CN106457403B - Preparation method of hollow metal nanoparticles - Google Patents

Preparation method of hollow metal nanoparticles Download PDF

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CN106457403B
CN106457403B CN201580030407.1A CN201580030407A CN106457403B CN 106457403 B CN106457403 B CN 106457403B CN 201580030407 A CN201580030407 A CN 201580030407A CN 106457403 B CN106457403 B CN 106457403B
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hollow
metal
nanoparticles
metal nanoparticles
hollow metal
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CN106457403A (en
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金洸贤
金相勋
黃教贤
赵俊衍
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LG Chem Ltd
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LG Chem 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
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds

Abstract

The present invention relates to a method for preparing hollow metal nanoparticles and hollow metal nanoparticles prepared thereby, and more particularly, to a method for preparing hollow metal nanoparticles including the steps of: preparing a solution comprising a first metal salt, a second metal salt, a stabilizer, and a solvent; and mixing the solution with a reducing agent to form hollow metal nanoparticles. The hollow metal nanoparticles prepared by the preparation method of the present invention have a very small size and a large specific surface area compared to conventional nanoparticles, and thus, can exhibit more excellent activity than conventional nanoparticles, and can be used in various fields, such as drug delivery vehicles and gas sensors.

Description

Preparation method of hollow metal nanoparticles
Technical Field
This application claims priority and benefit from korean patent application No.10-2014-0072464 filed in korean intellectual property office on 13.6.2014, which is incorporated by reference in its entirety.
The present application relates to a method for preparing hollow metal nanoparticles, and hollow metal nanoparticles prepared thereby.
Background
Nanoparticles are particles having a nano-scale particle size, and exhibit optical, electrical and magnetic characteristics completely different from those of bulk substances due to a large specific surface area and a quantum confinement effect in which energy required for electron transfer varies according to the size of the substance. Therefore, due to these characteristics, attention is focused on their applications in the fields of catalysts, electromagnetism, optics, medicines, and the like. Nanoparticles can be considered as intermediate states between bulk and molecule, and can be synthesized in two ways, namely, the "top-down" method and the "bottom-up" method.
Examples of the method of synthesizing metal nanoparticles include a method of reducing metal ions in a solution using a reducing agent, a method of synthesizing metal nanoparticles using gamma rays, an electrochemical method, and the like, but in the existing methods, it is difficult to synthesize nanoparticles having uniform size and shape, or economically mass-produce high-quality nanoparticles due to various reasons such as environmental pollution, high cost, and the like caused by the use of organic solvents.
Meanwhile, in order to prepare hollow metal nanoparticles of the related art, hollow metal nanoparticles have been prepared by the following method: particles having a low reduction potential, such as Ag, Cu, Co and Ni, are synthesized, the surfaces of the particles are replaced with a metal having a higher reduction potential, such as Pt, Pd or Au, than the particles, such as Ag, Cu, Co and Ni, by a potential difference replacement method, and Ag, Cu, Co, Ni and the like remaining inside the particles are dissolved by an acid treatment after the surface replacement. At this time, there is a problem in the process that post-treatment with acid is required, and since the potential difference replacement method is a natural reaction, several factors need to be controlled, and thus it is difficult to prepare uniform particles.
Further, when hollow metal nanoparticles are prepared without being supported on carbon, there are problems in that the shape of the particles is irregular and the size of the particles is large. Therefore, there is a need to develop a simpler method that can prepare uniform hollow metal nanoparticles having a smaller particle size.
Disclosure of Invention
Technical problem
The present application seeks to provide a method for preparing hollow metal nanoparticles, which does not cause environmental pollution and enables easy mass production of hollow metal nanoparticles at a low cost.
Further, the present application seeks to provide a hollow metal nanoparticle prepared by the preparation method.
The problems to be solved by the present application are not limited to the above technical problems, and other technical problems not mentioned may be obviously understood by those of ordinary skill in the art from the following description.
