JP5428066B2 - Nanocarbon material manufacturing apparatus and manufacturing method thereof - Google Patents

Description

  The present invention relates to a nanocarbon material manufacturing apparatus and manufacturing method, and more particularly to a nanocarbon material manufacturing apparatus and a manufacturing method thereof capable of mass-producing high-quality nanocarbon materials.

  For example, scanning probe microscope (SPM) probe, emitter for field emission display (FED), hydrogen storage material for fuel cell, negative electrode material for lithium secondary battery, high density integration Carbon nanotubes, which are expected to be used in a wide range of applications, such as circuits and high-performance resin composites, are being developed and researched.In particular, recently, a method for stable mass production of high-quality carbon nanotubes has been sought. Yes. Carbon nanotubes (CNTs) are carbon microcrystals produced in a cylindrical structure with a rounded graphite layer. Conventionally, as a manufacturing method thereof, an arc discharge method, a laser evaporation method, a chemical vapor deposition method ( CVD) and the like are known. In the arc discharge method, for example, a high voltage is applied between opposed carbon electrodes and arc discharge is performed under vacuum to generate and deposit carbon nanotubes on the cathode side. In the laser evaporation method, a catalyst is formed in a heated atmosphere. Laser light is applied to the mixed carbon to cause carbon and catalyst to vaporize and produce carbon nanotubes. Chemical vapor deposition (CVD) introduces a hydrocarbon gas together with a carrier gas into a heated high-temperature atmosphere. The carbon nanotubes are grown on the metal catalyst. The arc discharge method can produce CNTs with few defects and good quality, but it is difficult to obtain industrially usable quantities. In addition, the laser evaporation method can obtain single-walled CNTs with relatively high purity, and the tube diameter can be controlled by changing the conditions, but the yield is small and it is difficult to mass-produce this industrially. is there. Furthermore, the chemical vapor deposition (CVD) method is suitable for mass synthesis because a carbon compound as a carbon source can be supplied as a raw material gas, but the synthesized CNTs are generally considered to have poor crystallinity. Yes. On the other hand, the methods of Patent Documents 1 and 2 and Non-Patent Document 1 have been further proposed as methods for producing carbon nanotubes.

JP 2003-12312 A JP 2007-197306 A

K. Nakagawa et al., CatalysisLetters, 101,191 (2005), M. Nishitani-Gamo et al., Japanese Journal of AppliedPhysics, 46, 6329 (2007)

Patent Document 1 and Non-Patent Document 1 are methods of synthesizing CNTs by depositing a metal catalyst on a substrate and heating the substrate in an organic liquid. However, in these methods, the substrate is immersed in an organic liquid and CNT is synthesized in a state where the metal catalyst is in direct contact with the organic liquid (submerged substrate heating method). Since the catalyst on the substrate reacts with the organic liquid before reaching, carbon nanotubes with high purity could not be obtained stably. As for the catalyst, the catalyst material eluted in the organic liquid cannot be used because it is peeled off from the substrate when the carbon nanotube is synthesized. Therefore, it has been necessary to select, for example, iron, cobalt, iron-based alloy, etc., which are difficult to elute into an organic liquid, as a catalyst. Further, in order to increase the adhesion of the catalyst film to the substrate, an Fe thin film is deposited on the substrate by sputtering or vacuum evaporation, and the Fe thin film is deposited on the substrate by hydrogen plasma treatment to form Fe into islands. In addition, there is a problem that it is necessary to form fine particles and firmly bond to the substrate, and an expensive sputtering apparatus or plasma processing apparatus is required, resulting in high equipment costs and manufacturing costs. Further, in Patent Document 2, a quartz tube 11 in which a catalyst 18 is disposed is disposed in a heating furnace 12, a container 16 containing ethanol is disposed near the end of the same quartz tube, and an ethanol evaporating gas is disposed in the quartz tube. The CNT is synthesized by flowing to the catalyst side with a carrier gas flowing from one end side. This apparatus requires a large quartz tube container that is long in one direction to be placed in a heating furnace. Therefore, it is necessary to heat the quartz tube container and the entire carbon source gas therein to a high temperature. The process is complicated and the process time including heating and cooling is long. In addition, the equipment cost is high, and there is a problem that the attaching and detaching operation of the catalyst and the organic liquid at the time of concrete production is complicated and troublesome and the workability is inferior.

  The present invention has been made in view of the above-described conventional problems, and one object thereof is an extremely simple configuration, a high degree of freedom in selecting a metal catalyst, a simple method for supporting the substrate, and at the time of synthesis. An object of the present invention is to provide a nanocarbon material production apparatus and a nanocarbon material production method capable of mass-producing a good quality nanocarbon material by contacting only a high concentration carbon source gas with a catalyst.

In order to solve the above-mentioned problems, the present invention includes a tank body 2,200 having a closed space 2a formed therein and a communicating portion 9 with the organic liquid 6, and a catalyst-carrying substrate 4 disposed in the closed space 2a. The catalyst-carrying substrate 4 is disposed in a position where the supported catalyst 3 is exposed to the closed space 2a of the tank body 2 and the catalyst 3 is not in direct contact with the organic liquid 6, the heating device 5 for the catalyst-carrying substrate 4, and the tank body The organic liquid 6 disposed so as to be in contact with the closed space 2a of the tank body 2 and 200 in the communicating portion 9 of the tank 2 and the inert gas substituted with the evaporated gas VG when the organic liquid 6 is evaporated by heating the catalyst supporting substrate 4 An inert gas supply device 7 that is a gas IG and supplies the inert gas IG to the closed space 2a of the tank body 2,200, and the closed space 2a of the tank body 2,200 is a reaction space, Tanks 21a-21d, 201 of tank body 2,200 The communication part 9 between the organic liquid 6 and the tank body 2 and 200 is formed so that the entire surface F surrounded by ˜201d becomes the boundary part 8 between the reaction space and the organic liquid 6. It comprises carbon material manufacturing apparatuses 1 and 30.

  In that case, the tank body 200 of the nanocarbon material manufacturing apparatus 30 has a liquid tank that can store an organic liquid and immerse the entire tank body in the organic liquid, and the tank body has an inversion case having a lower surface opening as a communicating portion. The body is a closed space in the state of being immersed in an organic liquid, and is provided so as to be immersed in and withdrawn from the organic liquid in the liquid tank via a support mechanism. When the substrate is immersed in an organic liquid in the liquid tank, or when the temperature of the catalyst-supporting substrate is heated to the synthesis temperature, the inert gas is supplied into the tank during non-synthesis, including the inert gas in the closed space. During the synthesis of the nanocarbon material by heating the catalyst-supporting substrate in organic liquid, the supply of inert gas is stopped and replaced with evaporative gas of organic liquid, and the enclosed space is organic High concentration by liquid evaporation gas When, it may be configured to have.

  Moreover, the liquid surface F outer edge size of the organic liquid 6 facing the closed space 2a of the tank body 2,200 may be substantially the same as the inner size (x1, x2, y1, y2) of the tank body 2,200.

