CN102770368A - Apparatus and method for producing metal nanoparticles using granule-type electrodes - Google Patents

Apparatus and method for producing metal nanoparticles using granule-type electrodes Download PDF

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Publication number
CN102770368A
CN102770368A CN2011800105737A CN201180010573A CN102770368A CN 102770368 A CN102770368 A CN 102770368A CN 2011800105737 A CN2011800105737 A CN 2011800105737A CN 201180010573 A CN201180010573 A CN 201180010573A CN 102770368 A CN102770368 A CN 102770368A
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electrode
metal nanoparticle
metal
shell
particle
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CN102770368B (en
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崔珉荣
姜允在
金太均
宋容卨
韩柄善
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Amogreentech Co Ltd
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Amogreentech Co Ltd
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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
    • 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
    • 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
    • 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
    • B22F1/0551—Flake form nanoparticles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode
    • 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

Abstract

The present invention relates to an apparatus and method for producing metal nanoparticles using granule-type electrodes, in which a pair of electrode housings spaced apart from each other is filled with metal granules, and electrolysis is performed on the metal granules using alternating current, to thereby mass produce metal nanoparticles having a uniform shape in a continuous and inexpensive manner. The apparatus of the present invention comprises: a reaction container in which an electrolytic solution is contained; a first electrode and a second electrode which are formed by filling a first electrode housing and a second electrode housing, which are spaced apart from each other in the reaction container, with a plurality of metal granules or flakes; and a power supply device for applying alternating current power between the first electrode and the second electrode so as to induce an electrolysis reaction. The first electrode housing and the second electrode housing have a plurality of holes or slits formed at the opposite surfaces thereof, respectively, so as to discharge metal ions eluted by the electrolysis reaction.

Description

Utilize the metal nanoparticle preparation facilities and the method thereof of granular pattern electrode
Technical field
The present invention relates to utilize the metal nanoparticle preparation facilities and the method thereof of electrolysis; Relate in particular to a kind of alternating voltage that utilizes; Material as electrode; Particles filled in pair of electrodes shell what constitute with set interval by the metal identical with the metal nanoparticle that will obtain; By means of electrolysis, can be with cheap price, prepare the metal nanoparticle preparation facilities and the method thereof of utilizing the granular pattern electrode of metal nanoparticle of the nanometer size of homogeneous shape and homogeneous continuously in a large number.。
Background technology
Generally speaking; As the method that is used to obtain refining metallic powder, use chemical method such as coprecipitation, spray-on process, sol-gel process, electrolysis, reverse microemulsion process and utilize the mechanical means such as comminuting method of ball mill (ball mill), bruisher (stamp mill).
For example; With regard to the chemical method that is used to prepare silver powder; The main method of using is, through the neutralization reaction of utilizing aqueous slkali that silver nitrate aqueous solution is neutralized, in the sediment of silver oxide that generates or silver hydroxide; The method of using hydrazine or reducing agents such as hydrogen peroxide, formalin to reduce; Or in the deposition of the silver hydroxide that generates by said neutralization reaction, sneak into the method that the strong gases of reducing power such as hydrogen, carbon monoxide reduce, or in the alkaline ammino-complex aqueous solution, add reducing agents such as formalin, oxalic acid and reduce, thereby separate out the method for silver powder.
But, with regard to this preparation method in the past,, use slaine as electrolyte as initial substance, thereby not enough environmental protection, for removing nuisance, require a large amount of expenses and time, and have the uppity problem of particle size.
In addition, in the past owing to used interfacial agent and additive or nuisance, thereby there is the shortcoming of not enough environmental protection for stoping the particle growth that causes because of the metallic flocculation to use.
With regard to common electrolysis in the past, the electrode of the metal material that use will be synthesized and slaine, promptly nitrate, carbonate, sulfate etc. utilize electrolysis as electrolyte, make it to realize metallization at electrode surface, obtain particle.
Certainly, in electrolysis, as the electrolyte that is used to obtain metal dust; Why using poisonous metal salt, is because metal is water insoluble, if water-soluble the metal that combines with strong acid salt; Then be dissociated into ion easily, utilize reducing agent etc. can realize particlized.
In this case, produce nuisance, when improving temperature, produce pernicious gas as accessory substance, not enough environmental protection, the size of particle is also even inadequately.
And, as in the past, in the electrolysis of having used such as the slaine of nitrate, carbonate, sulfate etc.; The not enough environmental protection of initial substance itself; In neutralization and cleaning process, waste water handling problem not only takes place, and existence needs the trouble through cleaning process; In cleaning process, metal dust is run off in a large number.
In Korea S's publication 10-2004-105914 number, a kind of metal nanoparticle preparation method who utilizes electrolysis has been proposed, consider in the electrolysis of stating slaine in the past in the use; The not enough environmental protection of initial substance itself; Waste water handling problem etc. taking place, only use electrode and minor amounts of additives, deionized water (DI-water), applies outside power simultaneously; Induce the formation and the dispersion of metallic, thereby can prepare to environmental protection the nano particle of metal.
With reference to Fig. 1, the utilization that the said Korea S of further explain publication discloses for 10-2004-105914 number is the metal nanoparticle preparation method of electrolysis in the past below.
As shown in Figure 1; In the preparation of conventional metal nano particle, deionized water and the solution (2) that has mixed feature of environmental protection metal ion reducing agent or organic matter metal ion reducing agent as additive are dropped in the inside in container (1); In said solution (2), make two electrode bars (3) isolation configuration.In addition, in said solution (2), the agitator (5) that produces hyperacoustic ultrasonic generator (4) and agitating solution (2) be disposed at respectively said container about, under this formation state, direct current (DC) electric current access 2 electrode bars (3).
But said preparation method has in the past utilized the direct current solution, and the anode electrode rod all is made up of the composition identical with the metallic that will obtain with the cathode electrode rod, by means of potential difference, occurs in the phenomenon that generates metallic crystal on the electrode.
In addition, when utilizing said preparation method in the past to prepare metal nanoparticle, for example; The preparation nano grain of silver period of the day from 11 p.m. to 1 a.m inserts DC current (DC), and the metal cation that generates at anode (Anode) moves to negative electrode; Grow on every side at negative electrode (Cathode), generate the above micron-sized silver particles crystallization (Crystalline) of nanoscale, the phenomenon of caking takes place; And metallic generates even inadequately, has the problem that forms inhomogeneous particle.
In addition, according to said preparation method in the past, inserting DC current; Implement under the situation of electrolysis, at the anode place, the heat that produces when generating owing to the Ag+ ion; With OH-ions bind, has the problem that oxidative phenomena takes place, before unoxidized Ag+ ion is reduced the agent reduction as the companion ion of Ag+ ion; Under electric field action, move to negative electrode, the electronics that provides with negative electrode meets, and is reduced to silver again at cathode surface; Silver particles thereby growth gradually, the silver particles of growth be until growing to micron order, thereby cause the result who has consumed the Ag+ ion that will generate nano particle.
Therefore, even the Ag+ ion is reduced the agent reduction, by the dispersant end-blocking; The Nano silver grain that generation needs; Its amount is compared with the Ag2O growing amount of oxidation and the silver particles of growth, has only few amount to be present in the reaction solution, is not suitable for as high efficiency mass production method.
On the other hand; In the said metal nanoparticle preparation method who utilizes the dc electrolysis method in the past; As solving the technology that is not suitable for as the mass production method problem; Use alternating voltage to replace DC voltage when in korean registered patent 10-0820038 number, having proposed, the technology of preparation metal nanoparticle in electrolysis.
The copper nano-particle preparation method of said registered patent comprises: dissolving step will or can make copper realize dissolving in the metal ion propellant input water of Ionized material as metal ion reducing agent and the trisodium citrate of the material that can make the reduction of hydrazine or copper ion on the copper electrode surface; Ionization step; Isolation configuration copper electrode in said solution; Said electrode is made up of the composition identical with the metallic that will obtain, and by means of the electric energy and the said metal ion propellant that produce because of the alternating voltage that inserts electrode, in said solution, realizes ionization; Separate out step, in said solution, copper ion is reduced by said reducing agent, separates out copper particle.
But, according to said registered patent, though can obtain the fine copper nano particle, because the alternating voltage commonly used of use 110V ~ 220V (50 ~ 60Hz) of sine wave, thereby electrolytic efficiency is very low.Its reason is that the polarity of two electrodes of alternating current is exchanged with both fixed cycles; Under common alternating voltage commonly used, the polarity per second conversion of electrode 50 ~ 60 times, so; Though the metal ion that generates at the metal electrode place of a side is reduced; But before reduction, return the metal electrode of opposite side again, have the problem that productivity ratio greatly reduces.
