JP2006219364A - Manufacturing unit for fullerene base material, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem that the efficient refinement of a fullerene base material such as inclusion fullerene and heterofullerene can not be achieved by the currently used solvent extraction and liquid chromatography, because there is no solvent having sufficiently high solubility to a fullerene base material. <P>SOLUTION: In this method, an ionic or polarized fullerene base materials is refined using electrophoresis. In the method, a fullerene base material which is hard to dissolve in solvents can be efficiently refined and the mass refining of a high purity fullerene base material became possible. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a manufacturing apparatus and a manufacturing method used for separation and purification of fullerene base materials.

"Fullerene Chemistry and Physics" Hisashino Shinohara, Yahachi Saito Nagoya University Press

(Conventional purification method of fullerene base material)
Fullerene-based materials, for example, endohedral fullerenes, are carbon clusters in which fullerenes encapsulate atoms to be encapsulated such as alkali metals, and are expected to be applied to electronics and medicine. Examples of the method for producing the endohedral fullerene include a laser evaporation method, an arc discharge method, an ion implantation method, and a plasma irradiation method.

  In the products containing the endohedral fullerenes produced by these methods, in addition to the endohedral fullerenes, empty fullerenes, encapsulated target atoms and the like are included as impurities. Therefore, in order to produce a high purity endohedral fullerene, it is necessary to separate the endohedral fullerene and these impurities and purify the endohedral fullerene.

  The method for purifying the endohedral fullerene includes a method utilizing the difference in solubility in a specific solution (solvent extraction), a method utilizing the difference in column retention time (liquid chromatography), or solvent extraction and liquid chromatography. A combined method is used.

(Solvent extraction)
Fullerenes are generally soluble in nonpolar solvents (toluene, benzene, etc.) and insoluble or sparingly soluble in polar solvents (water, alcohol, etc.). On the other hand, endohedral fullerenes, such as Li @ C _60, are sparingly soluble in toluene. When the endohedral fullerene product is powdered, mixed and stirred in toluene, and filtered with a filter, most of the empty fullerene contained in the product is dissolved in toluene, and Li @ C _{60, which} is difficult to dissolve in toluene, is contained in the filter. Since it remains as a residue, Li @ C ₆₀ can be purified.

However, not all empty fullerenes are dissolved in toluene, and dimers and trimers containing empty fullerenes are difficult to dissolve in toluene, so that it is difficult to completely remove empty fullerenes from the residue. According to the solvent extraction, there is a problem that the endohedral fullerene such as Li @ C ₆₀ can be purified only to a purity of about 80%.

(Liquid chromatography)
Liquid chromatography is a separation and purification method frequently used in the field of organic chemistry. In liquid chromatography (open column liquid chromatography or high performance liquid chromatography (HPLC)), a substance to be separated is moved through a column (stationary phase) together with a solvent (moving bed). The separation target substance and the impurity are separated by utilizing the property that the elution time differs depending on the interaction between the separation target substance and the impurity at the solid-liquid interface. (Non-Patent Document 1)

For example, when 5 @ PPB is used as a column and ODCB (orthodichlorobenzene) is used as a mobile phase to separate Li @ C ₆₀ , C ₆₀ elutes first and Li @ C ₆₀ elutes later. However, since dimers and trimers containing empty fullerenes elute at the same time as Li @ C ₆₀ , there is still a problem that it is difficult to purify high purity Li @ C ₆₀ . Furthermore, the solubility of Li @ C ₆₀ in ODCB is not high enough, so the amount of Li @ C _{60 that} can be dissolved in a mobile phase solvent and purified at once by liquid chromatography is extremely small, and the purification efficiency is poor. there were.

Similarly, as another example of a fullerene-based material, a solvent having a sufficiently high solubility for nitrogen-derived heterofullerene C ₅₉ N has not been found. For this reason, there is a problem that C ₅₉ N cannot be efficiently purified by liquid chromatography.

  The present invention (1) has a container for containing an electrophoretic liquid, a stirring means for the electrophoretic liquid, a plurality of electrodes arranged at positions facing each other in the container, and a power source for applying a voltage between the electrodes. Then, the fullerene base material manufacturing apparatus is characterized in that the fullerene base material is separated and purified by electrophoresis from a substance containing the fullerene base material dispersed in the electrophoresis solution.