Technical scheme
An exemplary embodiment of the present application provides a method of preparing hollow metal nanoparticles, the method including: preparing a solution comprising a first metal salt, a second metal salt, a stabilizer, and a solvent; and mixing the solution with a reducing agent to form hollow metal nanoparticles.
Another exemplary embodiment of the present application provides a hollow metal nanoparticle prepared by the preparation method.
Advantageous effects
When hollow metal nanoparticles are prepared by the preparation method according to one exemplary embodiment of the present application, there are advantages in that hollow metal nanoparticles having a uniform size of several nanometers can be produced on a large scale, with the effect of reducing costs, the process is simple because a surfactant is not used, and environmental pollution is not generated because an organic solvent is not used in the preparation process.
Drawings
FIG. 1 shows a Transmission Electron Microscope (TEM) image of hollow metal nanoparticles prepared according to Experimental example 1;
FIG. 2 shows a Transmission Electron Microscope (TEM) image of hollow metal nanoparticles prepared according to Experimental example 2;
FIG. 3 shows a Transmission Electron Microscope (TEM) image of nanoparticles prepared according to Experimental example 3;
FIG. 4 shows a Transmission Electron Microscope (TEM) image of hollow metal nanoparticles prepared according to Experimental example 4;
FIG. 5 shows a Transmission Electron Microscope (TEM) image of hollow metallic nanoparticles prepared according to Experimental example 5;
FIG. 6 shows a Transmission Electron Microscopy (TEM) image of nanoparticles prepared according to Experimental example 6;
FIG. 7 shows a Transmission Electron Microscopy (TEM) image of nanoparticles prepared according to Experimental example 7;
fig. 8 shows a Transmission Electron Microscope (TEM) image of nanoparticles prepared according to experimental example 8.
Detailed Description
The benefits and features of the present application, and methods of accomplishing the same, will become apparent by reference to the exemplary embodiments and the accompanying drawings, which are described in detail below. However, the present application is not limited to the exemplary embodiments disclosed below, but may be embodied in various other forms and are provided for making the disclosure of the present application complete and for fully indicating the scope of the present invention to those skilled in the art to which the present application pertains, and the present application is limited only by the scope of the claims. The dimensions and relative dimensions of the elements shown in the figures may be exaggerated for clarity of illustration.
Unless otherwise specified, all terms including technical and scientific terms used in the present specification can be used in the meaning that can be commonly understood by one of ordinary skill in the art to which this application belongs. Furthermore, terms defined in commonly used dictionaries should not be interpreted ideally or excessively unless the terms are clearly and specifically defined.
Hereinafter, the present application will be described in more detail.
In the present specification, the term "hollow" means that the core portion of the hollow metal nanoparticle is empty. Furthermore, the term "hollow" may also be used in the same sense as a hollow core. The term "hollow" includes terms such as hollow, void, and porous. The hollow may include a space in which no internal substance exists, by 50% by volume or more, specifically 70% by volume or more, more specifically 80% by volume or more. Alternatively, the hollow may include a space whose interior is empty by 50% by volume or more, specifically 70% by volume or more, more specifically 80% by volume or more. Alternatively, the hollow comprises a space having an internal porosity of 50% by volume or more, specifically 70% by volume or more, more specifically 80% by volume or more.
A preparation method according to an exemplary embodiment of the present application includes: preparing a solution comprising a first metal salt, a second metal salt, a stabilizer, and a solvent; and mixing the solution with a reducing agent to form hollow metal nanoparticles.
According to an exemplary embodiment of the present application, the mixing of the solution with the reducing agent may include adding the reducing agent to the solution.
In an exemplary embodiment of the present application, the preparation method may use 0.1 mol% or less of a surfactant based on the first metal salt.
In an exemplary embodiment of the present application, in the preparation method, the content of the surfactant may be 0 mol% based on the first metal salt.