Therefore, the particle mean size of copper particle and skewness are because based on the crystallization of the change in polarity of electrode, the problem that exists a large amount of production efficiencys to descend.
On the other hand, the copper nano-particle of technology preparation in the past is as shown in Figure 2 with metal electrode, uses the electrode that is made up of tabular columnar electrode.The a pair of copper electrode of isolation configuration disposes tabular columnar electrode before reaction in electrolytic cell, and along with the carrying out of cell reaction, electrode is consumed gradually, and behind the reaction given time, the end of columnar electrode is deformed into the taper shape.
If two interelectrode intervals change along with the columnar electrode change in shape, potential difference then takes place to be changed, the energising amount of electric current reduces, since heating, the problem that the metal nanoparticle size that takes place to generate increases.
Therefore, for keeping set interval, every separated both fixed cycles should block crushed element and reinstall or be replaced by new electrode, thereby the use of electrode inadequately effectively, efficiently, and fall short of electrode life.And in batch production process, the operation of reinstalling of kind electrode needs manual operations termly to carry out with the replacing operation, thereby has the low problem of productivity ratio.
Summary of the invention
The problem that solves
Therefore; The object of the present invention is to provide a kind of metal nanoparticle preparation facilities and method thereof of utilizing the granular pattern electrode,, fill the particle or the chip that constitute by the metal material identical with the metal nanoparticle that will obtain in the pair of electrodes enclosure that is installed on by set interval in the electrolytic cell; Constitute electrode; Even thereby carry out electrolysis, interelectrode distance is also constant, can obtain the evenly metal nanoparticle of size.
Another object of the present invention is to provide a kind of metal nanoparticle preparation facilities; In electrolytic process, along with the consumption of metallic particles or chip, filling metallic particles for overlay or chip continuously; Thereby need not to prepare a large amount of metal nanoparticles easily continuously because of changing the electrode breaks in production.
Another purpose of the present invention is to provide a kind of metal nanoparticle preparation facilities, before metal ion forms crystallization, utilizes reducing agent to be reduced into metal nanoparticle; Before still unreduced metal ion grows into nanocrystal, polarity is changed, thereby; In AC power, select optimum frequency; Insert electrode, so that realize a large amount of productions of metal nanoparticle, can a large amount of metal nanoparticle of efficient production.
A purpose more of the present invention is to provide a kind of metal nanoparticle preparation facilities and method thereof, can be when utilizing the alternating current electrolysis method, and environmental protection ground preparation metal nanoparticle.
Technical scheme
For reaching as above purpose, according to a kind of form of the present invention, the present invention provides a kind of preparation facilities of metal nanoparticle, it is characterized in that, comprising: reaction vessel, and electrolysis solution holds; The the 1st and the 2nd electrode in the 1st and the 2nd electrode shell that the compartment of terrain is installed on each said reaction vessel interior is set, is filled a plurality of particles or the chip that are made up of the metal identical with the metal nanoparticle that will obtain and is formed; And power supply device, be used to carry out cell reaction and between the said the 1st and the 2nd electrode the incoming transport power supply; And the said the 1st and the 2nd electrode shell possesses a plurality of holes or seam at least on face in opposite directions, so that make along with cell reaction from the metal ion discharge of the said the 1st and the 2nd electrode stripping.
According to another kind of form of the present invention, the present invention provides a kind of preparation facilities of metal nanoparticle, it is characterized in that, comprising: reaction vessel, and electrolysis solution holds; The 1st electrode in being installed on the electrode shell of said reaction vessel interior, being filled a plurality of particles or the chip that are made up of the metal identical with the metal nanoparticle that will obtain and is formed; The 2nd electrode is set at interval with said the 1st electrode, is installed on the inside of said reaction vessel; And power supply device, be used to carry out cell reaction and between the said the 1st and the 2nd electrode the incoming transport power supply; And said electrode shell possesses a plurality of holes or seam, so that make along with cell reaction from the metal ion discharge of said the 1st electrode stripping.
The preparation facilities of metal nanoparticle of the present invention can also comprise supporting seat, with state of insulation space both set a distance, said the 1st electrode shell and the 2nd electrode shell is supported.
In addition, said supporting seat can also comprise on two sides: the 1st and the 2nd power line, insert the AC power between the said the 1st and the 2nd electrode from the power supply device supply; The the 1st and the 2nd electrode terminal is used to interconnect inner particle or the chip of filling of the 1st and the 2nd electrode shell.
The the said the 1st and the 2nd electrode shell can be respectively that cross sectional shape is rectangle or polygonal bucket.
In addition, the said the 1st and the 2nd electrode shell is made up of the 1st and the 2nd side plate, and each side in opposite directions has a plurality of convexities that are made up of zigzag, forms a plurality of holes or seam in the two sides of said convexity, and the said the 1st and the 2nd side plate is made up of the net that constitutes with Ti respectively.
And, the said the 1st and the 2nd electrode shell can be respectively diameter different, with the circular double-deck barrel structure of concentric shape configuration.At this moment, said preparation facilities can also comprise agitator, and the central authorities that its rotating shaft connects the 2nd electrode shell prolong, and the bearing that is supported on supporting seat supports revolvably, disposes impeller at the leading section of rotating shaft.
Said preparation facilities can also comprise conductive plate, inserts the inner space of the 1st and the 2nd electrode shell, realizes being in contact with one another with said particle or chip.
Said particle or chip are made up of any alloy more than a kind or 2 kinds of selecting in the group that constitutes at Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni and Pd; The size of said particle or chip is set at 0.05 to 10cm scope, is preferably set to 0.5 to 5mm scope.
The the said the 1st and the 2nd electrode shell can be any a kind that in the group that is made up of high molecular polymer, pottery, glass and titanium (Ti), selects.
Preferred said electrode shell has criss-cross spatial accommodation in inside, possess a plurality of holes or seam at downside, and the side of said the 2nd electrode and said electrode shell disposes in opposite directions, is made up of tabular.
In addition, preferred said electrode shell has criss-cross spatial accommodation in inside, possesses a plurality of holes or seam in the side, and the said electrode shell of said the 2nd electrode handle is contained in inside, is made up of drum or drum shape net.
Preferred said electrode shell is driven in rotation, and keeps the both set a distances between the 1st and the 2nd electrode, and said the 2nd electrode is made up of Ti.
Another form according to the present invention, the present invention provides a kind of preparation method of metal nanoparticle, it is characterized in that comprising: the electrolytic solution preparation process, in reaction vessel, make electrolyte and dispersant be dissolved in pure water, prepare electrolytic solution; The the 1st and the 2nd electrode forms step; Be disposed at said reaction vessel interior in opposite directions and on forward surface, possessing in the 1st and the 2nd electrode shell of a plurality of holes or seam; Filling forms the 1st and the 2nd electrode by a plurality of particles or chip that the metal identical with the metal nanoparticle that will obtain constitutes; Metal ion produces step, incoming transport power supply and carry out electrolysis between the said the 1st and the 2nd electrode, thus make metallic particles or chip in said electrolytic solution intermediate ionization, produce metal ion; And metal nanoparticle formation step, utilize reducing agent to make said metal ion reduction, form metal nanoparticle.
According to another form of the present invention, the present invention provides a kind of preparation method of metal nanoparticle, it is characterized in that comprising: the electrolytic solution preparation process, and in reaction vessel, make electrolyte and dispersant be dissolved in pure water, prepare electrolytic solution; The the 1st and the 2nd electrode installation steps are in electrode shell, filling the 1st electrode that a plurality of particles that are made up of the metal identical with the metal nanoparticle that will obtain or chip form and with the inside that is installed on said reaction vessel at least with one side the 2nd electrode in opposite directions of said the 1st electrode tabular or that round barrel shape constitutes; Metal ion produces step, incoming transport power supply and carry out electrolysis between the said the 1st and the 2nd electrode, thus make metallic particles or chip in said electrolytic solution, realize ionization, produce metal ion; And metal nanoparticle formation step, utilize reducing agent to make said metal ion reduction, form metal nanoparticle.
Said reducing agent drops in the electrolytic solution corresponding to the concentration of the metal ion that generates along with the carrying out of electrolysis, makes the concentration of reducing agent keep set level, and this can seek high yield, and the uniform particle size of gained nano particle distributes.
In addition, the frequency of said AC power (f) is set at 0 < f < 10Hz scope, and this is preferred aspect yield and size distribution.
And, in the present invention, preferably also comprise a step, periodically detect the particle of filling in the said the 1st and the 2nd electrode shell or the consumption of chip, fill new particle or chip.