  The present invention (2) is the fullerene base material manufacturing apparatus according to the invention (1), wherein the voltage applied between the electrodes is a DC voltage or an AC voltage.

  The present invention (3) is the fullerene base material manufacturing apparatus according to the invention (1) or the invention (2), wherein the stirring means is a piezoelectric body that generates ultrasonic vibrations.

  In the present invention (4), a carbonaceous material containing a fullerene base material is dispersed in the electrophoresis solution by stirring the electrophoresis solution, and then fullerene is applied by electrophoresis in which a voltage is applied between a plurality of electrodes in the electrophoresis solution. A method for producing a fullerene base material, wherein the base material is separated and purified.

  In the present invention (5), a substance containing a fullerene base material is dispersed in the electrophoresis solution by stirring the electrophoresis solution, and at the same time, a fullerene base material is applied by electrophoresis in which a voltage is applied between a plurality of electrodes in the electrophoresis solution. Is a method for producing a fullerene base material.

  The present invention (6) is the method for producing a fullerene base material according to the invention (4) or the invention (5), wherein the electrophoresis solution is stirred by ultrasonic vibration.

  The present invention (7) is characterized in that the pretreatment for removing unreacted reaction target atoms from the substance containing the fullerene base material is performed before the electrophoresis. ) Of the fullerene base material.

  The present invention (8) is the method for producing a fullerene base material according to the invention (4) or the invention (7), wherein the pretreatment is a treatment with water or an acid.

  The present invention (9) is the method for producing a fullerene base material according to the invention (4) or the invention (8), wherein the fullerene base material is an endohedral fullerene or a heterofullerene.

The present invention (10) is the method for producing a fullerene base material according to the invention (9), wherein the fullerene as a raw material of the fullerene base material is C ₆₀ , C ₇₀ or a mixed fullerene thereof.

The present invention (11), the fullerene base _{material, Li @ C 60, Li @} C 70, C 59 N, or method for producing a fullerene-based material of the invention (9), which is a C ₅₈ BN It is.

(1) Since the fullerene base material can be separated and purified by electrophoresis by dispersing the fullerene base material in an electrophoresis solution, even a fullerene base material that is hardly soluble in a solvent can be separated and purified with high efficiency.
(2) The ionic fullerene base material can be separated and purified with high efficiency by carrying out electrophoresis by applying a DC voltage to the electrode.
(3) A polarizable fullerene base material can be separated and purified with high efficiency by carrying out electrophoresis by applying an alternating voltage to an electrode.
(4) Since the fullerene base material is uniformly dispersed in the electrophoretic liquid by stirring the electrophoretic liquid containing the fullerene base material by ultrasonic vibration before electrophoresis, the amount of fullerene base material accumulated on the electrode increases. In addition, the recovery efficiency of the fullerene base material is improved.
(5) By continuing to stir the electrophoresis solution with ultrasonic vibration simultaneously with electrophoresis, precipitation of the fullerene base material during electrophoresis can be prevented, and the recovery efficiency of the fullerene base material is improved.
(6) By performing pretreatment such as treatment with water or acid before electrophoresis and removing unreacted target atoms, it is possible to prevent unnecessary ions from accumulating on the electrode simultaneously with the fullerene base material. .
(7) Electronics such as Li @ C ₆₀ , Li @ C ₇₀ , C ₅₉ N, or C ₅₈ BN, which are difficult to dissolve in solvents, can be obtained by dispersing the fullerene base material in the electrophoresis solution and electrophoresis. And efficient production of industrial materials expected to be applied in the medical field.
(8) C ₆₀ , C ₇₀ or a mixed fullerene thereof is easily available and inexpensive compared to other higher-order fullerenes.

  The best mode of the present invention will be described below.

  According to a first aspect of the present invention, there is provided a container for containing an electrophoretic liquid, a stirring means for the electrophoretic liquid, a plurality of electrodes arranged at positions facing each other in the container, and a power source for applying a voltage between the electrodes. The fullerene base material manufacturing apparatus is characterized in that the fullerene base material is separated and purified by electrophoresis from a substance containing the fullerene base material dispersed in the electrophoresis solution.