In an exemplary embodiment of the present application, the preparation method may not use a surfactant. The preparation method does not use a surfactant and thus has an effect of reducing costs, and thus, the preparation method is also advantageous in terms of mass production and eco-friendly processes. When a surfactant is used, the surfactant is adjacent to metal ions, and thus surrounds the surface of the particles or even remains inside the hollow, and therefore, there is a problem in that reactants do not easily approach the particles when nanoparticles are used in a catalytic reaction. Therefore, a post-treatment for removing the surfactant is required. Therefore, when a surfactant is not used according to an exemplary embodiment of the present application, there are advantages in that the preparation method becomes simple and has an effect of reducing costs, so that the case is advantageous for mass production.
In an exemplary embodiment of the present application, the first metal salt or the second metal salt may be ionized in a solution to provide a metal ion or radical ion comprising a metal ion. The first metal salt may include a first metal and the second metal salt may include a second metal. Here, the first metal and the second metal may be different from each other.
Here, the first metal and the second metal are different from each other, and may be selected from metals belonging to groups 3 to 15 of the periodic table, metalloids, lanthanoid metals, and actinide metals.
In one exemplary embodiment of the present application, the first metal may be specifically at least one selected from the group consisting of platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), gold (Au), cerium (Ce), silver (Ag), and copper (Cu). More specifically, the first metal may be selected from ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), cerium (Ce), and copper (Cu), and even more specifically, may be nickel (Ni).
In an exemplary embodiment of the present application, the second metal is different from the first metal, and may specifically be one selected from the group consisting of platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), gold (Au), cerium (Ce), silver (Ag), and copper (Cu). More specifically, the second metal may be selected from platinum (Pt), palladium (Pd), silver (Ag), and gold (Au), and even more specifically, may be platinum (Pt).
In an exemplary embodiment of the present application, the first metal salt may be represented by the following chemical formula 1, and the second metal salt may be represented by the following chemical formula 2.
[ chemical formula 1]
XAm
[ chemical formula 2]
BpYCq
In chemical formula 1 or chemical formula 2, X and Y may each independently be an ion of a metal selected from the group consisting of metals belonging to groups 3 to 15 of the periodic table, metalloids, lanthanoids, and actinides.
In chemical formula 1, X may be specifically an ion of a metal selected from the group consisting of platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), gold (Au), cerium (Ce), silver (Ag), and copper (Cu), more specifically, may be an ion of a metal selected from ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), cerium (Ce), and copper (Cu), and even more specifically, may be an ion of nickel (Ni).
In chemical formula 2, Y is different from X, and may be an ion of a metal selected from platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), gold (Au), cerium (Ce), silver (Ag), and copper (Cu), more specifically, may be an ion of a metal selected from platinum (Pt), gold (Au), silver (Ag), and palladium (Pd), even more specifically, may be an ion of platinum (Pt).
In chemical formula 1 or chemical formula 2, a and C may each independently be a monovalent anionic ligand, and in particular, may each independently be selected from NO3 -、NO2 -、OH-、F-、Cl-、Br-And I-The ligand of (1).
In chemical formula 2, B may be an ion of an element belonging to group 1 of the periodic table, and may be selected from H+、K+、Na+And NH3 +The ion of (2).
In chemical formula 1 or chemical formula 2, m may be 2 or 3, p may be 0, 2 or 4, and q may be 2, 4 or 6. The first metal salt may specifically be NiCl2、CoCl2、Ni(NO3)2、Pd(NO3)2Or RuCl3The second metal salt may specifically be K2PtCl4Or K2PtCl6。
For example, the first metal salt may provide Ni2+Cation, second metal salt can provide PtCl4 2-Anions, thus Ni2+Cation and PtCl4 2-The anions may together form a shell portion of the hollow metallic nanoparticle.
In an exemplary embodiment of the present application, the molar ratio of the first metal salt to the second metal salt may be 1:5 to 10:1, specifically, 2:1 to 5: 1. When the molar ratio is within this range, it is preferable that the molar ratio forms the shell of the hollow metal nanoparticles.
