JP2002255525A - Method for producing multi-layered fullerene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing multi-layered fullerene with better yield and by comparably easier method. SOLUTION: The method for producing multi-layered fullerene involves a step to integrate a generated material which contains multi-layered fullerene generated by pyrolysis of a carbon compound with irradiation of laser 40 to 60C fullerene, for example, under the existence of an optical sensitizer in an inert gas atmosphere on a heated grid substrate 60.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a multilayer fullerene compound having a structure in which two or three carbocyclic compounds are nested.

[0002]

BACKGROUND ART The present applicant has already filed a patent application for a novel multilayer fullerene compound having a structure in which two or three carbocyclic compounds are nested (Japanese Patent Application No. 11-3).
No. 42705, filing date: December 2, 1999).

In this patent application, C₆₀Fullerene
Heat treatment of carbon-containing material at a temperature of 2300 ° C or higher in the presence of
By doing so, the following multilayer fullerenes can be manufactured.
Is described. [1] C₂₄₀C in fullerene₆₀Nest fullerenes
Fullerene (hereinafter referred to as “first fullerene”
"). [2] C₅₆₀C in fullerene₂₄₀Nest fullerenes
Fullerene (hereinafter referred to as “second fullerene”
"). [3] C₅₆₀C in fullerene₂₄₀Nest fullerenes
And this C ₂₄₀C in fullerene₈₀Hula
-Layer fullerenes with nesting
"3rd fullerene").

[0004] However, at present, the above-mentioned methods have low yields and are only isolated and purified on a laboratory scale.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing the above-mentioned novel fullerene in a high yield with a relatively easy method.

[0006]

According to the production method of the present invention, a photosensitizer and a droplet in which a fullerene compound is dissolved are made to exist in a reaction chamber, and a laser is irradiated to produce the product by laser pyrolysis. And a step of accumulating objects on the substrate. According to the present invention, multilayer fullerenes can be obtained with high yield.

[0007] A fullerene compound is used as the carbon source of the raw material. Fullerene compound preferably contains a C ₆₀ fullerene 60 wt% or more. According to the inventors, C ₆₀ fullerene is soluble in organic solvents, rather than with such a starting material graphite or carbon black, it was confirmed production yield is good. The carbon source is
_{C 70, C 80, C 90} , C 120 in addition to the C ₆₀ fullerene,
Fullerenes such as C ₂₄₀ and C ₅₄₀ can be used.

In the present invention, the solution of the fullerene compound can be easily introduced into the reaction chamber in the form of fine droplets using an inert gas as a carrier gas. As the inert gas, helium gas, argon gas, or the like is used, and from the viewpoint of the yield of the product, argon gas is preferable.

The organic solvent for dissolving the fullerene compound is
The solvent is not particularly limited as long as the solvent dissolves the fullerene compound. Among them, hydrocarbon compounds such as benzene,
Aromatic hydrocarbon compounds such as toluene are preferred.

As the photosensitizer, lower unsaturated hydrocarbons or sulfur halides can be used, and ethylene, sulfur fluoride and the like are preferable.

The product obtained as a result of the laser irradiation is preferably integrated on a substrate having a grid structure. By using such a substrate, there is an advantage that the surface area of the substrate is increased and the yield is improved. Here, the grid structure refers to a structure in which a plurality of holes serving as gas passages are formed in a substrate. The temperature of the substrate is preferably 20
0 ° C to 800 ° C, more preferably 250 ° C to 500 ° C
It is.

A catalyst can be used if necessary.
Examples of such a catalyst include carbonyl compounds of a Group 8 transition metal such as iron carbonyl, cobalt carbonyl and nickel carbonyl, and Group 8 transition metal complexes such as iron acetylacetonate, cobalt acetylacetonate and nickel acetylacetonate. preferable.

In the present invention, a laser to be irradiated may be a pulsed yag laser, an excimer laser, a pulsed carbon dioxide laser, or the like.

The multilayer fullerene obtained by the present invention retains the properties of the fullerene compound (gas storage properties, superconducting properties, magnetic properties, photoelectric effects, rectifying properties, photosensitive properties, lubricating properties, catalytic action, physiological activity, etc.). In addition to that, it is expected that the hydrogen storage characteristics are particularly excellent.

[0015]

FIG. 1 schematically shows an embodiment of a manufacturing method according to the present invention.

