KR102007829B1 - Apparatus and method of preparing nanoparticle comprising metal - Google Patents

Abstract

The present invention relates to an apparatus for producing metal-containing nanoparticles, an embodiment of the present invention is a plasma reactor including a body, an opening accommodated in the body, the metal precursor fluid is introduced, the end portion into the plasma reactor Including a plasma electrode and a cooling fluid supply portion is inserted to expose the distal end inside the body to circulate the cooling fluid, it is possible to easily circulate and cool the metal-containing nanoparticles to produce a high purity metal-containing nanoparticles The present invention relates to an apparatus for producing metal-containing nanoparticles, which is excellent in conversion rate and productivity to metal-containing nanoparticles.

Description

A manufacturing apparatus and manufacturing method of a metal containing nanoparticles {APPARATUS AND METHOD OF PREPARING NANOPARTICLE COMPRISING METAL}

The present invention relates to a manufacturing apparatus and a manufacturing method of metal-containing nanoparticles.

For example, metal nanoparticle-related technologies are being researched in various technical fields such as technical fields related to electronic components of electronic devices such as notebooks and mobile phones, printed electronic technologies, catalysts, secondary batteries, and environmental applications.

However, the existing method of synthesizing metal nanoparticles may cause environmental pollution due to chemicals used in the synthesis, and the synthesis is performed under high temperature and high pressure conditions to use expensive equipment, or the energy consumption of the equipment is high and economical, Due to the long synthesis time, mass production is difficult. In addition, existing methods for synthesizing metal nanoparticles have problems such as non-uniformity of particle size distribution, low dispersibility, low purity, and thus are difficult to apply to the aforementioned technical field.

On the other hand, underwater plasma discharge refers to a technique for generating underwater plasma by underwater electric discharge. In general, such underwater plasma discharge is widely used to improve the water quality. For example, it is used directly or indirectly in ballast water, ultrapure water production, seawater desalination, and the like.

Such underwater plasma discharges can be effectively applied in various industrial fields based on the potential of plasma.

Korean Laid-Open Patent Publication No. 10-2015-0118737 discloses a technique related to a method for producing metal-containing nanoparticles.

Korean Patent Publication No. 10-2015-0118737

One object of the present invention is to provide a metal-containing nanoparticle production apparatus that can effectively control the particle size.

One object of the present invention is to provide an apparatus for producing metal-containing nanoparticles which can increase the purity of a product while improving productivity.

One object of the present invention is to provide a metal-containing nanoparticle production apparatus that can easily collect the produced metal-containing nanoparticle production apparatus.

One object of the present invention is to provide a method for producing metal-containing nanoparticles that can effectively control the particle size.

The present invention provides a method for producing metal-containing nanoparticles that can be mass-produced with high efficiency even under mild conditions.

The present invention is to provide a method for producing metal-containing nanoparticles that can easily collect the prepared metal-containing nanoparticles.

1. body; A plasma reactor received inside the body and including an opening into which a metal precursor fluid is introduced; A plasma electrode exposed at an end portion of the plasma reactor; And a cooling fluid supply part inserted into the body so as to expose the distal end to circulate the cooling fluid.

2. according to the above 1, further comprising a support for supporting the body, the cooling fluid supply is disposed between the support and the plasma reactor, the metal-containing nanoparticles manufacturing apparatus.

3. In the above 1, wherein the cooling fluid supply comprises a plurality of cooling fluid supply is arranged spirally along the side wall of the body, metal-containing nanoparticles manufacturing apparatus.

4. In the above 1, wherein the plasma electrode includes an electrode body, a first dielectric tube surrounding the electrode body, and a discharge gas supply unit for introducing a discharge gas between the electrode body and the first dielectric tube, the metal containing nano Particle manufacturing apparatus.

5. The apparatus of claim 4, wherein the plasma electrode further comprises a fixing part surrounding at least a portion of the first dielectric tube and fixing the discharge gas supply part.

6. In the above 4, wherein the plasma electrode further comprises a second dielectric tube surrounding the first dielectric tube, and a shield fluid supply for introducing a shield fluid between the first dielectric tube and the second dielectric tube, metal -Containing nanoparticle production apparatus.

7. The apparatus of claim 6, wherein the shield fluid supply part comprises a plurality of shield fluid supply parts spirally disposed along the sidewall of the second dielectric tube.

8. In the above 6, the inclination angle in the vertical section of the side wall of the shield fluid supply and the second dielectric tube is 30 to 60 °, metal-containing nanoparticles manufacturing apparatus.

9. In the above 6, wherein the end portion of the shield fluid supply portion protrudes into the space between the first dielectric tube and the second dielectric tube, metal-containing nanoparticles manufacturing apparatus.

10. The apparatus of claim 6, wherein the plasma electrode further comprises an additional fixing part surrounding at least a portion of the second dielectric tube and fixing the shield fluid supply part.

11. The above 1, further comprising a magnetic collector disposed below the plasma reactor, the metal-containing nanoparticles manufacturing apparatus.

12. The apparatus of claim 11, wherein the magnetic collection part comprises an electromagnet or a permanent magnet.

13. preparing a metal precursor aqueous solution comprising a solvent, a reducing agent and a metal precursor; Circulating a cooling fluid around the metal precursor aqueous solution; And generating metal-containing nanoparticles from the metal precursor aqueous solution through an underwater plasma discharge.

14. In the above 13, wherein the step of circulating the cooling fluid is performed in the body, the underwater plasma discharge is performed in a plasma reactor to which the metal precursor aqueous solution is supplied, the manufacturing method of the metal-containing nanoparticles.

15. The method according to the above 13, further comprising the step of controlling the size of the metal-containing nanoparticles by using a magnet, method for producing a metal-containing nanoparticles.

16. The method according to the above 15, wherein controlling the size of the metal-containing nanoparticles comprises bonding the metal-containing nanoparticles to the magnet.

17. The method of 16 above, wherein the underwater plasma discharge comprises a first underwater plasma discharge and a second underwater plasma discharge, and the step of coupling the metal-containing nanoparticles to the magnet is the first underwater plasma discharge and the second A method for producing metal-containing nanoparticles, carried out between underwater plasma discharges.

18. The method of 16 above, after the bonding of the metal-containing nanoparticles to the magnet, separating the metal-containing nanoparticles from the magnet; And adding an additional metal precursor to the aqueous metal precursor solution.

19. The method according to the above 18, wherein the second underwater plasma discharge is performed after the step of adding the additional metal precursor.

20. The method according to the above 13, wherein the metal precursor aqueous solution further comprises a carrier, method for producing metal-containing nanoparticles.