Technique effect
In sum; In the present invention, in the pair of electrodes shell of in electrolytic cell, installing, fill by the particle or the chip that constitute with the metal nanoparticle identical materials that will obtain with set interval; Constitute electrode; Even thereby carry out electrolysis, interelectrode distance does not change yet, and can obtain the evenly metal nanoparticle of size.
In addition, in the present invention, in electrolytic process, along with the consumption of metallic particles or chip, filling metallic particles for overlay or chip do not cause production to interrupt thereby do not exist because of changing electrode continuously, can prepare a large amount of metal nanoparticles easily continuously.
And, in the present invention, in AC power, select optimum frequency; Insert electrode; So that before metal ion forms crystallization, utilize reducing agent to make it to become originally metal nanoparticle, reverse before still unreduced metal ion grows into nanocrystal; Thereby can realize a large amount of productions of metal nanoparticle, can a large amount of metal nanoparticle of efficient production.
In addition, in the present invention, can be when utilizing the alternating current electrolysis method, environmental protection ground preparation metal nanoparticle.
Description of drawings
Fig. 1 shows the concise and to the point pie graph of metal nanoparticle preparation facilities in the past,
Fig. 2 shows before the use of the electrode that uses in the metal nanoparticle preparation facilities in the past and the photo that uses the back state,
Fig. 3 is the synoptic diagram of the metal nanoparticle preparation facilities of the present invention the 1st embodiment,
Fig. 4 is the stereogram that shows the granular pattern electrode of device use shown in Figure 3,
Fig. 5 is the vertical direction profile of granular pattern electrode shown in Figure 4,
Fig. 6 shows the stereogram of the metal nanoparticle preparation facilities of the present invention the 2nd embodiment with the granular pattern electrode,
Fig. 7 is the vertical view of the variation of the granular pattern electrode that shows that the 1st and the 2nd embodiment uses,
Fig. 8 and Fig. 9 are the concise and to the point profile and the upward views of the metal nanoparticle preparation facilities of the present invention the 3rd embodiment,
Figure 10 and Figure 11 are respectively the concise and to the point stereograms of the metal nanoparticle preparation facilities of the of the present invention the 4th and the 5th embodiment,
Figure 12 is the concise and to the point stereogram of the metal nanoparticle preparation facilities of the present invention the 6th embodiment,
Figure 13 and Figure 14 are respectively the profiles of granular pattern electrode that shows the metal nanoparticle preparation facilities of the 6th embodiment.
The specific embodiment
With reference to the accompanying drawings, specify the metal nanoparticle preparation facilities and the method thereof of the preferred embodiment of the present invention.
Fig. 3 is the synoptic diagram of the metal nanoparticle preparation facilities of the present invention the 1st embodiment, and Fig. 4 is the stereogram that shows the granular pattern electrode of device use shown in Figure 3, and Fig. 5 is the vertical direction profile of granular pattern electrode shown in Figure 4.
Extremely shown in Figure 5 like Fig. 3; The metal nanoparticle preparation facilities of the present invention the 1st embodiment is to be filled in the electrolytic solution (11) that has mixed additive in the pure water in reaction vessel (10) inside; In said electrolytic solution (11), add a plurality of metallics, for example add the particle (granule) or chip (the flake) (30a that constitute by silver; The 1st electrode (30) 40a) and the 2nd electrode (40) have the structure that disposes in opposite directions isolator each other by means of supporting seat (15).
In the bottom of the 1st electrode (30) and the 2nd electrode (40), configuration is used to stir the agitator (20) of electrolytic solution (11) selectively respectively, and the downside in said reaction vessel (10) is for indirect electrolytic solution (11) disposes heater (25).Top in reaction vessel (10) is connected with the power supply device (50) that is used for to the 1st electrode (30) and the 2nd electrode (40) incoming transport (AC) power supply.
Said agitator (20) for example can adopt following structure, that is, and and by being disposed at the outside drive unit (not shown) of reaction vessel (10), making the magnet piece rotation that is disposed at reaction vessel (10) inside.
In the 1st embodiment, as the metal nanoparticle that will obtain, for example, for obtaining Nano silver grain, as the 1st electrode (30) and the 2nd electrode (40), use a plurality of silver (Ag) particle or chip (30a, 40a).
But (30a 40a) outside the preparation Nano silver grain, can also prepare the metal nanoparticle of other kinds except that using silver-colored particle or chip in the present invention.That is, with regard to the present invention, as the 1st electrode (30) and the 2nd electrode (40), outside the silver (Ag) of particle-removing or chip form, such as copper (Cu), nickel (Ni), gold (Au), palladium (Pd), platinum (Pt), so long as material that can the stripping metal ion all can use.
At this moment, said the 1st electrode (30) and the 2nd electrode (40) are though be so that (30a 40a) is filled in the 1st and the 2nd electrode shell (32 that constitutes rectangular shape respectively a plurality of particles or chip (in following explanation, being called for short " particle "); 42) situation is an example; But in addition, the shape of electrode shell so long as within it portion hold particle, between the 1st electrode (30) and the 2nd electrode (40); The big person of contact area with electrolytic solution (11); So, the shape of the 1st and the 2nd electrode shell (32,42) does not have special restriction.
Particle (the 30a that is used for said the 2nd electrode (40) and the 1st electrode (30); 40a) can all use and metal nanoparticle (or particle) identical materials that will prepare, with regard to particle (30a, size 40a); If the 1st and the 2nd electrode shell (32; 42) be the structure with a plurality of seams, hole or net, then preferred 0.05 to 10cm, and more preferably 0.5 to 5mm.
In addition, (30a, the 1st and the 2nd electrode shell (32,42) 40a) keeps set interval by means of supporting seat (15) to have filled the particle that is used as the 1st electrode (30) and the 2nd electrode (40) respectively.Promptly; Supporting seat (15) is formed with a pair of rectangle through hole corresponding with the cross sectional shape of the 1st and the 2nd electrode shell (32,42), when making the 1st and the 2nd electrode shell (32; When 42) being incorporated into the through hole of supporting seat (15); Supporting seat (15) keeps set interval when supporting each electrode shell (32,42) upside with state of insulation.The remainder of the 1st and the 2nd electrode shell (32,42) is exposed to the downside of supporting seat (15), has set interval, each other in opposite directions.
On the other hand, in the forward surface and the side of the 1st and the 2nd electrode shell (32,42); Be formed with a plurality of seams or hole (hereinafter to be referred as " seam ") (33,43) respectively, said seam (33; 43) so long as can make electrolytic solution (11) be contained in the 1st and the 2nd electrode shell (32; 42) in the time of inner, the size and the structure of metal nanoparticle stripping that can electrolysis, any form all can.
Along with the carrying out of cell reaction, (30a 40a) is consumed, then can be continuously to the 1st and the 2nd electrode shell (32 like fruit granule; 42) therefore inner the filling need not change electrode, at the 1st and the 2nd electrode shell (32; 42) on the exterior face, seam (33,43) adopts particle (30a; The structure that 40a) can't leak can more form to electrode shell (32,42) outside more with being inclined upwardly.Wherein, the width setup of seam (33,43) must be less than particle (30a, size 40a), preferred 0.1-1mm.
Wherein, Material as the 1st and the 2nd electrode shell (32,42) can use the insoluble material to electrolytic solution (11), preferably uses the insulating properties material; The polymer system (polymer family) of nylon monomer-cast nylon (MC nylon), nylon, polyester, polystyrene, polyvinyl chloride for example; Carbon (carbon), pottery or glass, for example Pai Ruikesi (Pyrex) glass, or use has the titanium (Ti) that electrolytic solution (11) is insoluble and conduct electricity.
But the said the 1st and the 2nd electrode shell (32,42) is so long as have metal (for example silver) a plurality of seams, hole, lattice or net that ion can pass through on forward surface or side, and any form or material all can use.
In addition; The the said the 1st and the 2nd electrode shell (32,42) also can be that mutual forward surface in opposite directions is made up of titanium (Ti), forms the side plate with a plurality of seams, hole, lattice or net in addition; Make remainder with described polymer system (polymer family), pottery or glass, assembling constitutes then.
And, so long as material that metal ion can pass through or form also can be used the sack that is formed by cloth that the insoluble material of electrolytic solution is constituted or nonwoven.When using cloth or nonwoven as electrode shell, the 1st electrode (30) and the 2nd electrode (40) also can replace particle, use the powder with 0.5 μ m to 1cm particle diameter.