In addition, the present invention provides the inside of the tank body 2, 200 so that the entire surface F surrounded by the tank walls 21 a to 21 d and 201 a to 201 d of the tank body 2 200 forms the boundary 8 between the organic liquid 6 and the reaction space. The organic liquid 6 is disposed facing the reaction space, and the catalyst-supporting substrate 4 is disposed in a position where the catalyst 3 is not in direct contact with the organic liquid 6 and the catalyst 3 is exposed to the reaction space of the tank body 2,200. Then, except when the catalyst-carrying substrate 4 is heated to the synthesis temperature, an inert gas IG is supplied into the reaction space, and when the catalyst-carrying substrate 4 is heated to the synthesis temperature, the evaporation gas VG of the organic liquid 6 The carbon nanomaterial N is synthesized on the catalyst 3 while supplying the organic liquid evaporating gas VG over the entire surface F surrounded by the tank walls 21a to 21d and 201a to 201d of the tank body 2,200. Constructed from manufacturing method of nanocarbon material

  At that time, the tank body 200 is immersed in the liquid tank 31 containing the organic liquid 6 in a state where the inside of the tank body 200 having the opening 200A on the lower surface is used as a reaction space and the reaction space is filled with the inert gas IG, The nanocarbon material may be synthesized in the state.

In the nanocarbon material manufacturing apparatus of the present invention, an organic liquid is contained in a tank body closed inside, and the remaining volume space is used as a reaction space, and a synthesis condition is generated by heating the catalyst-carrying substrate to evaporate the organic liquid. Is used for vapor phase growth of a nanocarbon material on the catalyst. In particular, the communication space between the organic liquid and the tank body is formed so that the closed space of the tank body is a reaction space and the entire surface surrounded by the tank wall of the tank body is the boundary between the reaction space and the organic liquid. doing. Therefore, the organic liquid and the reaction space communicate with each other over the entire surface of the reaction space that is surrounded by the tank wall of the tank body and the organic liquid, thereby allowing the entire evaporated gas from the organic liquid to enter the reaction space without waste. A high-concentration carbon source gas atmosphere can be maintained.

The nanocarbon material manufacturing equipment includes the shape of the closed container, the constituent materials, the size, the mounting of the catalyst support substrate on the case body, the detachable configuration, the extraction of the nanocarbon material as a composite, and the specific case body Portions other than the essential constituent elements of the present invention, such as the shape, structure, constituent material, size, and structure for assembling / detaching the catalyst-carrying substrate, can be arbitrarily set.

Further, the present invention provides a gas phase space as a reaction space in contact with the organic liquid container and the organic liquid in the liquid tank without immersing the tank body in the organic liquid, and is in contact with the gas phase space. The nanocarbon material can be efficiently synthesized also by heating the substrate carrying the arranged catalyst and performing vapor phase growth on the catalyst with an evaporating gas of an organic liquid only under a high synthesis temperature condition.

  In the method for producing a nanocarbon material of the present invention, except that the catalyst-carrying substrate is heated to the synthesis temperature, an inert gas is supplied into the reaction space, and the catalyst-carrying substrate is heated to the synthesis temperature. The carbon nanomaterial is synthesized on the catalyst while supplying the organic liquid evaporative gas over the entire surface surrounded by the tank wall of the tank body by replacing with the organic liquid evaporative gas. Evaporated gas from the organic liquid is supplied to the reaction space without waste over the entire surface in contact with the organic liquid in the reaction space surrounded by the tank wall of the tank body, and a high concentration carbon source gas atmosphere can be maintained.

In another method, the tank is immersed in an organic liquid, and is heated to at least the synthesis temperature and has a catalyst supported on a part of the inner wall via an inert gas supplied from the outside. Thus, a vapor phase space is provided as a reaction space that can replace the vaporized organic liquid gas, and the vaporized organic liquid gas is saturated in the vapor phase space only at a high synthesis temperature. Then, in the synthesis temperature time zone or reaction time zone when the high temperature synthesis temperature condition is satisfied, only the evaporative gas of the organic liquid is present in the reaction space, which is the gas phase space, and the nanocarbon material is vapor-phase grown on the catalyst. The inert gas is continuously supplied to the gas phase space during the temperature increase or decrease except for the high synthesis temperature. The organic liquid is a carbon source and is a solution of an organic compound containing carbon. The synthesis temperature of the nanocarbon material is generally about 900 ° C., and the catalyst is replaced with an inert gas so that the catalyst does not come into contact with the evaporating gas and the organic liquid of the organic liquid during heating or during the temperature release to room temperature. This prevents impurities and amorphous carbon from being generated by a reaction at a temperature lower than the synthesis temperature.

  According to the nanocarbon material manufacturing apparatus and the nanocarbon material manufacturing method of the present invention, the tank body and the organic liquid are disposed so that the closed space and the organic liquid are in contact with each other, and the catalyst-supporting substrate disposed in the closed space is heated. Since the evaporation gas of organic liquid is generated in the reaction space formed by the closed space and the nanocarbon material is vapor-phase grown on the catalyst of the substrate at the synthesis temperature, (1) the heating structure of only the substrate is sufficient, and the apparatus is compact. And cost reduction can be achieved. (2) In addition, since a vacuum apparatus or the like is not required, the apparatus can be configured at low cost, and a process of returning from vacuum to atmospheric pressure is not required, and the grown nanocarbon material can be easily recovered. It is easy to operate and manage the process at the manufacturing stage. In addition, (3) a high-concentration atmosphere of carbon source gas and a large temperature gradient phase can be reliably realized with a simple configuration, and this can be done in a closed space, so it does not contain impurities that are likely to be generated by changes in the temperature of the substrate. High-quality nanocarbon materials can be synthesized and the growth efficiency can be greatly improved. (4) Furthermore, since it is the production | generation by the vapor phase growth method in an organic liquid, the heating temperature adjustment of the organic liquid by the heating through a board | substrate can be performed correctly, and production | generation control of a nanocarbon material can be performed accurately. (5) In addition, since the reaction space contains almost no carrier gas, it is possible to easily set control parameters for synthesis of single-walled and multi-walled carbon nanotubes related to temperature, gas concentration, density, etc. ( 6). In particular, the communication space between the organic liquid and the tank body is formed so that the closed space of the tank body is the reaction space, and the entire surface surrounded by the tank wall of the tank body is the boundary between the reaction space and the organic liquid. As a result, a sufficient amount of organic liquid can be secured as a carbon source that is necessary for the synthesis reaction and almost all of the synthesis reaction can be used, and the reaction space can be maintained in a high-concentration carbon source gas atmosphere. In addition, it is possible to produce a high-quality nanocarbon material in terms of crystallinity and purity.

