MESOPOROUS SILICA EMBEDDED WITH ALLOY PARTICLES AND PREPARATION METHOD THEREOF

Abstract

The present invention relates to mesoporous silica embedded with alloy particles, and a preparation method thereof, and it is possible to prevent the release of metal particles to the outside because the inside of spherical mesoporous silica is embedded with metal nanoparticles, and as the aggregation of the metal is prevented, the stability is excellent and the production yield is high during the preparation process, so that mesoporous silica can be mass-produced, the efficacy of metal nanoparticles may be maintained by preventing the oxidation of metal nanoparticles, and mesoporous silica can be produced at low costs.

Further, the inside of pores of mesoporous silica is embedded with metal nanoparticles, so that the discoloration and smell change phenomenon does not occur, and the far-infrared emission and deodorization effects are excellent.

Claims

1. Mesoporous silica embedded with alloy particles, wherein the inside of mesopores of the silica is embedded with metal particles, and the metal particles comprise the alloy particles having a core-shell structure.

2. The mesoporous silica of claim 1, wherein the mesoporous silica is spherical.

3. The mesoporous silica of claim 1, wherein the alloy particles have a core-shell structure, and the metal constituting the core has an ionization tendency higher than that of a metal constituting the shell.

4. The mesoporous silica of claim 3, wherein the metal constituting the core is selected from the group consisting of lithium (Li), magnesium (Mg), aluminum (Al), manganese (Mn), zinc (Zn), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), tin (Sn), and a mixture thereof.

5. The mesoporous silica of claim 3, wherein the metal constituting the shell is selected from the group consisting of copper (Cu), silver (Ag), platinum (Pt), palladium (Pd), and a mixture thereof.

6. A method for preparing mesoporous silica embedded with alloy particles, the method comprising: 1) putting mesoporous silica in which the inside of mesopores is embedded with a first metal into water and mixing the silica with the water; 2) putting a second metal compound into the mixed solution and preparing the first metal in the mesopores into alloy particles having a core-shell structure through an oxidation-reduction reaction with the first metal; and 3) washing and drying the mesoporous silica.

7. The method of claim 6, wherein the preparing of the mesoporous silica in which the inside of mesopores is embedded with the first metal comprises: a) putting alkylamine into a solvent and stirring the resulting solution; b) preparing a solution containing a first metal ion by putting the first metal compound into the solution in step a) and stirring the resulting solution; c) preparing mesoporous silica in which the inside of the mesopores is embedded with the first metal ion by putting a silica precursor into the solution containing the first metal ion and stirring the resulting solution; d) putting a reducing agent into the solution in step c) and reducing the first metal ion; and e) washing and drying the mesoporous silica.

8. The method of claim 6, wherein the preparing of the mesoporous silica in which the inside of mesopores is embedded with the first metal comprises: a) putting alkylamine into a solvent and stirring the resulting solution; b) preparing a solution containing a first metal ion by putting the first metal compound into the solution in step a) and stirring the resulting solution; c) putting a reducing agent into the solution in step b) and reducing the first metal ion; d) preparing mesoporous silica in which the inside of the mesopores is embedded with the first metal by putting a silica precursor into the solution in which the first metal ion is reduced and stirring the resulting solution; and e) washing and drying the mesoporous silica.

9. The method of claim 6, wherein the first metal is selected from the group consisting of lithium (Li), magnesium (Mg), aluminum (Al), manganese (Mn), zinc (Zn), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), tin (Sn), and a mixture thereof.

10. The method of claim 6, wherein the second metal compound is selected from the group consisting of AgNO.sub.3, CuCl.sub.2, Pt(OAC).sub.2, PdCl.sub.2, Au(OAc).sub.3, and a mixture thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0084] FIG. 1 is a flowchart of the preparation method of mesoporous silica according to an exemplary embodiment of the present invention.

[0085] FIG. 2 is a flowchart of the preparation method of mesoporous silica according to an exemplary embodiment of the present invention.

[0086] FIG. 3 is a flowchart of the preparation method of mesoporous silica according to an exemplary embodiment of the present invention.

[0087] FIG. 4 is an SEM photograph of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an exemplary embodiment of the present invention.

[0088] FIG. 5 is an SEM photograph of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an exemplary embodiment of the present invention.

[0089] FIG. 6 is an SEM EDAX result of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an exemplary embodiment of the present invention.

[0090] FIG. 7 is a TEM photograph of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an exemplary embodiment of the present invention.

[0091] FIG. 8 is a TEM photograph of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an exemplary embodiment of the present invention.

[0092] FIG. 9 is a TEM EDAX result of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an exemplary embodiment of the present invention.

[0093] FIG. 10 is a TEM EDAX result of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an exemplary embodiment of the present invention.

[0094] FIG. 11 is a result of a mapping for silver (Ag) element of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an embodiment of the present invention.

[0095] FIG. 12 is a result of a mapping for zinc (Zn) element of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an embodiment of the present invention.

[0096] FIG. 13 is a result of a mapping for oxygen (O) element of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an embodiment of the present invention.

[0097] FIG. 14 is a result of a mapping for silicon (Si) element of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an embodiment of the present invention.

[0098] FIG. 15 is a result of a mapping for carbon (C) element of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an embodiment of the present invention.

[0099] FIG. 16 is a result of a mapping for nitrogen (N) element of spherical mesoporous silica dispersed and embedded with alloy nanoparticles according to an embodiment of the present invention.

