KR101682382B1 - Core-shell composite nanoparticle and preparing method thereof - Google Patents

Abstract

Core composite nanoparticles, core-shell composite nanoparticles, a process for producing the core-shell composite nanoparticles, and an electrode catalyst for energy conversion or storage devices comprising the core-shell composite nanoparticles.

Description

CORE-SHELL COMPOSITE NANOPARTICLE AND PREPARING METHOD THEREOF BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to core-shell composite nanoparticles, a method for producing the core-shell composite nanoparticles, and an electrode catalyst for energy conversion or storage devices comprising the core-shell composite nanoparticles.

The design and manufacture of multifunctional core-shell structures have been proposed in various ways, and these structures are widely available for optical sensing, biosensing photocatalysts, electrochemical catalysts, and luminescent materials. Gold nanoparticles, which are noble metals, exhibit a specific surface plasmon resonance phenomenon. The surface plasmon resonance phenomenon is caused by the inherent wavevector of the collective oscillation motion of nano-sized noble metal surface electrons and the wave number of the incident light The amplified field is induced by resonance under the condition of vector matching. It can be utilized as a multi-functional core-shell structure by using it, and it can be applied to various fields as well as improved performance.

Fuel cells and batteries are electrochemical energy conversion and storage devices that directly convert chemical energy into electrical energy. The energy conversion efficiency is higher than that of the conventional internal combustion engine, and there is no pollutant, and it is attracting attention as an alternative power. Despite the above advantages, commercialization has been delayed due to high manufacturing cost. In the case of mass production of the stack, the cost of the electrode catalyst is higher than that of other materials, and a large amount of platinum catalyst or platinum supported on carbon A catalyst is used.

Korean Patent Laid-Open No. 10-2010-0119833 discloses that, by heat treatment, a precursor core / shell carbonized as a precursor composed of a material selected from (i) a transition metal oxide and (ii) a transition metal nitride is used as a catalyst support And a catalyst electrode for a fuel cell.

The present invention provides a core-shell composite nanoparticle, a method for producing the core-shell composite nanoparticle, and an electrode catalyst for an energy conversion or storage device comprising the core-shell composite nanoparticle.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

According to a first aspect of the present invention, there is provided a method for preparing a gold nanoparticle-containing solution, comprising: reacting a gold precursor and a reducing agent to prepare a gold nanoparticle-containing solution; Adding a monomer of a conductive polymer to the gold nanoparticle-containing solution and polymerizing the resultant to form a conductive polymer shell on the gold nanoparticle core; And introducing a first transition metal precursor and a second transition metal precursor into the conductive polymer shell to form first transition metal particles and second transition metal particles, .

A second aspect of the present invention is a method of manufacturing a conductive nanoparticle comprising a conductive polymer shell formed on a gold nanoparticle core and a first transition metal particle and a second transition metal particle formed on the conductive polymer shell, , Core-shell composite nanoparticles.

A third aspect of the invention provides an electrode catalyst for energy conversion or storage devices comprising core-shell composite nanoparticles according to the second aspect.

According to any one of the above-mentioned means for solving the above-mentioned problems, there is provided a core-shell composite nanoparticle comprising a conductive polymer shell formed on a gold nanoparticle core, first transition metal particles formed on the conductive polymer shell and second transition metal particles, A high activity inducing technique of an electrochemical catalyst to be used can be suggested.

