WO2014178455A1 - Method for manufacturing transition metal-silicone hollow microspheres - Google Patents

Abstract

A method for manufacturing transition metal-silicone hollow microspheres is disclosed. The method for manufacturing transition metal-silicone hollow microspheres, according to the present invention, comprises: (1) the first step for preparing a solution containing transition metals by adding a solvent to a transition metal precursor, and preparing a solution containing silicone by adding a solvent to a compound containing silicone; (2) the second step for forming transition metal-silicone hollow microspheres by reacting the solution containing the transition metals with the solution containing silicone, which are prepared in the first step; and (3) the third step for stabilizing the metal-silicone hollow microspheres by performing a heat treatment on the metal-silicone hollow microspheres formed through the second step. The method for manufacturing transition metal-silicone hollow microspheres, according to the present invention, can facilitate mass-production of the hollow microspheres which have a uniform small size and formed from composite material of transition metal and silicone.

Description

Method for preparing transition metal-silicon microspheres

The present invention relates to a method for producing a transition metal-silicon microspheres, and more particularly, to a method for producing a transition metal-silicon microspheres, in which a simple and bulky transition metal-silicon hollow sphere can be produced in large quantities. It is about.

The fine hollow spheres have a low density and a large specific surface area, and are capable of exchanging materials through micropores, and have a strong characteristic against physical impact or pressure due to their spherical shape. In addition to the properties of the micro hollow sphere itself, it is possible to impart various characteristics depending on the material to form the micro hollow sphere.

Currently, micro hollow spheres of metal materials, micro hollow spheres of organic or inorganic materials are known, and due to the characteristics of the materials and the characteristics of the micro hollow spheres, hydrogen storage media, building materials, heat radiation materials, sound insulation and electromagnetic shielding materials, beauty materials , Coating materials, filling materials, catalyst carriers, drug delivery materials, adsorbents for removing harmful substances, fuel cell electrode materials, etc. are being used. Recently, researches to be applied to high-tech industries are actively conducted. It is becoming.

Currently, most of the methods for producing the microspheres are prepared in the form of a spherical template that can be dissolved in a specific solvent, as disclosed in Korean Patent Laid-Open Publication No. 2009-0048964, covering the material to be prepared therewith. Then, it is based on the method of removing the inside template using a solvent. In addition, a method of injecting a gas and using the gas to be injected as a template is known, but in the case of manufacturing the fine hollow sphere by the above-described method, it is difficult to produce a very small hollow sphere, and the wall of the hollow sphere It has a relatively thick thickness and complicated process conditions, making it unsuitable for mass production.

In addition, conventionally known methods for manufacturing micro hollow spheres are mostly to manufacture micro hollow spheres with a single series of materials such as metal materials, organic materials, and inorganic materials, and thus are applicable to the manufacture of fine hollow spheres of composite materials such as metal-inorganic materials. There is a limit to doing so.

The present invention has been made to solve the above-mentioned conventional problems, an object of the present invention is to provide a method for producing a transition metal-silicon micro-hollow sphere that can easily produce a large amount of hollow spheres having a fine size.

Another object of the present invention is to provide a method for producing fine hollow spheres made of a composite material of a transition metal and silicon.

In order to achieve the above object, the present invention provides a method for producing a transition metal-silicon microspheres, the method for producing a transition metal-silicon microspheres,

(1) preparing a solution containing a transition metal by adding a solvent to the transition metal precursor, and preparing a solution containing silicon by adding a solvent to a compound containing silicon;

(2) a second step of forming a transition metal-silicon hollow sphere by reacting the solution containing the transition metal and the solution containing silicon prepared in the first step; And

(3) a third step of stabilizing the transition metal-silicon hollow sphere formed through the second step by heat treatment.

The reaction made in the second step is preferably performed for 5 to 50 hours in a temperature range of 100 to 300 ℃.

In addition, the heat treatment performed in the third step is preferably performed for 1 to 10 hours in a temperature range of 300 to 500 ℃ under a vacuum atmosphere.

According to the present invention described above, it is possible to easily produce a large amount of fine hollow sphere made of a composite material of a transition metal and silicon.

