KR101197190B1 - Axial heterostructure nanowires of metal oxides, and manufacturing method thereof - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal oxide hetero-nanowire formed in the longitudinal direction and a method for synthesizing the same, wherein the core-shell hetero-nanowire consists of a carbon nanotube shell containing therein an intermetallic compound or alloy containing two or more metal materials therein. After synthesis, the synthesized core-shell heteronanowires are oxidized in a general atmospheric atmosphere to remove carbon nanotubes existing at the same time, and at the same time, oxidizing intermetallic compounds or alloys present therein to lengthen each metal oxide. The present invention relates to a method for generating nanowires while separating them in directions.

Description

Axial heterostructure nanowires of metal oxides, and manufacturing method

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal oxide hetero-nanowire formed in the longitudinal direction and a method for synthesizing the same. After synthesis, the synthesized core-shell heteronanowires are oxidized in a general atmospheric atmosphere to remove carbon nanotubes existing at the same time, and at the same time, oxidizing intermetallic compounds or alloys present therein to lengthen each metal oxide. The present invention relates to a method for generating nanowires while separating them in directions.

Longitudinal heterogeneous nanowires are generally synthesized by a Vapor-Liquid-Solid (VLS) mechanism. Nano-sized catalyst particles are used for this synthesis method. The catalyst particles help to grow the nanowires by absorbing and diffusing the source material of the nanowires to be produced at high reaction temperature conditions.

The biggest feature of this conventional synthesis method is to alternately supply the desired gas, and to receive each gas supplied with the catalyst to form heterogeneous nanowires through catalysis.

This method of synthesis has the advantage that the heterogeneous structure is uniform and the control of each component is smooth, but the process is complicated and the source necessary for synthesizing heterogeneous nanowires for metals, especially metal oxides, must be supplied in the gas phase. In other words, the metal must be treated at a temperature above the melting point, which is associated with an increase in energy consumption, and also has a disadvantage in that mass production is not easy due to the nature of the process.

In the present invention, in order to overcome the disadvantages of the conventional method, based on the carbon nanotube shell, a large amount of radial heterogeneous nanowires including intermetallic compounds or alloys composed of two or more species therein, and oxidized it to carbon A method of mass synthesis of heterogeneous nanowires in the longitudinal direction was developed by oxidizing and separating intermetallic compounds or alloys present therein while removing nanotubes.

An object of the present invention is to provide a method for synthesizing a large amount of metal oxide hetero nanowires formed in the longitudinal direction through a very simple core-shell hetero nanowire synthesis method and an oxidation process.

The present invention for achieving the object as described above, iii) putting the metal oxide mixture into the reactor, and lowering the vacuum degree to remove the remaining oxygen in the reactor, injecting a transfer gas into the reactor and raising the temperature inside the reactor, ii ) Injecting a hydrocarbon gas into the reactor into which the transfer gas is introduced to react with the metal oxide mixture to synthesize heterogeneous nanowires composed of an intermetallic compound or an alloy core and a carbon nanotube shell, and iii) cooling the reactor to room temperature. After that, the present invention provides a method for synthesizing a longitudinally composed metal oxide heterogeneous nanowire comprising the step of raising the temperature in an oxidizing atmosphere and oxidizing the synthesized heterogeneous nanowire, and a metal oxide heterogeneous nanowire synthesized thereby. Shall be.

In the heterogeneous nanowire synthesis step composed of the intermetallic compound or the alloy core and the carbon nanotube shell, the reducing agent of the metal oxide mixture serves as a catalyst for synthesizing the carbon nanotubes, and indium oxide and Mixtures of tin oxides can be used. In this case, the mixing ratio of the indium oxide and tin oxide is preferably in the range of 6: 1 to 1: 6 based on the weight ratio, the reaction temperature of the metal oxide mixture and hydrocarbon gas is in the range of 550 ~ 850 ℃, reaction The time is preferably within 2 hours.

In addition, the hydrocarbon gas introduced into the reactor may be any one or two or more selected from acetylene, ethylene, and methane, and the amount of hydrocarbon gas introduced into the reactor is 2 to 10 based on the transport gas. It is preferably in the vol% range.

In addition, hydrogen gas may be introduced to assist the reaction between the metal oxide mixture and the hydrocarbon gas, and the amount of the hydrogen gas is preferably 5 vol% or less based on the transport gas.

At this time, the oxidation treatment temperature is in the range of 600 ~ 800 ℃ degree, the oxidation treatment time is in the range of 30 minutes to 3 hours, the temperature rise for the oxidation treatment is preferably in the range of 1 ~ 10 ^° C / min. In addition, the oxidation treatment may be performed in a general atmospheric atmosphere.