According to any one of the above-mentioned means for solving the problems, it is possible to reduce the amount of platinum used compared with the conventional core-shell nanoparticles using platinum, and to replace part of platinum with an inexpensive transition metal component, The electrode catalyst for the storage device can be synthesized and the activity for the oxidation-reduction reaction of the electrode catalyst for the synthesized energy device can attain an effect showing a level similar to or higher than that of the conventional electrode catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a method for producing core-shell composite nanoparticles in one embodiment of the present invention. FIG.
2A is a scanning electron microscope (SEM) image of AuNP @ PANI, in one embodiment of the invention.
FIG. 2B is an ultraviolet / visible light absorption spectrum of AuNP @ PANI in one embodiment of the present invention. FIG.
2C is an FT-IR spectrum of AuNP @ PANI in one embodiment of the present invention.
FIG. 2D is a cyclic voltammetry curve graph of AuNP @ PANI in one embodiment of the present invention.
Figure 2e is a graph of linear sweep voltammetry in an oxygen reduction reaction of AuNP @ PANI in one embodiment of the present invention.
FIG. 3A is an ultraviolet / visible ray absorption spectrum of AuNP @ PANI @ Pt in one embodiment of the present invention. FIG.
FIG. 3B is a transmission electron microscope (TEM) image according to the molar concentration ratio of AuNP @ PANI @ Pt in one embodiment of the present invention.
FIG. 3C is a graph of the linear principle pre-erosion in the oxygen reduction reaction according to the molar concentration ratio of AuNP @ PANI @ Pt in one embodiment of the present invention.
FIGS. 4A and 4B are a cyclic current and voltage curve graph of AuNP @ PANI @ Fe and a linear main prior art method in one embodiment of the present invention, and FIGS. 4C and 4D show, in one embodiment, AuNP @ PANI @ Co is a cyclic current-voltage curve graph and a linear-state predistortion.
4E and 4F are transmission electron microscope (TEM) images of AuNP @ PANI @ Fe and AuNP @ PANI @ Co in one embodiment of the invention.
FIG. 5A is a TEM image of AuNP @ PANI @ Pt _x Fe _x-1 in one embodiment of the present invention, and FIGS. 5B and 5C are TEM images of AuNP @ PANI @ Pt _x Fe _x- And a curve d in FIG.
FIG. 6A is a TEM image of AuNP @ PANI @ Pt _x Co _x-1 in one embodiment of the present invention, and FIGS. 6B and 6C are TEM images of AuNP @ PANI @ Pt _x Co _x- And a curve d in FIG.
FIG. 7 is a TEM-EDS mapping image of AuNP @ PANI @ Pt and AuNP @ PANI @ PtM in one embodiment of the present invention.
FIG. 8 is an X-ray diffraction pattern spectrum of AuNP @ PANI @ Pt and AuNP @ PANI @ PtM in one embodiment of the present invention.
FIG. 9 is a cyclic current-voltage curve graph of AuNP @ PANI @ Pt and AuNP @ PANI @ PtM in one embodiment of the present invention.
FIG. 10 is a linear principal anticorrosion graph of various core-shell composite nanoparticles in an oxygen reduction reaction, in one embodiment of the present invention. FIG.
11 is a graph for the Koutecky-Levich equation in one embodiment of the present application.
12 is a graph showing the results of the stability test in the embodiment of the present invention.
13 is a cyclic current-voltage curve graph of various core-shell composite nanoparticles in the methanol oxidation reaction in one embodiment of the present invention.
14 is a cyclic current-voltage curve graph of core-shell nanoparticles and Pt / C in a methanol oxidation reaction in one embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is "on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term "combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

In the entire specification of the present application, the description of "A @ B" means "A core-B shell nanoparticle" and the description of "A @ B @ C" it means. The A core-B @ C shell nanoparticle means a core-shell nanoparticle using A as a core and B containing C, that is, B @ C as a shell.

Hereinafter, embodiments of the present invention are described in detail, but the present invention is not limited thereto.

According to a first aspect of the present invention, there is provided a method for preparing a gold nanoparticle-containing solution, comprising: reacting a gold precursor and a reducing agent to prepare a gold nanoparticle-containing solution; Adding a monomer of a conductive polymer to the gold nanoparticle-containing solution and polymerizing the resultant to form a conductive polymer shell on the gold nanoparticle core; And introducing a first transition metal precursor and a second transition metal precursor into the conductive polymer shell to form first transition metal particles and second transition metal particles. do.

The core-shell composite nanoparticle gold nanoparticles of the present invention, the conductive polymer, the first transition metal / the second transition metal structure, use a conductive polymer, and the conventional gold nanoparticles, the nonconductive polymer, the Pt structure, for example, AuNP Compared to PVP-Pt, it has electric conductivity and has superior catalytic activity compared to general polymer. It can be manufactured at relatively low cost by replacing part of Pt with transition metal compared to gold nanoparticle (conductive polymer) Pt structure. can do.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a method for producing core-shell composite nanoparticles in one embodiment of the present invention. FIG.