The fine hollow spheres produced by the present invention have the characteristics that the size of the microspheres is uniform and small, and the wall thickness is thin, compared to the hollow spheres produced by the conventional method.

In addition, the fine hollow sphere prepared by the present invention can express the properties of the material having a transition metal and silicon in addition to the properties of the fine hollow sphere itself can be effectively applied to a variety of industries.

1 is a TEM image of manganese-silicon microspheres prepared according to an embodiment of the present invention.

Figure 2 shows the XRD data of the manganese-silicon microspheres prepared by the embodiment of the present invention.

3 is a TEM image of the manganese-silicon microspheres prepared by Comparative Example 1. FIG.

4 is a TEM image of manganese-silicon microspheres prepared by Comparative Example 2. FIG.

5 is a TEM image of manganese-silicon microspheres prepared by Comparative Example 3. FIG.

Hereinafter, the present invention will be described in detail.

Conventionally known methods for producing hollow spheres, most of which produce a hollow sphere using one or two or more metals, or a hollow sphere using one or more inorganic materials, such as to produce a hollow sphere using the same series of materials Was to make. In addition, as described above, a method of preparing a spherical template that can be dissolved in a specific solvent and covering the material to be manufactured thereon, and then removing the spherical template in the interior using a solvent. Thereby preparing a hollow sphere.

According to the conventional method as described above, the hollow spheres are relatively large, the wall thickness is relatively thick, the process conditions are complicated, and the control is not easy, so it is not suitable for mass production, and is a single series such as metal or inorganic materials. By manufacturing the hollow spheres of the material, there has been a limit in expressing a variety of functions.

Accordingly, the inventors of the present invention have studied a method for producing a micro hollow sphere made of a composite material of a transition metal and silicon, which is applied to various industrial fields due to its characteristics, and in the following process, a transition metal-silicon The present invention was completed by confirming that fine hollow spheres can be efficiently produced.

That is, the method for producing a transition metal-silicon microspheres according to an example of the present invention,

(1) preparing a solution containing a transition metal by adding a solvent to the transition metal precursor, and preparing a solution containing silicon by adding a solvent to a compound containing silicon;

(2) a second step of forming a transition metal-silicon hollow sphere by reacting the solution containing the transition metal and the solution containing silicon prepared in the first step; And

(3) and a third step of stabilizing by heat-treating the transition metal-silicon hollow sphere formed through the second step.

The transition metal precursor may be variously selected according to the characteristics of the transition metal to be imparted to the micro hollow spheres, as long as it is known as a transition metal precursor may be used. Among the various transition metals, in particular, manganese (Mn) is more environmentally friendly than other transition metals, and is relatively inexpensive and has a high energy density so that it can be efficiently applied to various fields. Therefore, it is preferable to use a manganese precursor as the transition metal precursor. Can be. The manganese precursor may be used as long as it is known as a manganese precursor. For example, Mn (NO ₃ ) ₂ .4H ₂ O, Mn (CH ₃ CO ₂ ) ₂ , Mn (CH ₃ CO ₂ ) ₂ .4H _2. O, Mn (ClO ₄ ) ₂ · 6H ₂ O, MnSO ₄ · xH ₂ O, MnSO ₄ · H ₂ O and mixtures thereof, but is not limited thereto.

In addition, the compound containing silicon may be used as long as the compound containing silicon. As an example, the compound containing silicon may include Na ₂ SiO ₃ , SiCl ₄ , Si (OCOCH ₃ ) ₄ , SiI ₄ , SiF ₄ , SiC ₃₂ H ₈ O ₂ , SiC ₄₈ H ₂₆ N ₈ O ₂ , SiC ₃₂ H ₁₈ N ₂ O ₂ and mixtures thereof, but is not limited thereto.

The solvent used in the first step may be used as long as it dissolves the compound including the transition metal precursor and silicon. Various organic solvents, water and the like can be used.

Among the solvents used in the first step, the solvent for dissolving the transition metal precursor is preferably alcohol, more preferably ethanol. As a result of experiments by selecting a variety of solvents to dissolve the transition metal precursor in the completion of the present invention, when using alcohol, in particular ethanol compared to other solvents, more reliable results were obtained. However, even when other solvents were used, fine hollow spheres could be produced, and thus, the solvent for dissolving the transition metal precursor is not limited to alcohol, in particular ethanol.