On the two sides of supporting seat (15), for example, be fixed with the 1st and the 2nd electrode terminal (34 of bolt shape respectively; 44), through bolt shape the 1st and the 2nd electrode terminal (34,44); Exchange (AC) voltage insert the inner particle of the 1st and the 2nd electrode shell (32,42) (30a, 40a).The the 1st and the 2nd electrode terminal (34,44) is connected in power supply device (50), incoming transport (AC) voltage through by means of a pair of power line (55) of terminal protecting with the connection of the 1st and the 2nd lug plate (35,45).At this moment, preferred said supporting seat (15), the 1st and the 2nd electrode terminal (34,44) and a pair of power line (55) are exposed to the outside of reaction vessel (10) and install, so that do not contact with electrolyte (11).
Be exposed on the outside a pair of power line (55), be connected with the power supply device (50) that is used for from required interchange (AC) power supply of the outside supply electrolysis of reaction vessel (10).Power supply device (50) for example can comprise: the function generator (function generator) that can select required ac power waveform of electrolysis and frequency; The amplifier that the curtage of the AC power that is used for function generator is produced amplifies, the output of amplifier is connected in the 1st electrode (30) and the 2nd electrode (40).
But power supply device of the present invention (50) comprises the power source special feeding mechanism, and the power supply of any kind of all can use; Wherein, said power source special feeding mechanism is meant be used for mass-produced production line; Can have in advance to the 1st and the 2nd electrode (30; 40) waveform and the frequency set preestablish the curtage of required size, supply AC power.In addition, in the present invention, in supply unit, can possess constant-current source, so that can be when electrolysis, the set current strength that supply is set between the 1st and the 2nd electrode (30,40).
The waveform of said AC power for example can be used sine wave (sine wave), square wave (square wave), triangular wave (triangle wave), sawtooth waveforms (sawtooth wave) and wait all waveforms, and the wave form varies of AC power only can be in a little difference of existence aspect the yield (yield) of the metal nanoparticle that generates and the shape of particle.
On the other hand; In the present invention; In the metal nanoparticle preparation that utilizes electrolytic method,, be the influence of examination frequency as the factor that influences yield; Make the frequency of AC power be changed to 0.1Hz, whether the yield of the nano particle that meanwhile obtains and size distribution and particle are grown investigate from 100Hz.
As a result, with regard to the yield of nano particle, as the frequency (f) of AC power, frequency (f) is preferably 0 < f < 10Hz, especially preferred 0.1≤f≤5Hz.In addition, when generating yield and size distribution and particle when all taking into account, most preferred interval is 0.1≤f≤1Hz.
If the frequency of supply power supply is 0Hz, promptly when being direct current (DC), in anode generation metal ion problem of oxidation; Unoxidized metal ion is reduced before the agent reduction; Under electric field action, move, meet, be reduced into metal at cathode surface with the electronics that provides to negative electrode; Metallic generates to micron order size, the problem that exists required metal nanoparticle yield to descend.
In addition, when the frequency (f) of AC power surpassed 10Hz, the tendency that exists yield sharply to reduce existed particle that the problem of growth is arranged slightly simultaneously.
When the frequency that makes AC power when 100Hz is changed to 0.1Hz; From 100Hz to 10Hz, frequency reduces more, and the degree of distribution and the particle size of metal nanoparticle also reduce more; Particularly when frequency when 10Hz is decreased to 0.1Hz, the degree of distribution and the particle size of metal nanoparticle also further reduce.
The reason that this phenomenon occurs is, is elevated to high-frequency from low frequency, and the polarity of two lateral electrodes is change fast gradually, and the ion of generation attracted to the electrode that changes to (-) polarity once more before participating in reduction reaction, gold-plated phenomenon takes place.That is, this means, the metal ion that generates in (+) electrode moment with the reducing agent reaction, be reduced into before the metal nanoparticle, when (+) electrode is transformed to (-) electrode, metal ion returns.
On the contrary, be reduced to low frequency from high-frequency, the phenomenon that the metal ion of generation is got back to (-) electrode more significantly reduces, and therefore, shows the phenomenon of the yield increase that generates nano particle.
Examination is in the metal nanoparticle preparation that has utilized electrolytic method of the present invention below, is used for generating the condition of the metal nanoparticle of the narrow size distribution (particle of homogeneous) with high yield (yield), homogeneous shape and required size (not enough 100nm).
Generally speaking; In the metal nanoparticle preparation that utilizes electrolytic method, not as chemical method, the amount of the metallic that decision will obtain; Putting into reaction vessel to the metal ion of the amount that meets the initial reaction condition reacts; But, generating metal ion at the metal electrode place continuously according to the time, the reaction of reducing through the ion that makes generation by means of reducing agent realizes.As a result, in this course of reaction, because the polarity of electrode and the interaction of nano particle, the metal nanoparticle of generation can show once more the characteristic of refurn electrode.But this phenomenon becomes aspect yield, that is, and and the greatest problem aspect the property produced in batches.
Aspect the preparation of the metal nanoparticle that utilizes electrolysis, for solving this batch process property problem, need be according to because of inserting the concentration of the metal ion that electric energy generates, be kept for making the concentration of the reducing agent of this metal ion species reduction aptly.
At this moment, the amount of metal ion of generation is by the current strength decision that inserts the AC power between two electrodes, and this current strength can utilize electrolytical concentration and the voltage that puts on electrode to regulate.According to the inventor's result of study,, when remaining on set level to the concentration of reducing agent, find that the yield of metal nanoparticle improves when the concentration of the metal ion of considering to utilize set current strength (current value) to generate.
Its reason is, if compare with reductant concentration, has generated more metal ion, and then the amount relative deficiency of reducing agent though the speed of metal ion reduction reduces relatively, can not produce big problem to yield.But when the amount relative deficiency of reducing agent, the size that particle then occurs becomes big side effect.On the contrary, if the concentration of metal ions that the concentration ratio of reducing agent generates is excessive, then reduction rate is too fast, generates the particle below the number nanometer, is utilizing dispersant to carry out end-blocking (capping) before, refurn electrode once more, thereby yield sharply reduces.
On the other hand, electrolytical kind and concentration are directly relevant with pH and current strength.Generally speaking, electrolyte generally is divided into acidic electrolyte bath, alkaline electrolyte and neutral electrolyte, if only use acidic electrolyte bath; Then since pH less than 7, for example, when as reducing agent; Input is during as the hydrazine of weak base, hydrazine and acidic electrolyte bath generation reactant salt.Therefore, must drop into the fully hydrazine as weak base of amount, could regulate reduction reaction speed, regulate the size of particle.
On the contrary; If only put into alkaline electrolyte, the pH that then forms reaction solution is the environment more than 7, in reaction solution; Electronics can move chance to be increased; The reaction speed as the hydrazine of weak base as reducing agent increases, and generates the nano level particle of number, appears at the phenomenon that receives refurn electrode before the dispersant protection.
In the present invention, consider this point, mix by the acid electrolyte of forming with alkalescence and use that pH is set at 7 to 9.
In addition, from the relation of the pH and the reductant concentration of reaction solution, when pH less than 7, reduce as the reaction speed of the hydrazine of reducing agent.Its reason is, because hydrazine is a weak base, and as electrolytical citric acid (citric acid) reaction, becomes neutrality until pH, compares with reduction reaction, preferentially participates in acid-base reaction.This becomes the reason that reduces the hydrazine reducing power.Therefore, after acid-base reaction is carried out reduction reaction appears, participate in the hydrazine amount of reduction of metal ion reaction littler than the actual hydrazine amount that makes an addition to reaction vessel, the result who causes reduction reaction to delay, the size of metallic increases.That is, the not enough preferred range of the input amount of reducing agent, though on yield, there is not big problem, the above phenomenon of hundreds of nanometers appears increasing in the size of particle.
If must use dispersant with dispersibility, be directly proportional with the concentration of the metal ion that between pH 7 ~ 9, generates, make the concentration of reducing agent remain on set level; So; Reduction reaction speed keeps more constantly, and yield (that is the property produced in batches) greatly increases.
The metal nanoparticle preparation method of electrolysis that utilizes of the present invention can utilize described metal nanoparticle preparation facilities to embody; Comprise: electrolytic solution (11) preparation process; In reaction vessel (10); Make dispersant and electrolyte dissolution in ultra-pure water (DI-water), prepare electrolytic solution (11); The the 1st and the 2nd electrode (30,40) configuration step, in said electrolytic solution (11), the 1st and the 2nd electrode (30,40) that the configuration of setpoint distance ground is made up of the metal material identical with the nano particle that will synthesize; Ionization step, according to electrolytic method, access has the AC power of set frequency (f) between said the 1st electrode (30) and the 2nd electrode (40), makes metal ionization in said electrolytic solution of the 1st and the 2nd electrode (30,40); And metal nanoparticle formation step, make said metal ion reduction by reducing agent, form metal nanoparticle.