The apparatus used in the manufacturing method of the present embodiment includes a gas introduction unit 10, a reaction chamber 20, and a gas discharge unit 30.
Having. The gas inlet 10 and the gas outlet 30 are connected to the reaction chamber 20. The reaction chamber 20 has an optical window 22 on a side surface serving as an entrance of the laser 40, and a grid substrate 60 is installed inside the reaction chamber 20 near the gas discharge unit 30. The grid substrate 60 is arranged so that the holes 62 are located along the gas flow path.

The microdroplets containing C ₆₀ fullerene compounds,
The mixed gas flow 70 holding the microdroplets containing the catalyst and the photosensitizer passes through the gas inlet 10, is introduced into the reaction chamber 20, and is discharged to the gas exhaust unit 30. The mixed gas flow 70 introduced into the reaction chamber 20 is irradiated with laser in the reaction section 50. The source material held by the gas stream is thermally decomposed by the laser, and the gas stream 80 of the pyrolyzed source material is used.
Pass through the holes 62 of the grid substrate 60 and are discharged to the exhaust unit 30. At this time, the multi-layer fullerene adheres to the grid substrate 60.

[0018] By the solution of C ₆₀ fullerene inert gas, a method of introducing into the reaction chamber as fine droplets,
In particular, any procedure may be used as long as it does not adversely affect the laser pyrolysis method. However, considering the introduction of a sensitizer or the like, the following method is preferred as a typical method.

In the following methods (a) to (d), generation of microdroplets of the raw material is performed as follows.

The first container has a gas introduction pipe and an exhaust pipe on its side, and contains therein a solution in which raw materials are dissolved. The exhaust pipe is finally connected to the gas inlet of the reaction chamber. The carrier gas is blown into the solution from the gas introduction tube, and generates a gas flow holding fine droplets of the solution.
The generated gas stream is introduced into an exhaust pipe. Each method (a)
(D) will be described more specifically with reference to FIG.

(A) As shown in FIG. 2A, the first container 130 has a gas introduction pipe 100 and an exhaust pipe 1 on its side.
The second container 140 is connected to the gas introduction pipe 100 and the exhaust pipe 120 on its side surface. The exhaust pipe 110 and the exhaust pipe 120 are connected at the joint 150, and then connected to the gas inlet 10 of the reaction chamber 20.

The solution 220 that the C ₆₀ fullerene is dissolved in an organic solvent is contained in the first container 130. Inert gas 200 is spinning top blown into the solution 220 through the gas introduction pipe 100, it generates a gas stream including the microdroplets by dissolving C ₆₀ fullerene. On the other hand, the gaseous photosensitizer 210 is blown into the second container 140 in which the solution 230 in which the catalyst is dissolved in the organic solvent is present, and a gas flow including the fine droplets in which the catalyst is dissolved is generated. Each gas flow is provided by exhaust pipes 110, 12
0 and mixed at the joint 150, and then introduced into the gas introduction unit 10.

(B) As shown in FIG. 2B, the first container 130 has a gas introduction pipe 100 and an exhaust pipe 1 on its side.
The second container 140 is connected to the gas introduction pipe 100 and the exhaust pipe 120 on its side surface. The exhaust pipe 110 and the exhaust pipe 120 are separately connected to the gas inlet 10 of the reaction chamber 20.

The solution 220 that the C ₆₀ fullerene is dissolved in an organic solvent is contained in the first container 130. Inert gas 200 is spinning top blown into the solution 220 through the gas introduction pipe 100, it generates a gas stream including the microdroplets by dissolving C ₆₀ fullerene. On the other hand, the gaseous photosensitizer 210 is blown into the second container 140 in which the solution 230 in which the catalyst is dissolved in the organic solvent is present, and a gas flow including the fine droplets in which the catalyst is dissolved is generated. Each gas flow is provided by exhaust pipes 110, 12
0 and are separately introduced into the gas introduction unit 10 of the reaction chamber 20.

(C) As shown in FIG. 2C, the first container 130 has a gas introduction pipe 100 and an exhaust pipe 1 on its side.
The exhaust pipe 110 is connected to the gas inlet 10 of the reaction chamber 20. The other gas introduction pipe 100 is connected to the gas introduction pipe 100 at a joint 150.

