KR101727643B1 - Carbon Nanotube Sponge-Metal Composite, and Method for Manufacturing the same - Google Patents

Abstract

The present invention provides a process for producing a precursor solution comprising the steps of: a) injecting a raw material solution containing a liquid carbon source and a catalyst precursor into a gasification furnace and vaporizing; b) continuously injecting the vaporized source gas into the reaction chamber to produce a carbon nanotube sponge so that the carbon nanotubes growing on the catalyst physically tangle with each other; c) modifying the surface of the carbon nanotube sponge with an oxidizing agent; And d) forming metal nanoparticles on the inside and the surface of the surface-modified carbon nanotube sponge. The present invention relates to a method for producing a carbon nanotube sponge-metal composite, A method for producing a carbon nanotube sponge-metal composite having excellent performance is provided.

Description

Technical Field [0001] The present invention relates to a carbon nanotube sponge-metal composite and a method for manufacturing the same,

TECHNICAL FIELD The present invention relates to a carbon nanotube sponge-metal composite and a method for manufacturing the same, and more particularly, to a method for manufacturing a carbon nanotube sponge-metal composite capable of effectively adsorbing and desorbing harmful substances such as volatile organic compounds .

Carbon nanotubes (CNTs) are carbon nanotubes arranged in a hexagonal shape and have a diameter of about 1 to 100 nm. Carbon nanotubes exhibit non-conductive, conductive, or semiconducting properties due to their unique chirality. They have strong tensile strengths greater than about 100 times greater than steel due to their strong covalent bonds, and are excellent in flexibility and elasticity, It is chemically stable.

In addition, methods for storing hydrogen in the energy field or removing harmful organic compounds that are harmful in the environment have been proposed using the characteristics of carbon nanotubes that adsorb gas molecules. In addition, studies are being conducted to induce functional groups on carbon nanotubes or to fix metal or metal oxides to increase their efficiency in order to adsorb, concentrate and store specific gas molecules.

However, the conventional method uses carbon nanotube powder. When the powder itself is used as an adsorbent, it is impossible to process or form a specific form, so that it is difficult to collect harmful substances after adsorbing harmful substances, Or a conductive foaming foam using a composition such as a crosslinking agent, a foaming agent, a foaming aid, and a crosslinking assistant (Korean Patent Laid-Open Publication No. 10-2012-0021697) or a separate heat source for detachment of harmful substances have.

Korean Patent Publication No. 10-2012-0021697 (2012.03.09)

In order to solve the above problems, it is an object of the present invention to provide a carbon nanotube sponge-metal composite which is excellent in adsorption and desorption performance of toxic substances and is easy to process.

Also, it is an object of the present invention to provide a carbon nanotube sponge-metal composite which can be used as a conductive heating element of itself and is excellent in desorbing performance of harmful substances.

According to an aspect of the present invention, there is provided a process for producing a gas mixture comprising: a) introducing a raw material solution containing a liquid carbon source and a catalyst source into a gasification furnace, b) continuously injecting the raw material gas into the reaction chamber to produce a carbon nanotube sponge that is physically entangled with the carbon nanotubes growing on the catalyst; c) modifying the surface of the carbon nanotube sponge with an oxidizing agent; And d) forming metal nanoparticles on the inside and the surface of the surface-modified carbon nanotube sponge, and a method for producing the carbon nanotube sponge-metal composite.

The raw material solution according to an exemplary embodiment of the present invention may contain 0.1 to 20 parts by weight of the catalyst source per 100 parts by weight of the carbon source of the liquid phase. At this time, the liquid carbon source may be any one or two or more selected from benzene, toluene, xylene, chlorobenzene, dichlorobenzene, (C 1 -C 5) alcohol and (C 5 -C 10) alkane. The catalyst source may be Fe-based, Co-based or Ni-based. The raw material solution may contain 0.01 to 5 parts by weight of B (CH ₃ ) ₃ , CH ₃ CN, (CH ₂ ) ₄ O, (CH 2) ₅ N, (CH 3) ₄ N _2, . ≪ / RTI > Such a raw material solution can be injected into the vaporization furnace at a rate of 50 to 500 μl / min.

