WO2011027637A1 - Procédé de séparation et de purification d'un sel de fullerène encapsulant un atome, à l'aide d'une phase mobile contenant un électrolyte - Google Patents

Procédé de séparation et de purification d'un sel de fullerène encapsulant un atome, à l'aide d'une phase mobile contenant un électrolyte Download PDF

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WO2011027637A1
WO2011027637A1 PCT/JP2010/062871 JP2010062871W WO2011027637A1 WO 2011027637 A1 WO2011027637 A1 WO 2011027637A1 JP 2010062871 W JP2010062871 W JP 2010062871W WO 2011027637 A1 WO2011027637 A1 WO 2011027637A1
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fullerene
salt
solvent
electrolyte
endohedral
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Japanese (ja)
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洋史 岡田
健 酒井
吉弘 小野
泰彦 笠間
研次 表
貴士 小室
博実 飛田
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株式会社イデアルスター
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/8859—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample inorganic compounds
    • G01N2030/8863—Fullerenes

Definitions

  • a high-performance liquid chromatography apparatus (High-Performance-Liquid-Chromatography: hereinafter abbreviated as "HPLC") using an eluent to which an electrolyte is added as a mobile phase can be efficiently used from a raw material containing an atom-containing fullerene salt.
  • HPLC High-Performance-Liquid-Chromatography
  • the present invention relates to a method for separating and purifying an atomic inclusion fullerene salt to be separated and purified.
  • Fullerene is a new molecular structure of carbon with a unique three-dimensional structure (cage structure) that has a highly symmetrical shape, such as soccer balls and rugby balls with a diameter of about 0.7 to 1.0 nm. It is a generic name for a group of carbon molecules represented by the general formula C 2n (2n ⁇ 60), which is composed of a carbon five-membered ring and two or more carbon six-membered rings and is closed in a spherical shell with a size of C 60 or more. . Specific examples include C 60 , C 70 , C 76 , C 82 , C 90 , and C 96 .
  • This fullerene has a free space in which several atoms can be placed inside the cage, and can serve as a capsule that stably holds even unstable atoms.
  • a material in which atoms (hereinafter referred to as M) are encapsulated in the inner cavity of this fullerene is called an atomic inclusion fullerene, and is a general term for molecules represented by the general formula M @ C 2n (2n ⁇ 60).
  • M is a single atom or a plurality of atoms or an atomic group containing them, and is not necessarily a single atom.
  • atomic inclusion fullerenes those in which the inclusion atoms are metal atoms are metal inclusion fullerenes. Research in this area has made significant progress in recent years because it is expected to develop new electrical properties as electrons move from internal atoms or metals to the carbon cage.
  • the inclusion metal atoms mainly include Group 3 elements (Sc, Y, La), lanthanide elements, and actinoid elements in the periodic table, and C 2n (2n ⁇ 82) as fullerenes. It has been studied (Non-Patent Document 2).
  • C 60 with the soccer ball-shaped structure is the most symmetric good fullerene is a convenient material in predicting analysis and physical properties after encasing an atom.
  • alkali metals belonging to Group 1 of the periodic table tend to be monovalent cations
  • alkali metal inclusion fullerenes electrons are given to the fullerene cage, and the fullerenes that have obtained the electrons have a negative charge, and the inclusion metal atoms are positive. It is expected to create new physical properties.
  • the lithium atom inclusion C 60 (chemical symbol Li @ C 60 ), which is very reactive and has an inclusion of lithium atoms whose oxidation number is always +1, has attracted attention, and its significant and specific properties (Since lithium atoms are said to be derived from the smallest diameter among group 1 elements having low ionization energy, that is, alkali metals), synthesis / separation techniques for application development are being studied. In particular, it has attracted attention as a material that contributes to improving the photoelectric conversion efficiency of organic thin-film solar cells that use clean solar energy.
  • the endohedral fullerene is synthesized by a laser vapor deposition method, an arc discharge method, an ion implantation method, a plasma irradiation method, or the like.