On the other hand, the metal oxide heterogeneous nanowires prepared by the above synthesis method has an average diameter of 50 ~ 150 nm, the length is 10㎛ or less.

The present invention synthesizes a heterogeneous nanowire composed of a carbon nanotube shell and an intermetallic compound or alloy core using an intermetallic compound or alloy of a metal having catalytic properties capable of producing carbon nanotubes, By oxidizing the core-shell hetero-nanowire at a temperature above the oxidation temperature, carbon nanotubes existing on the surface are removed, and intermetallic compounds or alloys present therein are oxidized and separated to form a new type of longitudinal hetero-nano. Synthesize the wire.

By using this principle, various materials can be used at the same time compared to the conventional method of synthesizing the lengthy heterogeneous nanowires. In addition to producing the heterogeneous nanowires in the longitudinal direction composed of various materials with a very simple process, It is easy.

1 is a flowchart illustrating a method for synthesizing an indium oxide-tin oxide hetero nanowire configured in the longitudinal direction according to the present invention.
Figure 2 is an XRD image of the indium oxide-tin oxide hetero nanowires configured in the longitudinal direction according to the present invention.
3A is an SEM image of core-shell heterogeneous nanowires first synthesized according to the present invention.
FIG. 3B is an SEM image of the indium oxide-tin oxide heterogeneous nanowires formed in the longitudinal direction finally obtained through the oxidation process. FIG.
4A to 4C are TEM images of heterogeneous nanowires having an indium / tin core and a carbon nanotube shell according to the present invention.
5A to 5D are TEM images of indium oxide-tin oxide hetero nanowires constructed in the longitudinal direction according to the present invention.
6A-6B show the line profile results of the indium oxide-tin oxide heterogeneous nanowire component constructed longitudinally in accordance with the present invention.
7A to 7E show a mapping image of an indium oxide-tin oxide hetero nanowire component constructed in a longitudinal direction according to the present invention.

Hereinafter, with reference to the accompanying drawings, a metal oxide heterogeneous nanowire and a method for synthesizing the same in the longitudinal direction of the present invention will be described in detail.

In the method for synthesizing heterogeneous nanowires of the present invention, i) adding a metal oxide mixture to a reactor, lowering the vacuum degree to remove residual oxygen in the reactor, and injecting a transfer gas into the reactor and raising the temperature inside the reactor, ii) Injecting a hydrocarbon gas into the reactor into which the transfer gas is introduced to react with the metal oxide mixture to synthesize heterogeneous nanowires composed of an intermetallic compound or an alloy core and a carbon nanotube shell, and iii) cooling the reactor to room temperature. In addition, the step of raising the temperature in the oxidizing atmosphere and then oxidizing the synthesized heterogeneous nanowires.

Looking at the formation process of the nanowires in detail with reference to Figure 1, first synthesize the carbon nanotube-based radial heterogeneous nanowires in order to synthesize longitudinal heterogeneous nanowires composed of heterogeneous materials in the growth direction of the nanowires.

In order to synthesize heterogeneous nanowires based on carbon nanotube shells, first, a metal oxide capable of acting as a catalyst capable of producing carbon nanotubes should be prepared. The result after reduction is determined in consideration of whether there is a suitable catalytic activity for synthesizing carbon nanotubes.

Metal oxides having catalytic activity vary, but in the following examples, indium oxide and tin oxide are selected.

The indium oxide and tin oxide metal oxide mixture is preferably mixed in a weight ratio range of 6: 1 to 1: 6, and the prepared metal oxide is homogenously mixed, filtered, and dried in an aqueous solution, and then placed in a reactor. .

Before starting the synthesis, any residual oxygen inside the reactor is removed using a vacuum pump, dropping the internal vacuum to a maximum of 10 ^-2 Torr. Then, using a transfer gas such as argon or nitrogen, the temperature of the reactor is increased to a synthesis temperature of 550 to 850 ° C.

When the temperature of the reactor rises to the synthesis temperature, hydrocarbon gas from a carbon source is supplied. As the hydrocarbon gas, any one or two or more of acetylene, methane, and ethylene may be used, and the synthesis time is preferably performed up to 2 hours.

At this time, hydrogen gas may be used as an auxiliary gas to promote the reduction of the metal oxide and to suppress the production of amorphous carbon. Too much hydrogen causes the reduction rate of the metal oxide to be too high, which promotes excessively the formation of intermetallic compounds or alloys of indium and tin, and thus the formation of nano-sized indium and tin intermetallic compounds or alloys serving as catalysts. Can be reduced relatively.