(Fullerene, fullerene base material, mixed fullerene)
In this specification, “fullerene” is a hollow carbon cluster material represented by C _n (n = 60, 70, 76, 78...), And examples thereof include C ₆₀ and C _70. it can. The “fullerene base material” refers to a material produced based on fullerene, and includes endohedral fullerenes, heterofullerenes, chemically modified fullerenes, fullerene polymers, and fullerene polymers.
The “encapsulated fullerene” is a fullerene in which one or more atoms are confined in the hollow portion of the cage-like fullerene molecule, and the atoms encapsulated in the fullerene include alkali metals such as Li and Na, Ca, Examples include alkaline earth metals such as Sr, transition metals such as Fe and Co, and halogen elements such as F.
“Heterofullerene” is a fullerene in which one or more carbon atoms constituting the fullerene molecule are replaced with atoms other than carbon, and examples of the atom replacing a carbon atom include nitrogen and boron.
The “reaction target atom” is an atom that is a raw material that reacts with fullerene to produce a fullerene base material, and includes, for example, an inclusion target atom in an inclusion fullerene and a substitution atom in a heterofullerene.
In addition, mixed fullerene can be used as the fullerene as a raw material. The “mixed fullerene” is a carbon cluster material in which a plurality of different types of fullerenes are mixed. When producing fullerene by the resistance heating method or the arc discharge method, 70 to 85% is C ₆₀ , 10 to 15% is C ₇₀ , and the remainder is C ₇₆ and C ₇₈ in the weight ratio among the generated fullerenes. , C ₈₄ and other higher fullerenes. Also in the production of fullerene by the combustion method, the weight ratio of C ₆₀ and C ₇₀ is larger than that of higher-order fullerene. Therefore, C ₆₀ and C ₇₀ are easily available and inexpensive compared with other higher-order fullerenes. Also, mixed fullerenes composed of C ₆₀ and C ₇₀ are commercially available from frontier carbon and the like, and can be easily obtained and used for the production of fullerene base materials.
Furthermore, the fullerene used as the raw material includes oxide fullerene. Fullerene oxide is a by-product that is synthesized in large quantities when fullerenes are plasma-treated to produce fullerene-based materials such as endohedral fullerenes, which can be reused to produce industrially more valuable fullerene-based materials. Can be manufactured.

  An eighth aspect of the present invention is the method for producing a fullerene base material according to any one of the fourth to seventh aspects, wherein the pretreatment is a treatment with water or an acid.

  Here, the “treatment with water or acid” is a treatment performed to remove encapsulated atoms that are not encapsulated such as alkali metal contained in the encapsulated fullerene product. As water, use water with few impurities such as pure water or purified water, and as acid, it is an acid that dissolves alkali metal (including when it reacts and dissolves), and when used in mass production process, It is preferable to use a highly safe acid. For example, dilute hydrochloric acid can be used. The term “treatment” as used herein refers to a process in which the product is powdered and then mixed and stirred in water or acid, or washed with water or acid and filtered through a filter to recover the residue. is there. In addition to water or acid, any liquid that dissolves the inclusion target atoms such as alkali metal and does not dissolve the inclusion fullerene can be used for the pretreatment of the purification step by electrophoresis according to the present invention.

Hereinafter, the significance of other terms used in the present specification will be clarified.
The “empty fullerene” is a fullerene in which all atoms constituting the fullerene molecule are composed of carbon atoms, and the atoms are not included in the hollow part of the fullerene molecule.

A molecule in which two or more molecules are polymerized or bonded is referred to as a “polymer”.
A “monomer” is a molecule (monomer) that is a polymer constituting unit of a polymer and is not polymerized with other molecules. For example, fullerene C ₆₀ and endohedral fullerene Li @ C ₆₀ are monomers.
A “dimer” is a molecule in which two monomers are polymerized or bonded, and (C ₆₀ ) ₂ , (Li @ C ₆₀ ) ₂ , (C ₆₀ )-(Li @ C ₆₀ ) are dimers.
A “trimer” is a molecule in which three monomers are polymerized or bonded, and (C ₆₀ ) ₃ , (Li @ C ₆₀ ) ₃ , (C ₆₀ ) (Li @ C ₆₀ ) ₂ , (C ₆₀ ) ₂ (Li @ C ₆₀₎ is a trimmer.