In one embodiment of the present invention, the core-shell composite nanoparticle includes a core layer of gold nanoparticles, and a shell layer of a first transition metal and a conductive polymer into which the second transition metal is introduced. The conductive polymer shell may include, for example, those formed on the surface of the core, but the present invention is not limited thereto.

In one embodiment of the invention, the first transition metal precursor and the second transition metal precursor are different from each other.

In one embodiment of the present invention, the conductive polymer shell formed on the gold nanoparticle core, the first transition metal particle and the second transition metal particle formed on the conductive polymer shell are formed by the method of manufacturing the core-shell composite nanoparticle The present invention relates to a method for producing a core-shell composite nanoparticle comprising the steps of: preparing a core-shell nanoparticle of core-shell type; May be used as a chemical electrode catalyst, but may not be limited thereto.

In one embodiment of the invention, the conductive polymer is selected from the group consisting of polyaniline, polythiophene, polypyrrole, poly (3,4-alkylenedioxythiophene), poly (3,4-dialkylthiophene) (Dialkoxythiophene), poly (3,4-cycloalkylthiophene), and combinations thereof. The term "

In one embodiment of the present invention, the first transition metal precursor and the second transition metal precursor can be easily introduced into the polymer shell using the conductive polymer to form the first transition metal precursor and the second transition metal precursor, An electrode catalyst for energy conversion or storage devices containing platinum and an additional transition metal can be produced at low cost.

In one embodiment herein, the first transition metal precursor may comprise, but is not limited to, a metal selected from the group consisting of Pt, Pd, and combinations thereof.

In one embodiment herein, the second transition metal precursor may comprise, but is not limited to, a metal selected from the group consisting of Fe, Co, Ni, Cu, Ru, and combinations thereof .

In one embodiment of the present invention, the use of the first transition metal precursor and the second transition metal precursor together is accomplished by adding a second transition metal precursor, which is relatively inexpensive to Pt, so that the amount of the first transition metal precursor, such as Pt, Thereby reducing the production cost and exhibiting excellent catalytic activity.

In one embodiment of the invention, the molar ratio of the monomer of the conductive polymer shell to the sum of the first transition metal precursor and the second transition metal precursor may be from about 1: 0.2 to about 1: 1, have. For example, the molar ratio of the monomer of the conductive polymer shell to the sum of the first transition metal precursor and the second transition metal precursor may be from about 1: 0.2 to about 1: 1, from about 1: 0.3 to about 1: 1, 1 to about 1: 1, from about 1: 0.5 to about 1: 1, from about 1: 0.6 to about 1: 1, from about 1: 0.7 to about 1: : 0.9 to about 1: 1, but the present invention is not limited thereto.

In one embodiment, the molar ratio of the first transition metal precursor to the second transition metal precursor ranges from about 1: 0.3 to about 1: 1, from about 1: 0.4 to about 1: 1, from about 1: 0.5 to about 1: 1: about 1: 0.6 to about 1: 1, about 1: 0.7 to about 1: 1, about 1: 0.8 to about 1: 1, or about 1: 0.9 to about 1: .

In one embodiment of the invention, the size of the gold nanoparticles may be from about 1 nm to about 100 nm, but is not limited thereto. For example, the gold nanoparticles may have a thickness of from about 1 nm to about 100 nm, from about 5 nm to about 100 nm, from about 10 nm to about 100 nm, from about 20 nm to about 100 nm, from about 30 nm to about 100 nm, From about 40 nm to about 100 nm, from about 50 nm to about 100 nm, from about 60 nm to about 100 nm, from about 70 nm to about 100 nm, from about 80 nm to about 100 nm, from about 90 nm to about 100 nm, From about 1 nm to about 40 nm, from about 1 nm to about 50 nm, from about 1 nm to about 40 nm, from about 1 nm to about 80 nm, from about 1 nm to about 70 nm, from about 1 nm to about 60 nm, 30 nm, about 1 nm to about 20 nm, about 1 nm to about 10 nm, or about 1 nm to about 5 nm.