In an exemplary embodiment of the present application, the solvent dissolves the first metal salt and the second metal salt, and particularly, the solvent may include water.
In an exemplary embodiment of the present application, the solvent may be water. At this time, since the present invention does not use an organic solvent as a solvent, a post-treatment process for treating the organic solvent is not required in the preparation process, having effects of reducing costs and preventing environmental pollution.
In an exemplary embodiment of the present application, the formation of the solution may be performed at a temperature of above 4 ℃ and below 100 ℃. In particular, the step may be carried out at a temperature of 4 ℃ to 80 ℃. If an organic solvent is used as the solvent, there is a problem in that the preparation must be performed at a high temperature exceeding 100 ℃, and thus, the cost in the process is increased. When the preparation method according to one embodiment of the present application is used, the preparation method is simple because the preparation can be performed at a low temperature of less than 100 ℃, and thus, the process has advantages and has a significant effect of reducing costs.
In an exemplary embodiment of the present application, the forming of the solution may be performed for 5 minutes to 120 minutes, more specifically, 10 minutes to 90 minutes, even more specifically, 20 minutes to 60 minutes.
In an exemplary embodiment of the present application, the rate of mixing the solution and the reducing agent may be greater than 0.1 ml/h. The mixing may be at a rate of adding the reducing agent to the solution.
For example, fig. 1 to 3 show Transmission Electron Microscope (TEM) images of hollow metal nanoparticles prepared according to experimental examples 1 to 3. It was confirmed that the nanoparticles of fig. 3 according to experimental example 3 (setting the rate of addition of the reducing agent to 0.1ml/h) were difficult to form hollows. In contrast, with the nanoparticles of FIGS. 1 and 2 according to Experimental examples 1 and 2, in which the rates of adding the reducing agent were set to 400ml/h and 100ml/h, respectively, it was confirmed that the hollows were uniformly formed.
In one exemplary embodiment of the present application, the reducing agent is not particularly limited as long as the reducing agent is a strong reducing agent having a standard reduction potential of-0.23V or less, specifically-4V to-0.23V, and has a reducing power that can reduce dissolved metal ions to precipitate as metal particles.
For example, the reducing agent may be selected from NaBH4、NH2NH2、LiAlH4And LiBEt3One or two or more of H.
When weak reducing agents are used, the reaction speed is slow and subsequent heating of the solution is required, making it difficult to achieve a continuous process, and thus there may be a problem in mass production, particularly, when ethylene glycol, which is one of weak reducing agents, is used, in that productivity is low in the continuous process due to a decrease in flow rate due to high viscosity.
In an exemplary embodiment of the present application, the stabilizer may include one or two or more selected from the group consisting of disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium citrate, and trisodium citrate.
The content of the stabilizer may be 3 times or more and less than 30 times, specifically 5 times to 25 times, more specifically 10 times to 25 times, in molar units, that of the first metal salt or the second metal salt. When the content of the stabilizer is within the above range, the hollow metal nanoparticles may be uniformly formed.
The stabilizer within the range is preferably used because it is difficult to form hollow metal nanoparticles when the stabilizer is not used, and the first metal salt and the second metal salt may aggregate with each other to form amorphous particles.
In an exemplary embodiment of the present application, when the average particle diameter of the hollow metallic nanoparticles is defined as 100%, the particle diameter including each of the hollow metallic nanoparticles may be in a range of 80% to 120%. That is, the particle diameter of the hollow metal nanoparticles may be in the range of 80% to 120% of the average particle diameter of the hollow metal nanoparticles. When the particle diameter is outside the above range, the size of the hollow metallic nanoparticles becomes nonuniform as a whole, and thus it may be difficult to secure unique physical property values required for the hollow metallic nanoparticles. For example, when hollow metal nanoparticles having a particle diameter outside the range are used as a catalyst for a fuel cell, the effect of improving the efficiency of the fuel cell may be somewhat undesirable.