The “product” refers to an unpurified fullerene base material produced by a laser evaporation method, an arc discharge method, an ion implantation method, a plasma irradiation method, or the like. In the product, impurities such as empty fullerene are contained in addition to the fullerene base material.
“Purified product” refers to a fullerene-based material that has been purified and improved in purity. It is said to be a purified product, even when the purity is not 100%.

  An “impurity” is a substance other than a monomer of a fullerene base material and a polymer containing the fullerene base material. For example, when a fullerene base material is manufactured by a plasma irradiation method, a reaction target atom that does not react with fullerene, a carbon compound with a small mass number generated by decomposition of fullerene, and an empty fullerene in the generated substance Monomers, dimers and trimers, all of which are impurities in the production of fullerene-based materials.

(Manufacturing method of fullerene base material)
The fullerene base material according to the present invention is, for example, a deposition substrate in which a reactive atom vapor is jetted onto a thermoionization plate heated in a vacuum vessel to generate a plasma flow, and the generated plasma flow is arranged downstream of the plasma flow. Can be produced by a method of depositing fullerene base material.

For example, the fullerene base material according to the present invention can be manufactured by a manufacturing apparatus shown in FIG. The fullerene base material manufacturing apparatus includes a plasma generation unit, a fullerene introduction unit, a tubular vacuum vessel 31 having a fullerene base material deposition unit, a vacuum pump 32 for exhausting the vacuum vessel 31, and an electromagnetic coil 33 for confining plasma. The First, a reaction target atomic material such as Li is heated in an oven 36 to be sublimated. The generated reaction target atomic vapor is introduced into the plasma generation section through the introduction tube 37, and the reaction target atomic plasma is generated on the thermoionization plate 35. The generated reaction target atomic plasma flows in the tube axis direction along a uniform magnetic field. In fullerene introduction, by injection to the plasma stream a vapor sublimed fullerene such as C ₆₀ in an oven 38, an electronic negative ion C ₆₀ is generated by adhering to C ₆₀ constituting the plasma flow. The plasma flow composed of positive ions of reaction target atoms and generated negative ions of C ₆₀ collides with the front surface of the deposition substrate 40 to which a positive bias voltage is applied by the bias power source 41 in the fullerene base material deposition portion, and the surface of the deposition substrate 40 The fullerene base material is deposited on the substrate.

(Treatment with water or acid)
The deposited film produced by the apparatus shown in FIG. 4 is peeled off from the deposited substrate and ground into a powder. The deposited film contains impurities such as empty fullerene and unreacted target atoms in addition to the fullerene base material. In particular, when alkali metal or alkaline earth metal is used as the reaction target atom, both the fullerene base material and the reaction target atom are likely to be positive ions when ionized in the electrophoresis solution. Therefore, before performing purification using electrophoresis according to the present invention, it is preferable to perform treatment with water or acid in advance to remove unreacted atoms to be reacted. While the reaction target atoms are easily dissolved in water or acid, the fullerene base material is difficult to dissolve in water or acid. Therefore, the reaction target atoms can be selectively removed by treatment with water or acid. By removing the reaction target atoms in advance, it is possible to improve the purity of the fullerene base material collected on the electrode in the separation and purification step by electrophoresis.

(Purification method)
FIG. 1 is a cross-sectional view of a purification apparatus for separating and purifying a fullerene base material of the present invention.
The purification apparatus includes a container 1, a piezoelectric body 5 for ultrasonic vibration attached to the container 1, a power source 6 for driving the piezoelectric body 5, two electrodes 3, 4, an electrode 3 disposed in the container 1. 4 includes a power source 9 that applies a DC or AC voltage. For purification, the electrophoresis solution 2 is placed in the container 1, and the fullerene-based material product powders 7 and 8 are placed in the electrophoresis solution 2. The electrophoresis solution 2 is stirred by ultrasonic vibration to disperse the fullerene base material molecules 7 constituting the powder and the impurities 8 such as empty fullerene in the electrophoresis solution 2. Electrophoresis is performed by applying a DC voltage or an AC voltage between the electrodes 3 and 4. During the electrophoresis, the ultrasonic vibration may be stopped or the vibration may be continued.