The oxidant of step c) may be a nitric acid aqueous solution, an aqueous sulfuric acid solution, an aqueous hydrochloric acid solution, an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous hydrazine solution, an aqueous ammonia solution, a potassium permanganate solution, a hydrogen peroxide solution, have.

In step d) according to an embodiment of the present invention, metal nanoparticles are placed on the inside and the surface of the carbon nanotube sponge by filtering a first mixed solution containing metal nanoparticles having a particle diameter of 1 to 50 nm with a carbon nanotube sponge Can be performed in a physical way. Or a chemical method of forming metal nanoparticles on the inside and the surface of a carbon nanotube sponge by reducing a metal precursor using a second mixed solution containing a carbon nanotube sponge, a metal precursor, a reducing solvent, a stabilizer and a capping agent .

According to another aspect of the present invention, there is provided a carbon nanotube sponge-metal composite produced by the method. The carbon nanotube sponge-metal composite may be a heating element that dissipates heat when a voltage is applied. It can be used for removing substances or for concentrating volatile organic compounds. In this case, the density of the carbon nanotube sponge according to an example may be 1 to 50 mg / cm 3, and the compressive strain of the carbon nanotube sponge (compression standard of 50 volume%) may be 10 KPa to 1 MPa.

The carbon nanotube sponge-metal composite according to the present invention can effectively absorb and desorb harmful substances such as volatile organic compounds. In addition, by having a sponge shape, processing is easy.

1 is a photograph of a carbon nanotube sponge-metal composite manufactured according to an example of the present invention.
2 is an electron microscope (SEM) image of a carbon nanotube sponge manufactured according to an example of the present invention.
3 is an electron microscope (SEM) image of a carbon nanotube sponge-metal composite prepared according to an example of the present invention.
4 is a schematic diagram showing the physical method of step d) according to an example of the present invention.
5 shows the results of EDS analysis of a carbon nanotube sponge-Pt composite prepared according to an example of the present invention.
6 is a graph showing adsorption performance of the carbon nanotube sponge-Co ₃ O ₄ composite prepared according to an example of the present invention.
FIG. 7 is a graph illustrating desorption performance of a carbon nanotube sponge-Co ₃ O ₄ composite prepared according to an example of the present invention.

A method of manufacturing a carbon nanotube sponge-metal composite according to the present invention includes:

a) injecting a raw material solution containing a liquid carbon source and a catalyst source into a gasification furnace and vaporizing the raw material gas; b) continuously injecting the raw material gas into the reaction chamber to produce a carbon nanotube sponge that is physically entangled with the carbon nanotubes growing on the catalyst; c) modifying the surface of the carbon nanotube sponge with an oxidizing agent; And d) forming metal nanoparticles on the inside and on the surface of the surface modified carbon nanotube sponge.

Since the carbon nanotube sponge-metal composite produced by the above production method is produced in the form of a sponge, harmful substances such as volatile organic compounds such as benzene, toluene, ethylbenzene and xylene can be effectively adsorbed, It can be used as a heating element that emits heat by itself when a voltage is applied so that the adsorbed organic compound can be desorbed instantaneously and can be concentrated to a high concentration in a short time. Therefore, even if the concentration of the organic compound in the fluid to be injected is very low, it can be concentrated to a high concentration to sensitively detect the organic compound.

Such a sponge structure is physically intertwined with each other as the carbon nanotubes grow gradually. By adjusting the content ratio of the raw material solution and the rate of injection into the reaction chamber, the sponge structure can be improved in the properties such as density and compression strain of the carbon nanotube sponge And it is possible to improve the absorption / desorption performance of harmful substances by controlling physical properties.

The surface modification of the carbon nanotube sponge causes functional groups such as a carboxyl group, a hydroxyl group, a carbonyl group, an ester group and a nitro group to be present. These functional groups are organic compounds having a π-bond, Compounds and the like can be easily adsorbed on the carbon nanotube sponge-metal composite, and the adsorption performance of the organic compound adsorption concentration apparatus can be further improved.

Since the carbon nanotube sponge-metal composite is synthesized in the form of a sponge, unlike the powdered carbon nanotube, it can be used in various sizes and shapes. Accordingly, the carbon nanotube sponge-metal composite can be easily handled in use as an adsorbent, A device for removing harmful substances including a carbon nanotube sponge-metal complex or a concentration device can be easily manufactured.