Therefore, not only the size of heterogeneous nanowires is made huge but also the synthesis yield of heterogeneous nanowires can be reduced, so that the amount of hydrogen supplied is preferably 0 to 5 vol%.

After the synthesis process is completed, the temperature of the reactor is cooled to room temperature in the carrier gas atmosphere, and then the resulting heterogeneous nanowires are taken from the carbon nanotube shell-based radial direction. This completes the synthesis of heterogeneous nanowires consisting primarily of a carbon nanotube shell and an indium / tin core.

Subsequently, the obtained core-shell heterogeneous nanowire in the radial direction is placed in a boat made of quartz or alumina, and then oxidation treatment is started. Oxidation temperature of the reactor is preferably 600 ~ 800 ^o C, which is less than 600 ^o C carbon nanotubes are difficult to incinerate with carbon monoxide or carbon dioxide by combining with oxygen, the oxidation of nanotubes already terminated above 800 ^o C This is because no further temperature rise is necessary. In addition, in the temperature range, most of the materials used as cores existing inside the carbon nanotubes may be converted into oxides.

The elevated temperature is controlled in the range of 1 to 10 ^o C / min. The rapid temperature rise causes rapid incineration of the carbon nanotube shell and excessive oxidation rate of the core material, so that the desired nanowire shape cannot be maintained.

The oxidation treatment time at the target temperature is carried out in the range of 30 minutes to 3 hours, the heat treatment atmosphere gas is performed in a general air atmosphere, it is not necessary to supply additional air. After the oxidation treatment, the temperature of the reactor is cooled to room temperature in an air atmosphere, and the sample is taken to finish synthesis of indium oxide-tin oxide hetero nanowires formed in the longitudinal direction.

Through the oxidation process as described above, the carbon shell of heterogeneous nanowires in the carbon nanotube shell-based radial direction is incinerated by reaction with oxygen. The incineration rate can be controlled according to the rising temperature rate of the reactor and the oxygen concentration control inside the reactor, of which the control of the rising temperature rate of the reactor is the most important control factor.

At 600 ^° C or higher, the intermetallic compound or alloy of indium / tin contained inside the carbon nanotube shell is present in solution. These oxides come into contact with oxygen with the incineration of the carbon nanotube shell. Will switch to.

In this process, the indium / tin intermetallic compound or alloy is divided into two and separated into indium oxide and tin oxide, and the two oxides maintain the shape of the nanowire, are arranged in the axial direction, and consequently formed in the longitudinal direction. Indium oxide-tin oxide heterogeneous nanowires are synthesized.

It was confirmed through the present invention that the indium oxide-tin oxide heterogeneous nanowires formed in the longitudinal direction are formed at an average diameter in the range of 50 to 150 nm, preferably 100 nm, and have a length of 10 μm or less.

Hereinafter, an embodiment of a carbon nanotube in which impurities such as a metal are not included therein according to an embodiment of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments, and those skilled in the art can implement various modified forms of the contents described herein within the scope of the present invention.

Example 1 XRD Results of the Indium Oxide Tin Oxide Heterogeneous Nanowires

Figure 2 shows an XRD image of the indium oxide-tin oxide hetero nanowires configured in the longitudinal direction according to the present invention. As-recieved is an XRD graph of a mixture of indium oxide and tin oxide, and 1st synthesis shows an XRD graph of the result obtained by reacting a mixture of indium oxide and tin oxide with acetylene for 1 hour at 750 degrees. InSn ₄ and In ₃ Sn were formed in the indium / tin intermetallic oxide.

Oxidation of the indium / tin intermetallic core-carbon nanotube heterogeneous nanowires was confirmed to remove all of the carbon nanotube shells, and the oxidation product was oxidized from the original sample, As-recieved. It was confirmed that they have the same crystal structure as indium and tin oxide.

Example 2 SEM image of the produced indium oxide-tin oxide hetero nanowires

3A to 3B are SEM images of the primary synthesized core-shell hetero-nanowires according to the present invention and indium oxide-tin oxide hetero-nanowires formed in the longitudinal direction obtained through the oxidation process.

FIG. 3A shows a core-shell heteronanowire synthesized primarily using a mixture of indium oxide and tin oxide, and partly free of indium / tin intermetallic compounds contained therein and an empty space was identified. The volume of was more than 90% of the space inside the carbon nanotube shell.