  When the fullerene base material to be purified is an ionic substance, separation and purification can be performed by direct current electrophoresis. If the fullerene base material becomes positive ions, it accumulates on the negative electrode. When the fullerene base material becomes negative ions, it accumulates on the positive electrode.

  When the fullerene base material to be purified is a polarizable substance, separation and purification can be performed by alternating current electrophoresis. In particular, when the fullerene base material is an endohedral fullerene, the fullerene base material is polarized by localization of the endohedral atoms in the fullerene molecule. On the other hand, empty fullerene, which is an impurity, has no internal atoms and is a highly symmetric molecule, so it is not polarized. Therefore, when an alternating electric field is applied by electrophoresis, the polarized fullerene base material is accumulated on the electrode. On the other hand, the impurities do not accumulate on the electrode and remain dispersed in the electrophoresis solution, and some impurities settle on the bottom of the container when the ultrasonic vibration is stopped.

(Electrophoresis solution)
As the electrophoretic liquid, any carbon substance mixture constituting the fullerene-based material product can be dispersed, and any solvent can be used as long as the carbon substance mixture is electrophoresed in the liquid. As the solvent, an aqueous solvent, an organic solvent, or a mixed solvent thereof can be used. For example, known solvents such as water, acidic solution, alkaline solution, alcohol, ether, petroleum ether, benzene, ethyl acetate, and chloroform can be used. More specifically, general-purpose organic solvents such as isopropyl alcohol (IPA), acetonitrile, ethyl alcohol, acetone, and toluene can be used.

(DC electrophoresis)
FIGS. 2A to 2C are cross-sectional views in order of steps according to the production method of the present invention for purifying a fullerene base material by direct current electrophoresis.

  In the electrophoresis solution 11, a powder of a product composed of a fullerene base material 14 and impurities 15 is placed (FIG. 2 (a)). The fullerene base material 14 is, for example, Li-included fullerene, and the impurity 15 is, for example, empty fullerene. An ultrasonic vibration is applied to the electrophoretic liquid 11 by the piezoelectric body 16. Particles such as the fullerene base material 14 and the impurities 15 are dispersed in the electrophoresis solution 11 (FIG. 2B). A DC voltage is applied between the electrodes 12 and 13 so that the electrode 12 is a negative electrode and the electrode 13 is a positive electrode. Due to the movement of electrons, the fullerene base material 14 becomes positive ions, and the empty fullerene 15 becomes negative ions. After performing electrophoresis for a sufficient time, positive ions accumulate on the negative electrode 12 side and negative ions accumulate on the positive electrode 13 side (FIG. 2 (c)).

  If ultrasonic stirring is continued at a low intensity during electrophoresis, the particles are unlikely to settle at the bottom of the container, thereby improving the recovery efficiency of the fullerene base material. When the fullerene base material becomes positive ions, the fullerene base material can be recovered by taking out the negative electrode, drying it, and peeling off the substances accumulated on the negative electrode surface. Since empty fullerene accumulates on the positive electrode side, it can be recovered by drying the positive electrode and peeling off the material accumulated on the surface. The empty fullerene can be reused, for example, as a raw material for producing the fullerene base material.

(AC electrophoresis)
3 (a) to 3 (c) are cross-sectional views in order of steps according to the production method of the present invention for purifying a fullerene base material by alternating current electrophoresis.

  A product powder composed of a fullerene base material 24 and impurities 25 is placed in the electrophoresis solution 21 (FIG. 3A). The fullerene base material 24 is, for example, Li-included fullerene, and the impurity 25 is, for example, empty fullerene. An ultrasonic vibration is applied to the electrophoretic liquid 21 by the piezoelectric body 26. Particles such as the fullerene base material 24 and the impurities 25 are dispersed in the electrophoresis solution 21 (FIG. 3B). An AC voltage is applied between the electrodes 22 and 23. The fullerene base material is polarized and moves toward the electrode 22 or 23 in the electrophoresis solution 21. On the other hand, since empty fullerene 25 is not polarized, it maintains a dispersed state in electrophoresis solution 21 (FIG. 3C). When the ultrasonic stirring is stopped after sufficient time for electrophoresis, the fullerene base material is accumulated on the electrode 12 or the electrode 13. On the other hand, a part of the empty fullerene 25 is dissolved in the electrophoresis solution, and a part is precipitated at the bottom of the container.