In the second step, a transition metal-silicon hollow sphere is formed by reacting the solution containing the transition metal prepared in the first step with a solution containing silicon. That is, in the second step, when the solution containing the transition metal and the solution containing silicon are reacted at a specific temperature range and reaction time, the two solutions react to form a transition metal-silicon composite, and as the reaction proceeds, The transition metal-silicon composite is dried into a hollow sphere shape to form a transition metal-silicon micro hollow sphere. In other words, after the transition metal-silicon composite is formed, if the reaction proceeds continuously, the transition metal-silicon composite formed due to the difference in the material properties of the transition metal and silicon is dried, and the reaction proceeds to form a hollow sphere. do. The transition metal-silicon micro hollow spheres formed in this step are in the shape of hollow spheres, but are not perfectly stabilized, and are perfectly stabilized through heat treatment to be described later.

At this time, the reaction is preferably carried out for 5 to 50 hours in the temperature range of 100 to 300 ℃, when the reaction temperature and the reaction time is less than the lower limit, the transition metal-silicon composite may not be sufficiently formed with a spherical shape If the reaction temperature and the reaction time exceeds the upper limit, the transition metal-silicon hollow sphere formed as the transition metal-silicon composite is cracked or crushed is spherical. It is not preferable because it may have a shape other than a phase.

The transition metal-silicon hollow sphere formed through the second step may be subjected to a process of washing and drying, wherein the washing and drying are for minimizing unwanted side reactions in the heat treatment process to be described later, As such, detailed description thereof will be omitted.

Next, the transition metal-silicon hollow sphere is heat-treated through the process of the third step, and the shape of the hollow sphere perfectly stabilized through the heat treatment.

The heat treatment is preferably carried out in a vacuum atmosphere, but not performed in a vacuum atmosphere, for example, when the heat treatment is performed in an air atmosphere, a part of the manufactured micro hollow spheres may be changed into transition metal oxide micro hollow spheres. Not. That is, when the heat treatment is performed in an air atmosphere, a part of the transition metal-silicon hollow spheres is changed to transition metal oxide hollow spheres, so that the transition metal-silicon micro hollow spheres and the transition metal oxide micro hollow spheres are simultaneously prepared to obtain the transition metal-silicon micro hollow spheres. Yield may be lowered, which is not preferred. When the heat treatment is performed under a vacuum atmosphere rather than an air atmosphere, the transition metal-silicon hollow spheres do not change into transition metal oxide hollow spheres, and thus, a stabilized transition metal-silicon microspheres can be obtained, thereby increasing the yield.

In addition, the heat treatment is preferably performed for 1 to 10 hours in the temperature range of 300 to 500 ℃, when the heat treatment temperature and time is less than the lower limit, the transition metal-silicon micro hollow spheres are not sufficiently stable, This is not preferable because there is a fear of lowering, and when the heat treatment temperature and time exceeds the upper limit, there is a possibility that the transition metal-silicon micro hollow spheres may be broken or the structure may be deformed.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

Example Preparation of Manganese-Si Micro Hollow Spheres

5.2 g of Mn (NO ₃ ) ₂ .4H ₂ O, a manganese precursor, was dissolved in 250 ml of ethanol to prepare a solution containing manganese. In addition, Na ₂ SiO ₃ , a compound containing silicon, was dissolved in distilled water to prepare a solution containing 0.5 M and 50 mL of silicon.

  The manganese-containing solution and the silicon-containing solution were reacted at 185 ° C. for 30 hours to prepare manganese-silicon micro hollow spheres.

Next, the prepared manganese-silicon microspheres were washed three times with distilled water, and then dried at 50 ° C. in a vacuum atmosphere for 5 hours.

Finally, the dried manganese-silicon microspheres were heat-treated at 400 ° C. for 2 hours in a vacuum atmosphere to prepare stabilized manganese-silicon microspheres.

Comparative Example

Only some of the conditions described in the following table were changed, and the manganese-silicon micro hollow spheres were prepared by the same method as the above example, which was selected as a comparative example.