In one embodiment of the present invention, the gold nanoparticles may be surface-modified, but are not limited thereto. Such a surface modification can be used in the art without any particular limitation in the materials and methods used for surface modification of gold nanoparticles.

A second aspect of the present invention is a method of manufacturing a conductive nanoparticle comprising a conductive polymer shell formed on a gold nanoparticle core and a first transition metal particle and a second transition metal particle formed on the conductive polymer shell, , Core-shell composite nanoparticles. That is, the core-shell composite nanoparticle according to the second aspect of the present invention comprises reacting a gold precursor and a reducing agent to prepare a gold nanoparticle-containing solution; Adding a monomer of a conductive polymer to the gold nanoparticle-containing solution and polymerizing the resultant to form a conductive polymer shell on the gold nanoparticle core; And introducing a first transition metal precursor and a second transition metal precursor to the conductive polymer shell to form first transition metal particles and second transition metal particles.

 In one embodiment of the invention, the conductive polymer is selected from the group consisting of polyaniline, polythiophene, polypyrrole, poly (3,4-alkylenedioxythiophene), poly (3,4-dialkylthiophene) (Dialkoxythiophene), poly (3,4-cycloalkylthiophene), and combinations thereof. The term "

In one embodiment of the invention, the first transition metal particles may include, but are not limited to, a metal selected from the group consisting of Pt, Pd, and combinations thereof.

In one embodiment of the invention, the second transition metal particles may comprise, but are not limited to, metals selected from the group consisting of Fe, Co, Ni, Cu, Ru, and combinations thereof .

In one embodiment of the present invention, the first transition metal precursor used in preparing the core-shell composite nanoparticles may comprise a metal selected from the group consisting of Pt, Pd, and combinations thereof. But may not be limited.

In one embodiment, the second transition metal precursor used in preparing the core-shell composite nanoparticles comprises a metal selected from the group consisting of Fe, Co, Ni, Cu, Ru, and combinations thereof. , But may not be limited thereto.

In one embodiment of the present invention, the molar ratio of the monomer of the conductive polymer shell to the sum of the first transition metal precursor and the second transition metal precursor used in preparing the core-shell composite nanoparticles is about 1: 0.2 to about 1: 1, but may not be limited thereto. For example, the molar ratio of the monomer of the conductive polymer shell to the sum of the first transition metal precursor and the second transition metal precursor may be from about 1: 0.2 to about 1: 1, from about 1: 0.3 to about 1: 1, 1 to about 1: 1, from about 1: 0.5 to about 1: 1, from about 1: 0.6 to about 1: 1, from about 1: 0.7 to about 1: : 0.9 to about 1: 1, but the present invention is not limited thereto.

In one embodiment of the present invention, the molar ratio of the first transition metal precursor to the second transition metal precursor used in preparing the core-shell composite nanoparticles is about 1: 0.3 to about 1: 1, about 1: 0.4 to about From about 1: 0.5 to about 1: 1, from about 1: 0.6 to about 1: 1, from about 1: 0.7 to about 1: 1, from about 1: 0.8 to about 1: But it may be, but not limited to, about 1: 1.

In one embodiment of the invention, the size of the gold nanoparticles may be from about 1 nm to about 100 nm, but is not limited thereto. For example, the gold nanoparticles may have a thickness of from about 1 nm to about 100 nm, from about 5 nm to about 100 nm, from about 10 nm to about 100 nm, from about 20 nm to about 100 nm, from about 30 nm to about 100 nm, From about 40 nm to about 100 nm, from about 50 nm to about 100 nm, from about 60 nm to about 100 nm, from about 70 nm to about 100 nm, from about 80 nm to about 100 nm, from about 90 nm to about 100 nm, From about 1 nm to about 40 nm, from about 1 nm to about 50 nm, from about 1 nm to about 40 nm, from about 1 nm to about 80 nm, from about 1 nm to about 70 nm, from about 1 nm to about 60 nm, 30 nm, about 1 nm to about 20 nm, about 1 nm to about 10 nm, or about 1 nm to about 5 nm.