21. In the above 20, the carrier is graphene (graphene), graphene oxide (graphene oxide), carbon nanotubes (carbon nanotube, CNT), graphite (carbon fiber), activated carbon and polymethyl A method for producing metal-containing nanoparticles, comprising at least one selected from the group consisting of (meth) acrylates.

22. The method of claim 13, wherein the metal-containing nanoparticles are selected from the group consisting of metal nanoparticles, metal oxide nanoparticles, metal-carrier composite particles, and metal oxide-carrier composite particles.

The metal-containing nanoparticle manufacturing apparatus of the present invention, for example, by circulating a cooling fluid around the plasma reactor, it is easy to circulate and cool the metal-containing nanoparticles, it is possible to manufacture high-purity metal-containing nanoparticles.

In addition, the apparatus for producing metal-containing nanoparticles of the present invention continuously exposes a metal precursor aqueous solution to an underwater plasma discharge, for example, to shorten the process time in manufacturing the metal-containing nanoparticles and to reduce the process conversion rate (from precursor to metal and metal oxide). Converted ratio) can be increased significantly, resulting in good productivity.

In addition, the apparatus for producing metal-containing nanoparticles of the present invention may include, for example, a detachable magnetic collector, thereby controlling the synthesis of the metal-containing nanoparticles having magnetic properties to uniformly control the size of the metal-containing nanoparticles or I can regulate it.

In addition, the method for producing metal-containing nanoparticles of the present invention can circulate or cool the metal-containing nanoparticles easily by circulating a cooling fluid around the metal-containing nanoparticles, thereby making it possible to manufacture high-purity metal-containing nanoparticles.

In addition, the method for producing metal-containing nanoparticles of the present invention can efficiently mass-produce metal-containing nanoparticles even under relaxed conditions, that is, at room temperature and atmospheric pressure.

In addition, the method for producing metal-containing nanoparticles of the present invention can prevent oxidation of the metal-containing nanoparticles, thereby producing highly pure metal-containing nanoparticles.

In addition, the method for producing metal-containing nanoparticles of the present invention can shorten the process time in manufacturing the metal-containing nanoparticles and significantly increase the process conversion rate.

In addition, the method for producing metal-containing nanoparticles of the present invention may include the step of binding and separating the metal-containing nanoparticles to a magnet, for example, by easily controlling the synthesis of the magnetic metal-containing nanoparticles, The metal containing nanoparticle size can be controlled.

1 is a perspective view schematically showing a metal-containing nanoparticle manufacturing apparatus according to embodiments of the present invention.
FIG. 2 is a plan view schematically illustrating an arrangement of a body and a cooling fluid supply part included in an apparatus for manufacturing metal-containing nanoparticles, according to some embodiments.
3 is a perspective view schematically showing a plasma electrode included in the metal-containing nanoparticle manufacturing apparatus according to some exemplary embodiments.
4 is a perspective view schematically showing a plasma electrode included in the metal-containing nanoparticle manufacturing apparatus according to some exemplary embodiments.
FIG. 5 is a plan view illustrating a shield fluid flow in the plasma electrode of FIG. 4.
6 is a graph showing the results of X-ray Photoelectron Spectroscopy (XPS) analysis of Examples 1 to 6 and Comparative Example 1. FIG.
7 is a graph showing the results of Fenton reaction analysis of Examples 1 to 6 and Comparative Example 1. FIG.
8 shows the SEM (Scanning Electron Microscopy) observation results of Example 7.
9 shows the SEM observation result of Example 8. FIG.
10 shows the results of X-ray diffraction (XRD) of Example 7.
11 shows the results of X-ray diffraction analysis of Example 8.
12 is a photograph for explaining the degree of dispersion of the particles over time after the ultrasonic treatment to the metal-containing nanoparticles of Examples 7 and 8.

Hereinafter, specific embodiments of the present invention will be described. However, this is only an example and the present invention is not limited thereto.

<Metal-containing nanoparticle manufacturing apparatus>

The present invention relates to an apparatus for producing metal-containing nanoparticles, an embodiment of the present invention is a plasma reactor including a body, an opening accommodated in the body, the metal precursor fluid is introduced, the end portion into the plasma reactor Including a plasma electrode and a cooling fluid supply portion is inserted to expose the distal end inside the body to circulate the cooling fluid, it is possible to easily circulate and cool the metal-containing nanoparticles to produce a high purity metal-containing nanoparticles The present invention relates to an apparatus for producing metal-containing nanoparticles, which is excellent in conversion rate and productivity to metal-containing nanoparticles.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Although the following describes preferred embodiments of the present invention, these embodiments are only illustrative of the present invention and are not intended to limit the scope of the appended claims, and various modifications to the embodiments within the scope and spirit of the present invention. Modifications and variations are apparent to those skilled in the art, and such variations and modifications are naturally within the scope of the appended claims.

On the other hand, in adding reference numerals to the components of each drawing, the same or similar reference numerals may be used for substantially the same components, even if shown on different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description may be omitted.

1 is a perspective view schematically showing a metal-containing nanoparticle manufacturing apparatus according to embodiments of the present invention.

Referring to FIG. 1, the metal-containing nanoparticle manufacturing apparatus includes a body 10, a plasma reactor 20, a plasma electrode 30, and a cooling fluid supply unit 40.

For example, a metal precursor aqueous solution or a metal precursor fluid may be introduced into the body 10 through the metal-containing nanoparticle manufacturing apparatus, and the metal precursor aqueous solution may be plasma discharged, cooled, and recovered in water to obtain metal-containing nanoparticles.

In the present specification, the metal-containing nanoparticles may be, for example, metal nanoparticles, metal oxide nanoparticles, metal-carrier composite particles, metal oxide-carrier composite particles, and the like, but are not limited thereto. .

The body 10 may accommodate the plasma reactor 20 and the like therein, and is not particularly limited as long as it can contain a fluid. However, as will be described later, when the plasma reactor 20 is connected to the body 10 through a grounding part to ground the aqueous solution inside the body 10, the body 10 may be formed of a conductive material.

The plasma reactor 20 is disposed inside the body 10 and includes an opening 22 into which the metal precursor fluid is introduced.

For example, the plasma reactor 20 may be provided as a reactor in which an underwater plasma discharge is performed. In some embodiments, the metal-containing nanoparticles may be manufactured by performing an underwater plasma discharge on the metal precursor fluid by the plasma electrode 30 in the plasma reactor 20.

In some embodiments, the plasma reactor 20 may include openings 22 at both ends as shown in FIG. 1, whereby metal precursors for the preparation of metal-containing nanoparticles introduced into the body 10 are provided. A fluid comprising a substance, a carrier and / or metal containing nanoparticles may flow into the plasma reactor 20 where an underwater plasma discharge is performed. The outflow direction F of the fluid may be as shown in FIG. 1, but is not limited thereto.