It is a schematic longitudinal cross-sectional view of the manufacturing apparatus of the nanocarbon material which concerns on 1st Embodiment of this invention. FIG. 2 is a schematic horizontal sectional view of the apparatus of FIG. 1. It is a flowchart figure which shows the manufacturing process of the nanocarbon material using the apparatus of FIG. (A) is a schematic longitudinal cross-sectional view of the nanocarbon material manufacturing apparatus according to the second embodiment of the present invention, and (b) is a communication part and a boundary part between the closed space of the tank body and the organic liquid (a) ( It is the figure which showed typically the part enclosed by the ellipse. FIG. 5 is a partially cutaway enlarged perspective view of a tank body portion of the apparatus of FIG. 4. It is an expansion longitudinal cross-section explanatory drawing of the tank part of the apparatus of FIG. FIG. 5 is an operation explanatory diagram of the apparatus of FIG. 4. FIG. 5 is an operation explanatory diagram of the apparatus of FIG. 4. FIG. 5 is an operation explanatory diagram of the apparatus of FIG. 4. FIG. 5 is an operation explanatory diagram of the apparatus of FIG. 4. It is a flowchart figure which shows the manufacturing process of the nanocarbon material using the apparatus of FIG. FIG. 5 is an enlarged vertical cross-sectional explanatory view of a tank body portion showing a modified embodiment of the apparatus of FIG. 4. FIG. 7 is an enlarged vertical cross-sectional explanatory view of a tank body portion showing another modified example of the apparatus of FIG. 4. It is a scanning electron micrograph of the carbon nanotube synthesized in the first example performed using the apparatus of FIG. It is another scanning electron micrograph of the carbon nanotube synthesized in the first example performed using the apparatus of FIG. It is another scanning electron micrograph of the carbon nanotube synthesized in the first example performed using the apparatus of FIG. (A), (b) is a figure which shows the Raman spectroscopic analysis result of the carbon nanotube synthesize | combined by varying the synthesis temperature with the apparatus of FIG. 2 is a scanning electron micrograph image showing carbon nanowalls and carbon nanoribbons whose generation was confirmed in the experiment of Example 1. FIG. It is a principal part enlarged image of FIG.

Hereinafter, a nanocarbon material manufacturing apparatus and a nanocarbon material manufacturing method according to embodiments of the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to the configurations of the following embodiments. First, the configuration of the nanocarbon material manufacturing apparatus will be described.

  FIG. 1 shows the basic configuration of a nanocarbon material production apparatus according to a first embodiment of the present invention. In this embodiment, the nanocarbon material production apparatus 1 has a closed space 2a therein. Tank 2, catalyst-carrying substrate 4 carrying catalyst 3, heating device 5, organic liquid 6 accommodated in tank 2, and inert gas supply device for supplying inert gas IG to closed space 2 a 7 and a boundary portion 8. The organic liquid 6 is accommodated in the tank body 2 which is closed inside, the remaining volume space is used as a reaction space, a synthesis condition is generated by heating the catalyst-carrying substrate, and the organic liquid evaporative gas is used as a carbon source gas to form nano particles on the catalyst. A carbon material is vapor-phase grown.

Here, the nanocarbon material refers to a carbon material in nanometer or micron unit, preferably a carbon material having a diameter of the order of nanometers and a length of several microns to several hundreds of microns. It is obtained by acting on a catalyst and refers to carbon having various shapes such as a fiber shape and a tube shape.

In FIG. 1, a tank body 2 is a rectangular or round tube with both ends closed, in which a closed space 2 a is formed by four circumferential walls 21 a to 21 d, a top wall 21 e and a bottom wall 21 f. It is formed of a shape tank. One of the four walls 21a to 21d and the top wall 21e or some of them is provided with an inspection opening / closing door (not shown).

In the tank body 2, for example, an organic liquid 6 as a carbon source is introduced and accommodated so that the liquid surface height is about a half of the tank body height.

In this embodiment, for example, alcohol is applied as the organic liquid. The organic liquid 6 is a carbon source for synthesizing nanocarbon materials such as carbon nanotubes, and hydrocarbons, alcohols, esters, ketones, organic acids, and other carbon compounds that are liquid at normal temperature and pressure are preferably used. The hydrocarbon is preferably a chain or cyclic hydrocarbon having 5 to 18 carbon atoms. For example, pentane, hexane, heptane, benzene, toluene and the like can be mentioned. As the alcohol, a linear or cyclic monohydric alcohol or polyhydric alcohol having 1 to 16 carbon atoms is preferable. For example, methanol, ethanol, 1-propanol, 2-butanol, ethylene glycol and the like can be mentioned, and methanol and ethanol are particularly preferable. The ester is preferably a chain or cyclic ester having 2 or more carbon atoms. For example, ethyl formate, methyl acetate, methyl butyrate and the like can be mentioned. The ketone is preferably a chain or cyclic ketone having 3 or more carbon atoms. For example, acetone, methyl ethyl ketone, and cyclohexane are mentioned. The organic acid is preferably a saturated or unsaturated carboxylic acid or oxycarboxylic acid having 1 to 10 carbon atoms. This includes, for example, formic acid, acetic acid, propionic acid, oleic acid. Furthermore, as other organic liquids, for example, easily available materials such as diethyl ether and diisopropyl ether can be selected.

A part of the closed space 2a, that is, the remaining closed space of the volume occupied by the organic liquid 6 in the entire space is defined as the reaction space 2b. That is, in this embodiment, the closed space part in the tank body 2 is made into the reaction space 2b, and the whole surface F enclosed by the four surrounding walls 21a-21d which are the tank walls of the tank body 2 as shown in FIG. A communication portion 9 between the organic liquid 6 and the tank body 2 is formed so as to be a boundary portion 8 between the reaction space 2 b and the organic liquid 6. Therefore, the organic liquid 6 and the reaction space 2b communicate with each other over the entire liquid contact surface with the organic liquid in the reaction space 2b surrounded by the tank wall of the tank body 2, and thereby, as described later, The entire evaporated gas is supplied to the reaction space 2b without waste, and a high concentration carbon source gas atmosphere can be maintained.

  Further, in the present embodiment, the liquid surface outer edge size F □ of the organic liquid 6 facing the closed space 2a of the tank body 2 is configured to be substantially the same as the inner size (x1, x2, y1, y2) of the tank body 2. ing. This makes it possible to secure a sufficient amount of organic liquid as a carbon source that is necessary for the synthesis reaction and that can be used for almost all of the synthesis reaction. The atmosphere can be maintained effectively. Further, the catalyst-carrying substrate 4 is provided so as to be freely inserted into and removed from the closed space 2 b of the tank body 2, and the liquid level F of the organic liquid 6 introduced into the tank body 2 is the boundary between the reaction space 2 b and the organic liquid 6. 8, the closed space 2 a of the tank body 2 is formed in a closed cylindrical shape. That is, the inner wall of the tank body is provided in a flat shape, so that the organic liquid is accommodated for the entire inner method of the tank body, and all the evaporated gas at the time of evaporation of the organic liquid is supplied to the reaction space so that the carbon source gas atmosphere is always in a high concentration. Can be maintained.

A cooling device 10 such as a cooling jacket is provided on the outer surface of the tank body 2 to cool the entire tank body.

  A heating device 5 such as a heater is installed in a closed space in the tank body 2, particularly in the reaction space 2 b. In the embodiment, the heater is arranged long in the vertical direction. Reference numeral 25 denotes a substrate temperature detection temperature sensor.