In one embodiment of the present invention, the core-shell composite nanoparticles may include, for example, those having a round particle shape, but are not limited thereto.

A third aspect of the invention provides an electrode catalyst for energy conversion or storage devices comprising core-shell composite nanoparticles according to the second aspect of the present invention.

The third aspect of the present invention relates to an electrode catalyst for an energy conversion or storage device comprising core-shell composite nanoparticles, and a detailed description of parts overlapping with the first aspect or the second aspect of the present invention is omitted, The description of the first aspect or the second aspect of the present invention can be similarly applied even if the description thereof is omitted in the third aspect of the present application.

In one embodiment of the invention, the use of platinum is reduced compared to conventional core-shell composite nanoparticles using platinum, and a portion of the platinum is replaced by an inexpensive transition metal component to provide an alloy nanoparticle-based energy conversion or storage device But the present invention is not limited thereto.

In one embodiment of the invention, the electrode catalyst for the energy conversion or storage device may be, but not limited to, an electrode catalyst for a fuel cell.

In one embodiment of the present invention, the electrode catalyst for the energy device may be a catalyst for a cathode, but the present invention is not limited thereto.

In one embodiment of the present invention, the electrode catalyst for the energy device may be, but not limited to, an anode catalyst.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are given for the purpose of helping understanding of the present invention, but the present invention is not limited to the following Examples.

[ Example ]

<Preparation of gold nanoparticles>

To prepare the gold nanoparticle-containing solution, add 1.5 mL of 0.025 M gold precursor (HAuCl ₄ , Sigma Aldrich) to 148.5 mL of distilled water and heat to 130 C with vigorous stirring. After that, 0.9 mL of 0.17 M sodium citrate (Sigma Aldrich) was further added, and the mixture was further heated for 20 minutes with stirring to finally prepare gold nanoparticles having a size of about 15 nm.

<Conductive polymer shell synthesis for gold nanoparticle core>

To the prepared gold nanoparticles, 40 mM sodium dodecyl sulfate and 2 mM aniline solution as a monomer of the conductive polymer were added, and 2 mM ammonium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) in an acidic solvent [10 mM HCl] polyaniline conductive polymer shells were synthesized by surfactant-assisted chemical oxidative polymerization using ammonium peroxodisulfate.

<Conductive Polymer of AuNP @ PANI In the shell  Introduction of metal nanoparticles>

To prepare the first transition metal particles (Pt) and second transition metal particles (Fe and Co) into the polyaniline conductive polymer shell after dispersing the prepared nanoparticles in distilled water, 2 mM aniline solution, which is a conductive polymer monomer, (1: 0.25, 1: 0.5, and 1: 1) of a transition metal precursor (using a 2 mM aqueous solution of H ₂ PtCl ₆ ) was added and stirred for 1 hour after ultrasonic treatment for 24 hours. Thereafter, 0.1 M sodium borohydride was added and stirred for 30 minutes. After centrifugation using a centrifuge, the supernatant was discarded and the remaining nanoparticles were dispersed in distilled water to form first transition metal particles in the conductive polymer shell Containing nanoparticles were obtained. The electrocatalytic activity and the TEM image of each of the first transition metal precursors were confirmed. The molar ratio of the first transition metal precursor to the first transition metal precursor was 1: 1, (Using a 2 mM aqueous solution of H ₂ PtCl ₆ ) and a second transition metal precursor (a 3.6 mM aqueous solution of FeCl ₂ .4H ₂ O and a 4 mM aqueous solution of CoCl ₂ .6H ₂ O aqueous solutions were respectively used according to the molar ratio (molar ratio of the first transition metal precursor: second transition metal precursor = 0.7: 0.3) to the nanoparticles containing the first transition metal particles and the second transition metal particles &Lt; / RTI &gt;