In an exemplary embodiment of the present application, the mixing of the solution with the reducing agent to form the hollow metal nanoparticles may be performed at a temperature ranging from 4 ℃ or more to less than 100 ℃. In particular, the step may be carried out at a temperature of 4 ℃ to 80 ℃. Since the preparation can be performed at a low temperature of less than 100 ℃, the present application is advantageous in terms of processes due to a simple preparation method, and has a significant effect of reducing costs.
For example, fig. 1, 4 and 5 show Transmission Electron Microscope (TEM) images of hollow metal nanoparticles prepared according to experimental examples 1, 4 and 5.
The nanoparticles in fig. 1, 4 and 5 were prepared at temperatures of 14 c, 25 c and 60 c, respectively, and it was confirmed that the hollow was uniformly formed under all the temperature conditions.
In an exemplary embodiment of the present application, the formation of the hollow metal nanoparticles may be performed for 5 minutes to 120 minutes, more specifically, 10 minutes to 90 minutes, even more specifically, 20 minutes to 60 minutes.
The preparation method according to an exemplary embodiment of the present application may further include centrifuging the solution including the hollow metallic nanoparticles in order to precipitate the hollow metallic nanoparticles included in the solution after the formation of the hollow metallic nanoparticles. Only the hollow metal nanoparticles separated after centrifugation may be collected. The step of sintering the hollow metal nanoparticles may be additionally performed, if necessary.
According to an exemplary embodiment of the present application, hollow metal nanoparticles having a uniform size of several nanometers may be prepared. With the prior art method, it is difficult to prepare hollow metal nanoparticles having a size of several nanometers, and it is more difficult to prepare hollow metal nanoparticles having a uniform size, however, with the preparation method of the present application, there is an advantage in that uniform hollow metal nanoparticles having a size of several nanometers can be simply prepared.
The average particle diameter of the hollow metal nanoparticles prepared according to an exemplary embodiment of the present application may be 30nm or less, 20nm or less, 10nm or less, and 6nm or less. The average particle diameter may be 1nm or more.
In the hollow metal nanoparticle, the thickness of the shell portion may be greater than 0nm and less than 5nm, greater than 0nm and less than 3nm, greater than 0nm and less than 1 nm.
According to an exemplary embodiment of the present application, it is difficult to form hollow metal nanoparticles having an average particle diameter of less than 1nm, and when the particle diameter of the hollow metal nanoparticles is below 30nm, there is a great advantage in that the nanoparticles can be used in various fields. Further, the particle diameter of the hollow metal nanoparticles is more preferably 20nm or less, 10nm or less, and 6nm or less. For example, when the formed hollow metal nanoparticles are used as a catalyst of a fuel cell, the efficiency of the fuel cell can be significantly improved.
An exemplary embodiment of the present application provides a hollow metal nanoparticle prepared by the preparation method.
The hollow metal nanoparticles prepared according to an exemplary embodiment of the present application may have a spherical shape.
The hollow metal nanoparticles according to an exemplary embodiment of the present application may be a hollow metal nanoparticle including a hollow core; and at least one hollow metallic nanoparticle comprising a shell of a first metal and/or a second metal.
In an exemplary embodiment of the present application, the shell may be present in at least one region of the hollow exterior, and may also be present over the entire surface of the hollow exterior. When the shell is present in some areas outside the hollow, the shell may also be present in the form of a discontinuous surface.
In an exemplary embodiment of the present application, the shell may also be a single layer, and may also be two or more layers.
In an exemplary embodiment of the present application, when the shell is a single layer, the shell may be present in a form in which the first metal and the second metal are mixed. At this time, the first metal and the second metal may also be uniformly or non-uniformly mixed.
In an exemplary embodiment of the present application, when the shell is a single layer, the atomic percentage ratio of the first metal and the second metal may be 1:5 to 10: 1.
