100569418C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104416165A (en) * | 2013-08-29 | 2015-03-18 | 三星电机株式会社 | Method of manufacturing metal powder and multi-layer ceramic capacitor |
Families Citing this family (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060254387A1 (en) * | 2005-05-10 | 2006-11-16 | Samsung Electro-Mechanics Co., Ltd. | Metal nano particle and method for manufacturing them and conductive ink |
| KR100836659B1 (en) * | 2006-07-06 | 2008-06-10 | 삼성전기주식회사 | Method for manufacturing metal nanoparticles |
| KR100790457B1 (en) * | 2006-07-10 | 2008-01-02 | 삼성전기주식회사 | Method for producing metal nanoparticles |
| US20090090214A1 (en) * | 2007-10-04 | 2009-04-09 | Chung Yuan Christian University | Method for forming nano-scale metal particles |
| KR100838254B1 (en) * | 2008-01-03 | 2008-06-17 | 주식회사 신일 | Silver colloid and producing method thereof |
| KR100851815B1 (en) | 2008-03-24 | 2008-08-13 | 주식회사 나노엠에스이 | A method of preparing nano silver powder |
| AU2009241334B2 (en) * | 2008-04-28 | 2012-07-19 | Tata Chemicals Limited | A process for the preparation of silver nano particles |
| KR101482532B1 (en) * | 2008-07-03 | 2015-01-16 | 주식회사 동진쎄미켐 | Preparation method for nano sized metal particle |
| JP5372450B2 (en) * | 2008-09-25 | 2013-12-18 | 独立行政法人科学技術振興機構 | Method for producing metal nanoparticles |
| KR100922224B1 (en) * | 2008-11-10 | 2009-10-20 | 나노바이오주식회사 | A method for preparing metal nanoparticles using mixed polymer as surfactant |
| DE102009015470A1 (en) * | 2008-12-12 | 2010-06-17 | Byk-Chemie Gmbh | Process for the preparation of metal nanoparticles and metal nanoparticles obtained in this way and their use |
| JP2013503260A (en) * | 2009-08-25 | 2013-01-31 | カンブリオス テクノロジーズ コーポレイション | Method for controlling the morphology of metal nanowires |
| KR101117694B1 (en) * | 2009-08-27 | 2012-03-02 | 삼성에스디아이 주식회사 | Method of preparing conductive nano ink composition |
| US20110059233A1 (en) * | 2009-09-04 | 2011-03-10 | Xerox Corporation | Method For Preparing Stabilized Metal Nanoparticles |
| KR101102877B1 (en) * | 2009-10-31 | 2012-01-11 | 한국세라믹기술원 | Copper powder for silver coated and manufacturing method |
| KR101043066B1 (en) * | 2009-11-25 | 2011-06-21 | 아주대학교산학협력단 | A method of preparing metal ferrite nanoparticles useful for contrast agents |
| CN102085574B (en) * | 2009-12-04 | 2012-12-12 | 深圳先进技术研究院 | Water-dispersible silver nanometer particles and preparation method thereof |
| US9487399B2 (en) * | 2010-08-17 | 2016-11-08 | Jalaledin Ghanavi | Method for the synthesis of metallic nano products |
| JP5688144B2 (en) * | 2010-08-19 | 2015-03-25 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | Borate luminescent material, preparation method and application thereof |
| KR101276693B1 (en) | 2010-10-29 | 2013-06-19 | 포항공과대학교 산학협력단 | Synthesis of zwitterion functionalized surface molecules for nanoparticles and the applications thereof |
| CN102079840B (en) * | 2011-01-04 | 2012-09-05 | 武汉理工大学 | Method for preparing Ag/PMMA (polymethyl methacrylate) nano composite material |
| CN102133644B (en) * | 2011-03-01 | 2012-12-19 | 宁波大学 | Method for preparing nickel nano particles |
| JP2014224276A (en) * | 2011-09-08 | 2014-12-04 | 学校法人 関西大学 | Method for producing copper nanoparticle having high dispersion stability |
| JP5310967B1 (en) * | 2011-11-18 | 2013-10-09 | 住友金属鉱山株式会社 | Silver powder manufacturing method |
| KR101349360B1 (en) * | 2012-01-27 | 2014-01-16 | 연세대학교 산학협력단 | Metal nano particle usable for photothermal therapy and method for preparing the same |
| KR101369881B1 (en) * | 2012-06-20 | 2014-03-19 | 한국과학기술원 | Preparing method for silver nano wire |
| CN103537707B (en) * | 2012-07-12 | 2015-12-02 | 国家纳米科学中心 | Five heavy twin gold and electrum particle and preparation method thereof |
| JP6106391B2 (en) * | 2012-09-14 | 2017-03-29 | Ｄｏｗａエレクトロニクス株式会社 | Plate-shaped copper powder, method for producing the same, and conductive paste |
| KR102172116B1 (en) | 2012-09-27 | 2020-10-30 | 로디아 오퍼레이션스 | Process for making silver nanostructures and copolymer useful in such process |
| CN103048304A (en) * | 2012-12-07 | 2013-04-17 | 江苏大学 | Preparation method of recyclable surface-enhanced Raman-spectrum active substrate |
| CN103394373B (en) * | 2013-04-27 | 2015-12-23 | 南京工业大学 | A kind of preparation method of hydrogenation catalyst |