In some embodiments, the plasma reactor 20 may be fixed to the inner wall of the body 10 through the reactor fixture 24 as shown in FIG. 1. The shape, size, placement position, etc. of the reactor fixing part 24 may be used without any limitation as long as it does not interfere with the flow of the fluid flowing inside and / or outside the body 10 and / or the plasma reactor 20.

The shape, shape, etc. of the plasma reactor 20 are not particularly limited and may be appropriately designed such that the metal precursor material and the metal-containing nanoparticles can be easily circulated. For example, the plasma reactor 20 may be formed to reduce the reactor width along the ground direction as shown in FIG. 1 in terms of allowing the metal precursor and / or carrier to be uniformly reacted by an underwater plasma discharge. Can be.

As shown in FIG. 1, the plasma electrode 30 may expose a distal end of the plasma electrode. The insertion direction of the plasma electrode 30 is not particularly limited. In some embodiments it is inserted from the top or bottom of the device through an opening in the body 10 to penetrate the inlet and / or outlet of the body 10, or from the support 50 to the interior of the body 10, which will be described later. It may be formed to be inserted. In one embodiment, the plasma electrode 30 may be inserted to penetrate the side wall of the body 10 and the plasma reactor 20, as shown in FIG. 1, to expose the distal end of the plasma reactor 20. have.

For example, the plasma electrode 30 may receive power from an external power source such as a power supply unit (not shown) to cause plasma discharge in a metal precursor aqueous solution or the like.

Positive or negative charges may be constantly generated through the plasma electrode 30, and positive or negative charges may be alternately generated, but preferably negative charges may be generated. If negative charges are generated, the oxidation of the metal containing nanoparticles may be further reduced.

In some embodiments, the plasma electrode 30 may be fixed to the outer wall of the body 10 through the fixing parts 34 and 37.

The cooling fluid supply unit 40 may be inserted to expose the distal end inside the body 10 as shown in FIG. 1 to circulate the cooling fluid. The cooling fluid supply 40 can be, for example, a tube or pipe that can penetrate the sidewall of the plasma reactor 20.

Cooling fluid may be introduced and supplied into the body 10 through the cooling fluid supply 40, for example, the cooling fluid may be circulated in the body 10 and / or the plasma reactor 20. Accordingly, since the aqueous solution of the gold precursor, which may include the metal precursor, the metal-containing nanoparticles and / or the carrier, can be easily circulated and cooled, a marked improvement in manufacturing efficiency can be expected.

The cooling fluid is not particularly limited as long as it can form a cooling fluid flow in the body 10, and may be, for example, a cooling gas or cooling water. The cooling gas may be exemplified by, for example, an inert gas such as helium, neon, argon, air, oxygen, nitrogen, or a combination of two or more, but is not limited thereto. The temperature of the cooling fluid can be appropriately adjusted according to the process conditions, the type, amount, and the like of the reactant.

In some embodiments, the cooling gas supply 40 may include a plurality of cooling fluid supplies as shown in FIG. 1. Although four cooling fluid supplies are shown for convenience of description in FIG. 1, two or more cooling fluid supplies 40 may be included in the metal-containing nanoparticle manufacturing apparatus.

When the cooling fluid supply unit 40 is provided in plural, the amount of the cooling fluid bubble or the cooling fluid flow formed is increased, so that the circulation and cooling of the metal precursor and / or the metal-containing nanoparticles can be more effectively performed.

The arrangement position of the cooling fluid supply unit 40 is not particularly limited, and may be designed in consideration of process conditions, types of metal precursors, and the like. In some embodiments, the cooling fluid supply, as shown in FIG. 1, is disposed between the plasma reactor 20 and the support 50 supporting the bottom of the device or the body 10 to be described later to provide cooling fluid flow. Formation at the bottom of the device can accelerate the circulation and cooling of the metal precursor and / or the metal containing nanoparticles.

In some embodiments, the metal-containing nanoparticle manufacturing apparatus may further include a support 50 for supporting the body 10. For example, the support 50 is disposed on the bottom of the body 10 to support the body 10, the metal-containing nanoparticle manufacturing apparatus can perform a plasma reaction stably.

In one embodiment, the support 50 may further include a magnetic collector (60). For example, the magnetic collector 60 may be disposed below the plasma reactor 20.

The magnetic collecting unit 60 may be disposed at the lower end of the plasma reactor 20 to collect or collect the metal-containing nanoparticles obtained by the underwater plasma discharge. For example, the metal precursors in the metal precursor fluid may be synthesized into metal-containing nanoparticles, such as metal nanoparticles, metal oxide nanoparticles, or complexes of these and carriers, which are magnetic by an underwater plasma discharge. When the collecting unit 60 is disposed or attached to the bottom of the plasma reactor 20, the synthesis or aggregation of the metal-containing nanoparticles is stopped, and when the magnetic collecting unit 60 is separated from the plasma reactor 20, additional plasma discharge is performed. Continuing the synthesis of metal containing nanoparticles may be carried out. Accordingly, since the synthesis of the metal-containing nanoparticles can be controlled, the size of the metal-containing nanoparticles can be uniformly controlled or controlled. For example, the magnetic collector 60 may be changed according to the plasma treatment or the synthesis time of the metal-containing nanoparticles. Desorption can control the size of the particles and obtain metal-containing nanoparticles of the desired size.

For example, the magnetic collecting unit 60 may be detachable from the plasma reactor 20, and the size of the metal-containing nanoparticles may be uniformly increased by repeating the underwater plasma discharge and the detaching and detaching of the magnet.

The arrangement of the magnetic collector 60 into the plasma reactor 20 may include not only a case where the magnetic collector 60 is directly attached, but also a case where the metal-containing nanoparticles can be guided toward the magnetic collector 60 in a spaced manner. .

The magnetic collecting unit 60 is not particularly limited as long as it can easily collect magnetic-containing metal-containing nanoparticles, and may include, for example, a magnet, and specifically, may include an electromagnet or a permanent magnet.

In some embodiments, the metal-containing nanoparticle manufacturing apparatus may further include a ground (not shown). The ground portion is provided to be electrically connected to the fluid accommodated in the body 10. By grounding the fluid contained in the body 10, the potential of the fluid becomes zero.

Since the aqueous metal precursor solution used as the fluid is a material capable of energizing, the current applied to the plasma electrode 30 can flow through the ground portion electrically connected to the fluid.

The connection object of the ground portion is not particularly limited as long as it can ground the fluid, for example, when the body 10 is formed of a conductive material as described above may be electrically connected to the fluid by grounding the body 10 It may be formed by directly contacting the ground portion with the fluid.