FIG. 3B shows longitudinal indium oxide-tin oxide heterogeneous nanowires obtained by oxidizing primary synthesized core-shell heterogeneous nanowires at 650 ° C. in an air atmosphere, and although similar in size, the presence of shells was not confirmed. Nanoparticles are partially observed on the surface of the nanowires. In addition, nucleus-like heterostructures were observed in the middle of the nanowires.

Example 3 TEM image of generated core-shell heterogeneous nanowires

4A-4C show TEM images of core-shell heteronanowires having an indium / tin core and carbon nanotube shells according to the present invention.

Figure 4a is a low magnification image of the core-shell heteronanowire, it was confirmed that the core is completely stacked by the carbon nanotubes, the indium / tin core in the carbon nanotubes were found to be more than 90% filled.

It is confirmed from the high magnification TEM image of FIG. 4B that the crystal structure of the core contained therein is indium / tin intermetallic oxide, which is represented by InSn ₄ or In ₃ depending on the mixing ratio of tin oxide and indium oxide as shown in FIG. 2. It was confirmed to be Sn.

The results for the core are more clearly seen in the STEM image of FIG. 4C, and the lattice distance of 0.34 nm was found to be externally stacked.

[Example 4] TEM image of the produced indium oxide-tin oxide hetero nanowires

5A to 5D show TEM images of indium oxide-tin oxide hetero nanowires constructed longitudinally in accordance with the present invention.

Figure 5a shows a low magnification image of the longitudinal indium oxide-tin oxide heteronanowires produced through the oxidation treatment of the core-shell heterogeneous nanowires at 650 ℃, the carbon nanotube shell as shown in Figure 4 externally observed Instead, it is confirmed that layers in which contrasting materials are generated in the middle of the nanowires are formed.

The STEM image of FIG. 5B clearly revealed this contrast. This contrast difference can be seen in structures in which different materials are interconnected because they have different specific gravity.

FIG. 5C is a high magnification image of FIG. 5A, and FIG. 5D shows XRD diffraction patterns for the top and bottom of the boundary layer of FIG. 5C. Analysis of each diffraction pattern clearly indicates that the bottom is indium oxide and the top is tin oxide.

Example 5 EDX Analysis of the Indium Oxide Tin Oxide Heterogeneous Nanowires

6a to 6b show the line profile results of the indium oxide-tin oxide hetero nanowire component constructed in the longitudinal direction according to the present invention.

6A is a TEM image where one boundary layer is identified in the middle of a nanowire. FIG. 6B shows the STEM image and the line profile of the components for FIG. 6A, with indium and oxygen at the bottom of the nanowires and tin and oxygen at the top. This clearly confirms the formation of indium oxide at the bottom and tin oxide at the top.

Example 6 STEM and Mapping Images of the Indium Oxide Tin Oxide Heterogeneous Nanowires

7A to 7E show a mapping image of an indium oxide-tin oxide hetero nanowire component constructed in a longitudinal direction according to the present invention.

One nanowire can be seen in the STEM image of FIG. 7A, where a mapping image of the entire component is shown in FIGS. 7C-7E. FIG. 7C shows indium, FIG. 7D shows tin, and FIG. 7E shows the oxygen component.

As a result, oxygen is found in every part of the nanowire for analysis. However, indium and tin were found to alternately along the length of the nanowire.

This result can be seen more clearly in Figure (b), which is a duplicate image of indium and tin. This makes it clear that the resulting nanowires are longitudinally constructed indium oxide-tin oxide heterogeneous nanowires.

As described above, heterogeneous nanowires composed of carbon nanotube shells and intermetallic compounds or alloy cores are synthesized using an intermetallic compound or alloy as a medium, and then oxidized to remove carbon nanotubes present on the surface. By oxidizing and separating intermetallic compounds or alloys present therein, new types of longitudinal heterowires can be synthesized.

Using this principle, it is possible to mass-produce longitudinal heterogeneous nanowires composed of various materials in a very simple process by using a variety of materials at the same time as compared to the conventional method of synthesizing longitudinal heterogeneous nanowires.

The present invention is not limited to the above-described specific embodiments and descriptions, and various modifications can be made to those skilled in the art without departing from the gist of the present invention claimed in the claims. And such modifications are within the scope of protection of the present invention.