DETAILED DESCRIPTION

[0100] Hereinafter, the Examples of the present invention will be described in detail such that a person skilled in the art to which the present invention pertains can easily carry out the present invention. However, the present invention can be implemented in various different forms, and is not limited to the Examples described herein.

Preparation Example 1

[0101] Preparation of spherical mesoporous silica including first metal After 1 mmol dodecylamine (DDA) was added to 20 mL of an aqueous ethyl alcohol solution at a concentration of 10%, the resulting solution was stirred at a temperature of 601 C. for 1 hour until the aqueous ethyl alcohol solution became clear, and then maintained while being stirred at room temperature for approximately 1 hour.

[0102] Thereafter, 5 ml of an aqueous solution containing a first metal ion was added thereto as in the following Table 1, and then the resulting solution was stirred with a magnetic bar for approximately 1 hour.

[0103] After 4 mmol tetraethoxyorthosilicate (TEOS) as a silica precursor was added thereto, spherical mesoporous silica in which the inside of the wall of mesopores was embedded with the first metal ion was prepared by vigorously stirring the resulting solution at room temperature for approximately 1 hour. After a first metal ion was reduced by adding 0.2 mmol NaBH.sub.4 as a reducing agent thereto and vacuum-filtration was performed under a pressure of 30 mmHg, the resulting product was washed three times using 200 ml of distilled water, and then washed three times using 100 ml of ethyl alcohol at 60 C., and dried at a temperature of 502 C. for 24 hours, thereby preparing mesoporous silica in which the inside of the wall of mesopores was embedded with the first metal.

TABLE-US-00001 TABLE 1 Content in aqueous First metal solution (molar Classification compound concentration) Example 1-1 Zn(NO.sub.3).sub.2 0.1 Example 1-2 ZnCl.sub.2 0.1 Example 1-3 ZnSO.sub.4 0.1 Example 1-4 Zn(OAc).sub.2 0.1 Example 1-5 SnCl.sub.2 0.1 Example 1-6 Sn(OAc).sub.2 0.1

Preparation Example 2

[0104] Preparation of Spherical Mesoporous Silica Including First Metal

[0105] After a gel solution was obtained by forming an aqueous first metal ion complex compound solution as in Example 1, a first metal ion was reduced by adding 0.2 mmol NaBH.sub.4 as a reducing agent thereto. Thereafter, after 4 mmol tetraethoxyorthosilicate (TEOS) as a silica precursor was added thereto, spherical mesoporous silica was obtained by vigorously stirring the resulting solution at room temperature for 1 hour, and then vacuum-filtration was performed at a pressure of 30 mmHg, the resulting product was washed three times using 200 ml of distilled water and washed three times using 100 ml of ethyl alcohol at 60 C., and then dried at a temperature of 502 C. for 24 hours, thereby preparing mesoporous silica in which the inside of the wall of pores was embedded with the first metal.

Preparation Example 3

[0106] Preparation of Spherical Mesoporous Silica in which Inside of Wall of Pores Contains Alloy Particles

[0107] An oxidation-reduction reaction with a first metal was performed by putting the second metal compound in the following Table 2 into an aqueous solution in which the spherical mesoporous silica embedded with the first metal prepared in Example 1-1 (Examples 3-5 and 3-6 were separately prepared by the method of Example 1) was put into water and stirring the resulting solution at room temperature for 1 hour.

[0108] After the reaction was terminated, the resulting product was vacuum-filtered under a pressure of 30 mmHg, washed three times using 200 ml of distilled water, washed three times using 100 ml of ethyl alcohol at 60 C., and then dried at a temperature of 502 C. for 24 hours, thereby preparing spherical mesoporous silica in which the inside of mesopores was embedded with alloy particles having a core-shell structure of a first metal and a second metal.

TABLE-US-00002 TABLE 2 Content (molar concentration) Second of second metal First metal compound in Classification metal compound aqueous solution Example 3-1 Zn AgNO.sub.3 0.1 Example 3-2 Zn CuCl.sub.2 0.1 Example 3-3 Zn Pt(OAC).sub.2 0.1 Example 3-4 Sn PdCl.sub.2 0.1 Example 3-5 Sn AgNO.sub.3 0.1 Example 3-6 Cu Au(OAc).sub.3 0.1

[0109] The SEM photographs of the spherical mesoporous silica dispersed and embedded with nano-sized alloy particles in Example 3-1 are as illustrated in FIGS. 4 and 5.

[0110] According to FIGS. 4 and 5, it can be confirmed that the spherical mesoporous silica is very uniformly standardized as a whole. The spherical mesoporous silica dispersed and embedded with nano-sized alloy particles has a particle size of 20 to 700 nm.

[0111] The TEM photograph results of the spherical mesoporous silica dispersed and embedded with nan-sized alloy particles in Example 3-1 are as illustrated in FIGS. 6 and 7.

[0112] According to FIGS. 6 and 7, it can be confirmed that nano-sized alloy particles are uniformly dispersed in the spherical mesoporous silica as a whole. It was confirmed that the size of alloy particles was exhibited as a black dot of 1 to 3 nm, and in FIGS. 11 to 16 mapping the same, it can be confirmed that silver, zinc, silicon, oxygen, carbon, and nitrogen are uniformly dispersed.

[0113] Although the preferred Examples of the present invention have been described in detail hereinabove, the right scope of the present invention is not limited thereto, and it should be understood that many variations and modifications of those skilled in the art using the basic concept of the present invention, which is defined in the following claims, will also fall within the right scope of the present invention.