2 is a plan view schematically illustrating an arrangement of a body 10, a plasma reactor 20, and a cooling fluid supply unit 40 included in an apparatus for manufacturing metal-containing nanoparticles according to some exemplary embodiments. For convenience of description, other components of the metal-containing nanoparticle manufacturing apparatus, for example, the plasma electrode 30, the support 50, the magnetic collector 60, and the like are omitted.

In some embodiments, the cooling fluid supply 40 may include a plurality of cooling fluid supplies 40 spirally disposed along the sidewall of the body 10. For example, as shown in FIG. 2, the plurality of cooling fluid supplies 40 are spirally disposed along the sidewall of the body 10 such that cooling fluid bubbles or flow of cooling fluid are transferred to the body 10 and / or the plasma reactor. It is formed in the (20) can be accelerated the cooling and circulation of the metal precursor and / or metal-containing nanoparticles can further improve the production efficiency of the metal-containing nanoparticles.

3 is a schematic perspective view of a plasma electrode 30 included in a metal-containing nanoparticle manufacturing apparatus according to some exemplary embodiments.

Referring to FIG. 3, the plasma electrode 30 according to some embodiments may include an electrode body 31, a first dielectric tube 32, and a discharge gas supply unit 33.

The electrode body 31 may receive power from an external power source such as a power supply unit (not shown) to cause plasma discharge. The electrode body 31 may be made of a metal material, for example, tungsten, molybdenum, titanium, stainless steel, or the like, but is not limited thereto.

As illustrated in FIG. 3, the first dielectric tube 32 may be provided to surround the electrode body 31 at the outside of the electrode body 31. For example, the first dielectric tube 32 may serve to protect the electrode body 31 or to protect the plasma generated by the electrode body 31, for example, the first dielectric tube 32. ) May surround the electrode body 31 such that the electrode body 31 protrudes a predetermined distance D from the end of the electrode body 31 (the side from which the plasma is emitted), so that the plasma formed by the electrode body 31 is formed in the first dielectric tube. It can be protected by (32).

In some embodiments, the first dielectric tube 32 may be a pipe that allows discharge gas to flow around the electrode body 31 as described below, for example the electrode body 31 and the first dielectric tube. The electrode body 31 may be wrapped so as to be spaced apart from the electrode body 31 by a predetermined distance so as to introduce a discharge gas therebetween.

The material of the first dielectric tube 32 is not particularly limited and may include, for example, alumina and / or quartz.

The discharge gas supply unit 33 may introduce a discharge gas between the electrode body 31 and the first dielectric tube 32. The discharge gas supply 33 may be, for example, a tube or a pipe passing through the first dielectric tube 32. Accordingly, plasma discharge in the metal precursor or the like may be caused by the discharge gas and the electrode body 31 introduced through the discharge gas supply unit 33 to form metal-containing nanoparticles.

The discharge gas introduced through the discharge gas supply unit 33 is not particularly limited, and may be, for example, an inert gas such as helium, neon, argon, air, oxygen, nitrogen, or a combination of two or more, but is not limited thereto. no.

In some embodiments, the plasma electrode 30 may further include a fixing part or a first fixing part 34 surrounding at least a portion of the first dielectric tube 32 and fixing the discharge gas supply part 33. have. The fixing part 34 may fix or protect the first dielectric tube and / or the discharge gas supply part 34, and when the plasma electrode 30 is inserted into the body 10 and / or the plasma reactor 20, the body ( 10 may serve to fix the plasma electrode 30 to the outer wall.

4 is a perspective view schematically illustrating a plasma electrode 30 included in an apparatus for manufacturing metal-containing nanoparticles according to some exemplary embodiments, and FIG. 5 is a perspective view of a shield fluid in the plasma electrode 30 shown in FIG. 4. A schematic plan view for explaining the flow.

4 and 5, the plasma electrode 30 included in the metal-containing nanoparticle manufacturing apparatus according to some embodiments includes the above-described electrode body 31, the first dielectric tube 32, and the discharge gas supply unit ( In addition to 33, the second dielectric tube 35 may further include a shield fluid supply 36.

The second dielectric tube 35 surrounds the first dielectric tube. The second dielectric tube 35 surrounds the first dielectric tube 32 and may protect the electrode body 31 and / or the first dielectric tube 32 and may protect the plasma formed from the electrode body 31. Can be.

In addition, the second dielectric tube 35 may be a tube or pipe for introducing a shielding fluid, which will be described later, between the first dielectric tube 32 and the second dielectric tube 34, for example, a second dielectric tube ( 35 may surround the first dielectric tube 32 to be spaced apart from the first dielectric tube 32 by a predetermined distance.

The shield gas supply 36 introduces a shield fluid between the first dielectric tube 32 and the second dielectric tube 35. For example, the distal end of the shield fluid supply 36 projects into the space between the first dielectric tube 32 and the second dielectric tube 35 so that the shield fluid can be introduced through the distal end of the shield fluid supply 36. Can be.

The shield fluid is supplied between the first dielectric tube 32 and the second dielectric tube 35 to assist plasma discharge by the electrode body 31 and to cool the electrode body 31. In addition, the shield fluid may form, for example, shield fluid bubbles or shield fluid flow, thereby further promoting circulation and cooling of metal precursors or metal-containing nanoparticles in the body 10 or the plasma reactor 20. Significant improvement in manufacturing efficiency can be expected. In addition, the shield fluid may serve to prevent the metal precursor and / or the metal-containing nanoparticles from entering the plasma electrode, thereby extending the life of the plasma electrode.

The kind of the shield fluid is not particularly limited, and for example, the shield fluid may be ozone (O ₃ ), oxygen (O ₂ ), nitrogen (N ₂ ), argon (Ar), helium (He), air (Air), or the like. Gas or combinations of two or more thereof.

In some embodiments, as shown in FIGS. 4 and 5, a plurality of shield fluid supplies 36 may be provided, and the plurality of shield fluid supplies 36 may include sidewalls of the second dielectric tube 35. As shown in FIG. 5, a bubble or a flow of the shield fluid is formed in a spiral direction, thereby cooling the electrode body 31 and promoting plasma reaction of the metal-containing nanoparticles. Can be further improved.

The inclination angle θ in the vertical cross section of the side wall of the shield fluid supply 36 and the second dielectric tube 35 is not particularly limited, and may be, for example, 30 to 60 degrees. When the inclination angle θ is in the above range, the particle circulating flow improving effect and the cooling effect of the metal precursor and / or the manufactured metal-containing nanoparticles according to the shield fluid flow through the shield fluid supply unit 36 may be further improved.

The shield fluid input direction of the shield fluid supply 36 to the second dielectric tube 35 is not particularly limited, and the shield fluid supply 36 further improves the degree of circulation of the metal precursor or the metal-containing nanoparticles. It is preferable to incline toward the distal end of the electrode 30 or the plasma reactor.