FIGS. 2A to 2D are the results of core-shell composite nanoparticles synthesized from gold nanoparticle cores prepared according to the above examples. FIG. 2A is a scanning electron microscope (SEM) image of AuNP @ (SEM) image. FIG. 2B shows ultraviolet / visible light absorption spectra when gold nanoparticles and a conductive polymer shell were synthesized, and a specific absorption peak of gold nanoparticles was observed between 500 nm and 550 nm. Also, as the conductive polymer shell was synthesized, the absorption peak of the conductive polymer was confirmed at 800 nm. In addition, the intrinsic peak of PANI was confirmed by the FT-IR spectrum, and FIGS. 2d and 2e were able to confirm the electrocatalytic activity of AuNP @ PANI. Then, the first transition metal precursor, platinum, was introduced into the polymer shell, and the result was confirmed by the absorbance peak of FIG. 3A. The absorbance was measured according to the introduction of platinum, and the result is shown in Fig. The molar ratio of the platinum precursor and the conductive polymer was controlled to confirm the amount of the platinum introduced into the polymer shell through the TEM image of FIG. 3b.

A linear sweep voltammetry was used to investigate the oxygen reduction reaction of the prepared core-shell composite nanoparticles. The Ag / AgCl electrode filled with 3 M KCl (potassium chloride) was used as a reference electrode, the Pt foil was used as a counter electrode, A three-electrode cell was prepared by coating nanoparticles having different molar ratios of platinum on a glassy carbon electrode (GCE) having a diameter of 3 mm and using the same as a working electrode, using a potentiostat, EcoChmie, Autolab). A rotating disk electrode (RDE) was used as the working electrode to measure the current and voltage according to the rotation speed. The electrolyte used was a 0.1 M perchloric acid aqueous solution saturated with oxygen gas, and the LSV measurement rate (scan rate) was 20 mV / s.

FIG. 3 (c) shows the core-shell composite nanoparticles prepared by the above-described method using an oxygen reduction reaction. In order to determine the electrocatalytic activity by substituting some of the platinum with the second transition metal by determining the molar ratio with the most excellent reaction activity, the cyclic voltammetry and the linear predistortion method using only the second transition metal (Figs. 4A to 4D). The experimental method for confirming the degree of catalytic activity was the same as above, and the cyclic voltammetric curve method and the linear principle preliminary method in the case of only the second transition metal without platinum showed no oxygen reduction reaction (FIGS. 4A to 4D) . Each nanoparticle was observed through the TEM image of FIGS. 4E and 4F.

FIG. 5A is a TEM image of AuNP @ PANI @ Pt _x Fe _x-1 , and FIGS. 5B and 5C are cyclic current and voltage curves of AuNP @ PANI @ Pt _x Fe _x-1 . FIG. 6A is a TEM image of AuNP @ PANI @ Pt _x Co _x-1 , and FIGS. 6B and 6C are cyclic current and voltage curves of AuNP @ PANI @ Pt _x Co _x-1 . FIGS. 5D and 6D show the linear principle of the nanoparticles in which platinum and a second transition metal are introduced, respectively. Even after introducing a second transition metal (Fe or Co) into platinum, the electrocatalytic activity and the oxygen reduction reaction Is happening.

FIG. 7 is a TEM-EDS mapping image of AuNP @ PANI @ PtM into which a second transition metal (Fe or Co) is introduced in this embodiment, showing that each element is contained in the nanoparticles , And that the distribution of the nanoparticles introduced into the conductive polymer shell is good. FIG. 8 is an X-ray diffraction pattern graph of AuNP @ PANI @ PtM in one embodiment of the present invention, and the inherent diffraction pattern of each element was analyzed and the change in crystallinity was observed.