  If ultrasonic stirring is continued at a low intensity during electrophoresis, the product particles are unlikely to settle on the bottom of the container, so that the recovery efficiency of the fullerene base material is improved. The fullerene base material can be recovered by taking out the electrode, drying it, and peeling off the substance accumulated on the electrode surface. On the other hand, empty fullerenes can be recovered by filtering the electrophoretic solution through a filter and taking out the residue. The empty fullerene can be reused, for example, as a raw material for producing the fullerene base material.

  The frequency of AC electrophoresis is preferably in the range of 10 Hz to 10 MHz. In particular, it is preferable to apply a high frequency of 1 kHz to 10 MHz. By setting the frequency range, the purity of the fullerene base material can be increased.

(Generation of Li-encapsulated fullerene)
For the production of the endohedral fullerene containing Li, a production apparatus having a structure shown in FIG. 4 having a structure in which an electromagnetic coil is arranged around a cylindrical stainless steel container was used. Li used as raw material used was unpurified Li for isotopes manufactured by Aldrich, and C ₆₀ used as raw material used was C ₆₀ manufactured by Frontier Carbon. The vacuum vessel 31 was evacuated to a vacuum degree of 4.2 × 10 ⁻⁵ Pa, and a magnetic field having a magnetic field strength of 0.2 T was generated by the electromagnetic coil 33. The encapsulated atom sublimation oven 36 was filled with solid Li and heated to a temperature of 480 ° C. to sublimate Li to generate Li 2 gas. The generated Li gas was introduced through a gas introduction pipe 37 heated to 500 ° C. and sprayed onto a thermoionization plate 35 heated to 2500 ° C. Li vapor was ionized on the surface of the thermal ionization plate 35, and a plasma flow composed of Li positive ions and electrons was generated. Further, C ₆₀ vapor heated and sublimated to 610 ° C. in the fullerene oven 38 was introduced into the generated plasma flow. A bias voltage of +10 V was applied to the deposition substrate 40 that was in contact with the plasma flow, and a thin film containing endohedral fullerene was deposited on the surface of the deposition substrate 40. Deposition was performed for about 1 hour, and a thin film having a thickness of 0.9 μm was deposited.

(Diluted hydrochloric acid treatment)
The thin film deposited on the deposition substrate was peeled off from the deposition substrate, and the powdered endohedral fullerene product (about 5 mg) was mixed with 500 ml of dilute hydrochloric acid and subjected to ultrasonic stirring for 10 minutes. After stirring, the mixture was allowed to stand at room temperature for 1 hour, filtered through a membrane filter, and the residue remaining on the filter was collected. The collected residue was dried and ground to give about 4 mg of product powder.

(Separation and purification of Li-encapsulated fullerene)
The powder of the product from which Li that was not encapsulated in fullerene was removed by the treatment with dilute hydrochloric acid was separated and purified by AC electrophoresis using the purification apparatus shown in FIG. 1, and high purity Li-encapsulated fullerene was recovered.

  A cylindrical container 1 was charged with an electrophoresis solution 2 composed of 100 ml of IPA. In the electrophoretic solution 2, two Al electrodes 3 and 4 were arranged facing each other. The distance between the electrodes 3 and 4 was 0.8 mm. The area of the opposing surface of the electrode was 3 cm × 3 cm. Separation and purification were carried out at room temperature of about 25 ° C. without particularly heating or cooling. A powder of a product that has been treated with dilute hydrochloric acid is placed in the electrophoresis solution 2. First, ultrasonic vibration is applied to the electrophoresis solution 2 by the piezoelectric body 5 for 10 minutes, and the electrophoresis solution 2 is stirred. The endohedral fullerene 7 and the impurities 8 were dispersed. In the dispersion step, the electrophoretic solution 2 was stirred with the relative intensity of ultrasonic vibration set to 10. Next, the relative intensity of the ultrasonic vibration was weakened to 2, and an alternating voltage was applied between the electrodes 3 and 4 for 1 hour for electrophoresis. The amplitude of the AC voltage Vp-p was 10 V, and the frequency was 10 MHz. During the electrophoresis, the color of the electrode surface gradually changed to brown. The application of AC voltage to the electrode was stopped, and at the same time, the ultrasonic vibration was stopped, and the purification apparatus was stationary for 10 minutes. After 10 minutes of rest, a dark brown powder precipitated at the bottom of the container.