In some embodiments, the plasma electrode 30 further includes at least a portion of the second dielectric tube 35, and further an additional fixture / second fixture 37 that secures the shield fluid supply 36. Can be. The additional fixture / second fixture 37 may secure or protect the second dielectric tube 35 and / or the shield fluid supply 36, and connect the plasma electrode 30 to the body 10 and / or the plasma. When inserted into the reactor 20 may serve to fix the plasma electrode 30 to the outer wall of the body 10.

In some embodiments, as shown in FIG. 4, the fixture 37 may wrap at least a portion of the second dielectric tube 35 to secure both the shield fluid supply 36 and the discharge gas supply 34. have.

<Method for Producing Metal-Containing Nanoparticles>

In addition, the present invention provides a method for producing a metal-containing nanoparticles, specifically preparing a metal precursor aqueous solution comprising a solvent, a reducing agent and a metal precursor; Circulating a cooling fluid around the aqueous metal precursor solution and generating metal-containing nanoparticles from the aqueous metal precursor solution through an underwater plasma discharge, thereby providing productivity (mass productivity, high conversion rate, high purity), dispersibility and product It provides a method for producing a metal containing nanoparticles of high purity.

According to embodiments, first, a metal precursor aqueous solution is prepared, and the metal precursor aqueous solution may include a solvent, a reducing agent, and a metal precursor.

As used herein, "metal" is meant to encompass both metals and alloys of one or more metals, or metal oxides thereof.

The metal precursor may be any precursor known in the art as long as it is a precursor capable of obtaining a metal through an underwater plasma discharge described later. For example, the metal precursor may be a nickel precursor or an iron precursor.

Specifically, the nickel precursor is nickel chloride (NiCl ₂ ), nickel sulfate (NiSO ₄ ), nickel hydroxide (Ni (OH) ₂ ), nickel acetate (Ni (OCOCH ₃ ) ₂ ), nickel acetylacetonate (Ni (C ₅₎ H ₇ O ₂ ) ₂ ), nickel carbonate (NiCO ₃ ), nickel cyclohexanebutyrate ([C ₆ H ₁₁ (CH ₂ ) ₃ CO ₂ ] ₂ Ni), nickel nitrate (Ni (NO ₃ ) ₂ ), nickel oxal Rate (NiC ₂ O ₄ ), nickel stearate (Ni (H ₃ C (CH ₂ ) ₁₆ CO ₂ ) ₂ ), nickel octanoate ([CH ₃ (CH ₂ ) ₆ CO ₂ ] ₂ Ni), and the like. .

In addition, the iron precursors are ferric chloride (FeCl ₂ ), ferric chloride tetrahydrate (FeCl ₂ · 4H ₂ O), ferric chloride (FeCl ₃ ), ferric chloride hexahydrate (FeCl ₃ · 6H ₂ O), ferric fluoride ( FeF ₂ ), ferric fluoride tetrahydrate (FeF ₂ · 4H ₂ O), ferric nitrate ferric nitrate (Fe (NO ₃ ) ₃ · 9H ₂ O), ferric acetate (Fe (CH ₃ CO ₂ ) ₂ ), ferric bromide ( FeBr ₂ ), Ferric Iodide (FeI ₂ ), Ferric Iodide Tetrahydrate (FeI ₂ · 4H ₂ O), Ferric Pyrophosphate (Fe ₄ (P ₂ O ₇ ) ₃ · H ₂ O), Ferrous Sulfate Heptahydrate (FeSO ₄ 7H ₂ O), ferrous sulfide (FeS), ferrous metatitanate (FeTiO ₃ ), and the like.

In some embodiments, the metal precursor aqueous solution may further be synthesized by further including a carrier in terms of preparing metal-containing nanoparticles or composite particles having further improved stability and durability.

For example, the carrier may form a complex with the metal precursor described above to form a metal-carrier complex or a metal oxide-carrier complex, improve electrical and chemical stability, and improve stability even in a nano-sized structure. As the surface area of the particles increases, the reactivity can be further improved when used as a catalyst.

For example, the carrier may include graphene, graphene oxide, carbon nanotubes (CNTs), graphite, carbon fibers, activated carbon, and polymethyl (meth) acryl. It may include a polymer such as a rate, a non-magnetic metal such as copper (Cu) or a combination of two or more thereof, but is not limited thereto. For example, through underwater plasma discharge, the metal-containing nanoparticles made of the metal precursor described above may be combined with a support to improve the stability and durability of the metal-containing nanoparticles while having excellent magnetic properties.

The reducing agent functions to reduce the metal precursor.

The reducing agent can be used without limitation as long as it can reduce the metal precursor, but for example, hydrazine, hydrazine hydrate, hydrazine hydrochloride, sodium borohydride, NaBH ₄ ), Tetrabutyammonium borohydride (TBAB) ((CH ₃ CH ₂ CH ₂ CH ₂ ) ₄ N (BH ₄ )), Lithium Aluminum hydride (LiAlH ₄ ), Sodium Hydride (Sodium hydride, NaH), borane dimethylamine complex (Borane dimethylamine complex, (CH ₃ ) ₂ NH.BH ₃ ) and alkanediol, HO (CH ₂ ) _n OH (n is an integer of 5 to 30)) Can be.

The solvent may be used without any limitation as long as it is a solvent capable of performing an underwater plasma discharge described later. For example, the solvent may include at least one of water and an organic solvent. The organic solvent may be preferably alcohol-based, including polyol, and specifically, may be ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and the like.

Method for producing metal-containing nanoparticles according to embodiments includes circulating a cooling fluid around the metal precursor aqueous solution.

By circulating the cooling fluid around the aqueous metal precursor solution, the degree of circulation of the metal precursor or the metal-containing nanoparticles can be further improved, and cooling can be easily performed. In particular, after the plasma reaction, the metal-containing nanoparticles can By further comprising a cooling step, which may be oxidized, the oxidation of the metal-containing nanoparticles may be further reduced.

The cooling means may be used without any limitation as long as it is a means capable of cooling the fluid, but for example, the cooling fluid may be circulated in a body containing a plasma reactor in which the underwater plasma discharge is performed. Accordingly, since the cooling fluid is circulated around the plasma reactor, the metal-containing nanoparticles can be cooled quickly and uniformly. Specifically, the cooling fluid or cooling gas bubbles may be circulated around the plasma reactor 20 through the cooling fluid supply unit 30 of the metal-containing nanoparticle manufacturing apparatus illustrated in FIG. 1 to circulate and cool the metal-containing nanoparticles.

According to embodiments, the metal precursor aqueous solution is plasma discharged in water to obtain metal-containing nanoparticles.

The metal-containing nanoparticles may include metal nanoparticles, metal oxide nanoparticle metal-carrier composite particles, and / or metal oxide-carrier composite particles.