| CN103406545B (en) * | 2013-07-15 | 2015-05-27 | 北京航空航天大学 | Micron-particle-size FeCo particles and preparation method thereof |
| US20150166810A1 (en) * | 2013-12-16 | 2015-06-18 | Nano And Advanced Materials Institute Limited | Metal Nanoparticle Synthesis and Conductive Ink Formulation |
| KR101671953B1 (en) * | 2015-03-24 | 2016-11-08 | 주식회사 알티엑스 | Method for Preparing Silver Nanoparticles and Silver Nanoparticles Prepared by the Same |
| KR101722992B1 (en) * | 2015-05-18 | 2017-04-04 | 국방과학연구소 | Gold nanofluids, silver nanofluids and production methods thereof |
| PL3124137T3 (en) * | 2015-07-30 | 2019-11-29 | Belenos Clean Power Holding Ag | Method for the production of msnx nanoparticles as anode materials for a rechargeable battery |
| WO2018038086A1 (en) * | 2016-08-25 | 2018-03-01 | Dic株式会社 | Aqueous metal nanoparticle dispersion |
| CN106541149B (en) * | 2016-12-07 | 2019-04-19 | 桂林电子科技大学 | A kind of accurate-size controls the preparation method of extra small nano-Ag particles |
| CN106964785A (en) * | 2017-04-20 | 2017-07-21 | 中国科学院深圳先进技术研究院 | A kind of preparation method of nano-Ag particles |
| CN107824182A (en) * | 2017-10-31 | 2018-03-23 | 四川爱尔西科技有限公司 | With formaldehyde at room temperature and the effective catalyst of carbon monoxide purification |
| CN108298502B (en) * | 2018-01-15 | 2021-06-01 | 东南大学 | Method for preparing dispersed nano metal oxide and nano metal powder |
| KR102151390B1 (en) * | 2018-10-30 | 2020-09-03 | 울산과학기술원 | Method of nano particle-graphene composite and the nano particle-graphene composite manufactured by the same |
| EP3656825B1 (en) * | 2018-11-22 | 2021-04-28 | Société BIC | Process for preparing aqueous gel inks with variable color, and aqueous gel inks thereof |
| CN109659281B (en) * | 2019-01-29 | 2020-05-01 | 中南大学 | High-thermal-conductivity electronic packaging composite material and preparation method thereof |
| CN109732102B (en) * | 2019-03-18 | 2020-09-01 | 湘潭市泽宇新材料科技有限公司 | Monodisperse conductive silver powder suitable for high-temperature and low-temperature silver pastes and preparation method thereof |
| CN111822696B (en) * | 2019-04-15 | 2023-04-18 | 中国科学院深圳先进技术研究院 | Monodisperse nano-copper particles for conductive ink and preparation method and application thereof |
| CN112705726A (en) * | 2020-12-17 | 2021-04-27 | 暨南大学 | Preparation method of shape-controllable nano silver powder |
| CN114906869B (en) * | 2022-04-25 | 2024-03-26 | 东南大学 | Preparation method of cerium oxide-based nano particles |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US275259A (en) * | 1883-04-03 | Corn-sheller | ||
| JPS63307208A (en) * | 1987-06-08 | 1988-12-14 | Chiyoda Chem Eng & Constr Co Ltd | Production of fine noble metal powder |
| JPH04235205A (en) * | 1991-01-09 | 1992-08-24 | Sumitomo Metal Ind Ltd | Production of copper powder |
| US6090858A (en) * | 1998-03-18 | 2000-07-18 | Georgia Tech Reseach Corporation | Shape control method for nanoparticles for making better and new catalysts |
| US6262129B1 (en) * | 1998-07-31 | 2001-07-17 | International Business Machines Corporation | Method for producing nanoparticles of transition metals |
| JP2000239713A (en) * | 1999-02-23 | 2000-09-05 | Tanaka Kikinzoku Kogyo Kk | Production of flaky silver powder |
| JP4238444B2 (en) * | 1999-12-16 | 2009-03-18 | 株式会社村田製作所 | Method for producing metal powder, conductive paste and ceramic electronic component |
| US7348365B2 (en) | 2001-04-30 | 2008-03-25 | Postech Foundation | Colloid solution of metal nanoparticles, metal-polymer nanocomposites and methods for preparation thereof |
| KR100484506B1 (en) * | 2002-04-16 | 2005-04-20 | 학교법인 포항공과대학교 | Metal-polymer nanocomposite with uniform shape and narrow size distribution and the method for preparing thereof |
| JP2004043892A (en) * | 2002-07-11 | 2004-02-12 | Sumitomo Electric Ind Ltd | Fine particle of noble metal and manufacturing method therefor |
| KR100487905B1 (en) | 2002-10-02 | 2005-05-06 | 한국과학기술연구원 | Shape anisotropic iron oxide nano-particles and synthetic method thereof |
| US7585349B2 (en) * | 2002-12-09 | 2009-09-08 | The University Of Washington | Methods of nanostructure formation and shape selection |
| US7157848B2 (en) * | 2003-06-06 | 2007-01-02 | Electrovac Fabrikation Elektrotechnischer Spezialartikel Gmbh | Field emission backlight for liquid crystal television |