A gaseous photosensitizer 210 is blown into the gas inlet tube 100 into which the inert gas 200 is blown from the other gas inlet tube 100 to generate a mixed gas. The first container 130 of the solution 240 prepared by dissolving C ₆₀ fullerene and catalyst in an organic solvent is present, crowded blowing the mixed gas, C ₆₀
It produces a gas stream containing microdroplets of dissolved fullerene and catalyst. Thereafter, the gas flow is introduced into the gas introduction unit 10 of the reaction chamber 20.

(D) As shown in FIG. 2D, the first container 130 has a gas introduction pipe 100 and an exhaust pipe 1 on its side.
10 are connected. Exhaust pipe 110 of first container 130
Is joined to the other gas introduction tube 100 at a joint 150, and then connected to the second container 140 as an introduction tube. The exhaust pipe 120 of the second container 140 is connected to the reaction chamber 2
0 gas introduction unit 10.

A gaseous photosensitizer 210 is placed in a first container 130 containing a solution 230 in which a catalyst is dissolved in an organic solvent.
To generate a gas flow containing fine droplets of the dissolved catalyst. Further, the inert gas 200 is introduced into the gas introduction pipe 100.
To produce a mixed gas stream. The mixed gas stream, crowded blown into the second container 140 of the solution 220 prepared by dissolving C ₆₀ fullerene in an organic solvent is present, is introduced to the gas inlet 10 of the subsequent reaction chamber 20.

[0029]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 In Example 1, raw materials were introduced by the method shown in FIG. Blowing argon gas at a flow rate of 150sccm saturated toluene solution of C ₆₀ fullerene to produce a argon gas holding fine droplets of a saturated toluene solution of C ₆₀ fullerene. On the other hand, ethylene gas was added to a toluene solution of iron carbonyl (concentration: 2 mol%).
Blowing was performed at a flow rate of 0 sccm to produce ethylene gas holding fine droplets of a toluene solution of iron carbonyl. After previously mixing the above two gases, they were introduced into a reaction chamber maintained at a pressure of 300 Torr. The mixed gas introduced into the reaction chamber was irradiated with a carbon dioxide gas laser (output: 100 W) having a frequency of 945 cm ^-1 . The pyrolysis product passed through a grid substrate heated to 300 ° C., which was installed at a position 20 mm from the reaction zone irradiated with the carbon dioxide laser.
At that time, the product adhered to the grid substrate. TEM (Transmission) of the product deposited on the grid substrate
From n Electron Microscopy photographs, it was confirmed that the composition of the thin film was 30% of the first fullerene, 1% of the second fullerene, 3% of the third fullerene, and the rest was amorphous carbon.

Example 2 In Example 2, raw materials were introduced by the method shown in FIG. 2 (b). Blowing argon gas at a flow rate of 150sccm saturated toluene solution of C ₆₀ fullerene to produce a argon gas holding fine droplets of a saturated toluene solution of C ₆₀ fullerene. On the other hand, ethylene gas was added to a toluene solution of iron carbonyl (concentration: 2 mol%).
The ethylene gas was blown at a flow rate of 0 sccm to generate ethylene gas holding fine droplets of a toluene solution of iron carbonyl. The above two gases were separately introduced into a reaction chamber maintained at a pressure of 300 Torr. The mixed gas introduced into the reaction chamber was irradiated with a carbon dioxide laser (output: 10) having a frequency of 945 cm ^-1.
0 W). The pyrolysis product was placed at a position 20 mm from the reaction zone irradiated with the laser, 300 ° C.
Passed through the heated grid substrate. The product then
Attached to grid substrate. From the TEM photograph of the product deposited on the grid substrate, it was confirmed that the composition of the thin film was 20% of the first fullerene, 1% of the second fullerene, 2% of the third fullerene, and the remainder was amorphous carbon. Was.

Example 3 In Example 3, raw materials were introduced by the method shown in FIG. 2 (c). Iron carbonyl was further dissolved in a saturated toluene solution of fullerene to a concentration of 2 mol%. A gas in which equal volumes of ethylene gas and argon gas were mixed was blown into the toluene solution at a flow rate of 300 sccm to generate a gas holding fine droplets of the present toluene solution. The mixed gas was introduced into a reaction chamber maintained at a pressure of 300 Torr. 945 cm ^-1 was added to the gas introduced into the reaction chamber.
Irradiation with a carbon dioxide laser (output: 100 W) having a frequency of The pyrolysis product passed through a grid substrate heated to 300 ° C., which was set at a position 20 mm from the reaction zone irradiated with the laser. At that time, the product adhered to the grid substrate. From the TEM photograph of the product deposited on the grid substrate, it was confirmed that the composition of the thin film was 25% of the first fullerene, 1% of the second fullerene, 2% of the third fullerene, and the remainder was amorphous carbon. Was.