At first, in the present invention, electrolytic solution (11) especially preferably in ultra-pure water, as additive, comprises electrolyte, reducing agent and dispersant in pure water.
Preferred said electrolytic solution mixing acidic electrolyte bath and alkaline electrolyte use, and are set at pH 7 to pH 9.At this moment, said electrolyte can mix citric acid (citric acid) and hydrazine (Hydrazine) use.
Said electrolyte can use in the group of being made up of the amine of nitric acid/formic acid (formic acid)/acetate (acetic acid)/citric acid (citric acid)/tartaric acid (tataric acid)/glutaric acid (glutaric acid)/caproic acid (hexanoic acid) acid of forming, the alkali metal salt/ammonia of said acid (NH3)/triethylamine (TEA:triethyl amine) and pyridine (pyridine), select any more than a kind or 2 kinds.
The electrolyte that particularly uses among the present invention as feature of environmental protection electrolyte, can use citric acid (citric acid), as required, can also use glycine amino acid such as (glycine).
In addition; As reducing agent, can use in the group of forming by hydrazine (hydrazine:N2H4), sodium hypophosphite (sodium hypophosphite:NaH2PO2), sodium borohydride (sodium borohydride:NaBH4), dimethylamine borane (DMAB:dimethylamine borane: (CH3) 2NHBH3)), formaldehyde (formaldehyde:HCHO) and ascorbic acid (ascorbic acid), select any more than a kind or 2 kinds.
Said reducing agent for example, preferably uses the organic matter ion reducing agent such as hydrazine (Hydrazine) as the environmental protection reducing agent.This organic matter ion reducing agent generates the nitrogen G&W and all consumes in reaction, thereby harmless after reaction finishes.
Said reducing agent is through reducing agent feeding mechanism (not shown), and the concentration of the metal ion that generates when carrying out cell reaction along with the incoming transport power supply drops in the electrolytic solution, so that make the concentration of reducing agent reach set level.
As stated, in the present invention, (DI-water) is the basis with pure water, do not use environmentally harmful electrolyte, uses environment-friendly type electrolyte and environment-friendly type organic matter ion reducing agent, thereby can obtain metal nanoparticle through method environmental protection, simple.
On the other hand; Said dispersant performance is carried out the effect of end-blocking to the surface of metal nanoparticle; Prevent along with electrolysis to dissociate and realize Ionized metal ion after being reduced the agent reduction from the 1st and the 2nd electrode (30,40), the metal nanoparticle refurn electrode of reduction also is attached on the electrode; Or the phenomenon that precipitates because of the flocculation between metal nanoparticle, can use water-soluble polymer dispersant or aqueous dispersion macromolecule dispersing agent.
Said water-soluble polymer dispersant can use the water system macromolecule dispersing agent of polypropylene, polyurethane or polysiloxanes system, and the aqueous dispersion macromolecule dispersing agent can use the aqueous high molecular dispersant of polypropylene, polyurethane or polysiloxanes system.
As said dispersant, common dispersants can be at the Disperbyk by BYK Chemie company TM-111, Byk TM-154, Disperbyk TM-180, Disperbyk TM-182, Disperbyk TM-190, Disperbyk TM-192, Disperbyk TM-193, Disperbyk TM-2012, Disperbyk TM-2015, Disperbyk TM-2090, Disperbyk TM-2091; The Tego of Evonik company TM715w, Tego TM735w, Tego TM740w TM, Tego TM745w TM, Tego TM750w, Tego TM755w, Tego TM775w; The Solsperse of Lubrizol company TM20000, Solsperse TM43000, Solsperse TM44000; The EFKA of Ciba company TM4585; The Orotan of Dow company TM731A, Orotan TM1124; The Tween 20 of Aldrich company, Tween 80; Polyethylene glycol (PEG:Polyethylene Glycol) 200, polyvinylpyrrolidone (PVP:polyvinylpyrrolidone) 10; That selects in the group that 000, PVP 55,000, poloxamer (poloxamer) 407 and poloxamer 188 are formed is any more than a kind or 2 kinds.
Said ultra-pure water (DI-water); Be meant to have anion and cationic 3 distilled water that exist in running water or the mineral water hardly, this is because in preparation during metal nanoparticle, when the anion and the cation that get into except that electrolyte and reducing agent; Impurity can appear in required metal nanoparticle; In addition, complex compound may be generated, metal nanoparticle can't be obtained.
The preparation of the metal nanoparticle that utilizes electrolysis of the present invention is as shown in Figure 3; In the reaction vessel (10) of metal nanoparticle preparation facilities; As the metal material identical with the Nano silver grain that will synthesize; (30a, the 1st electrode (30) and the 2nd electrode (40) that 40a) constitute are installed on supporting seat (15), make the 1st electrode (30) and the 2nd electrode (40) arranged spaced by a plurality of silver-colored particles respectively.
Then, in ultra-pure water (DI-water) 1L, drop into citric acid (Citric acid) 2.0mmol, drop into hydrazine 6.0mmol,, put into the Disperbyk of BYK Chemie company as dispersant as electrolyte as electrolyte TM-1908.0g, put into reaction vessel respectively after, utilize agitator (20) to stir, until fully the dissolving.
The aqueous solution that additive is all dissolved heats; After making aqueous temperature rise to 90 ℃, in reaction vessel, add cooling water consistently, under the state of the temperature that keeps setting; Frequency be 1Hz, the AC power that is made up of sine wave inserts between the 1st and the 2nd electrode; Simultaneously, current value is set to 4.3A, implements electrolysis.In addition, implement 1 hour 30 minutes electrolysis, simultaneously, utilize the pump constant speed to inject reducing agent hydrazine 18.0mmol, make it reaction.
After cell reaction; Measure the consumption of silver electrode, utilize FE-SEM that the Nano silver grain that exists in the reacting solution is analyzed, the result can know; The Nano silver grain major part that obtains exists with the nano particle of 12nm to 20nm size, can confirm to show very narrow silver particles degree of distribution.
As stated, the preparation of the metal nanoparticle that utilizes electrolysis of the present invention the 1st embodiment can obtain the little of tens nanometer level and the Nano silver grain of even size and homogeneous shape.
In addition, in the present invention, if substituted metal plate or rod; It is become particle shape, be filled in the pair of electrodes shell, make it keep set interval; Constitute pair of electrodes, utilize AC power to implement electrolysis, so; Even carry out electrolysis, 2 interelectrode distances do not change yet, and can prepare the metal nanoparticle of the nanometer size of homogeneous shape and homogeneous in a large number.
In addition, in the present invention, when electrolysis is carried out, fill new particle along with the consumption of the particle of filling in the pair of electrodes shell, thereby can not interrupt electrowinning process, prepare a large amount of metal nanoparticles continuously.As a result, in the present invention, need not to change the electrode that consumes in the electrowinning process, replenish the clipped wire of grain shape, thereby can prevent the interruption of electrowinning process, can boost productivity to the inner space of electrode shell.
Fig. 6 shows the stereogram of the metal nanoparticle preparation facilities of the present invention the 2nd embodiment with the granular pattern electrode.
As shown in Figure 6, the metal nanoparticle preparation facilities of the present invention the 2nd embodiment is compared with the granular pattern electrode of the 1st embodiment shown in Figure 3 with the granular pattern electrode, and difference is at the 1st and the 2nd electrode shell (32; 42) on the forward surface, replace seam, form a plurality of hole (33a; 43a), all the other formations are identical.
Therefore,, give identical reference marks, and omit detailed description this to the inscape identical with the 1st embodiment.
In the 2nd embodiment, (33a, 43a) (30a, the structure that 40a) can't leak can more form to the outside of electrode shell (32,42) more with being inclined upwardly as making particle in the hole.
Fig. 7 is the vertical view that shows the variation of the granular pattern electrode that uses among the 1st and the 2nd embodiment.
As shown in Figure 7, shown in the corpuscular the 1st and the 2nd electrode (30,40) be to be further to improve conductance, (30a, the inner space of the 1st and the 2nd electrode shell (32,42) 40a) is inserted the example of conductive plate (37) respectively along its length being filled with a plurality of particles.At this moment, conductive plate (37) is by (30a, 40a) identical materials constitutes with particle.
As stated, be inserted with the situation of conductive plate (37) in the 1st and the 2nd electrode shell (32,42) inside, can further improve conductance, can seek to increase electrolytic efficiency.
For with the identical inscape of said the 1st embodiment, given identical reference marks, and omitted detailed description this.
Fig. 8 and Fig. 9 are the concise and to the point profile and the upward views of the metal nanoparticle preparation facilities of the present invention the 3rd embodiment.
In the metal nanoparticle preparation facilities of the 3rd embodiment, for the inscape identical, given identical reference marks, and omitted detailed description this with the metal nanoparticle preparation facilities of the 1st embodiment.