  Furthermore, the catalyst-carrying substrate 4 is provided so that the position can be changed between a position heated by the heater of the heating device 6 and a position where the heater is pulled up and taken out. For example, silica, alumina, zeolite, MgO, zirconia, or titania can be used for the catalyst support substrate 4. That is, the catalyst carrying substrate 4 is supported by an unillustrated insertion / removal device, and is provided so as to be freely inserted into and removed from the reaction space 2b of the tank body 2 in the vertical direction along the heater. When the catalyst-carrying substrate 4 is disposed in the reaction space 2b, the catalyst 3 carried thereon is in a position exposed to the reaction space 2b that is a closed space of the tank body 2, and the catalyst 3 is directly applied to the organic liquid 6. It is arrange | positioned in the position which is not made to contact. Examples of the catalyst 5 include metal catalysts such as Cr, Fe, Co, Ni, Cu, Mo, Pt, Pd, Rh, Ir, Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu, etc. can be mentioned. A combination of these metals can also be used. An electrode 11 drawn out from the heater is provided, and is connected to a power source (not shown) to supply heating power. Reference numeral 12 denotes a slide shutter that hermetically seals the interior when the catalyst-carrying substrate 4 is inserted into the reaction space 2b.

Further, an inert gas supply port 13 is installed in the tank wall of the tank body 2, and the inert gas IG is supplied from the inert gas supply device 7 through the gas supply pipe 14 into the reaction space 2 b. Since the accommodated organic liquid 6 is disposed in the closed space of the tank body, the inert gas supply port 13 is installed at a position higher than the liquid level. Further, an organic liquid supply port 15 is installed at a position lower than the inert gas supply port 13. The installation height of the organic liquid supply port 15 is not limited to this, and may be higher than the inert gas supply port 13 or may be provided not only on the peripheral wall of the tank body but also on the top wall. The organic liquid 6 is introduced from the organic liquid supply device 16 into the closed space 2 a of the tank body 2 through the organic liquid supply pipe 17.

In FIG. 1, the top wall 21e is provided with a reflux device 18 that penetrates the jacket portion and protrudes outside the tank body. The reflux device 18 is a reflux means for cooling the evaporated gas from the organic liquid by heating and refluxing it to the tank body side. In this embodiment, the reflux device 18 penetrates the jacket portion of the top wall 21e and is outside the tank body 2. And a cooling pipe device 22 that circulates and communicates with the condensing pipe portion 20 into the closed cylinder pipe 19. A refrigerant fluid such as water is allowed to flow through the cooling pipe of the cooling pipe device 22 to condense and liquefy the evaporated gas in the condensation pipe portion 20 and return it to the case body. In the figure, reference numeral 23 denotes a relief hole for evaporating gas or inert gas of organic liquid. Reference numeral 24 denotes an upper supply valve for supplying an inert gas as required, and is connected to the inert gas supply device 7 via a supply pipe.

In this embodiment, an inert gas supply device, an external power source, a catalyst carrier substrate 4 insertion / extraction device, and a control device (not shown) electrically connected to the heating device are provided to perform process control. Yes.

Next, the operation of the nanocarbon material of the first embodiment will be described with reference to FIG. In FIG. 3, the organic liquid supply device 16 is driven to supply, for example, an ethanol liquid from the organic liquid supply port 15 to the closed space of the tank body 2, for example, filling about half of the volume space (S 1). At this time, the amount of the organic liquid determines the reaction space volume that is the remainder of the closed space, and the catalyst for synthesizing the nanocarbon material is arranged in this reaction space, so that the organic liquid is charged to the extent that a certain amount of reaction space volume can be secured. The amount needs to be set.

Next, the inert gas supply device 7 is driven to supply an inert gas IG such as argon gas Ar from the inert gas supply port 13 to fill the reaction space 2b with a high concentration (S2). This is because oxygen is purged so that an oxide film is formed on the catalyst before the synthesis of the nanocarbon material and vapor phase growth is not hindered.

Next, the catalyst-carrying substrate 4 is inserted into the reaction space 2b and brought into close contact with the heater 5a of the heating device 5 by, for example, a guide provided on the substrate (S3).

Next, the heater 5a of the heating device is energized and heated (S4). For example, when the carbon source organic liquid is methanol or ethanol, evaporation starts from the surface at about 64 ° C. or about 78 ° C., and evaporated gas is generated in the reaction space (S5). The inert gas supply is stopped after the heating apparatus starts heating (S6). As a result, the evaporation gas and the inert gas are replaced, and the concentration of the evaporation gas gradually increases in the reaction space 2b.

The reaction space 2b gradually increases in concentration in the reaction space 2b when the temperature rises, and becomes a high concentration organic liquid evaporation gas atmosphere at the synthesis temperature. When the catalyst-supporting substrate 4 reaches a synthesis temperature of the target nanocarbon material, for example, 900 ° C., the nanocarbon material is vapor-phase grown on the catalyst (S7). At this time, the reaction space 2b is in a state in which a high concentration of carbon source gas exists and new evaporation gas is continuously generated. In the reaction space, the organic liquid having a melting point of about 60 ° C. to 80 ° C. and the substrate 4 having a temperature of 900 ° C. are arranged close to each other, thereby forming a large temperature gradient. In this reaction space atmosphere, carbon source gas is decomposed by catalyst particles on the surface of the high-temperature substrate, and carbon atoms dissolve into the catalyst particles and become supersaturated, so that carbon atoms precipitate and grow on the surface from the inside of the catalyst. it is conceivable that.

After completion of the synthesis reaction, heating by the heating device 5 is stopped, and during this time, the inert gas IG is restarted to be supplied to the reaction space 2b until the temperature of the catalyst-carrying substrate 4 returns to room temperature (S8). This prevents impurities other than carbon and amorphous carbon from being generated in the process of lowering the temperature of the catalyst 3. Further, the evaporative gas of the organic liquid is aggregated by cooling in the reaction space 2b as the gas phase space by stopping the heater, and the organic liquid 6 enters the reaction space 2b, and the generated nanocarbon material is removed from the substrate. It can be prevented from peeling.

Thereafter, the catalyst-carrying substrate 4 is pulled out of the reaction space 2b and moved out of the tank body (S9), and a desired nanocarbon material is recovered (S10).