FIG. 9 is a cyclic current-voltage curve graph of AuNP @ PANI @ Pt and AuNP @ PANI @ PtM, showing adsorption and desorption of hydrogen and adsorption and desorption of oxygen in each nanoparticle. FIG. 10 is a graph showing the relationship between the oxygen content of the core-shell composite nanoparticles and the specific surface area of the core-shell composite nanoparticles containing the second transition metal (Co) Compared to the catalytic activity of the nanoparticles, it was better than the other comparative samples. 11 is a graph showing the inverse number (1 / j) of the current density of the electrochemical oxygen reduction reaction measured in the RDE experiment by calculating the Koutecky-Levich equation for the inverse number (ω ^-1/2 ) of the square root of the number of rotations have. The number of electrons in the reference voltage is calculated as 4 in the case of core-shell composite nanoparticles, so that the electron transfer reaction in which oxygen is reduced to hydrogen peroxide and the reaction corresponding to the reduction of hydrogen peroxide generated as a by- It means something happened. 12 shows the results of the stability test of the core-shell composite nanoparticles according to the present embodiment, and shows the current value with time at a specific voltage. It was confirmed that the core-shell composite nanoparticles according to this example had better stability than the comparative sample Pt / C.

FIG. 13 shows the methanol oxidation reaction in order to show that the core-shell composite nanoparticles according to this embodiment can be used not only as a catalyst for a cathode of a fuel cell but also as a catalyst for an anode. The cyclic current voltage of the core-shell composite nanoparticles according to this example was measured. As the electrolyte, 1 M methanol was used in 0.1 M perchloric acid aqueous solution saturated with an inert gas, and the scan rate of the circulation current voltage was measured at 50 mV / s. According to the above results, it was confirmed that the core-shell composite nanoparticles containing platinum and the second transition metal had excellent activity in the methanol oxidation reaction, and the methanol / Oxidation reaction was observed. The core-shell plasmon nanoparticles comprising the platinum nanoparticles and the second transition metal nanoparticles prepared according to the above embodiments are fully utilized as a cathode catalyst for a metal-air battery as well as a catalyst for a cathode and an anode of a fuel cell Respectively.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims (12)

Reacting the gold precursor and the reducing agent to prepare a gold nanoparticle-containing solution;
Adding a monomer of a conductive polymer to the gold nanoparticle-containing solution and polymerizing the resultant to form a conductive polymer shell on the gold nanoparticle core;
Introducing a first transition metal precursor into the conductive polymer shell to form first transition metal particles; And
Introducing the first transition metal precursor and a second transition metal precursor to replace a portion of the first transition metal particles with second transition metal particles
/ RTI &gt;
Wherein the molar ratio of the monomer of the conductive polymer shell to the sum of the first transition metal precursor and the second transition metal precursor is 1: 0.2 to 1:
(Method for producing core - shell composite nanoparticles).
The method according to claim 1,
The conductive polymer may be at least one selected from the group consisting of polyaniline, polythiophene, polypyrrole, poly (3,4-alkylenedioxythiophene), poly (3,4-dialkylthiophene) (3,4-cycloalkylthiophene), and combinations thereof. &Lt; Desc / Clms Page number 20 &gt;
The method according to claim 1,
Wherein the first transition metal precursor comprises a metal selected from the group consisting of Pt, Pd, and combinations thereof.
The method according to claim 1,
Wherein the second transition metal precursor comprises a metal selected from the group consisting of Fe, Co, Ni, Cu, Ru, and combinations thereof.
delete The method according to claim 1,
Wherein the size of the gold nanoparticles is 1 nm to 100 nm.
6. A method for manufacturing a conductive polymer membrane, comprising the steps of: preparing a conductive polymer shell formed on a gold nanoparticle core by a method according to any one of claims 1 to 4, and a first transition metal particle formed on the conductive polymer shell and a second transition A core-shell composite nanoparticle comprising metal particles.
8. The method of claim 7,
Wherein the first transition metal particles comprise a metal selected from the group consisting of Pt, Pd, and combinations thereof.
8. The method of claim 7,
Wherein the second transition metal particles comprise a metal selected from the group consisting of Fe, Co, Ni, Cu, Ru, and combinations thereof.
An electrode catalyst for an energy conversion or storage device comprising core-shell composite nanoparticles according to claim 7.
11. The method of claim 10,
Wherein the electrode catalyst for the energy conversion or storage device is a catalyst for a cathode.
11. The method of claim 10,
Wherein the electrode catalyst for the energy conversion or storage device is a catalyst for an anode.

Images