Hereinafter, a method for producing a carbon nanotube sponge-metal composite will be described in more detail.

First, according to an example of the present invention, a raw material solution is prepared by dissolving a catalyst source in a liquid carbon source. At this time, the raw material solution may contain 0.1 to 20 parts by weight of the catalyst source per 100 parts by weight of the carbon source of the liquid phase. By using such a ratio of the raw material solution, the carbon nanotubes grown on the catalyst have appropriate diameters and lengths, so that the carbon nanotubes are physically tangled to each other, thereby effectively forming the carbon nanotube sponge. Specifically, for example, the synthesized carbon nanotube may have an average diameter of 10 to 50 nm.

If the catalyst source is too small compared to the carbon source, the carbon nanotubes may grow to a very small size and may be difficult to entangled with each other, so that it may be difficult to manufacture the carbon nanotubes in a sponge shape. On the other hand, when the amount of the catalyst is too large as compared with the carbon source, a large amount of carbon nanotubes may grow and grow to an insufficient length to be entangled with each other, which may also be difficult to produce in the form of a sponge. Or sponge-like shape, the density thereof may be too large, or it may be inappropriate to wear and detoxify harmful substances due to conductive problems.

By using the raw material solution appropriately containing the carbon source and the catalyst source, the carbon nanotubes can be tightly coupled with each other, and the sponge shape having a density effective for adsorption / desorption of harmful substances can be obtained. That is, as the density is adjusted to an appropriate range, the harmful substances flow well into the pores of the carbon nanotube sponge and can be effectively adsorbed. Also, since the electric resistance has an appropriate value according to the density of the appropriate range, It is possible to effectively remove and remove toxic substances.

The specific density (apparent density) may be specifically in the range of 1 to 50 mg / cm3, more preferably 5 to 20 mg / cm3. If the density of the carbon nanotubes is too low, the flexibility of the sponge is increased, but the restoration force is lowered and the workability is lowered. When the density is too high, the mechanical strength is increased but the flexibility is decreased.

In addition, the compression strain of the carbon nanotube sponge can be controlled by using a raw material solution suitably containing a carbon source and a catalyst source. The compressive strain shows the degree of elasticity of the carbon nanotube sponge, and the compressive strain of the carbon nanotube sponge can be 10 to 10 MPa to 1 MPa. By having such a compressive strain, it is possible to maintain the shape and shrinkage rate even if compression and restoration are repeated several hundred times or more, and it is easy to work with high flexibility.

For example, aromatic compounds such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, (C1-C5) alkylbenzenes such as benzene, toluene, ) Alcohol and (C5-C10) alkane, and the like can be used.

Catalyst source according to an example is recommended to use a Fe-based, Co-based or Ni-based compound is very soluble in the carbon source of the liquid, which is specifically exemplified _{by, FeC 10 H 10, Fe (} CO) 5, Fe (NO 3 _{) 2, Fe (NO 3)} 3, Fe (OAc) 2, FeCl 2, Co (NO 3) 2, can use the _{Co 2 (CO) 8, Co} (OAc) 2, Ni (NO 3) 2 , etc., and , FeC ₁₀ H ₁₀ (ferrocene), and Fe (CO) ₅ are more preferable.

In order to improve the physical properties such as density and compression strain of the carbon nanotube sponge, the raw material solution according to an exemplary embodiment of the present invention may include 0.01 to 5 parts by weight of B (CH ₃ ) _3, CH ₃ CN, (CH ₂ ) ₄ O, (CH) ₅ N, (CH) ₄ N _2, or a mixture thereof.

When the raw material solution is prepared as described above, it is injected into the vaporization furnace and is vaporized with the raw material gas. At this time, the catalytic source can be vaporized into the metal atom state by the high temperature of the vaporization furnace. The reaction temperature of the vaporization furnace for this purpose is not particularly limited as long as it is capable of effectively vaporizing the raw material solution, and may be, for example, 200 to 500 ° C.

The method of injecting the gas into the furnace is not particularly limited as long as it is a commonly used method for injecting a liquid sample. Specifically, it can be injected using a microsyringe pump, for example.