  As described above, in the nanocarbon material production apparatus of the present embodiment, the nanocarbon material production apparatus 1 includes a tank body 2 having a closed space 2a therein, a catalyst-carrying substrate 4 carrying a catalyst 3, and heating. A device 5, an organic liquid 6 accommodated in the tank body 2, an inert gas supply device 7 for supplying an inert gas IG to the closed space 2 a, and a boundary portion 8 are provided. The organic liquid 6 is accommodated in the tank body 2 which is closed inside, the remaining volume space is used as a reaction space, a synthesis condition is generated by heating the catalyst-carrying substrate, and the organic liquid evaporative gas is used as a carbon source gas to form nano particles on the catalyst. Vapor growth of carbon material. At this time, the amount of organic liquid as a carbon source that is necessary for the synthesis reaction and can be used almost completely in the synthesis reaction can be secured at all times. To maintain. In particular, the communication portion 9 between the organic liquid 6 and the tank body 2 is formed so that the entire surface surrounded by the tank wall of the tank body becomes the boundary portion 8 between the reaction space 2 b and the organic liquid 6. As a result, the evaporative gas of the organic liquid 6 can be generated from the entire contact surface with the organic liquid in the reaction space 2b surrounded by the tank wall, and the reaction space can be constantly maintained in a high concentration carbon source gas atmosphere. In addition to being able to synthesize high-quality, high-quality carbon nanotubes that do not contain impurities that are likely to be generated due to changes in temperature, the reaction space does not contain carrier gas, etc., so it is related to temperature, gas concentration, density, etc. This makes it easy to set control parameters for single- and multi-layer tube synthesis. In addition, it is not necessary to control the injection / exhaust of the carrier gas in a vacuum apparatus or an open type, and the structure of the tank body itself is simple, so that the cost of the apparatus can be reduced. In addition, since the grown carbon nanotubes are prevented from flowing away from the catalyst by being brought into contact with the liquid, it is not necessary to limit the method of fixing the catalyst to the substrate, and thus freedom of catalyst selection High degree. That is, for example, a solvent in which a metal salt as a catalyst is supported on zeolite or the like, and fixed to the substrate by applying treatment to the substrate and drying can also be applied. In addition, an organic metal film that is used as an efficient catalyst for single- and double-walled carbon nanotubes by chemical vapor synthesis can also be used. Examples of the organometallic catalyst include metal carbonyl, carbene complex, metallocene including ferrocene, and the like. In addition, metalloid compounds such as silicon, arsenic, and boron can be used. In addition, it is possible to easily control the film thickness with good accuracy by dip coating, spin coating, dripping, etc., and this makes it possible to easily synthesize single-walled and double-walled carbon nanotubes.

In the above embodiment, the insertion position of the catalyst-supporting substrate 4 with respect to the reaction space 2b of the tank body 2 is a position closer to the left end in the cross section in FIG. 1, but may be a right end, a position closer to the center, etc. An insertion / removal configuration in the direction can be adopted. Further, although the heater 5a of the heating device is fixedly installed in the tank body 2, it may be configured to be able to be inserted into and removed from the reaction space together with the catalyst carrying substrate or independently. The tank body 2 may have a cylindrical shape, an elliptical cylindrical shape, a polygonal cylindrical shape, or the like.

Moreover, as a manufacturing method of these nanocarbon materials, reaction in the tank body 2 is performed so that the entire surface F surrounded by the peripheral walls 21a to 21d of the tank body 2 forms a boundary 8 between the organic liquid 6 and the reaction space 2b. The organic liquid 6 is disposed facing the space 2b, the catalyst supporting substrate 4 is disposed in a position where the catalyst 3 is not in direct contact with the organic liquid 6 and the catalyst 3 is exposed to the reaction space 2b of the tank body 2. While the inert gas IG is supplied into the reaction space 2b, the catalyst-carrying substrate 4 is heated to replace the evaporating gas of the organic liquid 6 when the material is at the synthesis temperature of the material, and the peripheral walls 21a to 21d of the tank body 2 are replaced. The carbon nanomaterial is synthesized on the catalyst 3 while supplying the organic liquid evaporative gas over the entire enclosed surface F.

  Next, the nanocarbon material manufacturing apparatus 30 according to the second embodiment of the present invention will be described with reference to FIGS. 4 to 10. The same members as those in the first embodiment will be described with the same reference numerals. The nanocarbon material manufacturing apparatus 30 according to the second embodiment includes a liquid tank 31, an organic liquid 6 filled in the liquid tank 31, a tank body 200 having a closed space 2 a therein, and a catalyst carrying the catalyst 3. The carrier substrate 4, the heating device 5, an inert gas supply device 7 that supplies an inert gas IG to the closed space 2 a, and a boundary portion 8 are provided.

  In this embodiment, the tank body 200 is composed of an inverted case body having the lower surface opening 200A as the communication portion 9, and the organic liquid 6 is placed in a liquid tank 31 larger than the tank body. And the whole tank body 200 is inserted and immersed in the organic liquid 6 in the liquid tank 31, with the opening surface arranged in the inverted state. The entire tank body 200 is supported via the support mechanism 32 so as to be immersed in and withdrawn from the organic liquid 6 in the liquid tank 31.

  In this embodiment, since only the lower surface opening 200A is opened to the organic liquid 6 side, when the tank body 200 is immersed in the liquid in an inverted state, the closed space in the tank body is closed by the tank body and the organic liquid. Accordingly, when an inert gas is supplied from the outside to the closed space in this state, an inert gas or an evaporating gas of an organic liquid is supplied to the closed space by a kind of upward displacement method.

  Specifically, in FIG. 4A, the liquid tank 31 is formed of a hollow container body that contains the organic liquid 6 and whose upper surface is freely opened and closed, and the upper surface opening 51 can be opened and closed by the lid member 33. Closed. The four circumferential walls and the bottom wall of the liquid tank 31 form the double wall with the peripheral wall and the bottom wall of the liquid tank 31, and a cooling medium such as a cooling fluid and a solid is disposed in the gap to form the cooling device 10. Then, the liquid tank 31 is cooled.

  The tank body 200 is supported by the lid member 33 and is supported in a suspended manner at a position below the lid member. Therefore, a state in which the tank body 200 is immersed in the organic liquid 6 according to the opening and closing of the lid member 33 and a state in which the nanocarbon material synthesized by being pulled up is recovered are formed.

  Specifically, in FIG. 4A, an electrode rod R as an electrode 35 connected to the external power source 34 is provided on the lid member 33 so that its upper end protrudes upward from the lid member 33, and the lower portion has the lid member 33. It penetrates and the lower end side is fixed to the tank body 200, and the tank body 200 is supported at the lower position by the lid member 33. Therefore, when the opening of the liquid tank 31 is closed with the lid member 33, the entire tank body 200 is immersed in the organic liquid 6 of the liquid tank 31 as it is. Here, the support mechanism 32 includes a lid member 33 constituting a support body of the tank body 200, and an electrode rod R that fixes the upper part to the lid member 33 and supports the tank body 200 on the lower side.

  A reflux device 18 for condensing and refluxing the evaporated gas of the organic liquid 6 flowing through the opening 36 drilled in the center of the lid member 33 is provided so as to protrude upward from the lid member 33. The reflux device 18 includes a closed tube 19 that is open at only one end that communicates with the opening 36, and a cooling tube device 22 that enters the closed tube 19 into the condensation tube portion 20 and circulates and communicates with the outside. . A refrigerant fluid such as water is flowed into the cooling pipe of the cooling pipe device 22 to condense and liquefy the evaporative gas in the condensing pipe part 20 and return it to the organic liquid storage part of the liquid tank 31. In the figure, reference numeral 37 denotes a relief hole for an inert gas or an organic liquid evaporating gas. Further, in the present embodiment, a valve 38 for introducing an inert gas IG from the outside to the lid member 33 as necessary, and a gas introduction pipe 42 of an inert gas supply device 7 to be described later pass through the lid. The lower end is disposed or supported in the organic liquid.

  As the organic liquid, the same carbon source liquid as that in the first embodiment can be used.