In an exemplary embodiment of the present application, when the shell is a single layer, the shell may exist in a state in which the first metal and the second metal are present in a gradient, the first metal may be present in an amount of 50 vol% or more or 70 vol% or more in a portion contacting the hollow core in the shell, and the second metal may be present in an amount of 50 vol% or more or 70 vol% or more in a surface portion contacting the outside of the nanoparticle in the shell.
In an exemplary embodiment of the present application, when the shell is a single layer, the shell may also contain only the first metal or the second metal.
In an exemplary embodiment of the present application, at least one region in the shell may also be formed in a porous form. At this time, the shell contains only the first metal or the second metal, or may contain both the first metal and the second metal. At this time, the porosity of the shell may be 20 vol% or less or 10 vol% or less.
Hollow metal nanoparticles according to an exemplary embodiment of the present application may include a hollow core; one or two or more first shells comprising a first metal; and one or two or more second shells comprising a second metal.
In an exemplary embodiment of the present application, the first shell may be present in at least one region of the hollow exterior, and may also be present over the entire surface. The first shell may also be present in the form of a discontinuous surface when present in some areas of the hollow exterior.
The second shell may be present in at least one region of the outer surface of the first shell, and may be present in the form of an entire surface surrounding the outer surface of the first shell. When the second shell is present in some areas of the outer surface of the first shell, the second shell may also be present in the form of a discontinuous surface.
In an exemplary embodiment of the present application, the hollow metallic nanoparticles may include a hollow core, a first shell in which negatively charged second metal ions are present in at least one region of the exterior of the hollow, and a second shell in which positively charged first metal ions are in turn present in at least one region of the exterior surface of the first shell.
In an exemplary embodiment of the present application, the hollow metallic nanoparticles may include a hollow core, a first shell in which positively charged first metal ions are present in at least one region of the exterior of the hollow, and a second shell in which negatively charged second metal ions are present in at least one region of the exterior surface of the first shell.
The hollow metal nanoparticles prepared according to the preparation method of one exemplary embodiment of the present application may be used in the field where nanoparticles are generally used instead of existing nanoparticles. The hollow metal nanoparticles of the present application have much smaller size and larger specific surface area than the nanoparticles of the prior art, and thus can exhibit better activity than the nanoparticles of the prior art. In particular, the hollow metal nanoparticles prepared according to the preparation method of the present application may be used in various fields, such as catalysts, drug delivery, and gas sensors. Hollow metal nanoparticles can also be used as catalysts or as active substance preparations in cosmetics, pesticides, animal nutrients or food supplements, and also as pigments in electronics, optical components or polymers.
Hereinafter, the present invention will be described in detail with reference to examples in order to specifically describe the present invention. However, the embodiments according to the present invention may be modified in various forms, and should not be construed that the scope of the present invention is limited to the embodiments to be described in detail below. Embodiments of the present invention are provided to more fully explain the present invention to those of ordinary skill in the art.
< Experimental example 1>
0.03mmol of NiCl as the first metal salt was added at a temperature of 14 deg.C20.01mmol of K as the second metal salt2PtCl40.18mmol of trisodium citrate as a stabilizer was added to 40ml of water and dissolved in water to form a solution, which was stirred for 30 minutes. At this time, NiCl2And K2PtCl4In a molar ratio of 3: 1.
subsequently, 0.03mmol of NaBH as reducing agent4400ml/h was added to the solution and the resulting mixture was allowed to react for 30 minutes. After the mixture was centrifuged at 10,000rpm for 10 minutes, the precipitate remaining after discarding the supernatant was redispersed in 20ml of water, and then the centrifugation process was repeated once more to produce hollow metal nanoparticles composed of a hollow core and a shell comprising Ni and Pt.
Fig. 1 shows a Transmission Electron Microscope (TEM) image of hollow metal nanoparticles prepared according to experimental example 1. The hollow metal nanoparticles obtained by the Scherrer equation calculation method for HR-TEM of fig. 1 have a particle size of about 5 nm.