At this time, it is preferable to adjust the amount of the raw material solution depending on the volume of the reaction chamber, but specifically, it may be injected into the gasification furnace at a rate of, for example, 50 to 500 μl / min. This is because the injection amount of the raw material gas injected into the reaction chamber can be controlled by controlling the injection rate of the raw material solution into the vaporization furnace, so that the carbon nanotube sponge can have a more effective density for adsorbing and desorbing harmful substances have.

If the amount of the raw material solution injected is too small as compared with the volume of the reaction chamber, the growth rate may be too slow, and it may be difficult to manufacture the carbon nanotubes in a sponge shape as the carbon nanotubes grow apart from each other. On the other hand, if the amount of the raw material solution injected is too large compared to the volume of the reaction chamber, the density becomes too high and the flexibility is reduced.

Next, the carbon nanotube sponge can be produced by injecting the vaporized source gas into the reaction chamber at a constant rate. The carbon source in the vaporized raw material gas can be pyrolyzed to carbon by the high temperature of the reaction chamber. The catalytic source vaporized from the vaporization furnace to the metal atom state can be decomposed into a fine catalyst of several tens to several nanometers To form a cluster. Accordingly, the carbon is adsorbed on the catalyst particles to allow the carbon nanotubes to grow, and the carbon nanotubes can grow in a single-wall, multi-wall, or a mixture thereof. Such carbon nanotubes are physically tangled with each other as they grow, have a shape similar to a sponge, and can be made of carbon nanotube sponge.

The reaction temperature of the reaction chamber for this purpose is not particularly limited as long as it can effectively decompose the vaporized carbon source and the catalyst source can be well formed into the catalyst particles. For example, it may be 700 to 1000 ° C. If the reaction temperature is too low, the carbon source may not be decomposed well to carbon, so that growth of carbon nanotubes may be difficult.

The manufacturing method according to an exemplary embodiment of the present invention may include forming a mixed gas atmosphere before injecting the raw material gas into the reaction chamber, wherein the flow rate of the mixed gas is 1000 to 5000 sccm of the inert gas and 100 to 1000 sccm of the reducing gas . At this time, the inert gas may be Ar, Ne, or He, and the reducing gas may be H ₂ or the like.

In this case, the mixed gas according to an exemplary embodiment may further include NH ₃ or N ₂ to improve the physical properties such as the density and compressive strain of the carbon nanotube sponge, and the flow rate may be 100 to 1000 sccm .

The carbon nanotube sponge according to the production method of the present invention may be one prepared by using only the raw material solution, but may be carbon nanotubes grown on the surface of heat ray, glass fiber, quartz fiber or carbon fiber prepared in the reaction chamber May be physically tangled with one another.

Next, the surface of the carbon nanotube sponge can be modified by using an oxidizing agent. Accordingly, a functional group such as a carboxyl group, a hydroxyl group, a carbonyl group, an ester group, a nitro group or the like is introduced into the defect of the carbon nanotubes, so that the metal nanoparticles can be more adhered to the carbon nanotubes. In addition, unnecessary catalyst and contaminants can be removed by using an oxidizing agent.

The surface modification according to an example can be carried out using a commonly used oxidizing agent. Specifically, for example, a strong acid such as an aqueous nitric acid solution, an aqueous sulfuric acid solution or an aqueous hydrochloric acid solution, or an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide, A strong base such as an aqueous solution, a potassium permanganate solution, a hydrogen peroxide solution, or the like, or spraying an oxidizing gas such as ozone onto a carbon nanotube sponge.

Next, when the carbon nanotube sponge is prepared as described above, the carbon nanotube sponge-metal composite can be manufactured by forming metal nanoparticles on the inside and the surface of the carbon nanotube sponge. When the metal nanoparticles are formed on the carbon nanotube sponge, the adsorption characteristics of the harmful substances can be changed by changing the composition of the metal nanoparticles. The carbon nanotube sponge, which is a heating element, It is possible to desorb and concentrate harmful substances effectively even when a low voltage is applied.

At this time, the composite may be prepared so that the metal nanoparticles have 0.1 to 30 parts by weight based on 100 parts by weight of the carbon nanotube sponge. Within this range, the adsorption / desorption and concentration effect of harmful substances can be improved.