Like Fig. 8 and shown in Figure 9, the metal nanoparticle preparation facilities of the present invention the 3rd embodiment is realized maximization for making the area in opposite directions between the 1st electrode (60) and the 2nd electrode (70), proposes the example of the drum shape electrode shell of the double-deck barrel structure of employing.
The drum shape the 1st of the present invention the 3rd embodiment and the 2nd electrode shell (62,72) are made up of the double-deck barrel structure of lower end closed, can fill a plurality of particles (60a, annular spatial accommodation 70a) respectively so that possess.
With regard to the present invention the 3rd embodiment; In reaction vessel (10) inside; Use is different at diameter, with the 1st and the 2nd electrode shell (62 of the double-deck barrel structure of concentric shape configuration; 72) fill respectively by the most particles (60a, the 1st electrode (60) 70a) and the 2nd electrode (70) that constitute with the metal nanoparticle identical materials that will obtain inside.
The 1st electrode (60) and the 2nd electrode (70) are interconnected by a plurality of connecting portions (12) of equal length between the 1st electrode shell (62) and the 2nd electrode shell (72), thus configuration isolator each other.As a result, with respect to mutual all outer peripheral faces in opposite directions, the interval between the 1st electrode shell (62) and the 2nd electrode shell (72) is set at and keeps constant, and the interval between the 1st electrode (60) and the 2nd electrode (70) also is set at and keeps constant.
In addition, on the inner peripheral surface of the 1st electrode shell (62), be formed with a plurality of seams or hole (63), in opposite directions the outer peripheral face of the 2nd electrode shell (73) with it, be formed with a plurality of seams or hole (73).
On the other hand; In the 3rd embodiment, for changing the electrolytic solution (11) that reaction vessel (10) inside holds, dispose impeller the following subordinate of the 1st electrode (60) and the 2nd electrode (70); Be agitator (20); The rotating shaft (22) of agitator (20) connects the 2nd electrode shell (72) central authorities and is configured, in the lower inner part of the 2nd electrode shell (72) by means of the bearing (14) that is supported by a plurality of connecting portions (13), an end of supporting rotating shaft (20) revolvably.
In reaction vessel (10) inside; Accommodate in ultra-pure water the electrolytic solution (11) that has mixed electrolyte, dispersant and reducing agent as additive; Downside in said reaction vessel (10), for indirect electrolytic solution (11) disposes the heater (not shown), the top in reaction vessel (10); Through a pair of power line (55), be connected with the power supply device (50) that is used for to the 1st electrode (60) and the 2nd electrode (70) incoming transport (AC) power supply.
The metal nanoparticle preparation facilities of the present invention the 3rd embodiment that as above constitutes is realized maximization for making the area in opposite directions between the 1st electrode (60) and the 2nd electrode (70); Adopt the drum shape the 1st and the 2nd electrode shell (62 of double-deck barrel structure; 72); Thereby area increases in opposite directions, can seek to increase the yield of metal nanoparticle.
In addition, in the 3rd embodiment, substituted metal plate or rod change it into particle shape; Keep set compartment of terrain to be filled in the 1st and the 2nd electrode shell (62,72), constitute the 1st and the 2nd electrode (60,70); If utilize AC power to implement electrolysis, so, even carry out electrolysis; Distance between the 1st and the 2nd electrode (60,70) does not change, and can prepare the metal nanoparticle of the nanometer size of homogeneous shape and homogeneous in a large number.
In addition, in the present invention, when electrolysis is carried out, along with the 1st and the 2nd electrode shell (62; (new particle (60a is filled in 60a, consumption 70a) to the particle of filling 72); 70a), do not interrupt electrowinning process, just can prepare a large amount of metal nanoparticles continuously.As a result, in the present invention, need not to change the electrode that electrowinning process consumes, replenish granular clipped wire through inner space, thereby can prevent the interruption of electrowinning process, can boost productivity by means of series-operation to electrode shell.
Figure 10 and Figure 11 are respectively the concise and to the point stereograms of the metal nanoparticle preparation facilities of the present invention the 4th and the 5th embodiment.
Like Figure 10 and shown in Figure 11; The metal nanoparticle preparation facilities of the present invention the 4th and the 5th embodiment and the difference of the 1st to the 3rd embodiment have been to hold respectively the electrode shell (82 of particle (not shown); 82a), the 4th and the 5th embodiment only uses an electrode shell.
With by electrode shell (82; Granuloplastic the 1st electrode (80) that holds 82a) the 2nd electrode (90 in opposite directions; 90a); Just by when inserting the AC power that is used for electrolysis, realizing that the plectane or the drum of switching on constitute, hold particle electrode shell (82,82a) realize by means of the rotating driving device (not shown) rotating.
The 2nd electrode of the 4th and the 5th embodiment (90,90a) be chosen to be such as Ti etc. can stripping in electrolytic solution metal material.
The metal nanoparticle preparation facilities of the present invention the 4th embodiment shown in figure 10 can be that to have cross section for example by the electrode shell that holds particle (82) be that the structure of the spatial accommodation of cross shape constitutes.The shape of electrode shell (82) except that said cross, for example star bucket, drum, polygon bucket etc., so long as can hold the barrel structure of particle, Any shape all can.Therefore, the 1st electrode (80) is made up of a plurality of particles that hold in the electrode shell (82).
At this moment, because discoideus the 2nd electrode (90) is disposed at the downside of the 1st electrode (80), so the seam (83) of the electrode shell (82) that the metal ion of stripping is discharged during electrolysis is disposed at downside (84).
The lower panel (84) of said electrode shell (82) keeps set interval to be configured with discoideus the 2nd electrode (90), between the 1st and the 2nd electrode (80,90), continues to keep set interval.
In addition, said electrode shell (82) then need not use other agitator after realizing rotation, can be expected to obtain to promote the effect from the metal ion stripping of the 1st electrode (80) discharge.
After said electrode shell (82) is realized rotation, when cell reaction, the 1st and the 2nd electrode (80; 90) continue to keep set interval between; Meanwhile, formed the metal ion of generation and the effecting reaction environment of reducing agent, can make the efficient of mixing realize maximization.
Unaccounted member symbol 91 is represented conduit (91) among Figure 10, and confession is used for holding to the power line of the 2nd electrode (90) the incoming transport power supply of reaction vessel (10) bottom surface configuration.
The electrode shell that holds particle (82a) that the metal nanoparticle preparation facilities of the present invention the 5th embodiment shown in figure 11 uses constitutes with the structure identical with the electrode shell (82) of the 4th embodiment.
The difference part of the present invention the 5th embodiment and the 4th embodiment is, with the 1st electrode (80a) the 2nd electrode (90a) in opposite directions in the electrode shell (82) that surrounds the 1st electrode (80a), constitute with the drum with set thickness or the drum of net (net) structure.
At this moment, because the 2nd electrode (90a) of round barrel shape is disposed at the side of the 1st electrode (80a), therefore, the seam (83a) of the electrode shell (82a) that the metal ion of stripping is discharged during electrolysis is disposed at the side of electrode shell (82a).
When said electrode shell (82a) when being cross, the 2nd electrode (90a) of 4 sides (84a) and round barrel shape keeps set interval to be configured, so (80a also continues to keep set interval between 90a) at the 1st and the 2nd electrode.
In addition, said electrode shell (82a) then need not use other agitator after realizing rotation, can be expected to performance and promote from the effect of the metal ion stripping of the 1st electrode (80a) discharge.
The the described the 4th and the 5th embodiment since only use an electrode shell (82,82a), be easy to the particle that is consumed is replenished the advantage of managing so have.
Figure 12 is the concise and to the point stereogram of the metal nanoparticle preparation facilities of the present invention the 6th embodiment, and Figure 13 and Figure 14 are respectively the profiles that shows the granular pattern electrode of metal nanoparticle preparation facilities shown in the 6th embodiment.
In Figure 12, (particularly the 1st and the 2nd side plate (34a, 44a)) is set at identical distance use, but for the structure of side in opposite directions is described, for convenience, has shown the state that launches set angle in the side in opposite directions of the 1st electrode (300a) and the 2nd electrode (400a).
The metal nanoparticle preparation facilities of the present invention the 6th embodiment provides a kind of electrode structure, when electrolysis, from the ion stripping of electrode the electrode bight than the bight outside other parts many, can realize what is called " edge effect (Edge Effect) " maximization.