(Mass spectrometry)
The electrode of the purifier was taken out of the electrophoresis solution and dried, and the brown substance deposited on the electrode was peeled off and recovered as substance A. In addition, the electrophoretic solution was filtered through a membrane filter, and the dark brown residue remaining on the filter was dried and recovered as substance B. The recovered substance A and substance B were subjected to composition analysis by laser desorption mass spectrometry. In substance A, the peak with mass number 727 appeared at a relative intensity of 95: 5 with respect to the peak with mass number 720. Since the peak with mass number 727 corresponds to Li @ C60 and the peak with mass number 720 corresponds to C60, it was confirmed that the Li-containing fullerene having a purity of 95% could be purified by a purifier. On the other hand, in substance B, the peak with mass number 727 appeared at a relative intensity of 10:90 with respect to the peak with mass number 720. It was confirmed that the amount of Li-encapsulated fullerene contained in the substance B was small, and it was confirmed that the Li-encapsulated fullerene could be efficiently recovered by the purification method according to the present invention.

It is sectional drawing of the refiner | purifier of the fullerene base material of this invention. (a) thru | or (c) are process order sectional drawings concerning the manufacturing method of this invention which refine | purifies fullerene base material by DC electrophoresis. (a) thru | or (c) are process order sectional drawings concerning the manufacturing method of this invention which refine | purifies fullerene base material by alternating current electrophoresis. It is sectional drawing of the manufacturing apparatus of fullerene base material.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Container 2, 11, 21 Organic solvent 3, 4, 12, 13, 22, 23 Electrode 5, 16, 26 Piezoelectric body 6 Ultrasonic drive power supply 7, 14, 24 Enclosed fullerene 8, 15, 25 Empty fullerene 9 Separation and purification power source 31 Vacuum vessel 32 Vacuum pump 33 Electromagnetic coil 34 Heating filament 35 Thermoionization plate 36 Reaction target atom sublimation oven 37 Reaction target atom vapor introduction tube 38 Fullerene sublimation oven 39 Resublimation cylinder 40 Deposit substrate 41 Bias voltage application power source

Claims (11)

A container for containing an electrophoresis solution, a stirring means for the electrophoresis solution, a plurality of electrodes arranged at positions facing each other in the container, and a power source for applying a voltage between the electrodes. An apparatus for producing a fullerene base material, wherein the fullerene base material is separated and purified by electrophoresis from a substance containing the dispersed fullerene base material. The fullerene base material manufacturing apparatus according to claim 1, wherein the voltage applied between the electrodes is a DC voltage or an AC voltage. The fullerene base material manufacturing apparatus according to claim 1, wherein the stirring means is a piezoelectric body that generates ultrasonic vibrations. After dispersing the carbonaceous material containing the fullerene base material in the electrophoresis solution by stirring the electrophoresis solution, separating and purifying the fullerene base material by electrophoresis applying a voltage between a plurality of electrodes in the electrophoresis solution. A method for producing a fullerene base material. A substance containing a fullerene base material is dispersed in the electrophoretic liquid by stirring the electrophoretic liquid, and at the same time, the fullerene base material is separated and purified by electrophoresis in which a voltage is applied between a plurality of electrodes in the electrophoretic liquid. A method for producing a fullerene base material. 6. The method for producing a fullerene base material according to claim 4, wherein the electrophoresis solution is stirred by ultrasonic vibration. The fullerene base material production according to any one of claims 4 to 6, wherein a pretreatment for removing unreacted atoms from the substance containing the fullerene base material is performed before the electrophoresis. Method. The method for producing a fullerene base material according to claim 4, wherein the pretreatment is a treatment with water or an acid. The method for producing a fullerene base material according to any one of claims 4 to 8, wherein the fullerene base material is an endohedral fullerene or a heterofullerene. The fullerene base material manufacturing method according to claim 9, wherein the fullerene used as a raw material of the fullerene base material is C ₆₀ , C _70, or a mixed fullerene thereof. The fullerene base _{material, Li @ C 60, Li @} C 70, C 59 N, or method for producing a fullerene-based material according to claim 9, wherein it is a C ₅₈ BN.

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