  As described above, the tank body 200 is disposed in the organic liquid 6 in the form of an upside down case in which the lower surface is opened and the open wall surface is disposed downward. Specifically, the tank body 200 has an opening 200A on the lower surface, and is formed in a hollow three-dimensional rectangular shape whose lower surface is opened by the four peripheral walls 201a to 201d and the top wall 201e. In particular, in the present embodiment, the wall 201 is configured such that the side wall 201b of the four circumferential walls is also used as the catalyst carrying substrate 4. The catalyst carrying substrate 4 is integrally formed or assembled as one wall portion of the tank body 200. The tank body 200 is a heat-resistant material that does not chemically react with the organic liquid, and is composed of, for example, quartz glass or other structure wall. It is necessary to measure the internal temperature of the tank body 200 to detect the synthesis temperature of the nanocarbon material such as a carbon nanotube. When a non-permeable material such as an opaque material is used, a transmission window for temperature measurement, etc. It is good to form. Further, a radiation thermometer 40 as a heating temperature detecting means for detecting the heating temperature of the catalyst carrying substrate 4 and a temperature sensor (not shown) for detecting the temperature inside the case are installed. The specific external shape, internal structure, and material of the tank body 200 can be arbitrarily set as long as the heat synthesis condition generation and the replacement function of the inert gas and the organic liquid evaporation gas are not impaired.

  The catalyst-carrying substrate 4 is a base on which carbon nanotubes are grown by heating, and is a support means for carrying the catalyst 3. As the substrate material, for example, silica, alumina, zeolite, MgO, zirconia, titania can be used. Furthermore, an inorganic material such as a silicon substrate, a heat-resistant glass substrate, or a quartz substrate, an organic material such as a polymer substrate, or a composite material thereof can be selected. 4 to 6, the catalyst-carrying substrate 4 is attached in close contact with a heater 5a connected to the lower end of the electrode rod R constituting the electrode 35 via a holder (not shown). Thus, the entire tank body 200 is determined in position in the liquid and the direction of the opening, and is stably supported by the lid member 33. The heating device 5 includes a heater 5a, an electrode 35, and an external DC power supply 34.

  Examples of the catalyst 5 include metal catalysts such as Cr, Fe, Co, Ni, Cu, Mo, Pt, Pd, Rh, Ir, Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu, etc. can be mentioned. A combination of these metals can also be used.

  As a method of supporting a metal catalyst on a substrate, a carrier impregnated by dissolving a metal salt in a solvent such as water or alcohol is applied on the substrate by dip coating or spin coating, and dried to fix the catalyst on the substrate. Can be used. Note that sputtering, vacuum deposition, ion plating, thermal CVD, laser CVD, or any other thin film forming means may be used if cost is not considered. Furthermore, in this embodiment, all or part of the structural material of the tank body 200 can be formed of the metal catalyst material.

  And the inside of the tank body 200 is made into the reaction space 2b, and the evaporative gas VG of the organic liquid 6 is introduced from the lower surface opening 200A as the communication part 9 and contacts the catalyst 3. That is, in this embodiment, the whole closed space 200a of the tank body 200 is used as a reaction space, and the four-walled wall that is the tank wall of the tank body 200 as shown in FIGS. 4 (a), 4 (b), and FIGS. A communication portion 9 between the organic liquid 6 and the tank body 2 is formed so that the entire surface F surrounded by 201a to 201d becomes a boundary portion 8 between the reaction space (200a) and the organic liquid 6. Therefore, the organic liquid 6 and the reaction space communicate with each other over the entire liquid contact surface with the organic liquid in the reaction space surrounded by the tank wall of the tank body 200, so that the entire evaporated gas VG from the organic liquid 6 is wasted. Without being supplied to the reaction space, a high concentration carbon source gas atmosphere can be maintained.

Furthermore, the inert gas supply apparatus 7 which supplies an inert gas to the closed space in the tank body 200 as said reaction space is provided. The inert gas supply device 7 is a substance that hardly causes a chemical reaction or has low reactivity, such as a rare gas such as argon (Ar), helium (He), neon (Ne), or nitrogen (N ₂ ) gas. When necessary, the gas is supplied into the reaction space of the case body and the organic liquid 6 is prevented from entering the reaction space when the tank body 200 is disposed in the organic liquid 6 of the sealed container. In this embodiment, the inert gas IG is supplied into the tank body 200 except when the catalyst-carrying substrate 4 is heated by the heating device and carbon is vapor-grown at the synthesis temperature. The That is, the inert gas supply device 7 drives and supplies the inert gas to the reaction space in the tank body via the inert gas introduction pipe 42 arranged so that the outlet 41 faces the lower surface opening 200A of the tank body 200. The inert gas supply device 7 is not necessarily limited to the configuration in which the inert gas introduction pipe 42 in which the outlet 41 is disposed so as to face the lower surface opening 200A is provided separately from the tank body, and for example, the inert gas introduction pipe 42 is provided. May be directly connected to one of the peripheral walls of the tank body 200 to communicate with the tank body.

  As shown in FIG. 4, in this embodiment, a management device 44 electrically connected to an inert gas supply device 7, an external power source 34, and a radiation thermometer 40 (FIG. 6) as a substrate temperature detection sensor is provided. ing. The management device 44 controls the steps such as insertion and pulling of the tank body 200 into the organic liquid 6, heating by the heating device 5, generation of the synthesis temperature condition, and completion of synthesis while detecting the temperature with the substrate temperature detection sensor. For example, a controller having an arithmetic control function is used.

  Next, the operation and manufacturing method of the nanocarbon material of the second embodiment will be described with reference to the process flowcharts of FIGS. 7 to 10 and FIG. 11. First, the organic liquid 6 is introduced and stored in the liquid tank 31. At this time, the entire tank body 200 is at least completely immersed, and in that state, an amount of organic liquid having a margin in the depth direction is introduced from the lower surface opening 200A of the tank body to the bottom wall of the liquid tank (S11). . Next, an operation is performed so that the lid member 33 is closed at the upper opening of the liquid tank while introducing an inert gas into the tank body 200 from the inert gas introduction pipe 42 by an external gas supply driving device. 4 is immersed in the organic liquid 6 (FIG. 7) (S12). At this time, since the inert gas IG continues to be injected into the tank body 200 (S13), the liquid pressure rises when these devices are moved down into the liquid, and the organic liquid enters the tank body, that is, the reaction space. Intrusion is prevented (FIG. 8).

  Next, energization of the heater 5a is started via the power source 34 and the electrode 35 to heat the catalyst carrying substrate 4 (S14). At this time, the inert gas IG is continuously introduced until the substrate temperature reaches the synthesis temperature. When lower alcohols such as methanol and ethanol are used as the organic liquid 6, they have boiling points of 64.7 ° C. and 78.3 ° C., and soon after the start of heating, evaporation starts from the surface of the organic liquid (S15). For example, a high concentration carbon source gas atmosphere is generated in the reaction space before reaching a high synthesis temperature of about 900 degrees. At this time, since the inert gas IG is continuously introduced into the tank body 200, the portion of the organic liquid facing the lower surface opening 200A of the tank body 200 cannot enter the reaction space. Therefore, the organic liquid is kept from coming into direct contact with the catalyst supported in the reaction space while increasing the concentration of the evaporated gas in the reaction space. As a result, impurities other than the target substance such as carbon are synthesized at a temperature lower than the set temperature, so that a nanocarbon material with poor quality is not generated.