In this case, the metal nanoparticles preferably have an average particle diameter of about 1 to 50 nm, more preferably an average particle diameter of 5 to 10 nm. When the metal nanoparticles having such a size are uniformly dispersed on the inside and the surface of the carbon nanotube sponge, they exhibit a high harmful substance removing effect. However, if the metal nanoparticles are not properly dispersed, The improvement may be insignificant.

In addition, when carbon nanotube sponge-metal complexes are prepared by mixing one or more different metal nanoparticles, the catalytic oxidation efficiency can be enhanced or the characteristics for removing harmful substances can be further improved.

The step of forming the metal nanoparticles on the inside and the surface of the carbon nanotube sponge according to an example may be performed by a physical or chemical method.

As a specific example, the physical method is a method in which a first mixed solution containing metal nanoparticles having an average particle size of 1 to 50 nm, more preferably 5 to 10 nm, is filtered with a carbon nanotube sponge, The metal nanoparticles can be positioned. In this case, the metal nanoparticles may be referred to as transition metals or oxides of transition metals, and the transition metals may be metals of groups 3 to 12. It is more preferable to use Pt, Zn, Ni, Fe, Cu, Al, Co, Ti, Au, Ag, Pd, Cd, Rh, Cr, V, Au, Pd, Rh, Ir or oxides thereof are preferably used.

As another example, a metal precursor may be subjected to a reduction reaction using a second mixed solution containing a carbon nanotube sponge, a metal precursor, a reducing solvent, a stabilizer, and a capping agent to form metal nanoparticles on the inside and the surface of the carbon nanotube sponge Can be carried out by a chemical method.

The metal precursor according to an exemplary embodiment of the present invention may be a precursor compound of the transition metal described above. Specific examples thereof include PtCl ₂ , Pt (C ₅ H ₇ O ₂ ) ₂ , AuCl ₃ , Na ₂ PdCl ₄ , But are not limited to, PdCl ₂ , Pd (OAc) ₂ , RhCl ₃ , [Rh (COD) Cl] ₂ , IrCl ₃ , and [Ir (COD) Cl] ₂ .

The reducing solvent according to an embodiment of the present invention is a glycol solvent such as ethylene glycol, diethylene glycol, polyethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, hexylene glycol, But is not limited thereto.

The capping agent according to an exemplary embodiment of the present invention may be an amine compound such as oleylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, But is not limited thereto.

The stabilizer according to an exemplary embodiment of the present invention may be a nonionic surfactant, a cationic surfactant, a polyacrylic acid, a polyvinylpyrrolidone, a polyvinyl alcohol, a polydimethylsilane, a polysulfonic acid, a fatty acid or a mixture thereof, It is not.

The second mixed solution according to an example is prepared so as to contain 0.1 to 30 parts by weight of a metal precursor, 1000 to 10000 parts by weight of a reducing solvent, 1 to 50 parts by weight of a stabilizer, and 1 to 10 parts by weight of a capping agent based on 100 parts by weight of a carbon nanotube sponge. . Within such a range, the metal nanoparticles can be formed well on the inside and the surface of the carbon nanotube sponge, and the physical properties such as the density and compression strain of the carbon nanotube sponge can be maintained.

In addition, the second mixed solution according to one example may further include other additives conventionally used in the polyol reduction method.

The carbon nanotube sponge-metal composite manufactured according to an exemplary embodiment of the present invention has excellent adsorption / desorption performance of volatile organic compounds and the like, and thus can be used for various purposes such as removal of harmful substances, air cleaner, and concentration of volatile organic compounds have.

Hereinafter, a method for preparing a carbon nanotube sponge-metal composite according to the present invention will be described in more detail with reference to the following examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In addition, the following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the drawings presented below may be exaggerated in order to clarify the spirit of the present invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

In addition, the unit of the additives not specifically described in the specification may be% by weight.

The physical properties of the carbon nanotube sponge prepared through the following examples and comparative examples were measured as follows.

(Density measurement)

Ten masses of carbon nanotube sponge pieces cut into 1 cm3 square cubes were measured and their densities were calculated by the average mass.