  • impurities such as empty fullerenes and non-encapsulated metal atoms are contained in addition to the endohedral fullerenes of the metal atoms. For this reason, in order to produce a highly pure endohedral fullerene, it is necessary to separate the endohedral fullerene and other impurities from the synthesized product before purification.
  • Non-Patent Documents 1 and 2 and Patent Documents 1 to 5 various techniques have been disclosed in Non-Patent Documents 1 and 2 and Patent Documents 1 to 5 regarding methods for separating and purifying endohedral fullerenes or separated endohedral fullerenes.
  • Each document will be described below.
  • the chemical formula M @ Cn is a general formula representing an endohedral fullerene, and indicates that an atom or molecule M is encapsulated in a fullerene cage composed of n carbon atoms.
  • Non-Patent Document 1 is a report by researchers of the Campbell group. Non-Patent Document 1 reports the generation of lithium inclusion C 60 by an ion implantation method.
  • LIDI-TOF-MS laser desorption ionization time-of-flight mass spectrometer
  • C 60 / Li @ C 60 is about 1/4 and still contains a lot of C 60 , and it is a state that gives a single peak or has a peak that overwhelms others. It is hard to say that it is in a separated (isolated) state.
  • Non-Patent Document 2 describes that separation of metal-encapsulated fullerene is extremely difficult, and in FIG. 8.9 (c), from La @ C 82 single peak in LDI-TOF-MS, La @ C The fact that 82 was successfully isolated is described.
  • metal-encapsulated fullerene is separated and purified by two-stage HPLC using two stationary phases (columns) having different adsorption mechanisms. The principle is described as follows. “Metal-encapsulated fullerenes often appear on chromatograms at the same retention time as empty fullerenes. In such a case, the target metal inclusion fullerene can be completely separated from the empty fullerene by using a plurality of stationary phases having different adsorption functions. (Page 206).
  • the LDI-TOF-MS diagram of the pyridine extract at room temperature shows that Ca @ C 60 and Ca @ C 70 are not completely isolated, and Ca @ C 60 , Ca @C 70, C 60, C 70 , C 74 is an indication that they are mixed. That is, Ca @ C 60 or Ca @ C 70 is accompanied by other endohedral fullerenes or empty fullerenes, and is separated into a single peak or a single state having a peak overwhelming others. It cannot be said that it is in an isolated state (isolation).
  • Non-Patent Document 2 As a separation / purification method widely applied to various fullerenes including C 60 fullerene, a sublimation method, an HPLC method, a solubility difference method, and the like are known.
  • the sublimation method is a separation / purification method using a difference in sublimation temperature depending on substances, and is used for separation / purification of various fullerenes.
  • the solubility difference method is a separation / purification method that utilizes a difference in solubility of a substance in a solvent and is generally widely used including extraction and washing (illustrated in Patent Documents 1 to 3 described later).
  • the HPLC method which is a type of column chromatography, determines the difference in the interaction (adsorbability, partition coefficient, etc.) between the target substance and the stationary phase (solid) and mobile phase (developing solution, organic solvent, water, etc.). This is a separation / purification method used (illustrated in Patent Documents 4 and 5 described later).
  • Patent Document 1 discloses a method of separating a first fullerene group and a second fullerene group in a fullerene mixture as follows. That is, (Step 1) A fullerene mixture containing the first and second fullerene groups is prepared. (Step 2) A stable fullerene cation is formed in a solvent for either one of the first or second fullerene group, and the fullerene cation is separated from the other fullerene group. Here, the selective formation of cations is carried out by chemical oxidation, electrochemical oxidation, or chemical addition of a cationic electrophilic group. (Step 3) Cationized fullerene and neutral fullerene are separated by a recrystallization or precipitation technique.
  • desirable fullerenes are chemically modified to impart different chemical properties to target fullerenes and non-target fullerenes, thereby enabling separation and purification of these fullerenes.
  • separation of the first fullerene group and the second fullerene group separation of metal-encapsulated fullerene and empty fullerene is also exemplified.