Since the method of manufacturing the metal-containing nanoparticles according to the embodiments is performed by plasma discharge in water, metal precursors, etc., which are not easily dissolved in water, may be easily dissolved to prepare particles. In addition, it is possible to efficiently synthesize a large amount of the metal-containing nanoparticles without using other chemicals used in the existing metal nanoparticle manufacturing method, it is possible to effectively prevent oxidation.

The underwater plasma discharge may be performed in a plasma reactor to which the aqueous metal precursor solution is supplied, for example, in the plasma reactor 20 of the above-described metal-containing nanoparticle manufacturing apparatus as shown in FIG. 1. have.

The underwater plasma discharge method may be, for example, various methods using conventional AC, DC, pulse, RF, microwave, and the like. The pulse supply may be, for example, by an apparatus including a pulse generator and a pulse discharge unit, and may adjust the particle size by adjusting the conditions of the plasma.

In addition, the underwater plasma discharge according to an embodiment of the present invention, for example, by applying a high voltage voltage to the electrode inserted in the water, to dissociate or ionize the water molecules around the electrode; An underwater plasma generation method for forming bubbles in water (optionally injecting bubbles into the water) and forming an electric field to discharge the bubbles in the bubbles; Raising the temperature of the surface of the electrode inserted in water to a boiling point to form bubbles on the surface of the electrode (bubble formation by Joule Heating in a narrow space in the electrode) and to discharge the bubbles; Pulse underwater plasma discharge method; Capillary plasma discharge method or the like.

In some embodiments, the method may further include sonicating the metal precursor aqueous solution after obtaining the metal-containing nanoparticles.

By further comprising the step of ultrasonication, it is possible to further improve the effect of the decrease in cohesion and increase in dispersibility between the metal-containing nanoparticles.

If the ultrasonic treatment method is to increase the dispersibility between the metal-containing nanoparticles, ultrasonic treatment methods known in the art can be used without particular limitation, and the type of ultrasonic generator, the region of the wavelength or the treatment time can be appropriately selected. Can be used.

In the method of manufacturing the metal-containing nanoparticles according to an embodiment, the metal precursor aqueous solution may be circulated to pass through the site where the plasma is generated.

Specifically, during the underwater plasma discharge, the metal precursor aqueous solution is exposed to the underwater plasma discharge while passing through the portion where the plasma is generated, and the metal precursor aqueous solution passing through the portion where the plasma is generated is circulated to pass through the portion where the plasma is generated The metal precursors included in the aqueous metal precursor solution may be uniformly exposed to the plasma.

Accordingly, the aqueous metal precursor solution is not limited to one-time but continuously exposed to the plasma discharge in water, it is possible to further improve the purity, productivity and economy of the metal-containing nanoparticles.

Method for producing a metal-containing nanoparticles according to an embodiment of the present invention may further comprise the step of recovering the metal-containing nanoparticles obtained by the plasma discharge in water.

Recovery methods known in the art may be used without particular limitation, for example, may be a filter using a filter, a method of collecting by using a magnetic.

In addition, the manufacturing method of the metal-containing nanoparticles according to an embodiment of the present invention may further include the step of obtaining the dried metal-containing nanoparticles by drying the recovered metal-containing nanoparticles in a non-oxidizing atmosphere after the recovery step. .

For example, the non-oxidizing atmosphere may be a vacuum, a reducing gas atmosphere, an inert gas atmosphere, or the like, and a nitrogen environment may be used as the inert gas atmosphere.

Method for producing a metal-containing nanoparticles according to an embodiment of the present invention may further comprise the step of controlling the size of the metal-containing nanoparticles using a magnet. For example, controlling the size of the metal containing nanoparticles may include coupling the metal containing nanoparticles to the magnet.

As used herein, "bonding" includes those in which the metal-containing nanoparticles are directly attached to the magnet or indirectly induced adjacent to the magnet.

For example, the metal precursors in the aforementioned aqueous metal precursor solution may be synthesized into metal-containing nanoparticles by an underwater plasma discharge, and the metal-containing nanoparticles may be magnetic particles, for example. Therefore, when magnets are approached to magnetic metal precursors and / or metal-containing nanoparticles after performing an underwater plasma discharge, continuous synthesis or aggregation of the metal precursors into metal-containing nanoparticles is interrupted, and the metal-containing nanoparticles It may be induced adjacent, or may be coupled or attached to a magnet. By controlling the synthesis of the metal-containing nanoparticles through this, it is possible to control or control the size of the metal-containing nanoparticles and to make the size of the metal-containing nanoparticles uniform.

In addition, by using the magnet to guide the metal-containing nanoparticles in the direction of the magnet or bonded to the magnet, it may be easy to recover or collect the metal-containing nanoparticles.

The magnetic metal-containing nanoparticles may be used without limitation as long as the metal-containing nanoparticles having magnetic properties can be magnetized through an underwater plasma discharge. Containing nanoparticles.

In addition, the magnetic metal precursor and / or metal-containing nanoparticles may be synthesized into metal-carrier composite particles or metal oxide-carrier composite particles by further including a carrier in addition to the metal precursor described above in terms of improving durability. . For example, the carrier may include graphene, graphene oxide, carbon nanotubes (CNTs), graphite, carbon fibers, activated carbon, and polymethyl (meth) acryl. It may include a polymer such as a rate, a non-magnetic metal such as copper, or a combination of two or more thereof, but is not limited thereto. For example, through underwater plasma discharge, metal-containing nanoparticles, such as the metal-carrier composite particles or metal oxide-carrier composite particles described above, have excellent magnetic properties and improve the stability and durability of the metal-containing nanoparticles, Excellent chemical stability.

In the method of manufacturing a metal-containing nanoparticles according to an embodiment, the metal precursor and the carrier are included in a metal precursor aqueous solution to prepare or synthesize metal-containing nanoparticles, such as metal-carrier composite particles, metal oxide-carrier composite particles In this case, in the aspect that the metal and the carrier can be easily combined to form the composite particles more easily, the ultrasonic treatment may be performed before performing the underwater plasma discharge.

In addition, the above-described magnet may be detachable from the reactor or the reaction site of the metal-containing nanoparticles, and the size of the metal-containing nanoparticles may be uniformly increased by repeating the plasma discharge and combining and separating the magnets two or more times. It may be.

In the method of manufacturing a metal-containing nanoparticles according to an embodiment, the underwater plasma discharge may include a first underwater plasma discharge and a second underwater plasma discharge, the step of coupling the metal-containing nanoparticles to the magnet is It may be performed between a first underwater plasma discharge and the second underwater plasma discharge.