Example 4 In Example 4, raw materials were introduced by the method shown in FIG. Ethylene gas was blown into the toluene solution of iron carbonyl (concentration: 2 mol%) at a flow rate of 150 sccm to generate an ethylene gas stream containing fine droplets of this toluene solution. Argon gas was added and mixed at a flow rate of 150 sccm, and the mixed gas stream was further blown into a saturated toluene solution of fullerene, and a gas stream containing fine droplets of the saturated toluene solution of fullerene was introduced into the reaction chamber. 945 cm ^-1 was added to the gas introduced into the reaction chamber.
Irradiation with a carbon dioxide laser (output: 100 W) having a frequency of The pyrolysis product passed through a grid substrate heated to 300 ° C., which was set at a position 20 mm from the reaction zone irradiated with the laser. At that time, the product adhered to the grid substrate. From the TEM photograph of the product deposited on the grid substrate, it was confirmed that the composition of the thin film was 17% of the first fullerene, 1% of the second fullerene, 1% of the third fullerene, and the remainder was amorphous carbon. Was.

Example 5 In Example 5, raw materials were introduced by the method shown in FIG. 2 (c). A mixed gas stream containing fine droplets of toluene in which iron carbonyl and fullerene were dissolved, produced in the same manner as in Example 3, was introduced at a flow rate of 200 sccm into a reaction chamber maintained at a pressure of 600 Torr. The gas introduced into the reaction chamber was irradiated with a carbon dioxide gas laser (output: 150 W) having a frequency of 945 cm ^-1 . Pyrolysis product is 20m from the reaction zone irradiated by laser
m, and passed through a grid substrate heated to 300 ° C. At that time, the product adhered to the grid substrate. From the TEM photograph of the product deposited on the grid substrate,
It was confirmed that the composition of the thin film was 20% of the first fullerene, and the remainder was amorphous carbon.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing an embodiment of the present invention.

FIGS. 2A to 2D are diagrams showing a method of introducing a solution in which a raw material is dissolved into fine droplets into a reaction chamber.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 Gas introduction part 20 Reaction chamber 22 Optical window 30 Gas exhaust part 40 Laser 50 Reaction part 60 Grid substrate 62 Grid substrate hole 70 Mixed gas flow 80 Gas flow of pyrolyzed raw material 100 Gas introduction pipe 110 Exhaust pipe 120 Exhaust with a solution 240 C ₆₀ fullerene and catalyst dissolved tubes 130 first container 140 solution 230 catalyst second container 150 to dissolve the junction 200 inert gas 210 gaseous photosensitizers 220 C ₆₀ fullerene of the gas exhaust pipe Dissolved solution

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yasumasa Takeuchi 3-2-1 Sakado, Takatsu-ku, Kawasaki-shi, Kanagawa F-term in the International Fundamental Materials Laboratory Co., Ltd. 4G046 CA00 CA02 CB03 CC05 CC06 CC08

Claims (7)

[Claims] 1. A multilayer fullerene comprising a step of irradiating a laser with a photosensitizer and a droplet in which a fullerene compound is dissolved in a reaction chamber, and accumulating products generated by laser pyrolysis on a substrate. Manufacturing method. 2. The method for producing a multi-layer fullerene according to claim 1, further comprising a step of introducing the solution of the fullerene compound into the reaction chamber in a state of a droplet using an inert gas as a carrier gas. 3. The fullerene compound according to claim 1, wherein the C ₆₀ fullerene is 60% by weight.
A method for producing a multilayer fullerene, comprising the above. 4. The method for producing a multilayer fullerene according to claim 1, wherein the photosensitizer is a lower unsaturated hydrocarbon or a sulfur halide. 5. The method according to claim 1, wherein the substrate has a grid structure. 6. The method for producing a multilayer fullerene according to claim 1, wherein the solvent in which the fullerene compound is dissolved is an aromatic hydrocarbon. 7. The method for producing a multilayer fullerene according to claim 1, wherein the temperature of the substrate is 200 ° C. to 800 ° C.