Specifically, the particle diameter of the formed hollow metal nanoparticles was measured for 200 or more hollow metal nanoparticles based on fig. 1 using graphic software (MAC-View), and the average particle diameter obtained by the obtained statistical distribution was 5 nm.
< Experimental example 2>
An experiment was performed to prepare hollow metal nanoparticles in the same manner as in experimental example 1, except that the rate of adding the reducing agent was set to 100 ml/h.
Fig. 2 shows a Transmission Electron Microscope (TEM) image of the hollow metal nanoparticles prepared according to experimental example 2. The hollow metal nanoparticles obtained by the Scherrer equation calculation method for HR-TEM of fig. 2 have a particle size of about 16 nm.
Specifically, the particle diameter of the formed hollow metal nanoparticles was measured for 200 or more hollow metal nanoparticles based on fig. 2 using graphic software (MAC-View), and the average particle diameter obtained by the obtained statistical distribution was 16 nm.
< Experimental example 3>
An experiment was performed to prepare hollow metal nanoparticles in the same manner as in experimental example 1, except that the rate of adding the reducing agent was set to 0.1 ml/h.
Fig. 3 shows a Transmission Electron Microscope (TEM) image of the hollow metal nanoparticles prepared according to experimental example 3. The hollow metal nanoparticles obtained by the Scherrer equation calculation method for HR-TEM of fig. 3 have a particle size of about 12 nm.
Specifically, the particle diameter of the formed hollow metal nanoparticles was measured for 200 or more hollow metal nanoparticles based on fig. 3 using graphic software (MAC-View), and the average particle diameter obtained by the obtained statistical distribution was 12 nm.
From fig. 1 to 3, it was confirmed that the nanoparticles of fig. 3 according to experimental example 3, in which the rate of adding the reducing agent was set to 0.1ml/h, were difficult to form hollows. In contrast, with the nanoparticles of FIGS. 1 and 2 according to Experimental examples 1 and 2, in which the rates of adding the reducing agent were set to 400ml/h and 100ml/h, respectively, it was confirmed that the hollows were uniformly formed.
Therefore, more preferably, the reducing agent is added at a rate exceeding 0.1 ml/h.
< Experimental example 4>
The experiment was performed to prepare hollow metal nanoparticles in the same manner as experimental example 1, except that the experiment was performed under the temperature condition of 25 ℃.
Fig. 4 shows a Transmission Electron Microscope (TEM) image of the hollow metal nanoparticles prepared according to experimental example 4. The hollow metal nanoparticles obtained by the Scherrer equation calculation method for HR-TEM of fig. 4 had a particle size of about 17 nm.
Specifically, the particle diameter of the formed hollow metal nanoparticles was measured for 200 or more hollow metal nanoparticles based on fig. 4 using graphic software (MAC-View), and the average particle diameter obtained by the obtained statistical distribution was 17 nm.
< Experimental example 5>
The hollow metal nanoparticles were prepared by performing the experiment in the same manner as experimental example 1, except that the experiment was performed under the temperature condition of 60 ℃.
Fig. 5 shows a Transmission Electron Microscope (TEM) image of the hollow metal nanoparticles prepared according to experimental example 5. The hollow metal nanoparticles obtained by the Scherrer equation calculation method for HR-TEM of fig. 5 had a particle size of about 13 nm.
Specifically, the particle diameter of the formed hollow metal nanoparticles was measured for 200 or more hollow metal nanoparticles based on fig. 5 using graphic software (MAC-View), and the average particle diameter obtained by the obtained statistical distribution was 13 nm.
< Experimental example 6>
An experiment was performed in the same manner as in experimental example 1, except that 0.3mmol of trisodium citrate was used as a stabilizer, and the measurement result was a TEM image and is shown in fig. 6.
In fig. 6, it can be confirmed that, in most of the nanoparticles, no hollow is formed.