The first underwater plasma discharge and the second underwater plasma discharge are terms used to express that the underwater plasma discharge is divided into two or more different steps, and the present invention relates to the third underwater plasma discharge and the fourth underwater plasma discharge. The discharge or more underwater plasma discharges may be performed as a continuously separated step.

Coupling the metal-containing nanoparticles to the magnet may be performed between the first underwater plasma discharge and the second underwater plasma discharge to facilitate size control of the metal-containing nanoparticles, and to stably and uniformly contain metal. The size of the nanoparticles can be increased.

For example, when the metal-containing nanoparticles are bonded to the magnet after the first underwater plasma discharge is performed, the size of the metal-containing nanoparticles can be controlled uniformly, and then the metal is carried out as the second underwater plasma discharge is performed. The containing nanoparticles can be continuously synthesized to increase the size to a uniform degree.

For example, in the method of manufacturing the metal-containing nanoparticles according to one embodiment, after the step of coupling the metal-containing nanoparticles to the magnet, separating the metal-containing nanoparticles from the magnet and further metal precursor The method may further include adding to the aqueous metal precursor solution.

When the metal-containing nanoparticles and the magnet are separated, the continuous synthesis or aggregation of the metal-containing nanoparticles by an underwater plasma discharge may be continued. For example, the method of preparing the metal-containing nanoparticles according to the embodiment may be the addition. The second underwater plasma discharge may be performed after the step of adding a metal precursor, whereby the metal-containing nanoparticles formed by the first underwater plasma discharge and the additional metal precursor are synthesized or aggregated to uniformly increase in size and control. Obtained metal-containing nanoparticles can be obtained.

The additional metal precursor may be used without limitation the aforementioned metal precursor.

The above-described method is for active materials of secondary batteries requiring metal-containing nanoparticles to have a uniform size, for filter particles in air cleaners, for water treatment purification, for multi-layer ceramic capacitor (MLCC) particles, and magnetic devices. For electronic devices such as magnetic sensors, magnetic resonance imaging (MRI), ferflufluid, spin electronics, or catalysts for environmental parts such as water purification and air purification, solar cell particles, fuel cell particles, electromagnetic shielding Particularly preferably, the particles can be used.

Underwater plasma  Discharge System for Discharge>

The apparatus for producing metal-containing nanoparticles of the present invention described above may further include, without limitation, a discharge system for underwater plasma discharge known in the art for underwater plasma discharge of the present invention.

For example, the pulse power supply system as an embodiment for underwater plasma discharge of the present invention may include a power supply unit, a voltage amplifier, a pulse circuit unit and a pulse discharge unit. For a detailed description thereof, the contents of Korean Patent Laid-Open No. 2012-0136884 are used.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Experimental Example  One

One. Example  1 to 6 and Comparative example  One

To prepare a metal precursor aqueous solution having the composition and content shown in Table 1. The aqueous metal precursor solution was put into a reactor as shown in FIG. 1, while 20 ° C. air was introduced at a rate of 15 lpm from the shield fluid supply part of the plasma electrode, and oxygen gas was introduced at a rate of 8 pm from the discharge gas supply part. Submerged plasma treatment for 5 minutes Fe ₃ O ₄ nanoparticles (Example 1), Fe ₃ O ₄ -graphene oxide (GO) composite particles (Examples 2 to 6), graphene oxide (GO) particles ( Comparative Example 1) was prepared.

division Metal precursor reducing agent menstruum Support ingredient content
(g) ingredient content
(mL) ingredient content
(mL) ingredient content
(mg) Example 1
(Fe ₃ O ₄ ) FeCl ₂ 0.5 Hydrazine 20 Ultrapure water
(Deionized water) 150 - - Example 2
(Fe ₃ O ₄ + GO (25 wt%)) FeCl ₂ 0.5 Hydrazine 20 Ultrapure water 150 Graphene oxide
(Graphene oxide, GO) 0.55 Example 3
(Fe ₃ O ₄ + GO (20 wt%)) FeCl ₂ 0.5 Hydrazine 20 Ultrapure water 150 Graphene oxide 0.44 Example 4
(Fe ₃ O ₄ + GO (15 wt%)) FeCl ₂ 0.5 Hydrazine 20 Ultrapure water 150 Graphene oxide 0.33 Example 5
(Fe ₃ O ₄ + GO (10 wt%)) FeCl ₂ 0.5 Hydrazine 20 Ultrapure water 150 Graphene oxide 0.22 Example 6
(Fe ₃ O ₄ + GO (5 wt%)) FeCl ₂ 0.5 Hydrazine 20 Ultrapure water 150 Graphene oxide 0.11 Comparative Example 1
(GO) - - Hydrazine 20 Ultrapure water 150 Graphene oxide 2,200

2. Experimental Example

The average particle diameter (D ₅₀ ), conversion (%), dispersibility, and fenton reaction results of the prepared nanoparticles were measured and described in Table 2, respectively.

(1) dispersibility evaluation

Each of the prepared aqueous samples containing the nanoparticles of Examples 1 to 6 and Comparative Example 1 were stirred to sufficiently disperse the nanoparticles, and then left to measure the time for all the nanoparticles to precipitate.

Set the dispersibility of the sample with the longest time to settle all the nanoparticles (hereinafter, settling time) to 100%, and calculate the relative ratio of the settling time of the remaining samples as the dispersibility of the remaining samples based on the settling time. It was.

(2) XPS  Measure

X-ray Photoelectron Spectroscopy (XPS) was measured on the nanoparticles of the prepared examples and the results are shown in FIG. 6.

(3) Fenton  Response evaluation

Hydrogen peroxide (H ₂ O ₂ ) was added to the prepared nanoparticles of Examples and Comparative Examples to measure the decomposition rate of Acid Orange 7 according to Equation 1 below, and the results are shown in FIG. 7. Table 2 shows the decomposition rate of Acid Orange 7 after 180 minutes.

[Equation 1]

% Decomposition = (1-C / C ₀ ) × 100

(C ₀ : initial amount of Acid Orange 7, C: amount of Acid Orange 7 after a certain time)

division Average particle size (D ₅₀ ) % Conversion Dispersibility Fenton Response Assessment Example 1
(Fe ₃ O ₄ ) 25.0 nm 100 100 78 Example 2
(Fe ₃ O ₄ + GO (25 wt%)) 42.0mm 100 71 62 Example 3
(Fe ₃ O ₄ + GO (20 wt%)) 41.2 nm 100 73 88 Example 4
(Fe ₃ O ₄ + GO (15 wt%)) 40.5 nm 100 75 92 Example 5
(Fe ₃ O ₄ + GO (10 wt%)) 39.7 nm 100 76 95 Example 6
(Fe ₃ O ₄ + GO (5 wt%)) 39.1 nm 100 78 100 Comparative Example 1
(GO) 33.2 nm 100 85 12

Referring to the experimental results, it can be seen that the metal-containing nanoparticles of the examples have an average particle size of nano-size, and also excellent dispersibility.