For this reason; The metal nanoparticle preparation facilities of the 6th embodiment is for holding the particle (not shown), and (32a 42a) has following structure: a mutual side in opposite directions is respectively by the 1st and the 2nd side plate (34a for the 1st and the 2nd electrode shell that for example constitutes with square tubbiness; 44a) constitute; (34a 44a) is made up of the insoluble electrode material such as Ti the 1st and the 2nd side plate, protrudes both take the altitudes.
At this moment, (32a 42a) can be as the electrode shell of the 1st to the 3rd embodiment for the said the 1st and the 2nd electrode shell; Use is to the insoluble insulating properties material of electrolytic solution; The polymer system (polymer family) of nylon monomer-cast nylon (MC nylon), nylon, polyester, polystyrene, polyvinyl chloride for example, carbon (carbon), pottery or glass, for example Pai Ruikesi (Pyrex) glass; (34a 44a) can use titanium (Ti) as the insoluble material that can conduct electricity to the 1st and the 2nd side plate.
As a result, when using titanium (Ti) as the 1st and the 2nd electrode shell (32a, the 1st and the 2nd side plate (34a 42a); In the time of 44a), (34a is 44a) with the 1st and the 2nd electrode shell (32a for the 1st and the 2nd side plate; A plurality of particles of filling 42a) are in contact condition, therefore, and when AC power inserts particle; The the 1st and the 2nd side plate (34a, 44a) energising of realization and a plurality of particles.
The the 1st and the 2nd side plate (34a, 44a) shown in figure 13, jagged a plurality of convexities (corresponding to screw thread) (35a; 45a) the set height of protrusion, and convexity in opposite directions (corresponding to screw thread) (35a, the interval between 45a) is set at identical; At each convexity (35a; Side 45a), form a plurality of holes or seam (33a, 43a).The the described the 1st and the 2nd side plate (34a, Ti sheet material that 44a) can crooked net (net) structure forms, and (33a 43a) arranges regularly to make a plurality of holes or seam.
In addition, (34a 44a) is jagged a plurality of convexity (corresponding to screw thread) (35a owing to the said the 1st and the 2nd side plate; 45a) the structure of protrusion; So compare with slab construction, area increases in opposite directions, can seek to improve the efficient that obtains metal nanoparticle along with electrolysis.
Therefore, if to particle incoming transport power supply, the 1st and the 2nd side plate (34a; (35a 45a) realizes energising with a plurality of particles, then according to edge effect (Edge Effect) to mutual convexity in opposite directions 44a); At the 1st and the 2nd electrode shell (32a; 42a), be filled in a side, form a plurality of particle release electronics of a plurality of particles of the 1st electrode (300a), the stripping quantity of the metal ion of stripping in the electrolytic solution is increased to the 2nd electrode (400a) of opposite side.
In addition, the metal nanoparticle preparation facilities of the present invention the 6th embodiment is shown in figure 14, at the 1st and the 2nd electrode shell (32a; 42a), be set at the 1st and the 2nd side plate (34a, convexity (35a 44a); 45a) be disposed at the convexity on opposite and the structure between the convexity, at this moment, compare with slab construction; Area in opposite directions increases, and can seek to improve the efficient that obtains metal nanoparticle along with electrolysis.
And, the 1st and the 2nd electrode shell of the present invention the 6th embodiment (32a, 42a) in; Though proposed the 1st and the 2nd side plate (34a, convexity 44a) (35a, 45a) structure arranged in parallel to each other along the vertical direction; But; Also can by the 1st and the 2nd side plate (34a, convexity 44a) (35a, 45a) along continuous straight runs in parallel to each other structure arranged constitute.
As stated; In the present invention, in the pair of electrodes enclosure that is installed on set interval in the electrolytic cell, fill by the particle or the chip that constitute with the metal nanoparticle identical materials that will obtain; Constitute electrode; Even thereby carry out electrolysis, two interelectrode distances do not change yet, and can obtain the metal nanoparticle of homogeneous shape and homogeneous size.
In addition, in the present invention, in electrowinning process, fill new metallic particles or chip continuously, thereby need not to prepare a large amount of metal nanoparticles easily continuously because of changing the electrode breaks in production along with the consumption of metallic particles or chip.As a result, in the present invention, need not to change the electrode that in electrowinning process, consumes,, can prevent the interruption of electrowinning process, can boost productivity through in electrode shell, replenishing particle.
And, in the present invention, before metal ion forms crystallization; Utilize reducing agent to be reduced into metal nanoparticle, before still unreduced metal ion grows into nanocrystal, polarity is changed; Thereby, in AC power, select optimum frequency, insert electrode; So that realize a large amount of productions of metal nanoparticle, can a large amount of metal nanoparticle of efficient production.
In said embodiment explanation; As the material of particle or chip, be to be that example describes, still with the little argent of ionization tendency (Ag); Even be applied to the big metal of ionization tendency; For example Mg, Al, Zn, Fe, Cu, or the little Pt of ionization tendency, Au etc. also can obtain similar results.
In addition; In said embodiment explanation; As the material of particle or chip, used fine silver (Ag), but when using the alloy of in the group of forming by Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni and Pd, selecting more than 2 kinds; When for example using alloys such as Ag-Cu, Ag-Mg, Ag-Al, Ag-Ni, Ag-Fe, Cu-Mg, Cu-Fe, Cu-Al, Cu-Zn, Cu-Ni, can obtain alloy nano particle.
And alloy nano particle has the fusing point that is lower than preceding each melting point metal of alloy, when the ink of alloy nano particle has been used in preparation, can be expected to obtain lower sintering temperature.
The industrial utilization possibility
The present invention can utilize simple operation; Environmental protection ground, produce the metal nanoparticle that applications such as metallic ink, medical treatment, clothes, cosmetics, catalyst, electrode material, electronic material are used in a large number equably; Particularly Nano silver grain can be widely used in the metal nanoparticle preparation.

Claims (20)

1. the preparation facilities of a metal nanoparticle is characterized in that, comprising:
Reaction vessel, electrolysis solution holds;
The the 1st and the 2nd electrode in the 1st and the 2nd electrode shell that the compartment of terrain is installed on each said reaction vessel interior is set, is filled a plurality of particles or the chip that are made up of the metal identical with the metal nanoparticle that will obtain and is formed; And
Power supply device, be used to carry out cell reaction and between the said the 1st and the 2nd electrode the incoming transport power supply; And,
The the said the 1st and the 2nd electrode shell possesses a plurality of holes or seam at least on face in opposite directions, so that discharge from the metal ion of the said the 1st and the 2nd electrode stripping according to cell reaction.
2. the preparation facilities of metal nanoparticle according to claim 1 is characterized in that:
Also comprise supporting seat,, said the 1st electrode shell and the 2nd electrode shell are supported with state of insulation space both set a distance.
3. the preparation facilities of metal nanoparticle according to claim 2 is characterized in that,
Said supporting seat also comprises on two sides: the 1st and the 2nd power line, insert the AC power between the said the 1st and the 2nd electrode from the power supply device supply; The the 1st and the 2nd electrode terminal is used to interconnect inner particle or the chip of filling of the 1st and the 2nd electrode shell.
4. the preparation facilities of metal nanoparticle according to claim 1 is characterized in that:
The the said the 1st and the 2nd electrode shell is that cross sectional shape is respectively rectangle or polygonal bucket.
5. the preparation facilities of metal nanoparticle according to claim 4 is characterized in that:
The the said the 1st and the 2nd electrode shell is made up of the 1st and the 2nd side plate, and they have a plurality of convexities that are made up of zigzag in each side in opposite directions, form a plurality of holes or seam in the two sides of said convexity.
6. the preparation facilities of metal nanoparticle according to claim 5 is characterized in that:
The the said the 1st and the 2nd side plate is made up of the net that constitutes with Ti respectively.
7. the preparation facilities of metal nanoparticle according to claim 1 is characterized in that:
The the said the 1st and the 2nd electrode shell be respectively diameter different, with the circular double-deck barrel structure of concentric shape configuration.
8. the preparation facilities of metal nanoparticle according to claim 1 is characterized in that:
Said particle or chip are made up of any alloy more than a kind or 2 kinds of selecting in the group that constitutes at Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni and Pd.
9. the preparation facilities of metal nanoparticle according to claim 1 is characterized in that:
The size of said particle or chip is set at 0.05 to 10cm scope, is preferably set to 0.5 to 5mm scope.
10. the preparation facilities of a metal nanoparticle is characterized in that, comprising:
Reaction vessel, electrolysis solution holds;
The 1st electrode in being installed on the electrode shell of said reaction vessel interior, being filled a plurality of particles or the chip that are made up of the metal identical with the metal nanoparticle that will obtain and is formed;
The 2nd electrode is set at interval with said the 1st electrode, is installed on the inside of said reaction vessel;
And power supply device, be used to carry out cell reaction and between the said the 1st and the 2nd electrode the incoming transport power supply; And,
Said electrode shell possesses a plurality of holes or seam, so that the metal ion from said the 1st electrode stripping is discharged along with cell reaction.