(Compression strain measurement)

(SV-1K, manufactured by Core Tech Co., Ltd., Korea). When the pressing pressure per unit area was changed, the shrinkage of the carbon nanotube sponge was measured and the compressive strain was measured based on 50 vol% compression.

(EDS measurement)

And measured using an Energy Dispersive X-ray Spectrometer (Hitachi & Horiba, S4800 & EDS).

(Adsorption / desorption performance)

The adsorption rate of carbon nanotube sponge - metal composite was measured by gas chromatography using a gas chromatograph. Standard gas (BTEX) was prepared by mixing benzene, toluene, ethylbenzene and xylene, and standard gas was produced at 1 ppm each using high purity air (99.999%).

[Example 1]

5 g of ferrocene was dissolved in dichlorobenzene to prepare a raw material solution so as to have a final volume of 50 ml. The reaction chamber was set at about 860 DEG C, and a mixed gas of 2000 sccm of Ar and 200 sccm of H ₂ was flowed into the reaction chamber to replace the oxygen therein, and the reaction chamber was left to stand.

Thereafter, the raw material solution was continuously injected into the vaporization furnace at about 300 캜 at a rate of 100 ㎕ / min using a microsyringe pump. The raw material solution injected into the gasification furnace was vaporized into a raw gas state and injected into the reaction chamber. The reaction was performed for 4 hours to prepare a carbon nanotube sponge.

The density of carbon nanotube sponge prepared by this method was measured as 12 ㎎ / ㎤, and the compressive strain (50 volume% compression standard) was 50 KPa.

The carbon nanotube sponge was injected with oxygen at 0.5 kg / cm3 using an ozone generator and treated with ozone at 128 mg / h for 6 hours to modify the surface of the carbon nanotube sponge to minimize its physical properties.

Next, 5 mg of Co ₃ O ₄ nanopowder (Sigma, Cat. No. 637025) having an average particle size of about 50 nm or less was dispersed in 50 ml of methanol to prepare a mixed solution, and about 100 mg of carbon The nanotube sponge was filtered to form Co ₃ O ₄ nanoparticles on the inside and the surface of the carbon nanotube sponge.

The adsorption performance of benzene, toluene, ethylbenzene and xylene was confirmed using the carbon nanotube sponge-Co ₃ O ₄ composite prepared in Example 1 (see FIG. 6).

Next, a voltage of 20 V was applied to the carbon nanotube sponge-Co ₃ O ₄ complex adsorbed on 200 ml of the standard gas (BTEX, 1 ppm each) to cause self-heating (250 ° C), whereby the amount of the desorbed organic compound To confirm desorption and concentration performance (see FIG. 7). It is difficult to measure the standard gas (BTEX, 1 ppm each) by gas chromatography without adsorption / desorption and concentration. However, when a carbon nanotube sponge-Co ₃ O ₄ composite of the present invention was used to adsorb / desorb / concentrate a trace amount of gas sample, a standard gas sample was measured. Thus, the carbon nanotube sponge- It can be confirmed that it is very effective for desorption and concentration.

[Example 2]

Except that the method of forming the metal nanoparticles was carried out in the same manner as in Example 1. [

16 mg of polyvinylpyrrolidone (Cat. No. K-30) and 20 mg of oleylamine (Aldrich, Cat) were added to 20 ml of ethylene glycol (Cat. No. E0343) No. O7805) was completely dissolved and then 2.9 mg of Pt (C ₅ H ₇ O ₂ ) ₂ (Pasteur) was added again to prepare a mixed solution.

The carbon nanotube sponge was cut to a size of about 1 cm 3 and impregnated with about 1 g of the prepared mixture. The inside of the reactor was purged in a nitrogen atmosphere to prevent oxidation of the platinum nanoparticles. After incubation at room temperature for about 30 minutes, the temperature was gradually raised to 190 ° C for 1 hour and further reduced for 1 hour.

After completion of the reduction reaction, the reaction mixture was naturally cooled. Thereafter, the washing process was repeated using a sufficient amount of methanol until the reaction reagent remaining in the carbon nanotube sponge was completely removed. The cleaned carbon nanotube sponge-metal composite was dried in an oven at 90 DEG C for 1 hour. The results of the EDS analysis of the carbon nanotube sponge-Pt composite thus prepared are shown in FIG.