< Experimental example 7>
An experiment was performed in the same manner as experimental example 1 except that no stabilizer was used, and the measurement results were TEM images and are shown in fig. 7 and 8.
In fig. 7 and 8, it can be confirmed that in most of the nanoparticles, no hollow is formed and aggregated amorphous particles are synthesized.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to only these embodiments but can be prepared in various forms, and it will be understood by those skilled in the art that the present invention can be embodied in other specific forms without changing the technical spirit or essential features of the invention. The above-described embodiments are therefore to be understood as being illustrative in all respects and not restrictive.

Claims (20)

1. A method of preparing hollow metallic nanoparticles, the method comprising:
preparing a solution comprising a first metal salt, a second metal salt, a stabilizer, and a solvent; and
mixing the solution with a reducing agent to form hollow metal nanoparticles,
wherein, the preparation method does not use a surfactant,
wherein the reducing agent is added at a rate of 100ml/h to 400 ml/h.
2. The production method according to claim 1, wherein the standard reduction potential of the reducing agent is-0.23V or less.
3. The method of claim 1, wherein the reducing agent is selected from NaBH4、NH2NH2、LiAlH4And LiBEt3One or two or more of H.
4. The preparation method of claim 1, wherein the stabilizer comprises one or two or more selected from the group consisting of disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium citrate, and trisodium citrate.
5. The production method according to claim 1, wherein the content of the stabilizer is 3 times or more and less than 30 times that of the first metal salt or the second metal salt in a molar unit.
6. The production method according to claim 1, wherein the solvent is water.
7. The preparation method of claim 1, wherein the first metal salt is represented by the following chemical formula 1, and the second metal salt is represented by the following chemical formula 2:
[ chemical formula 1]
XAm
[ chemical formula 2]
BpYCq
In chemical formula 1 or chemical formula 2,
x and Y are each independently an ion of a metal selected from the group consisting of metals belonging to groups 3 to 15 of the periodic Table of the elements, metalloids, lanthanides and actinides,
a and C are each independently a monovalent anionic ligand,
b is an ion of an element belonging to group 1 of the periodic Table of the elements,
m is 2 or 3, p is 0, 2 or 4, q is 2, 4 or 6.
8. The production method according to claim 7, wherein X is an ion of a metal selected from the group consisting of platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), gold (Au), cerium (Ce), and copper (Cu).
9. The production method according to claim 7, wherein Y is an ion of a metal selected from platinum (Pt), gold (Au), silver (Ag) and palladium (Pd).
10. The method of claim 7, wherein A and C are each independently selected from NO3 -、NO2 -、OH-、F-、Cl-、Br-And I-。
11. The method according to claim 7, wherein B is selected from H+、K+、Na+And NH3 +。
12. The method of claim 1, wherein the molar ratio of the first metal salt to the second metal salt in the solution is from 1:5 to 10: 1.
13. The production method according to claim 1, wherein the hollow metal nanoparticles are produced at a temperature of 4 ℃ or more and less than 100 ℃.
14. The method according to claim 1, wherein the particle diameter of each hollow metal nanoparticle is 80 to 120% of the average particle diameter of the hollow metal nanoparticles.
15. The production method according to claim 1, wherein the average particle diameter of the hollow metal nanoparticles is 20nm or less.
16. The production method according to claim 1, wherein the average particle diameter of the hollow metal nanoparticles is 10nm or less.
17. The production method according to claim 1, wherein the average particle diameter of the hollow metal nanoparticles is 6nm or less.
18. The production method according to claim 1, wherein the hollow metal nanoparticles are spherical.
19. The method according to claim 1, wherein a volume of the hollow is 50 vol% or more of a total volume of the hollow metal nanoparticles.
20. The method for preparing according to claim 1, wherein the hollow metal nanoparticles comprise:
a hollow core; and
at least one shell comprising a first metal and a second metal.
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