11. the preparation facilities of metal nanoparticle according to claim 10 is characterized in that:
Said electrode shell at least with said the 2nd electrode side in opposite directions on form a plurality of holes or seam.
12. the preparation facilities of metal nanoparticle according to claim 10 is characterized in that:
Said electrode shell has criss-cross spatial accommodation in inside, possess a plurality of holes or seam in the side, and the said electrode shell of said the 2nd electrode handle is contained in inside, is made up of drum or drum shape net.
13. the preparation facilities according to claim 10 or 12 described metal nanoparticles is characterized in that:
Said electrode shell is driven in rotation, and said the 2nd electrode is made up of Ti.
14. the preparation method of a metal nanoparticle is characterized in that comprising:
The electrolytic solution preparation process in reaction vessel, makes electrolyte and dispersant be dissolved in pure water, prepares electrolytic solution;
The the 1st and the 2nd electrode forms step; Be disposed at said reaction vessel interior in opposite directions and on forward surface, possessing in the 1st and the 2nd electrode shell of a plurality of holes or seam; Filling forms the 1st and the 2nd electrode by a plurality of particles or chip that the metal identical with the metal nanoparticle that will obtain constitutes;
Metal ion produces step, incoming transport power supply and carry out electrolysis between the said the 1st and the 2nd electrode, thus make metallic particles or chip in said electrolytic solution intermediate ionization, produce metal ion; And
Metal nanoparticle forms step, utilizes reducing agent to make said metal ion reduction, forms metal nanoparticle.
15. the preparation method of metal nanoparticle according to claim 14 is characterized in that:
Said reducing agent drops in the electrolytic solution corresponding to the concentration of the metal ion that generates along with the carrying out of electrolysis, makes the concentration of reducing agent keep set level.
16. the preparation method of metal nanoparticle according to claim 14 is characterized in that:
The frequency of said AC power (f) is 0 < f < 10Hz.
17. the preparation method of metal nanoparticle according to claim 14 is characterized in that:
Said particle or chip are made up of any alloy more than a kind or 2 kinds of selecting in the group that constitutes at Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni and Pd.
18. the preparation method of metal nanoparticle according to claim 13 is characterized in that:
The size of said particle or chip is set at 0.05 to 10cm scope, is preferably set to 0.5 to 5mm scope.
19. the preparation method of a metal nanoparticle is characterized in that comprising:
The electrolytic solution preparation process in reaction vessel, makes electrolyte and dispersant be dissolved in pure water, prepares electrolytic solution;
The the 1st and the 2nd electrode installation steps are the 1st electrode of in electrode shell, filling a plurality of particles that are made up of the metal identical with the metal nanoparticle that will obtain or chip and forming with the inside that is installed on said reaction vessel at least with one side the 2nd electrode in opposite directions of said the 1st electrode tabular or that round barrel shape constitutes;
Metal ion produces step, incoming transport power supply and carry out electrolysis between the said the 1st and the 2nd electrode, thus make metallic particles or chip in said electrolytic solution, realize ionization, produce metal ion; And
Metal nanoparticle forms step, utilizes reducing agent to make said metal ion reduction, forms metal nanoparticle.
20. the preparation method of metal nanoparticle according to claim 19 is characterized in that: said electrode shell is driven in rotation, and said the 2nd electrode is made up of Ti.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105229203A (en) * 2013-04-11 2016-01-06 赛丹思科大学 For reclaiming the method for platinum metals from catalytic structure
CN111542138A (en) * 2020-05-08 2020-08-14 香港中文大学（深圳） Electroheating method and application of ion conductor
CN111850613A (en) * 2020-07-29 2020-10-30 湖南化工职业技术学院（湖南工业高级技工学校） Preparation method of PtIr nanosol
CN114400333A (en) * 2022-01-18 2022-04-26 江苏擎动新能源科技有限公司 Catalyst and preparation method thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101415148B1 (en) * 2012-09-25 2014-08-06 한국항공대학교산학협력단 THE SYNTHESIZING TECHNIQUE OF GELATIN/Ag NANOPARTICLE ANTIMICROBIAL BIOCOMPOSITE AND DEVICE FOR MANUFACTURING AND METHOD FOR PREPARATION THEREOF
KR102228796B1 (en) * 2020-09-21 2021-03-17 주식회사 윤퓨처스 Method and apparatus for manufacturing metal nanoparticles
RU2755222C1 (en) * 2020-12-26 2021-09-14 федеральное государственное автономное образовательное учреждение высшего образования "Казанский (Приволжский) федеральный университет" (ФГАОУ ВО КФУ) Plasma-ultrasonic method for producing metal powder (options)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2508222Y (en) * 2001-10-25 2002-08-28 武汉大学 Solid polymer electrolyte carbon monooxide sensor
JP2005103723A (en) * 2003-10-01 2005-04-21 National Institute Of Advanced Industrial & Technology Single crystallization method and device of metal nanowire
CN101075690A (en) * 2006-05-15 2007-11-21 索尼株式会社 Lithium ion battery
KR100820038B1 (en) * 2007-01-08 2008-04-07 한양대학교 산학협력단 Fabrication of copper nano particle for metal ink on ink-jet technology
KR20090006031A (en) * 2008-11-27 2009-01-14 영남대학교 산학협력단 Provided apparatus of 3-axis alternating current magnetic field for locational control of the magnetic material in body
JP2009215146A (en) * 2008-03-13 2009-09-24 Panasonic Corp Metal-containing nanoparticle, carbon nanotube structure grown by using the same, electronic device using the carbon nanotube structure, and method for manufacturing the device

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1476055A (en) * 1975-03-05 1977-06-10 Imp Metal Ind Kynoch Ltd Eletro-winning metals
US4684448A (en) * 1984-10-03 1987-08-04 Sumitomo Light Metal Industries, Ltd. Process of producing neodymium-iron alloy
US4707239A (en) * 1986-03-11 1987-11-17 The United States Of America As Represented By The Secretary Of The Interior Electrode assembly for molten metal production from molten electrolytes
JPH04157193A (en) * 1990-10-19 1992-05-29 Tome Sangyo Kk Production of superfine metal grain
US5820653A (en) * 1993-04-19 1998-10-13 Electrocopper Products Limited Process for making shaped copper articles
KR100555584B1 (en) * 2003-06-10 2006-03-03 좌용호 The Fabrication of Metal Nanoparticles by Application of Electro-Decomposition Method
US20060243595A1 (en) * 2004-09-16 2006-11-02 Global Ionix Inc. Electrolytic cell for removal of material from a solution
KR20060120716A (en) * 2005-05-23 2006-11-28 주식회사 엔씨메탈 The manufacturing method of metal-micro particles used of pulse-type energy
KR20080074264A (en) * 2007-02-08 2008-08-13 김종배 A manufacturing equipment of nano-silver
KR100907877B1 (en) * 2007-03-15 2009-07-14 윤의식 Method for preparing metal nanoparticle colloidal solution and method for preparing metal nanoparticle powder

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2508222Y (en) * 2001-10-25 2002-08-28 武汉大学 Solid polymer electrolyte carbon monooxide sensor
JP2005103723A (en) * 2003-10-01 2005-04-21 National Institute Of Advanced Industrial & Technology Single crystallization method and device of metal nanowire
CN101075690A (en) * 2006-05-15 2007-11-21 索尼株式会社 Lithium ion battery
KR100820038B1 (en) * 2007-01-08 2008-04-07 한양대학교 산학협력단 Fabrication of copper nano particle for metal ink on ink-jet technology
JP2009215146A (en) * 2008-03-13 2009-09-24 Panasonic Corp Metal-containing nanoparticle, carbon nanotube structure grown by using the same, electronic device using the carbon nanotube structure, and method for manufacturing the device
KR20090006031A (en) * 2008-11-27 2009-01-14 영남대학교 산학협력단 Provided apparatus of 3-axis alternating current magnetic field for locational control of the magnetic material in body

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105229203A (en) * 2013-04-11 2016-01-06 赛丹思科大学 For reclaiming the method for platinum metals from catalytic structure
CN111542138A (en) * 2020-05-08 2020-08-14 香港中文大学（深圳） Electroheating method and application of ion conductor
CN111850613A (en) * 2020-07-29 2020-10-30 湖南化工职业技术学院（湖南工业高级技工学校） Preparation method of PtIr nanosol
CN114400333A (en) * 2022-01-18 2022-04-26 江苏擎动新能源科技有限公司 Catalyst and preparation method thereof

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