TABLE 1 Production conditions of Examples and Comparative Examples

Characteristic evaluation

1 is a TEM image of manganese-silicon microspheres prepared according to an embodiment of the present invention. As shown in FIG. 1, the manganese-silicon microspheres prepared according to the embodiment of the present invention may have a uniform hollow sphere shape while having a size of about 6 to 7 nm or less.

Figure 2 shows the XRD data of the manganese-silicon microspheres prepared by the embodiment of the present invention. As shown in FIG. 2, in the case of the manganese-silicon micro hollow spheres prepared according to the embodiment of the present invention, it was confirmed that the micro hollow spheres were made of manganese-silicon composite (MnSiO ₃ ).

3 is a TEM image of the manganese-silicon microspheres prepared by Comparative Example 1. FIG. As shown in FIG. 3, in the case of Comparative Example 1, it could be confirmed that there was a portion that could not be rolled into a hollow sphere shape.

4 is a TEM image of manganese-silicon microspheres prepared by Comparative Example 2. FIG. As shown in FIG. 4, in the case of Comparative Example 2, it could be confirmed that the hollow sphere shape was partially broken due to excessive reaction.

5 is a TEM image of manganese-silicon microspheres prepared by Comparative Example 3. FIG. As shown in FIG. 5, in the case of Comparative Example 3, the hollow sphere shape was broken or collapsed due to excessive heat treatment.

Although the present invention has been described with reference to the above-described embodiments and the accompanying drawings, other embodiments may be configured within the spirit and scope of the present invention. Therefore, the scope of the present invention is defined by the appended claims and equivalents thereof, and is not limited by the specific embodiments described herein.

Claims (10)

1. (1) preparing a solution containing a transition metal by adding a solvent to the transition metal precursor, and preparing a solution containing silicon by adding a solvent to a compound containing silicon;

   (2) a second step of forming a transition metal-silicon hollow sphere by reacting the solution containing the transition metal and the solution containing silicon prepared in the first step; And

   (3) A method for producing a transition metal-silicon microspheres comprising a third step of stabilizing by heat-treating the transition metal-silicon hollow spheres formed through the second step.
2. The method of claim 1,

   Method for producing a transition metal-silicon microspheres further comprising the step of washing and drying the transition metal-silicon hollow sphere formed through the second step after the second step.
3. The method of claim 1,

   The transition metal precursor is a method for producing a transition metal-silicon microspheres, characterized in that the manganese precursor.
4. The method of claim 3,

   The manganese precursors are Mn (NO ₃ ) ₂ 4H ₂ O, Mn (CH ₃ CO ₂ ) ₂ , Mn (CH ₃ CO ₂ ) ₂ 4H ₂ O, Mn (ClO ₄ ) ₂ · 6H ₂ O, MnSO ₄ XH ₂ O, MnSO ₄ H ₂ O and a mixture thereof, the method for producing a transition metal-silicon micro hollow spheres.
5. The method of claim 1,

   The compound containing silicon is Na ₂ SiO ₃ , SiCl ₄ , Si (OCOCH ₃ ) ₄ , SiI ₄ , SiF ₄ , SiC ₃₂ H ₈ O ₂ , SiC ₄₈ H ₂₆ N ₈ O ₂ , SiC ₃₂ H ₁₈ N ₂ Method for producing a transition metal-silicon microspheres characterized in that it is selected from the group consisting of O ₂ and mixtures thereof.
6. The method of claim 1,

   The solvent applied to the transition metal precursor is alcohol (alcohol), characterized in that the transition metal-silicon micro hollow sphere production method.
7. The method of claim 6,

   The alcohol (alcohol) is a method for producing a transition metal-silicon microspheres, characterized in that ethanol (ethanol).
8. The method of claim 1,

   The reaction made in the second step is a method for producing a transition metal-silicon microspheres, characterized in that for 5 to 50 hours in a temperature range of 100 to 300 ℃.
9. The method of claim 1,

   The heat treatment in the third step is a method for producing a transition metal-silicon microspheres, characterized in that the vacuum atmosphere.
10. The method of claim 1,

    Heat treatment made in the third step is a method for producing a transition metal-silicon microspheres, characterized in that made for 1 to 10 hours in a temperature range of 300 to 500 ℃.

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