| KR100965373B1 (en) * | 2003-06-10 | 2010-06-22 | 삼성전자주식회사 | Photosensitive Metal Nanoparticle and Method of forming Conductive Pattern by using the same |
| US7923072B2 (en) * | 2004-01-14 | 2011-04-12 | University Of South Florida | Silver crystals through Tollen's reaction |
| KR100588520B1 (en) * | 2004-03-11 | 2006-06-14 | 한국에너지기술연구원 | Preparation of Heat Transfer Fluid Using Single Step Process involving Liquid Phase Control |
| DE602004021679D1 (en) * | 2004-06-30 | 2009-08-06 | St Microelectronics Srl | Inkjet printed active film sensor and method of making the sensor |
| JP4451252B2 (en) * | 2004-09-02 | 2010-04-14 | エスアイアイ・ナノテクノロジー株式会社 | Near-field microscope probe, manufacturing method thereof, and scanning probe microscope using the probe |
| KR100652251B1 (en) * | 2004-09-03 | 2006-12-01 | 학교법인연세대학교 | Method for Preparing Water-soluble Nanoparticles via Multi-Functional Group Ligand Assisted Surface Modification Processes |
| US20060115536A1 (en) * | 2004-11-12 | 2006-06-01 | Board Of Regents, The University Of Texas System | Glycerin based synthesis of silver nanoparticles and nanowires |
| US20060189113A1 (en) * | 2005-01-14 | 2006-08-24 | Cabot Corporation | Metal nanoparticle compositions |
| US7625637B2 (en) * | 2006-05-31 | 2009-12-01 | Cabot Corporation | Production of metal nanoparticles from precursors having low reduction potentials |
-
2006
- 2006-05-25 KR KR1020060047267A patent/KR100790948B1/en not_active IP Right Cessation
-
2007
- 2007-02-21 US US11/708,571 patent/US20070275259A1/en not_active Abandoned
- 2007-03-02 JP JP2007052309A patent/JP2007314869A/en active Pending
- 2007-04-11 CN CNB2007100794970A patent/CN100569418C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104416165A (en) * | 2013-08-29 | 2015-03-18 | 三星电机株式会社 | Method of manufacturing metal powder and multi-layer ceramic capacitor |
| CN104416165B (en) * | 2013-08-29 | 2017-09-29 | 三星电机株式会社 | Manufacture the method and multilayer ceramic capacitor of metal-powder |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100790948B1 (en) | 2008-01-03 |
| CN101077530A (en) | 2007-11-28 |
| JP2007314869A (en) | 2007-12-06 |
| KR20070113692A (en) | 2007-11-29 |
| US20070275259A1 (en) | 2007-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100569418C (en) | The metal nanoparticle of making method of metal nanoparticles and making thus | |
| KR100754326B1 (en) | Manufacturing Method of Metal Nanoparticle | |
| JP4851383B2 (en) | Method for producing metal nanoparticles, metal nanoparticles, and conductive ink | |
| EP2883922B1 (en) | Metal nanoparticle synthesis and conductive ink formulation | |
| KR100954425B1 (en) | Method for preparation of silver powder by continuous solution reduction | |
| KR100716201B1 (en) | Metal nanoparticles and method for manufacturing thereof | |
| CN101104205B (en) | Method for manufacturing copper nano granule | |
| JP5639045B2 (en) | Method for producing fine particle group comprising solid solution type alloy fine particles | |
| JP5827341B2 (en) | Reactor for silver powder production and continuous production method | |
| JP2008013846A (en) | Method for producing metal nanoparticle, and metal nanoparticle | |
| CN104625046B (en) | The manufacture method of core shell structure micron and nano composite spherical powder | |
| JP2009024254A (en) | Production method of nickel nanoparticle | |
| US10226822B2 (en) | Method for preparing metal nanoparticles using a multi-functional polymer and a reducing agent | |
| KR20080035315A (en) | Silver nano-particles and preparation method thereof | |
| KR20130090803A (en) | Method of producing metal nano-particles | |
| CN101015774A (en) | Nano-metal dispersion and its preparation method | |
| JP5647415B2 (en) | Preparation of nanoparticles containing iron and titanium | |
| KR101066545B1 (en) | Metal Nanoparticles of Various Sizes and Shapes Having Functional Groups and Method for Preparing the Same | |
| Yin et al. | Emulsion-assisted synthesis of monodisperse binary metal nanoparticles | |
| Liu et al. | Synthesis and size control of nano/submicron copper particles by feeding strategies | |
| KR20130078186A (en) | Method of producing metal nano-particles using micro reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091216 Termination date: 20160411 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |