CN102770368B - 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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CN102770368B
CN102770368B CN201180010573.7A CN201180010573A CN102770368B CN 102770368 B CN102770368 B CN 102770368B CN 201180010573 A CN201180010573 A CN 201180010573A CN 102770368 B CN102770368 B CN 102770368B
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electrode
metal
metal nanoparticle
chip
particle
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CN102770368A (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 metal nanoparticle preparation facilities and the method thereof of granular pattern electrode
Technical field
The present invention relates to utilize metal nanoparticle preparation facilities and the method thereof of electrolysis, relate in particular to one and utilize alternating voltage, as the material of electrode, particles filled in thering is the pair of electrodes shell at set interval what formed by the metal identical with the metal nanoparticle that will obtain, by means of electrolysis, can be with cheap price, prepare in a large number continuously metal nanoparticle preparation facilities and the method thereof of utilizing granular pattern electrode of the metal nanoparticle of the nanosized of homogeneous shape and homogeneous.。
Background technology
Generally speaking, as the method for obtaining refining metallic powder, use the chemical methodes 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 for the preparation of silver powder, the main method using is, through utilizing aqueous slkali to make the neutralization reaction of silver nitrate aqueous solution neutralization, in the sediment of the silver oxide generating or silver hydroxide, use hydrazine or hydrogen peroxide, the method that the reducing agents such as formalin reduce, or sneak into hydrogen in the precipitation of the silver hydroxide generating by described neutralization reaction, the method that the gas that the reducing powers such as carbon monoxide are strong reduces, or add formalin in the alkaline ammino-complex aqueous solution, the reducing agents such as oxalic acid reduce, thereby separate out the method for silver powder.
But, with regard to this preparation method in the past, as initial substance, use slaine as electrolyte, thereby environmental protection not, 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 having used as stoping because of metallic interfacial agent and additive or the nuisance that the particle growth that causes uses that flocculate, thereby there is the shortcoming of inadequate environmental protection.
With regard to common electrolysis in the past, electrode and the slaine of the metal material that use will be synthetic, nitrate, carbonate, sulfate etc., as electrolyte, utilize electrolysis, make it to realize metallization at electrode surface, obtain particle.
Certainly, in electrolysis, as the electrolyte for obtaining metal dust, why using poisonous metal salt, is because metal is water insoluble, if the metal that handle is combined with strong acid salt is water-soluble, easily be dissociated into ion, utilize reducing agent etc. can realize particlized.
In this case, produce nuisance as accessory substance, in the time improving temperature, produce pernicious gas, environmental protection not, the size of particle is also even not.
And, as in the past, in the electrolysis having used such as the slaine of nitrate, carbonate, sulfate etc., initial substance environmental protection not itself, in neutralization and cleaning process, not only there is waste water handling problem, and have the trouble that need to pass through cleaning process, in cleaning process, metal dust is run off in a large number.
In No. 10-2004-105914th, Korea S's publication, a kind of metal nanoparticle preparation method who utilizes electrolysis has been proposed, consider in the electrolysis of stating in the use slaine in the past, initial substance environmental protection not itself, there is waste water handling problem etc., only use electrode and a small amount of additive, deionized water (DI-water), apply outside power simultaneously, induce formation and the dispersion of metallic, thereby can prepare to environmental protection the nano particle of metal.
Below with reference to Fig. 1, further describe the metal nanoparticle preparation method who utilizes Electrolytic method that described Korea S publication discloses for No. 10-2004-105914.
As shown in Figure 1, in metal nanoparticle preparation in the past, in the inside of container (1), drop into 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, in described solution (2), make two electrode bars (3) isolation configuration.In addition, in described solution (2), the agitator (5) that produces hyperacoustic ultrasonic generator (4) and agitating solution (2) is disposed at respectively to the upper and lower of described container, under this formation state, direct current (DC) electric current 2 electrode bars of access (3).
But described preparation method has in the past utilized direct current solution, anode electrode rod is all made up of the composition identical with the metallic that will obtain with cathode electrode rod, by means of potential difference, occurs in the phenomenon that generates metallic crystal on electrode.
In addition, preparation method in the past prepares metal nanoparticle described in utilize, for example, prepare the nano grain of silver period of the day from 11 p.m. to 1 a.m, access DC current (DC), the metal cation generating at anode (Anode) is to movable cathode, growth around negative electrode (Cathode), generate micron-sized silver particles crystallization (Crystalline) more than nanoscale, there is the phenomenon of caking, and metallic generates even not, there is the problem that forms inhomogeneous particle.
In addition, according to described preparation method in the past, at access DC current, implement in the situation of electrolysis, at anode place, the heat producing while generation due to Ag+ ion, OH-ions binding with the companion ion as Ag+ ion, there is the problem that oxidative phenomena occurs, before unoxidized Ag+ ion is reduced agent reduction, under electric field action to movable cathode, the electronics providing with negative electrode meets, again be reduced to silver at cathode surface, silver particles thereby gradually growth, the silver particles of growth is until grow to micron order, thereby cause the result having consumed the Ag+ ion of generation nano particle.
Therefore,, even if Ag+ ion is reduced agent reduction, be dispersed agent end-blocking, generate the Nano silver grain needing, its amount is compared with the Ag2O growing amount of oxidation and the silver particles of growth, only has few amount to be present in reaction solution, is not suitable as high efficiency mass production method.
On the other hand, in the described metal nanoparticle preparation method who utilizes DC electrolysis method in the past, as solving the technology that is not suitable as mass production method problem, while having proposed in electrolysis in No. 10-0820038th, Korean registered patent, use alternating voltage to replace DC voltage, prepare the technology of metal nanoparticle.
The copper nano-particle preparation method of described registered patent comprises: dissolving step will dissolve in the metal ion propellant that can make the metal ion reducing agent of material of hydrazine or copper ion reduction and trisodium citrate or can make copper realize Ionized material on copper electrode surface drops into water; Ionization step, isolation configuration copper electrode in described solution, described electrode is made up of the composition identical with the metallic that will obtain, and by means of the electric energy and the described metal ion propellant that produce because of the alternating voltage of access electrode, in described solution, realizes ionization; Separate out step, in described solution, copper ion is reduced by described reducing agent, separates out copper particle.
But according to described registered patent, although can obtain fine copper nano particle, owing to using the conventional alternating voltage (50 sinusoidal wave ~ 60Hz) of 110V ~ 220V, 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 conventional alternating voltage, the polarity conversion per second of electrode 50 ~ 60 times, so, although the metal ion generating at the metal electrode place of a side is reduced, but before reduction, return to the metal electrode of opposite side, there is the problem that productivity ratio greatly reduces.
Therefore, the particle mean size of copper particle and skewness, due to the crystallization of the change in polarity based on electrode, the problem that exists a large amount of production efficiency to decline.
On the other hand, the preparation of the copper nano-particle of conventional art with metal electrode as shown in Figure 2, use the electrode being formed by tabular columnar electrode.In electrolytic cell, a pair of copper electrode of isolation configuration configures tabular columnar electrode before reaction, and along with the carrying out of cell reaction, electrode is consumed gradually, and after reaction given time, the Leading Edge Deformation of columnar electrode becomes tapering shape.
If two interelectrode intervals change along with columnar electrode change of shape, there is potential difference and change, the energising amount of electric current reduces, due to heating, the problem that the metal nanoparticle size that occurs to generate increases.
Therefore, for keeping set interval, every both fixed cycles, should block crushed element and reinstall or be replaced by new electrode, thus the use of electrode not effectively, efficient, fall short of electrode life.And in batch production process, reinstalling operation and changing operation of kind electrode needs manual operations termly to carry out, thereby has the problem that productivity ratio is low.
Summary of the invention
The problem solving
Therefore; the object of the present invention is to provide a kind of metal nanoparticle preparation facilities and method thereof of utilizing granular pattern electrode; being installed on the pair of electrodes enclosure in electrolytic cell by set interval; fill the particle or the chip that are formed by the metal material identical with the metal nanoparticle that will obtain; form electrode; even thereby carry out electrolysis, interelectrode distance is also constant, can obtain the metal nanoparticle of even 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 without because changing electrode breaks in production, a large amount of metal nanoparticle of continuous production easily.
Another object of the present invention is to provide a kind of metal nanoparticle preparation facilities, 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, access electrode, to realize a large amount of productions of metal nanoparticle, can efficiently prepare a large amount of metal nanoparticles.
A further object of the present invention is to provide a kind of metal nanoparticle preparation facilities and method thereof, can, in utilizing alternating current electrolysis method, prepare to environmental protection metal nanoparticle.
Technical scheme
For reaching as above object, according to a kind of form of the present invention, the invention provides a kind of preparation facilities of metal nanoparticle, it is characterized in that, comprising: reaction vessel, electrolysis solution holds; The the 1st and the 2nd electrode, is installed in the 1st and the 2nd electrode shell of reaction vessel interior described in each compartment of terrain is set, and fills the multiple particles or the chip that are made up of the metal identical with the metal nanoparticle that will obtain and forms; And power supply device, be used to and carry out cell reaction and to incoming transport power supply between the described the 1st and the 2nd electrode; And the described the 1st and the 2nd electrode shell at least possesses multiple holes or seam on face in opposite directions, to the metal ion from the described the 1st and the 2nd electrode stripping along with cell reaction is discharged.
According to another kind of form of the present invention, the invention provides a kind of preparation facilities of metal nanoparticle, it is characterized in that, comprising: reaction vessel, electrolysis solution holds; The 1st electrode, in the electrode shell that is installed on described reaction vessel interior, fills the multiple particles or the chip that are made up of the metal identical with the metal nanoparticle that will obtain and forms; The 2nd electrode, with described the 1st electrode setting interval, is installed on the inside of described reaction vessel; And power supply device, be used to and carry out cell reaction and to incoming transport power supply between the described the 1st and the 2nd electrode; And described electrode shell possesses multiple holes or seam, to the metal ion from described the 1st electrode stripping along with cell reaction is discharged.
The preparation facilities of metal nanoparticle of the present invention can also comprise supporting seat, with state of insulation space both set a distance, described the 1st electrode shell and the 2nd electrode shell is supported.
In addition, described supporting seat can also comprise on two sides: the 1st and the 2nd power line, accesses the AC power between the described the 1st and the 2nd electrode from power supply device supply; The the 1st and the 2nd electrode terminal, for interconnecting inner particle or the chip of filling of the 1st and the 2nd electrode shell.
The the described the 1st and the 2nd electrode shell can be respectively that cross sectional shape is rectangle or polygonal bucket.
In addition, the described 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 the multiple projections that are made up of zigzag, forms multiple holes or seam in the two sides of described projection, and the described the 1st and the 2nd side plate is made up of the net forming with Ti respectively.
And the described the 1st and the 2nd electrode shell can be respectively diameter Double Layer Circular barrel structure different, that configure with concentric shape.Now, described preparation facilities can also comprise agitator, and the central authorities that its rotating shaft connects the 2nd electrode shell extend, and the bearing that is supported on supporting seat supports revolvably, disposes impeller at the leading section of rotating shaft.
Described preparation facilities can also comprise conductive plate, and the inner space of insertion the 1st and the 2nd electrode shell is realized and being in contact with one another with described particle or chip.
Described particle or chip are made up of any one kind or two or more alloy of selecting in the group forming at Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni and Pd; the size of described particle or chip is set as 0.05 to 10cm scope, is preferably set to 0.5 to 5mm scope.
The the described the 1st and the 2nd electrode shell can be any a kind that in the group being made up of high molecular polymer, pottery, glass and titanium (Ti), selects.
Preferred described electrode shell has criss-cross spatial accommodation in inside, possess multiple holes or seam at downside, and the side of described the 2nd electrode and described electrode shell configures opposite to each other, is made up of tabular.
In addition, preferred described electrode shell has criss-cross spatial accommodation in inside, possesses multiple holes or seam in side, and electrode shell is contained in inside described in described the 2nd electrode handle, is made up of drum or drum-shaped net.
Preferred described electrode shell is driven in rotation, and keeps the both set a distances between the 1st and the 2nd electrode, and described the 2nd electrode is made up of Ti.
Another form according to the present invention, the invention provides a kind of preparation method of metal nanoparticle, it is characterized in that comprising: 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 forms step, be disposed at opposite to each other described reaction vessel interior and on forward surface, possessing in the 1st and the 2nd electrode shell of multiple holes or seam, fill the multiple particles or the chip that are formed by the metal identical with the metal nanoparticle that will obtain, form the 1st and the 2nd electrode; Metal ion produces step, incoming transport power supply carry out electrolysis between the described the 1st and the 2nd electrode, thus make metallic particles or chip at described electrolytic solution intermediate ion, produce metal ion; And metal nanoparticle formation step, utilize reducing agent to make described metal ion reduction, form metal nanoparticle.
According to another form of the present invention, the invention provides a kind of preparation method of metal nanoparticle, it is characterized in that comprising: 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 installation steps, filling the 1st electrode that multiple particles of being made up of the metal identical with the metal nanoparticle that will obtain or chip form and with the tabular or barrel-shaped inside that is at least installed on described reaction vessel with the one side of described the 1st electrode the 2nd electrode in opposite directions forming in electrode shell; Metal ion produces step, to incoming transport power supply between the described the 1st and the 2nd electrode and carry out electrolysis, thereby makes metallic particles or chip realize ionization in described electrolytic solution, produces metal ion; And metal nanoparticle formation step, utilize reducing agent to make described metal ion reduction, form metal nanoparticle.
The concentration of the metal ion that described reducing agent generates corresponding to the carrying out along with electrolysis drops in electrolytic solution, 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 described AC power (f) is set as 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 described 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 installing with set interval in electrolytic cell; fill the particle or the chip that are formed by the material identical with the metal nanoparticle that will obtain; form electrode; even thereby carry out electrolysis, interelectrode distance does not also change, and can obtain the metal nanoparticle of even 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 continuously, causes production to interrupt thereby do not exist because changing electrode, a large amount of metal nanoparticle of continuous production easily.
And, in the present invention, in AC power, select optimum frequency, access electrode, so that before metal ion is formed as crystallization, utilize reducing agent to make it originally to become metal nanoparticle, reverse before unreduced metal ion still grows into nanocrystal, thereby can realize a large amount of productions of metal nanoparticle, can efficiently prepare a large amount of metal nanoparticles.
In addition, in the present invention, can, in utilizing alternating current electrolysis method, prepare to environmental protection metal nanoparticle.
Brief description of the drawings
Fig. 1 shows the concise and to the point pie graph of metal nanoparticle preparation facilities in the past,
Fig. 2 be show before the use of the electrode using in metal nanoparticle preparation facilities in the past with use after the photo of 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 Fig. 3 shown device use,
Fig. 5 is the vertical direction profile of the electrode of granular pattern shown in Fig. 4,
Fig. 6 is the stereogram that shows the metal nanoparticle preparation facilities granular pattern electrode of the present invention the 2nd embodiment,
Fig. 7 is the top view that shows the variation of the granular pattern electrode of the 1st and the 2nd embodiment use,
Fig. 8 and Fig. 9 are 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 that shows the granular pattern electrode of the metal nanoparticle preparation facilities of the 6th embodiment.
Detailed description of the invention
With reference to the accompanying drawings, describe metal nanoparticle preparation facilities and the method thereof of the preferred embodiment of the present invention in detail.
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 Fig. 3 shown device use, and Fig. 5 is the vertical direction profile of the electrode of granular pattern shown in Fig. 4.
As shown in Figures 3 to 5, the metal nanoparticle preparation facilities of the present invention the 1st embodiment is the electrolytic solution (11) that has mixed additive in reaction vessel (10) inside is filled in pure water, in described electrolytic solution (11), add multiple metallics, for example add the particle (granule) or chip (the flake) (30a that are formed by silver, the 1st electrode (30) 40a) by means of supporting seat (15), has the structure mutually configuring in opposite directions isolator with the 2nd electrode (40).
In the bottom of the 1st electrode (30) and the 2nd electrode (40), be configured for selectively respectively the agitator (20) that stirs electrolytic solution (11), at the downside of described reaction vessel (10), for indirect electrolytic solution (11) disposes heater (25).On the top of reaction vessel (10), be connected with for the power supply device (50) to the 1st electrode (30) and the 2nd electrode (40) incoming transport (AC) power supply.
Described agitator (20) for example can adopt following structure,, by being disposed at the outside drive unit (not shown) of reaction vessel (10), make to be disposed at the inner magnet piece rotation of reaction vessel (10).
In the 1st embodiment, for example, as the metal nanoparticle that will obtain; for obtaining Nano silver grain; as the 1st electrode (30) and the 2nd electrode (40), use multiple silver (Ag) particle or chip (30a, 40a).
But the present invention, except using silver-colored particle or chip (30a, 40a) to prepare outside Nano silver grain, can also prepare the metal nanoparticle of other kinds.; for 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); as long as material that can stripping metal ion, all can use.
Now; described the 1st electrode (30) and the 2nd electrode (40) are although be with multiple particles or chip (being called for short in the following description " particle ") (30a; 40a) be filled in the 1st and the 2nd electrode shell (32 that forms respectively rectangular shape; 42) situation is example; but in addition; the shape of electrode shell is as long as holding particle therein; between the 1st electrode (30) and the 2nd electrode (40); the large person of contact area with electrolytic solution (11); so; the shape of the 1st and the 2nd electrode shell (32,42) is not particularly limited.
For the particle (30a of described the 2nd electrode (40) and the 1st electrode (30), 40a) can all use the material identical with the metal nanoparticle that will prepare (or particle), with regard to particle (30a, size 40a), if the 1st and the 2nd electrode shell (32,42) be the structure with multiple seams, hole or net,, preferably 0.05 to 10cm, more preferably 0.5 to 5mm.
In addition, fill respectively the particle (30a as the 1st electrode (30) and the 2nd electrode (40), the the 1st and the 2nd electrode shell (32,42) 40a) keeps set interval by means of supporting seat (15).; supporting seat (15) is formed with and the 1st and the 2nd electrode shell (32; 42) a pair of rectangle through hole corresponding to cross sectional shape; when making the 1st and the 2nd electrode shell (32; 42) while being incorporated into the through hole of supporting seat (15); supporting seat (15), support each electrode shell (32,42) upside with state of insulation time, keeps set interval.The remainder of the 1st and the 2nd electrode shell (32,42) is exposed to the downside of supporting seat (15), has set interval, mutually in opposite directions.
On the other hand, at the 1st and the 2nd electrode shell (32,42) forward surface and side, be formed with respectively multiple seams or hole (hereinafter to be referred as " seam ") (33,43), described seam (33,43) as long as making electrolytic solution (11) be contained in the 1st and the 2nd electrode shell (32,42) inner time, size and the structure of metal nanoparticle stripping that can electrolysis, any form all can.
Along with the carrying out of cell reaction, as fruit granule (30a, 40a) is consumed, can be continuously to the 1st and the 2nd electrode shell (32,42) inner filling, therefore does not need to change electrode, at the 1st and the 2nd electrode shell (32,42) on exterior face, the structure that seam (33,43) adopts particle (30a, 40a) to leak, can more more be inclined upwardly and form to electrode shell (32,42) outside.Wherein, the width of seam (33,43) is set to such an extent that be less than the size of particle (30a, 40a), preferably 0.1-1mm.
Wherein, as the 1st and the 2nd electrode shell (32,42) material can use the insoluble material to electrolytic solution (11), preferably use insulating properties material, the polymer system (polymer family) of for example nylon monomer-cast nylon (MC nylon), nylon, polyester, polystyrene, polyvinyl chloride, 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 described the 1st and the 2nd electrode shell (32,42) for example, as long as having metal (silver) multiple seams, hole, lattice or net that ion can pass through on forward surface or side, any form or material all can use.
In addition, the the described the 1st and the 2nd electrode shell (32,42) can be also that mutual forward surface is in opposite directions made up of titanium (Ti), form in addition the side plate with multiple seams, hole, lattice or net, make remainder with described polymer system (polymer family), pottery or glass, then assembling forms.
And, as long as material or form that metal ion can pass through, also can use the sack being formed by the cloth that the insoluble material of electrolytic solution is formed or nonwoven.In the time 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 respectively the 1st and the 2nd electrode terminal (34 of bolt shape, 44), by bolt shape the 1st and the 2nd electrode terminal (34,44), exchange (AC) voltage access the 1st and the 2nd electrode shell (32,42) inner particle (30a, 40a).The the 1st and the 2nd electrode terminal (34; 44) pass through by means of the 1st and the 2nd lug plate (35 for terminal protecting; 45) a pair of power line (55) connecting, is connected in power supply device (50), incoming transport (AC) voltage.Now, preferred described supporting seat (15), the 1st and the 2nd electrode terminal (34,44) and a pair of power line (55) outside that is exposed to reaction vessel (10) install, to do not contact with electrolyte (11).
Be exposed to outside a pair of power line (55) above, be connected with the power supply device (50) of interchange (AC) power supply required for the outside supply electrolysis from reaction vessel (10).Power supply device (50) for example can comprise: the function generator (function generator) that can select the required AC power waveform of electrolysis and frequency; The amplifier amplifying for the curtage of the AC power to function generator generation, 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) is including power source special feeding mechanism, the power supply of any kind all can use, wherein, described power source special feeding mechanism, refers to for mass-produced production line, can have in advance for the 1st and the 2nd electrode (30,40) waveform and the frequency set, preset 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 in the time of electrolysis, to the set current strength that between the 1st and the 2nd electrode (30,40), supply is set.
The waveform of described AC power for example can be applied all waveforms such as sine wave (sine wave), square wave (square wave), triangular wave (triangle wave), sawtooth waveforms (sawtooth wave), and the wave form varies of AC power only can exist a little difference aspect the yield (yield) of the metal nanoparticle generating and shape of particle.
On the other hand, in the present invention, in the metal nanoparticle preparation that utilizes electrolytic method, as the factor that affects yield, for the impact of examination frequency, make the frequency of AC power be changed to 0.1Hz from 100Hz, whether the yield to the nano particle meanwhile obtaining and size distribution and particle are grown and are investigated.
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 preferably 0.1≤f≤5Hz.In addition, when yield and size distribution and particle being generated while all taking into account, most preferred interval is 0.1≤f≤1Hz.
If the frequency of supply power supply is 0Hz, in the time being direct current (DC), in anode generation metal ion problem of oxidation, before unoxidized metal ion is reduced agent reduction, under electric field action, to movable cathode, meet with the electronics providing, be reduced into metal at cathode surface, metallic generates to micron order size, the problem that exists required metal nanoparticle yield to decline.
In addition, in the time that the frequency (f) of AC power exceedes 10Hz, the tendency that exists yield sharply to reduce, the problem that simultaneously exists particle slightly to grow.
In the time making the frequency of AC power be changed to 0.1Hz from 100Hz, from 100Hz to 10Hz, frequency more reduces, and degree of distribution and the particle size of metal nanoparticle also more reduce, particularly, in the time that frequency is decreased to 0.1Hz from 10Hz, degree of distribution and the particle size of metal nanoparticle also further reduce.
The reason that occurs this phenomenon is, be elevated to high-frequency from low frequency, the polarity of two lateral electrodes gradually changes fast, and the ion of generation is before participating in reduction reaction, again attracted to the electrode that changes to (-) polarity, gold-plated phenomenon occurs.That is, this means, the metal ion generating in (+) electrode moment is reacting with reducing agent, and before being reduced into metal nanoparticle, in being transformed to (-) electrode from (+) 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 significantly reduces, and therefore, shows the phenomenon of the yield increase that generates nano particle.
Examine or check below in the metal nanoparticle preparation that has utilized electrolytic method of the present invention, there is the condition of the metal nanoparticle of the narrow size distribution (particle of homogeneous) of high yield (yield), homogeneous shape and required size (not enough 100nm) for generation.
Generally speaking, in the metal nanoparticle preparation that utilizes electrolytic method, not as the chemical method, the amount of the metallic that decision will obtain, the metal ion of amount that meets initial reaction condition is put into reaction vessel to react, but continuously according to the time, generating metal ion at metal electrode place, the reaction of reducing by the ion that makes by means of reducing agent to generate realizes.As a result, in this course of reaction, due to the polarity of electrode and the interaction of nano particle, the metal nanoparticle of generation can show again the characteristic of refurn electrode.But this phenomenon becomes aspect yield, that is, and the greatest problem aspect production.
Aspect the preparation of metal nanoparticle that utilizes electrolysis, for solving this production problem, need to, according to the concentration of the metal ion generating because of access electric energy, be kept for aptly the concentration of the reducing agent that makes this metal ion species reduction.
Now, the amount of metal ion of generation determines by the current strength that accesses the AC power between two electrodes, and the voltage that this current strength can be utilized electrolytical concentration and put on electrode regulates.According to the inventor's result of study, when considering the concentration of the metal ion that utilizes set current strength (current value) generation, when the concentration of reducing agent is remained on to set level, find that the yield of metal nanoparticle improves.
Its reason is, if compared with reductant concentration, has generated more metal ion, and the amount relative deficiency of reducing agent, although the speed of metal ion reduction reduces relatively, can not produce large problem to yield.But, in the time of the amount relative deficiency of reducing agent, occur that the size of particle becomes large side effect.On the contrary, if the concentration of metal ions that the concentration ratio of reducing agent generates is excessive, reduction rate is too fast, generates the particle below number nanometer, is utilizing dispersant to carry out end-blocking (capping) before, refurn electrode again, thereby yield sharply reduces.
On the other hand, electrolytical kind and concentration are directly relevant to pH and current strength.Generally speaking, electrolyte is generally divided into acidic electrolyte bath, alkaline electrolyte and neutral electrolyte, if only use acidic electrolyte bath, because pH is less than 7, for example, when as reducing agent, while dropping into 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 forms reaction solution is more than 7 environment; in reaction solution; electronics can moving machine can increase; the reaction speed that is used as the hydrazine as weak base of reducing agent increases, and generates the nano level particle of number, appears at and is subject to the dispersant protection phenomenon of refurn electrode before.
In the present invention, consider this point, mix by the acid electrolyte forming with alkalescence and use, pH is set as 7 to 9.
In addition, from the relation of pH and the reductant concentration of reaction solution, in the time of pH less than 7, reduce as the reaction speed of the hydrazine of reducing agent.Its reason is, because hydrazine is weak base, and reacts as electrolytical citric acid (citric acid), until pH becomes neutrality, compared with reduction reaction, preferentially participates in acid-base reaction.This becomes the reason that reduces hydrazine reducing power.Therefore, after acid-base reaction is carried out, there is reduction reaction, participate in the hydrazine amount of the reduction reaction of metal ion less than the actual hydrazine amount that makes an addition to reaction vessel, the result that causes reduction reaction to delay, the size of metallic increases.That is, preferred scope that the input amount of reducing agent is not enough, although there is no large problem on yield, there is increasing to phenomenons more than hundreds of nanometers in the size of particle.
If must use the dispersant with dispersibility, be directly proportional to the concentration of the metal ion generating between pH 7 ~ 9, make the concentration of reducing agent remain on set level, so, reduction reaction speed keeps more constantly, and yield (, production) greatly increases.
The metal nanoparticle preparation method who utilizes electrolysis 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 described electrolytic solution (11), the 1st and the 2nd electrode (30,40) that setpoint distance ground configuration is made up of the metal material identical with nano particle that will be synthetic; Ionization step, according to electrolytic method, between described the 1st electrode (30) and the 2nd electrode (40), access has the AC power of set frequency (f), makes metal ionization in described electrolytic solution of the 1st and the 2nd electrode (30,40); And metal nanoparticle formation step, make described metal ion reduction by reducing agent, form metal nanoparticle.
First, in the present invention, electrolytic solution (11), in pure water, especially preferably, in ultra-pure water, as additive, comprises electrolyte, reducing agent and dispersant.
Preferred described electrolytic solution mixing acidic electrolyte bath and alkaline electrolyte use, and are set as pH 7 to pH 9.Now, described electrolyte can mix citric acid (citric acid) and hydrazine (Hydrazine) use.
Described electrolyte can use select in the group being made up of the amine of nitric acid/formic acid (formic acid)/acetic acid (acetic acid)/citric acid (citric acid)/tartaric acid (tataric acid)/glutaric acid (glutaric acid)/caproic acid (hexanoic acid) acid forming, the alkali metal salt/ammonia of described acid (NH3)/triethylamine (TEA:triethyl amine) and pyridine (pyridine) one kind or two or more arbitrarily.
The electrolyte particularly using in the present invention, as feature of environmental protection electrolyte, can use citric acid (citric acid), as required, can also use the amino acid such as glycine (glycine).
In addition, as reducing agent, can use by hydrazine (hydrazine:N2H4), sodium hypophosphite (sodium hypophosphite:NaH2PO2), sodium borohydride (sodium borohydride:NaBH4), dimethylamine borane (DMAB:dimethylamine borane:(CH3) 2NHBH3)), select in the group that forms of formaldehyde (formaldehyde:HCHO) and ascorbic acid (ascorbic acid) one kind or two or more arbitrarily.
Described reducing agent, as environmental protection reducing agent, for example, preferably uses the organic matter ion reducing agent such as hydrazine (Hydrazine).This organic matter ion reducing agent generates nitrogen G&W and all consumes in reaction, thereby harmless after reaction finishes.
Described reducing agent is by reducing agent feeding mechanism (not shown), and the concentration of the metal ion of generation, drops in electrolytic solution, to make the concentration of reducing agent reach set level when carrying out cell reaction along with incoming transport power supply.
As mentioned above, in the present invention, taking pure water (DI-water) as basis, do not use environmentally harmful electrolyte, use environment-friendly type electrolyte and environmental-protection organic matter ion reducing agent, thereby can obtain metal nanoparticle by method environmental protection, simple.
On the other hand, described dispersant performance is carried out the effect of end-blocking to the surface of metal nanoparticle, prevent along with electrolysis from the 1st and the 2nd electrode (30,40) dissociate and realize Ionized metal ion and be reduced after agent reduction, the metal nanoparticle refurn electrode of reduction is also attached on electrode, or the phenomenon precipitating because of the flocculation between metal nanoparticle, can use water-soluble polymer dispersant or aqueous dispersion macromolecule dispersing agent.
Described water-soluble polymer dispersant can use the water system macromolecule dispersing agent of polypropylene, polyurethane or polysiloxanes system, and aqueous dispersion macromolecule dispersing agent can use the aqueous high molecular dispersant of polypropylene, polyurethane or polysiloxanes system.
As described 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; Tween 20, the Tween 80 of Aldrich company; Polyethylene glycol (PEG:Polyethylene Glycol) 200, polyvinylpyrrolidone (PVP:polyvinylpyrrolidone) 10, that 000, in the group of PVP 55,000, poloxamer (poloxamer) 407 and PLURONICS F87 composition, selects is one kind or two or more arbitrarily.
Described ultra-pure water (DI-water), refer to and have hardly the anion and cationic 3 distilled water that in running water or mineral water, exist, this is because preparing the metallic nanoparticle period of the day from 11 p.m. to 1 a.m, in the time entering anion except electrolyte and reducing agent and cation, in required metal nanoparticle, there will be impurity, in addition, complex compound may be generated, metal nanoparticle cannot be obtained.
The preparation of the metal nanoparticle that utilizes electrolysis of the present invention as shown in Figure 3, in the reaction vessel (10) of metal nanoparticle preparation facilities, as the metal material identical with Nano silver grain that will be synthetic, respectively by multiple silver-colored particle (30a, the 1st electrode (30) and the 2nd electrode (40) that 40a) form are installed on supporting seat (15), make the 1st electrode (30) and the 2nd electrode (40) arranged spaced.
Then, in ultra-pure water (DI-water) 1L, drop into citric acid (Citric acid) 2.0mmol as electrolyte, drop into hydrazine 6.0mmol as electrolyte, as dispersant, put into the Disperbyk of BYK Chemie company tM-1908.0g, puts into respectively after reaction vessel, utilizes agitator (20) to stir, until dissolve completely.
The aqueous solution that additive is all dissolved heats, aqueous temperature is risen to after 90 DEG C, in reaction vessel, add cooling water consistently, keeping under the state of the temperature of setting, frequency be 1Hz, between the AC power that formed by sine wave access the 1st and the 2nd electrode, meanwhile, current value is set to 4.3A, implements electrolysis.In addition, implement the electrolysis of 1 hour 30 minutes, meanwhile, utilize pump constant speed to inject reducing agent hydrazine 18.0mmol, make it reaction.
After cell reaction, the consumption of measuring silver electrode, utilizes FE-SEM to analyze the Nano silver grain existing in reacting solution, and result is known, the Nano silver grain major part obtaining exists with the nano particle of 12nm to 20nm size, can confirm to show very narrow silver particles degree of distribution.
As mentioned above, 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 are become particle shape, be filled in pair of electrodes shell, make it keep set interval, form pair of electrodes, utilize AC power to implement electrolysis, so, even if carry out electrolysis, 2 interelectrode distances also do not change, and can prepare in a large number the metal nanoparticle of the nanosized of homogeneous shape and homogeneous.
In addition, in the present invention, when electrolysis is carried out, fill new particle along with the consumption of the particle of filling in pair of electrodes shell, thereby can not interrupt electrowinning process, prepare continuously a large amount of metal nanoparticles.As a result, in the present invention, without changing the electrode consuming in electrowinning process, supplement the clipped wire of grain shape to the inner space of electrode shell, thereby can prevent the interruption of electrowinning process, can boost productivity.
Fig. 6 is the stereogram that shows the metal nanoparticle preparation facilities granular pattern electrode of the present invention the 2nd embodiment.
As shown in Figure 6, the metal nanoparticle preparation facilities of the present invention the 2nd embodiment is with compared with the granular pattern electrode of granular pattern electrode and the 1st embodiment shown in Fig. 3, difference is at the 1st and the 2nd electrode shell (32,42) on forward surface, replace seam, form multiple holes (33a, 43a), all the other formations are identical.
Therefore, for the inscape identical with the 1st embodiment, give identical reference marks, and omit the detailed description to this.
In the 2nd embodiment, hole (33a, 43a), as the structure that particle (30a, 40a) cannot be leaked, can more more be inclined upwardly and form to the outside of electrode shell (32,42).
Fig. 7 is the top view that shows the variation of the granular pattern electrode using in the 1st and the 2nd embodiment.
As shown in Figure 7, shown in the corpuscular the 1st and the 2nd electrode (30,40) be for further improving conductance, be filled with multiple particle (30a, the the 1st and the 2nd electrode shell (32 40a), 42) inner space, inserts respectively the example of conductive plate (37) along its length.Now, conductive plate (37) is made up of the material identical with particle (30a, 40a).
As mentioned above, 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 the inscape identical with described the 1st embodiment, give identical reference marks, and omitted the detailed description to this.
Fig. 8 and Fig. 9 are 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 with the metal nanoparticle preparation facilities of the 1st embodiment, give identical reference marks, and omitted the detailed description to this.
As shown in Fig. 8 and Fig. 9, the metal nanoparticle preparation facilities of the present invention the 3rd embodiment, for making the area in opposite directions between the 1st electrode (60) and the 2nd electrode (70) realize maximization, proposes the example of the drum-shaped electrode shell that adopts double-layered bucket structure.
Drum-shaped the 1st and the 2nd electrode shell (62,72) of the present invention the 3rd embodiment is made up of the double-layered bucket structure of lower end closed, to possess the annular spatial accommodation that can fill respectively multiple particles (60a, 70a).
With regard to the present invention the 3rd embodiment, in reaction vessel (10) inside, use the 1st and the 2nd electrode shell (62 of double-layered bucket structure different at diameter, that configure with concentric shape, 72) inside, fill respectively the 1st electrode (60) and the 2nd electrode (70) of the most particles (60a, 70a) that formed by the material identical with the metal nanoparticle that will obtain.
The 1st electrode (60) and the 2nd electrode (70) are interconnected by multiple connecting portions (12) of equal length between the 1st electrode shell (62) and the 2nd electrode shell (72), thus configuration isolator mutually.Result, with respect to mutual all outer peripheral faces in opposite directions, interval between the 1st electrode shell (62) and the 2nd electrode shell (72) is set as keeping constant, and the interval between the 1st electrode (60) and the 2nd electrode (70) is also set as keeping constant.
In addition, on the inner peripheral surface of the 1st electrode shell (62), be formed with multiple seams or hole (63), on the outer peripheral face of the 2nd electrode shell (73) in opposite directions with it, be formed with multiple seams or hole (73).
On the other hand, in the 3rd embodiment, the electrolytic solution (11) holding for changing reaction vessel (10) inside, lower subordinate at the 1st electrode (60) and the 2nd electrode (70) configures impeller, 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) being supported by multiple connecting portions (13), one end of supporting rotating shaft (20) revolvably.
In reaction vessel (10) inside, accommodate the electrolytic solution (11) that has mixed electrolyte, dispersant and reducing agent in ultra-pure water as additive, at the downside of described reaction vessel (10), for indirect electrolytic solution (11) disposes heater (not shown), on the top of reaction vessel (10), by a pair of power line (55), be connected with for the power supply device (50) 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 is for making the area in opposite directions between the 1st electrode (60) and the 2nd electrode (70) realize maximization as constructed as above, adopt drum-shaped the 1st and the 2nd electrode shell (62 of double-layered bucket structure, 72), thereby area change in opposite directions, can seek to increase the yield of metal nanoparticle.
In addition, in the 3rd embodiment, substituted metal plate or rod, changed into particle shape, keep set compartment of terrain to be filled in the 1st and the 2nd electrode shell (62,72), form the 1st and the 2nd electrode (60,70), if utilize AC power to implement electrolysis, so, even if carry out electrolysis, distance between the 1st and the 2nd electrode (60,70) does not change, and can prepare in a large number the metal nanoparticle of the nanosized of homogeneous shape and homogeneous.
In addition, in the present invention, when electrolysis is carried out, along with the consumption of the particle (60a, 70a) of filling in the 1st and the 2nd electrode shell (62,72), fill new particle (60a, 70a), do not interrupt electrowinning process, just can prepare continuously a large amount of metal nanoparticles.As a result, in the present invention, without the electrode of changing electrowinning process consumption, supplement granular clipped wire by the inner space to electrode shell, thereby can prevent the interruption of electrowinning process, can boost productivity by means of series-operation.
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.
As shown in Figures 10 and 11, the metal nanoparticle preparation facilities of the present invention the 4th and the 5th embodiment and the 1st has been to hold respectively the electrode shell (82 of particle (not shown) to the difference of the 3rd embodiment, 82a), the 4th and the 5th embodiment only uses an electrode shell.
With by electrode shell (82, granuloplastic the 1st electrode (80) holding 82a) the 2nd electrode (90 in opposite directions, 90a), just formed by plectane or the drum that can realize energising in the time that access is used for the AC power of electrolysis, hold the electrode shell (82,82a) of particle and realize rotation by means of rotating driving device (not shown).
The 2nd electrode (90,90a) of the 4th and the 5th embodiment be chosen to be such as Ti etc. can stripping in electrolytic solution metal material.
The metal nanoparticle preparation facilities of the 4th embodiment of the present invention as shown in figure 10 can be the structure formation by the electrode shell that holds particle (82) with the spatial accommodation that for example cross section is cross shape.The shape of electrode shell (82) except described cross, such as star bucket, drum, polygon bucket etc., as long as holding the barrel structure of particle, any shape all can.Therefore, the 1st electrode (80) is made up of the multiple particles that hold in electrode shell (82).
Now, because the 2nd discoideus electrode (90) is disposed at the downside of the 1st electrode (80), so the seam (83) of the electrode shell (82) that when electrolysis, the metal ion of stripping is discharged is disposed at downside (84).
The lower panel (84) of described electrode shell (82) keeps set interval to be configured with the 2nd discoideus electrode (90), between the 1st and the 2nd electrode (80,90), continues to keep set interval.
In addition, described electrode shell (82) is realized after rotation, does not need to use other agitator, can be expected to obtain the effect that promotes the digestion of metallic ion of discharging from the 1st electrode (80).
Described electrode shell (82) is realized after rotation, in the time of cell reaction, and the 1st and the 2nd electrode (80,90) between, continue to keep set interval, meanwhile, form the metal ion of generation and the effecting reaction environment of reducing agent, can make the efficiency of mixing realize maximization.
In Figure 10, unaccounted member symbol 91 represents conduit (91), holds for the power line of the 2nd electrode (90) the incoming transport power supply for to the configuration of reaction vessel (10) bottom surface.
The electrode shell that holds particle (82a) that the metal nanoparticle preparation facilities of the 5th embodiment of the present invention as shown in figure 11 uses, forms 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,, in surrounding the electrode shell (82) of the 1st electrode (80a), form to there is the drum of set thickness or the drum of net (net) structure with the 1st electrode (80a) the 2nd electrode (90a) in opposite directions.
Now, because the 2nd barrel-shaped electrode (90a) is disposed at the side of the 1st electrode (80a), the seam (83a) of the electrode shell (82a) that therefore, the metal ion of stripping is discharged when electrolysis is disposed at the side of electrode shell (82a).
In the time that described electrode shell (82a) is cross, 4 sides (84a) and the 2nd barrel-shaped electrode (90a) keep set interval to be configured, so, between the 1st and the 2nd electrode (80a, 90a), also continue to keep set interval.
In addition, described electrode shell (82a) is realized after rotation, does not need to use other agitator, can be expected to performance and promote from the effect of the digestion of metallic ion of the 1st electrode (80a) discharge.
The the 4th and the 5th described embodiment is owing to only using an electrode shell (82,82a), manages so have advantages of that the particle being easy to being consumed supplements.
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 of side in opposite directions of the 1st electrode (300a) and the 2nd electrode (400a), 44a)) being set as identical distance uses, but for the structure of side is in opposite directions described, for convenience, shown the state that launches set angle.
The metal nanoparticle preparation facilities of the present invention the 6th embodiment provides a kind of electrode structure, in the time of electrolysis, from the ion stripping of electrode electrode bight than bight outside other parts many, can realize what is called " edge effect (Edge Effect) " and maximize.
For this reason, the metal nanoparticle preparation facilities of the 6th embodiment is for holding particle (not shown), the the 1st and the 2nd electrode shell (32a for example forming with square tubbiness, 42a) there is following structure: a mutual side is in opposite directions respectively by the 1st and the 2nd side plate (34a, 44a) form, the the 1st and the 2nd side plate (34a, 44a) is made up of the insoluble electrode material such as Ti, protrudes both take the altitudes.
Now, the the described the 1st and the 2nd electrode shell (32a, 42a) can be as the 1st to the electrode shell of the 3rd embodiment, use the insoluble insulating properties material to electrolytic solution, the polymer system (polymer family) of for example nylon monomer-cast nylon (MC nylon), nylon, polyester, polystyrene, polyvinyl chloride, carbon (carbon), pottery or glass, for example Pai Ruikesi (Pyrex) glass, the the 1st and the 2nd side plate (34a, 44a) can be used as the titanium (Ti) of the insoluble material that can conduct electricity.
Result, when using titanium (Ti) as the 1st and the 2nd electrode shell (32a, when the 1st and the 2nd side plate (34a, 44a) 42a), the 1st and the 2nd side plate (34a, 44a) with the 1st and the 2nd electrode shell (32a, multiple particles of filling 42a) are in contact condition, therefore, and in the time of AC power access particle, the the 1st and the 2nd side plate (34a, 44a) is realized the energising with multiple particles.
The the 1st and the 2nd side plate (34a, 44a) as shown in figure 13, jagged multiple projection (corresponding to screw thread) (35a, 45a) protrude set height, the interval between projection (corresponding to screw thread) (35a, 45a) is in opposite directions set as identical, at each projection (35a, side 45a), forms multiple holes or seam (33a, 43a).The the 1st and the 2nd described side plate (34a, 44a) can bending net (net) structure Ti sheet material form, multiple holes or seam (33a, 43a) are arranged regularly.
In addition, due to the described the 1st and the 2nd side plate (34a, 44a) be jagged multiple projection (corresponding to screw thread) (35a, the structure of 45a) protruding, so compared with slab construction, area change in opposite directions, can seek to improve the efficiency that obtains metal nanoparticle along with electrolysis.
Therefore, if to particle incoming transport power supply, the the 1st and the 2nd side plate (34a, mutual projection (35a in opposite directions 44a), 45a) realize energising with multiple particles, according to edge effect (Edge Effect), at the 1st and the 2nd electrode shell (32a, 42a), the multiple particles that are filled in a side, form the 1st electrode (300a) are to multiple particle release electronics of the 2nd electrode (400a) of opposite side, and stripping is increased to the stripping quantity of the metal ion in electrolytic solution.
In addition, the metal nanoparticle preparation facilities of the present invention the 6th embodiment as shown in figure 14, in the 1st and the 2nd electrode shell (32a, 42a), be set as the 1st and the 2nd side plate (34a, projection (35a 44a), 45a) be disposed at the structure between projection and the projection on opposite, now, compared with slab construction, area change in opposite directions, can seek to improve the efficiency that obtains metal nanoparticle along with electrolysis.
And, at the 1st and the 2nd electrode shell (32a of the present invention the 6th embodiment, 42a), although proposed the structure that the projection (35a, 45a) of the 1st and the 2nd side plate (34a, 44a) is arranged along the vertical direction in parallel to each other, but, also the structure that can be arranged in parallel to each other by projection (35a, the 45a) along continuous straight runs of the 1st and the 2nd side plate (34a, 44a) forms.
As mentioned above; in the present invention; being installed on the pair of electrodes enclosure in electrolytic cell with set interval; fill the particle or the chip that are formed by the material identical with the metal nanoparticle that will obtain; form electrode; even thereby carry out electrolysis, two interelectrode distances also do not change, and can obtain the metal nanoparticle of homogeneous shape and homogeneous size.
In addition, in the present invention, in electrowinning process, fill continuously new metallic particles or chip along with the consumption of metallic particles or chip, thereby without because changing electrode breaks in production, a large amount of metal nanoparticle of continuous production easily.As a result, in the present invention, without change the electrode consuming in electrowinning process, by supplement particle in electrode shell, can prevent the interruption of electrowinning process, can boost productivity.
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, access electrode, to realize a large amount of productions of metal nanoparticle, can efficiently prepare a large amount of metal nanoparticles.
In described embodiment explanation; as the material of particle or chip; being the argent (Ag) little taking ionization tendency describes as example; but; even if be applied to the metal that ionization tendency is large; for example Mg, Al, Zn, Fe, Cu, or little Pt, the Au etc. of ionization tendency, also can obtain similar results.
In addition; in described embodiment explanation; as the material of particle or chip; use fine silver (Ag); but when use the alloy of more than two kinds of selecting in the group being formed by Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni and Pd; for example, while using the 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 lower than each melting point metal before alloy, in the time that preparation has been used the ink of alloy nano particle, can be expected to obtain lower sintering temperature.
Industrial utilization possibility
The present invention can utilize simple operation, environmental protection ground, produce in a large number the metal nanoparticle that the applications such as metallic ink, medical treatment, clothes, cosmetics, catalyst, electrode material, electronic material are used equably, particularly Nano silver grain, can be widely used in metal nanoparticle preparation.

Claims (20)

1. a preparation facilities for metal nanoparticle, is characterized in that, comprising:
Reaction vessel, electrolysis solution holds;
The the 1st and the 2nd electrode, is installed in the 1st and the 2nd electrode shell of reaction vessel interior described in each compartment of terrain is set, and fills the multiple particles or the chip that are made up of the metal identical with the metal nanoparticle that will obtain and forms;
Supporting seat, with state of insulation space both set a distance, supports described the 1st electrode shell and the 2nd electrode shell; And
Power supply device, is used to and carries out cell reaction and to incoming transport power supply between the described the 1st and the 2nd electrode; And,
The the described the 1st and the 2nd electrode shell at least possesses multiple holes or seam on face in opposite directions, to discharge from the metal ion of the described the 1st and the 2nd electrode stripping according to cell reaction;
The width of described multiple hole or seam is set to such an extent that be less than the size of described multiple metallic particles or chip.
2. the preparation facilities of metal nanoparticle according to claim 1, is characterized in that,
Described supporting seat also comprises on two sides: the 1st and the 2nd power line, accesses the AC power between the described the 1st and the 2nd electrode from power supply device supply; The the 1st and the 2nd electrode terminal, for interconnecting inner particle or the chip of filling of the 1st and the 2nd electrode shell.
3. the preparation facilities of metal nanoparticle according to claim 1, is characterized in that:
The the described the 1st and the 2nd electrode shell is that cross sectional shape is respectively rectangle or polygonal bucket.
4. the preparation facilities of metal nanoparticle according to claim 3, is characterized in that:
The the described the 1st and the 2nd electrode shell is made up of the 1st and the 2nd side plate, and they have the multiple projections that are made up of zigzag in each side in opposite directions, form multiple holes or seam in the two sides of described projection.
5. the preparation facilities of metal nanoparticle according to claim 4, is characterized in that:
The the described the 1st and the 2nd side plate is made up of the net forming with Ti respectively.
6. the preparation facilities of metal nanoparticle according to claim 1, is characterized in that:
The the described the 1st and the 2nd electrode shell is respectively diameter Double Layer Circular barrel structure different, that configure with concentric shape.
7. the preparation facilities of metal nanoparticle according to claim 1, is characterized in that:
Described particle or chip are made up of any one kind or two or more alloy of selecting in the group forming at Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni and Pd.
8. the preparation facilities of metal nanoparticle according to claim 1, is characterized in that:
The size of described particle or chip is set as 0.05 to 10cm scope.
9. the preparation facilities of metal nanoparticle according to claim 1, is characterized in that:
The size of described particle or chip is set as 0.5 to 5mm scope.
10. a preparation facilities for metal nanoparticle, is characterized in that, comprising:
Reaction vessel, electrolysis solution holds;
The 1st electrode, in the electrode shell that is installed on described reaction vessel interior, fills the multiple particles or the chip that are made up of the metal identical with the metal nanoparticle that will obtain and forms;
The 2nd electrode, with described the 1st electrode setting interval, is installed on the inside of described reaction vessel;
And power supply device, be used to and carry out cell reaction and to incoming transport power supply between the described the 1st and the 2nd electrode; And,
Described electrode shell with described the 2nd electrode side in opposite directions on possess multiple holes or seam; to discharge from the metal ion of described the 1st electrode stripping along with cell reaction, the width of described multiple holes or seam is set to such an extent that be less than the size of described multiple metallic particles or chip.
The preparation facilities of 11. metal nanoparticles according to claim 10, is characterized in that:
Described electrode shell has criss-cross spatial accommodation in inside, possess multiple holes or seam in side, and electrode shell is contained in inside described in described the 2nd electrode handle, is made up of drum or drum-shaped net.
12. according to the preparation facilities of the metal nanoparticle described in claim 10 or 11, it is characterized in that:
Described electrode shell is driven in rotation, and described the 2nd electrode is made up of Ti.
The preparation method of 13. 1 kinds of metal nanoparticles, is characterized in that comprising:
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 opposite to each other described reaction vessel interior and on forward surface, possessing in the 1st and the 2nd electrode shell of multiple holes or seam, fill the multiple particles or the chip that are formed by the metal identical with the metal nanoparticle that will obtain, form the 1st and the 2nd electrode;
Metal ion produces step, incoming transport power supply carry out electrolysis between the described the 1st and the 2nd electrode, thus make metallic particles or chip at described electrolytic solution intermediate ion, produce metal ion; And
Metal nanoparticle forms step, utilizes reducing agent to make described metal ion reduction, forms metal nanoparticle.
The preparation method of 14. metal nanoparticles according to claim 13, is characterized in that:
The concentration of the metal ion that described reducing agent generates corresponding to the carrying out along with electrolysis drops in electrolytic solution, makes the concentration of reducing agent keep set level.
The preparation method of 15. metal nanoparticles according to claim 13, is characterized in that:
The frequency (f) of described AC power is 0<f<10Hz.
The preparation method of 16. metal nanoparticles according to claim 13, is characterized in that:
Described particle or chip are made up of any one kind or two or more alloy of selecting in the group forming at Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni and Pd.
The preparation method of 17. metal nanoparticles according to claim 13, is characterized in that:
The size of described particle or chip is set as 0.05 to 10cm scope.
The preparation method of 18. metal nanoparticles according to claim 13, is characterized in that:
The size of described particle or chip is set as 0.5 to 5mm scope.
The preparation method of 19. 1 kinds of metal nanoparticles, is characterized in that comprising:
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, the 1st electrode of filling multiple particles of being made up of the metal identical with the metal nanoparticle that will obtain or chip and form in electrode shell with the tabular or barrel-shaped inside that is at least installed on described reaction vessel with the one side of described the 1st electrode the 2nd electrode in opposite directions forming;
Metal ion produces step, to incoming transport power supply between the described the 1st and the 2nd electrode and carry out electrolysis, thereby makes metallic particles or chip realize ionization in described electrolytic solution, produces metal ion; And
Metal nanoparticle forms step, utilizes reducing agent to make described metal ion reduction, forms metal nanoparticle.
The preparation method of 20. metal nanoparticles according to claim 19, is characterized in that:
Described electrode shell is driven in rotation, and described the 2nd electrode is made up of Ti.
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