  When the synthesis temperature reaches about 900 ° C., the introduction of the inert gas from the inert gas introduction pipe 42 is stopped (S16), while the heating by the heater 5a is maintained and the heating is continued for the required synthesis time (FIG. 6). ). By stopping the introduction of the inert gas, the inert gas IG injected so far is replaced with the organic liquid evaporating gas VG (FIG. 9), and the reaction space is saturated with the organic liquid evaporating gas VG. In this state, only the carbon source gas comes into contact with the catalyst 3, and the nanocarbon material N grows in a gas phase atmosphere (S17). As this reaction mechanism is presumed to some extent, the carbon source gas is decomposed by the catalyst particles on the substrate surface at a high temperature, and the carbon atoms dissolve into the catalyst particles and become supersaturated, so that the carbon atoms are deposited from the inside of the catalyst to the surface. It is considered to grow.

  When the nanocarbon material N grows and the synthesis is completed, the inert gas IG is supplied from the inert gas introduction pipe 42 by driving the external inert gas supply device 7 at the same time, immediately before, or immediately after the heater 41 is turned off. Is resumed into the tank body 200 (FIG. 10). The supply of the inert gas IG into the tank body 200 is continued until the temperature of the catalyst carrying substrate 4 returns to room temperature (S18). This prevents impurities other than carbon and amorphous carbon from being generated in the process of lowering the temperature of the catalyst 3. Further, the organic gas is aggregated by cooling the organic gas in the reaction space as the gas phase space when the heater is stopped, and the nanocarbon material N generated by the organic liquid 6 entering the reaction space can be prevented from peeling off from the substrate. . Then, the lid member 33 is operated while the inert gas IG is introduced into the tank body 200 to pull out the tank body 200 from the organic liquid 6 and collect the nanocarbon material (S19) and (S20). In this manner, the organic liquid evaporates while keeping the catalyst 3 and the organic liquid 6 in non-contact by exchanging the evaporated gas VG of the organic liquid 6 from the lower surface opening 200A of the tank body 200 and the inert gas IG supplied from the outside. The process of saturating the gas VG in the reaction space and synthesizing the nanocarbon material N under the synthesis temperature condition of the catalyst-carrying substrate 4, and before and after the catalyst-carrying substrate 4 reaches the synthesis temperature And a step of supplying an inert gas from the outside into the tank at the time of non-heating and cooling after the stop.

  As described above, according to the method for producing a nanocarbon material of the present embodiment, the tank body cooperating with the substrate supported by exposing the catalyst in the reaction space is immersed in the organic liquid as the carbon source, The catalyst-carrying substrate is heated in the state. During the synthesis at the synthesis temperature of the nanocarbon material, the evaporating gas of the immersion liquid is saturated in the reaction space, and in the time zone below the synthesis temperature, the reaction space is filled with an inert gas and only the carbon source gas is filled in a specific temperature range. Synthesize by contacting with catalyst. This makes it possible not only to synthesize good quality nanocarbon materials that do not contain impurities that are likely to be generated due to changes in temperature of the substrate, but also because the reaction space does not contain carrier gas, etc. It is easy to set control parameters for single-layer and multi-layer tube synthesis. In addition, it is not necessary to control the injection and exhaust of the carrier gas in a vacuum apparatus or an open type, and the structure of the tank body itself is simple, so that the entire apparatus can be downsized and the apparatus cost can be reduced. Not only does it prevent the nanocarbon material from flowing away from the catalyst by contacting the grown nanocarbon material with the liquid, so there is no need to limit the method of fixing the catalyst to the substrate. High degree of freedom. That is, for example, a solvent in which a metal salt as a catalyst is supported on zeolite or the like, and fixed to the substrate by applying treatment to the substrate and drying can be applied. In addition, an organic metal film that is used as an efficient catalyst for single- and double-walled carbon nanotubes by chemical vapor synthesis can also be used. Examples of the organometallic catalyst include metal carbonyl, carbene complex, metallocene including ferrocene, and the like. In addition, metalloid compounds such as silicon, arsenic, and boron can be used. In addition, it is possible to easily control the film thickness with good accuracy by dip coating, spin coating, dripping, etc., and this makes it possible to easily synthesize single-walled and double-walled carbon nanotubes.

  Also in this embodiment, since the entire liquid surface area F of the organic liquid 6 charged into the tank body 2 is the internal size of the tank body as it is, all of the evaporated gas at the time of evaporation of the organic liquid reacts. It is possible to continue to maintain a high concentration carbon source gas atmosphere supplied to the space.

  The configuration of the second embodiment described above is not limited. For example, as shown in FIG. 12, the catalyst-carrying substrate 4 carrying the catalyst 3 may be arranged on the top wall 201e side and also used as the top wall, and the heater 5a may be closely arranged on the substrate 4. In addition, as shown in FIG. 13, the heater 5 a and the catalyst carrying substrate 4 can be installed at the center of the lower surface opening 200 </ b> A, and the organic liquid can be introduced as an evaporating gas from the gaps on both sides of the substrate 4. The tank body 200 may have a cylindrical shape, an elliptical cylindrical shape, a polygonal cylindrical shape, or the like.

  In order to verify that the nanocarbon material can be produced using the apparatus of the present invention, the present inventor conducted the following experiment.

<Organic Solution> High purity ethanol (99.5%) as a carbon source organic liquid was accommodated in the liquid tank of the apparatus of FIG.
<Substrate> A carbon nanotube synthesis test was performed using a silicon substrate having a Si (100) plane orientation and a size of 9 × 15 × 0.5 mm ³ . The substrate was ultrasonically cleaned in advance in acetone, and further oxidized in the atmosphere at 1000 ° C. for 1 hour to form a SiO ₂ film on the substrate surface.
<Preparation of catalyst>
(1) 0.1 g of zeolite (ultra-stabilized Y-type, average pore diameter 0.74 nm) was ultrasonically dispersed in a solution of iron acetate and cobalt acetate as catalyst raw materials dissolved in 4 ml of ethanol. The metal weight ratio was 2.5 wt% with respect to the zeolite.
(2) Ethanol was evaporated and dried at 80 ° C.
(3) The obtained dry powder was ultrasonically dispersed again in 4 ml of ethanol solution.
(4) Ethanol was evaporated at 80 ° C., and the catalyst raw material was supported on the zeolite.
(5) An iron acetate-carrying zeolite was dispersed in ethanol at a ratio of 0.7 wt% to obtain a catalyst raw material carrier dispersion.
(6) A catalyst raw material carrier dispersion was dropped onto a Si substrate heated to 100 ° C. to form a catalyst raw material carrier coating film.
<Synthesis> The Si substrate coated with the catalyst raw material support in (6) was set in the tank body 200, and the tank body 200 was placed in ethanol while being introduced into the tank body 200 while introducing nitrogen (N ₂ ) gas. . Then, while measuring the substrate surface temperature from the outside with a radiation thermometer, a direct current was passed through the carbon heater 5a behind the substrate to heat the substrate. The substrate surface temperature was changed from 700 ° C. to 1100 ° C. in increments of 50 ° C., and the synthesis temperature conditions were changed to perform synthesis experiments. During the temperature rising to the set synthesis temperature, nitrogen (N ₂ ) gas is continuously introduced into the tank body 200. When the substrate surface temperature reaches the set synthesis temperature, the nitrogen gas introduction is stopped and replaced with nitrogen gas. Then, the ethanol evaporation gas saturated in the reaction space and the catalyst were reacted to grow carbon nanotubes for 10 minutes. When the introduction of nitrogen gas is stopped and the ethanol evaporating gas enters the reaction space and is replaced with nitrogen gas, nitrogen gas, ethanol gas, and gas generated by the reaction form bubbles in the tank body 200 from the gas phase reaction space. Was observed (see FIG. 9). Nitrogen gas introduction was restarted 10 minutes after the nitrogen gas introduction stop, and at the same time, the energization of the heater was stopped. And the tank body 200 was taken out from ethanol together with the carbon nanotubes deposited on the substrate after the substrate temperature returned to room temperature.