Claims (15)

a) injecting a raw material solution containing a liquid carbon source and a catalyst source into a gasification furnace and vaporizing the raw material gas;
b) continuously injecting the source gas into the reaction chamber to produce a carbon nanotube sponge that is physically entangled with the carbon nanotubes grown on the catalyst;
c) modifying the surface of the carbon nanotube sponge with an oxidizing agent; And
d) forming metal nanoparticles on and in the surface of the surface modified carbon nanotube sponge;
Wherein the metal nanoparticles are oxides of a transition metal or a transition metal. The method for manufacturing a carbon nanotube sponge-metal composite for absorbing and desorbing volatile organic compounds. The method according to claim 1,
Wherein the raw material solution contains 0.1 to 20 parts by weight of a catalyst source per 100 parts by weight of a liquid carbon source. 3. The method of claim 2,
The carbon source of the liquid phase is any one or two or more selected from among benzene, toluene, xylene, chlorobenzene, dichlorobenzene, (C 1 -C 5) alcohol and (C 5 -C 10) alkane. Sponge-metal composite. 3. The method of claim 2,
Wherein the catalyst source is an Fe-based, Co-based or Ni-based compound. 3. The method of claim 2,
The raw material solution may contain 0.01 to 5 parts by weight of B (CH ₃ ) _3, CH ₃ CN, (CH ₂ ) ₄ O, (CH 2) ₅ N, (CH 3) ₄ N ₂ , A method for manufacturing a carbon nanotube sponge-metal composite for absorbing and desorbing volatile organic compounds further comprising a mixture. The method according to claim 1,
Wherein the raw material solution is injected into the vaporization furnace at a rate of 50 to 500 占 퐇 / min. The method for manufacturing a carbon nanotube sponge-metal composite for volatile organic compound adsorption / desorption. The method according to claim 1,
The oxidizing agent in step c) may be selected from the group consisting of nitric acid aqueous solution, sulfuric acid aqueous solution, hydrochloric acid aqueous solution, potassium hydroxide aqueous solution, aqueous sodium hydroxide solution, hydrazine aqueous solution, ammonia aqueous solution, potassium permanganate solution, hydrogen peroxide solution, ozone, Wherein the carbon nanotube sponge - The method according to claim 1,
In the step d), a first mixed solution containing metal nanoparticles having an average particle diameter of 1 to 50 nm is filtered with the carbon nanotube sponge to obtain a physical method of positioning the metal nanoparticles on the inside and the surface of the carbon nanotube sponge Wherein the carbon nanotube sponge-metal composite is prepared by a method comprising the steps of: The method according to claim 1,
The metal nanoparticle sponge may be subjected to a reduction reaction using a second mixed solution containing the carbon nanotube sponge, the metal precursor, the reducing solvent, the stabilizer, and the capping agent to form metal nanoparticles Wherein the carbon nanotube sponge-metal composite is prepared by a chemical method of forming a carbon nanotube sponge-metal composite. A carbon nanotube sponge-metal composite according to any one of claims 1 to 9, wherein the metal is a transition metal or an oxide of a transition metal, which is a carbon nanotube sponge- Metal complex. 11. The method of claim 10,
Wherein the carbon nanotube sponge has a density of 1 to 50 mg / cm < 3 >. 11. The method of claim 10,
Wherein the carbon nanotube sponge has a compressive strain (compression volume of 50 vol%) of 10 KPa to 1 MPa, and the carbon nanotube sponge-metal composite for absorbing and desorbing volatile organic compounds. 11. The method of claim 10,
Wherein the carbon nanotube sponge-metal composite is a heating element that dissipates heat when a voltage is applied, the carbon nanotube sponge-metal composite being used for absorbing and desorbing volatile organic compounds. 14. The method of claim 13,
Wherein the carbon nanotube sponge-metal composite is a volatile organic compound adsorption / desorption / removal carbon nanotube sponge-metal composite for removing harmful substances or concentrating volatile organic compounds. A method for adsorbing and desorbing volatile organic compounds by using the carbon nanotube sponge-metal composite according to claim 10 as an adsorbent.

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