In addition, referring to Figure 6 it was confirmed that the metal-containing nanoparticles of the examples are uniformly produced to an excellent level, the conversion rate is also excellent. In addition, referring to Figure 7, it can be confirmed that Fe ₃ O ₄ (Example 1) or Fe ₃ O ₄ -GO composite particles (Examples 2 to 6) have a good level of decomposition rate for the dye, such as leachate or dyeing wastewater It can be seen that it can be easily applied to the processing of.

Experimental Example  2

1. Examples 7 and 8

(1) Example 7

In the metal-containing nanoparticle of Example 7, a metal precursor aqueous solution containing 20 g of NiCl ₂ , 1,000 mL of ultrapure water, and 20 mL of hydrazine was placed in a reactor as shown in FIG. 1, and air at 20 ° C. was supplied from the shield fluid supply of the plasma electrode. At a rate of 1 pm, nitrogen gas was introduced at a rate of 8 pm from the discharge gas supply unit. A magnet was installed on the upper part of the support and the lower part of the plasma reactor. After performing the plasma treatment in water for 10 minutes, the nickel nanoparticles attached to the magnet were collected separately.

(2) Example 8

Metal-containing nanoparticles were prepared in the same manner as in Example 7, except that no magnet was used.

2. Experimental Example

(1) SEM observation

Scanning electron microscopy (SEM) observation of the metal-containing nanoparticles of Examples 7 and 8 shows SEM observation results of Example 7 in FIG. 8, and SEM observation results of Example 8 is shown in FIG. 9.

(2) XRD analysis

X-ray diffraction analysis (XRD) of the metal-containing nanoparticles of Examples 7 and 8 was measured, and the results of Example 7 are shown in FIG. 10 and the results of Example 8 are shown in FIG. 11.

(3) evaluation of dispersibility through ultrasonic treatment

After ultrasonic treatment of the metal-containing nanoparticles of Examples 7 and 8, the dispersibility of the nanoparticles over time was visually evaluated. The result is shown in FIG.

Referring to FIGS. 8 and 10, the particles of Example 7 prepared using the magnetic collector were prepared with metal particles containing nanoparticles having a uniform average size and a high purity of about 18.1 nm with an average particle size (FWHM). You can see that.

9 and 11, the particles of Example 8 without using the magnetic collector were about 83.69 nm in average size of the particles evaluated at full width at half maximum, and thus, the particles were slightly larger than those in Example 7.

Referring to FIG. 12, even after 2 hours of sonication, the particles of Example 7, which were small in size and uniform, had excellent dispersibility. However, the particles of Example 8 were found to have somewhat lowered dispersibility.

10 body 20 plasma reactor
30: plasma electrode 31: electrode body
32: first dielectric tube 33: discharge gas supply unit
34: fixing part / first fixing part 35: second dielectric tube
36: shield fluid supply part 37: additional fixing part / second fixing part
40: cooling fluid supply 50: support
60: magnetic collector θ: inclination angle
F: flow direction of fluid

Claims (22)

Body;
A plasma reactor received inside the body and including an opening into which a metal precursor fluid is introduced;
A plasma electrode exposed at an end portion of the plasma reactor; And
And a cooling fluid supply part inserted to expose the distal end inside the body to circulate the cooling fluid.
The plasma electrode includes an electrode body, a first dielectric tube surrounding the electrode body, and a discharge gas supply unit for introducing a discharge gas between the electrode body and the first dielectric tube, metal-containing nanoparticle manufacturing apparatus.
The method of claim 1, further comprising a support for supporting the body,
And the cooling fluid supply unit is disposed between the support and the plasma reactor.
The apparatus of claim 1, wherein the cooling fluid supply part comprises a plurality of cooling fluid supply parts spirally disposed along a side wall of the body.
delete The apparatus of claim 1, wherein the plasma electrode further comprises a fixing part surrounding at least a portion of the first dielectric tube and fixing the discharge gas supply part.
The metal-containing nanostructure of claim 1, wherein the plasma electrode further comprises a second dielectric tube surrounding the first dielectric tube, and a shield fluid supply for introducing a shield fluid between the first dielectric tube and the second dielectric tube. Particle production apparatus.
The apparatus of claim 6, wherein the shield fluid supply includes a plurality of shield fluid supplies disposed spirally along sidewalls of the second dielectric tube.
The apparatus of claim 6, wherein the inclination angle in the vertical cross section of the side wall of the shield fluid supply and the second dielectric tube is 30 to 60 °.
The apparatus of claim 6, wherein the distal end of the shield fluid supply portion projects into the space between the first dielectric tube and the second dielectric tube.
7. The apparatus of claim 6, wherein the plasma electrode further comprises an additional fixture surrounding at least a portion of the second dielectric tube and securing the shield fluid supply.
The apparatus of claim 1, further comprising a magnetic collector disposed under the plasma reactor.
The apparatus of claim 11, wherein the magnetic collecting part comprises an electromagnet or a permanent magnet.
Preparing a metal precursor aqueous solution including a solvent, a reducing agent, and a metal precursor;
Circulating a cooling fluid around the metal precursor aqueous solution;
Generating metal-containing nanoparticles from the metal precursor aqueous solution through an underwater plasma discharge; And
Bonding the metal-containing nanoparticles to a magnet;
The underwater plasma discharge includes a first underwater plasma discharge and a second underwater plasma discharge, and the coupling of the metal containing nanoparticles to the magnet is performed between the first underwater plasma discharge and the second underwater plasma discharge. , Method for producing metal-containing nanoparticles.
The method of claim 13, wherein circulating the cooling fluid is performed in the body,
The underwater plasma discharge is performed in a plasma reactor to which the metal precursor aqueous solution is supplied.
delete delete delete The method of claim 13, further comprising, after the step of coupling the metal containing nanoparticles to the magnet, separating the metal containing nanoparticles from the magnet; And adding an additional metal precursor to the aqueous metal precursor solution.
The method of claim 18, wherein the second underwater plasma discharge is performed after adding the additional metal precursor.
The method of claim 13, wherein the aqueous metal precursor solution further comprises a carrier.
The method of claim 20, wherein the carrier is graphene, graphene oxide, carbon nanotubes (CNTs), graphite, carbon fibers, activated carbon, and polymethyl (meth). Method for producing a metal-containing nanoparticles, including at least one selected from the group consisting of acrylate.
The method of claim 13, wherein the metal-containing nanoparticles are selected from the group consisting of metal nanoparticles, metal oxide nanoparticles, metal-carrier composite particles, and metal oxide-carrier composite particles.

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