14, 15, and 16 show scanning electron microscopes (SEM) of carbon nanotubes grown on the same substrate in the experiment of Example 1 above.
In a microscope (SEM) image, FIG. 14 shows a double-walled carbon nanotube, and FIGS. 15 and 16 show a single-walled carbon nanotube. In the double-walled carbon nanotube of FIG. 14, the tubes are arranged in a nested manner, and narrow stripes are seen. From FIG. 15, single-walled carbon nanotubes that are bundles of several bundles with a diameter of about 1.0 [nm] on a double line with dark side surfaces are confirmed. Moreover, in FIG. 16, one single-walled carbon nanotube with high crystallinity is confirmed.

FIGS. 17A and 17B show Raman spectroscopy spectra of the carbon nanotubes synthesized as a result of the experiment of Example 1 when the synthesis temperature is 850 ° C. and 900 ° C. FIG. The measurement was performed at a laser wavelength of 532 [nm]. A peak (RBM: radial breathing mode) was observed at 232 cm ⁻¹ in both cases where the synthesis temperature of (a) was 850 ° C. and the synthesis temperature of (b) was 900 ° C., confirming the synthesis of single-walled carbon nanotubes. Is done. The signal is stronger at the synthesis temperature of 900 ° C. in (b), indicating that more carbon nanotubes are generated. Further, the diameter of the carbon nanotube at this time is 248/232 = 1.07 nm from 248 / (Raman Raman shift (cm ⁻¹ )).

  In the experiment of Example 1 performed using the apparatus of FIG. 4, the formation of carbon nanowalls and carbon nanoribbons (graphene) was confirmed together with carbon nanotubes on the same catalyst. In FIG. 18 of the scanning electron micrograph image, the carbon nanowall CW is seen as lint, the mass ZL is zeolite, and the carbon nanoribbon (graphene) is seen as a string that bridges the zeolite. ) CR. FIG. 19 is an enlarged image of FIG.

  The nanocarbon material production apparatus and the nanocarbon material obtained by the method of the present invention can be used in the fields of electronics, nanotechnology, environment, energy, and various composite materials. For example, in the electronics field, the present invention can be applied to field effect transistors and other electronic devices, nanowiring, flat panel displays (field emission electron sources), transparent electrodes, and the like. In the nanotechnology field, it can be used in nano tweezers, scanning probe microscope probes, nano test tubes, and so on. In the environment and energy fields, applications in gas sensors, hydrogen storage materials, lithium batteries, solar cells, etc. can be expected. Further, in the medical field, applications such as nanocapsules and injection needles used for in-vivo transport / release of drugs are conceivable.

DESCRIPTION OF SYMBOLS 1,30 Nanocarbon material manufacturing apparatus 2,200 Tank 2a Closed space 2b Reaction space 3 Catalyst 4 Catalyst support substrate 5 Heating device 6 Organic liquid 7 Inert gas supply device 8 Boundary portion 9 Communication portion 10 Cooling device 16 Organic liquid Supply devices 21a to 21d, 201a to 201d Quadrilateral wall 31 Liquid tank 33 Lid member IG Inert gas VG Evaporative gas F Surface N surrounded by tank wall Nanocarbon material

Claims (5)

A tank body having a communication space with the organic liquid and forming a closed space inside;
A catalyst-carrying substrate disposed in a closed space, the catalyst-carrying substrate disposed in a position where the supported catalyst is exposed to the closed space of the tank body and the catalyst is not in direct contact with the organic liquid;
A heating device for the catalyst-carrying substrate;
An organic liquid disposed so as to be in contact with the closed space of the tank body at the communicating portion of the tank body;
An inert gas supply device that is an inert gas that is substituted for the evaporated gas when the organic liquid is evaporated by heating the catalyst-carrying substrate, and that supplies the inert gas to the closed space of the tank body,
The communication space between the organic liquid and the tank body is formed so that the closed space of the tank body is a reaction space and the entire surface surrounded by the tank wall of the tank body is the boundary between the reaction space and the organic liquid. An apparatus for producing a nanocarbon material characterized by the above. It has a liquid tank that contains the organic liquid and can immerse the entire tank body in the organic liquid,
The tank body consists of a reversing case body with the opening at the bottom as a communication part. The inside of the tank body is a closed space when immersed in an organic liquid, and can be immersed in and lifted from the organic liquid in the liquid tank via a support mechanism. Provided,
Further, when the tank body is immersed in the organic liquid in the liquid tank, or when the catalyst-carrying substrate is heated to the synthesis temperature, the inert gas is introduced into the tank body during non-synthesis. A mode in which the closed space is supplied to a high concentration state by an inert gas,
During the synthesis of the nanocarbon material by heating the catalyst-carrying substrate in the organic liquid, the supply of the inert gas is stopped and replaced with the evaporative gas of the organic liquid, and the enclosed space is brought into a high concentration state by the evaporative gas of the organic liquid The apparatus for producing a nanocarbon material according to claim 1, further comprising:   The apparatus for producing a nanocarbon material according to claim 1 or 2, wherein the liquid surface outer edge size of the organic liquid facing the closed space of the tank body is substantially the same as the inner size of the tank body. Place the organic liquid facing the reaction space in the tank body so that the entire surface surrounded by the tank wall of the tank body forms a boundary between the organic liquid and the reaction space,
Place the catalyst-carrying substrate in a position where the catalyst is not in direct contact with the organic liquid and with the catalyst exposed to the reaction space of the tank body,
A tank of a tank body that supplies an inert gas into the reaction space except when the catalyst-carrying substrate is heated to the synthesis temperature, and replaces the organic liquid evaporative gas when the catalyst-carrying substrate is heated to the synthesis temperature. A method for producing a nanocarbon material, comprising synthesizing a nanocarbon material on a catalyst while supplying an organic liquid evaporating gas over the entire surface surrounded by a wall.   It is characterized by immersing the tank body in a liquid tank containing an organic liquid in a state where the inside of the tank with the lower surface opened is a reaction space and the reaction space is filled with an inert gas, and the nanocarbon material is synthesized in that state. The method for producing a nanocarbon material according to claim 4.