Claims (20)

Iii) placing the metal oxide mixture into the reactor, lowering the vacuum to remove residual oxygen in the reactor, and then injecting a feed gas into the reactor and raising the temperature inside the reactor;
Ii) injecting a hydrocarbon gas into the reactor into which the transfer gas is introduced to react with the metal oxide mixture to synthesize heterogeneous nanowires composed of an intermetallic compound or an alloy core and a carbon nanotube shell; And
Iii) cooling the reactor to room temperature, and then raising the temperature in an oxidizing atmosphere to oxidize the synthesized heterogeneous nanowires;
Synthesis method of a metal oxide heterogeneous nanowire configured in the longitudinal direction comprising a.
The method of claim 1,
In the heterogeneous nanowire synthesis step consisting of the intermetallic compound or the alloy core and the carbon nanotube shell, the reduced oxide of the metal oxide mixture acts as a catalyst for synthesizing the carbon nanotubes, the metal oxide heterogeneous nanoparticles in the longitudinal direction Synthesis method of wire.
The method of claim 2,
Method for synthesizing a metal oxide heterogeneous nanowires in the longitudinal direction characterized in that the metal oxide mixture is a mixture of indium oxide and tin oxide.
The method of claim 3,
The mixing method of the indium oxide and tin oxide is a method of synthesizing the metal oxide heterogeneous nanowires in the longitudinal direction, characterized in that the range of 6: 1 ~ 1: 6 based on the weight ratio.
The method of claim 3,
The reaction temperature between the metal oxide mixture and the hydrocarbon gas ranges from 550 to 850 ° C., and the reaction time is within 2 hours.
The method of claim 1,
The hydrocarbon gas flowing into the reactor is one or two or more selected from acetylene, ethylene and methane, and the amount of hydrocarbon gas flowing into the reactor is in the range of 2 to 10 vol% based on the transfer gas. Method for synthesizing a metal oxide heterogeneous nanowire configured in the longitudinal direction, characterized in that.
The method of claim 1,
Hydrogen gas is introduced to assist the reaction between the metal oxide mixture and the hydrocarbon gas, and the synthesis of the metal oxide heterogeneous nanowires in the longitudinal direction is characterized in that the inflow amount of the hydrogen gas is 5 vol% or less based on the transport gas. Way.
The method of claim 1,
The oxidation treatment temperature is a method of synthesizing a metal oxide heterogeneous nanowire configured in the longitudinal direction, characterized in that the range of 600 ~ 800 ℃.
The method of claim 1,
The oxidation treatment time is 30 minutes to 3 hours, wherein the synthesis method of the metal oxide heterogeneous nanowires configured in the longitudinal direction.
The method of claim 1,
Synthesis method of a metal oxide heterogeneous nanowire configured in the longitudinal direction, characterized in that the temperature rise for the oxidation treatment is in the range of 1 ~ 10 ^o C / min.
The method of claim 1,
The oxidation treatment is a method of synthesizing a metal oxide heterogeneous nanowires configured in the longitudinal direction, characterized in that proceed in a general atmospheric atmosphere.
Iii) inserting the metal oxide mixture into the reactor, lowering the vacuum degree to remove residual oxygen in the reactor, injecting a feed gas into the reactor and raising the temperature inside the reactor, ii) adding hydrocarbon gas to the reactor into which the feed gas is introduced. Injecting and reacting with the metal oxide mixture to synthesize heterogeneous nanowires composed of an intermetallic compound or an alloy core and a carbon nanotube shell, and iii) cooling the reactor to room temperature, and then increasing the temperature in an oxidizing atmosphere. Longitudinally composed metal oxide heterogeneous nanowires synthesized through oxidizing heterogeneous nanowires.
The method of claim 12,
The metal oxide heterogeneous nanowire of claim 1, wherein the metal oxide mixture is a mixture of indium oxide and tin oxide.
The method of claim 13,
The mixed ratio of the indium oxide and tin oxide is a metal oxide heterogeneous nanowire, characterized in that the range of 6: 1 ~ 1: 6 based on the weight ratio.
The method of claim 13,
The reaction temperature between the metal oxide mixture and the hydrocarbon gas ranges from 550 to 850 ° C., and the reaction time is within 2 hours.
The method of claim 12,
The oxidation treatment temperature is a metal oxide heterogeneous nanowire configured in the longitudinal direction, characterized in that the 600 ~ 800 ℃ range.
The method of claim 12,
The oxidation treatment time is a metal oxide heterogeneous nanowire configured in the longitudinal direction, characterized in that the range of 30 minutes to 3 hours.
The method of claim 12,
Metal oxide heterogeneous nanowires, characterized in that the temperature rise for the oxidation treatment is in the range of 1 ~ 10 ^o C / min.
The method of claim 13,
A metal oxide heterogeneous nanowire configured in a longitudinal direction, wherein the average diameter is formed in the range of 50 to 150 nm.
The method of claim 13,
A metal oxide heterogeneous nanowire having a length of 10 μm or less.

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