  • a sublimated fullerene material containing M @ C2n which is easily oxidized (oxidation potential is 0.8 V or less) is contacted with an oxidizing agent (AgSbF 6 ) in a first solvent. It is shown, and purified M @ C2n using techniques thereby forming a first solution containing a cation of M @ C 2n.
  • an oxidizing agent and a proton agent are used in the cation formation process.
  • Patent Literature 1 presents three methods. Each method will be described below.
  • Method 1 (page 25 (Table 3))
  • Soot is sublimated at 750 ° C. to sublimate fullerene having a low sublimation temperature and a small number of carbon atoms, thereby removing the remaining giant fullerenes without sublimation. Then, the fullerene sublimate is collected under anaerobic conditions.
  • Insoluble substances (C 74 , M @ C 60 , M @ C 70 , other M @ C 2n ) can be removed by extracting the sublimate with ODCB (o-dichlorobenzene) and then filtering. extracting soluble filtrate the (M @ C 82, empty C 2n) in ODCB.
  • ODCB o-dichlorobenzene
  • the soluble filtrate (M @ C 82 , empty C 2n ) is oxidized with [Ag + ] [SbF 6 ⁇ ] in ODCB, and then filtered. This removes the precipitated Ag metal precipitate and leaves [M @ C 82 + ] [SbF 6 ⁇ ] and neutral C 2n which are soluble mixtures in the ODCB.
  • Method 1 The soluble mixture is precipitated in hexane and filtered, and contains C 60 and C 70 which are soluble filtrates, insoluble [M @ C 82 + ] [SbF 6 ⁇ ] and neutral C 2n . Separate the solid. (6) Thereafter, M @ C 82 final product is obtained after various steps. In Method 1, M @ C 82 is processed as a final product, and M @ 60 and M @ 70 are removed by ODCB extraction and filtration during the process. It is not. Furthermore, Method 1 is separation / purification using a solubility difference method, and is not separation / purification by the HPLC method.
  • Method 2 (page 30 (Table 4))
  • Soot is sublimated at 750 ° C. to sublimate fullerene having a low sublimation temperature and a small number of carbon atoms, thereby removing the remaining giant fullerenes without sublimation.
  • the fullerene sublimate is collected under anaerobic conditions.
  • the sublimate is extracted with an oxidizing agent in which [Ag + ] [SbF 6 ⁇ ] is mixed in ODCB, and then filtered.
  • the precipitated insoluble substances (M @ C 60 , M @ C 70 , C 74 ) are removed and Ag metal precipitates are removed, and [Mm @ C 2n + ] [ SbF 6 ⁇ ] and neutral C 2n are left.
  • (4) Precipitate a filtrate soluble in ODCB in hexane, filter, and filter C 60 and C 70 which are soluble in hexane, and [Mm @ C 2n + ] [SbF 6 ⁇ ] insoluble in hexane. And a solid containing neutral C 2n of reduced polarity.
  • the final product of Mm @ C 2n is obtained after the processing in various steps.
  • Method 2 the final product is Mm @ C 2n , but n is 36 or more (Patent Document, page 29, paragraph number [0019]). That is, M @ C 60 is not isolated or purified.
  • M @ C 60 and M @ C 70 have become insoluble substances without being oxidized.
  • Gd @ C 72 and Gd @ C 82 coexist in the final product (see FIG. 6 of Patent Document 1).
  • This method 2 is also separation / purification using the solubility difference method, and not the HPLC method.
  • Patent Document 1 [Method 3 (page 33 (Table 5))
  • Patent Document 2 Patent Document 3
  • Patent Document 3 Patent Document 2 and Patent Document 3 are already filed by the inventors of the present application.
  • a plasma flow containing ions composed of atoms to be included is generated in a vacuum vessel, and the ions in the generated plasma flow are reacted with fullerene vapor generated by a fullerene oven to be contained on a deposition substrate. A film containing fullerene is formed.
  • FIG. 6 is a schematic explanatory diagram for explaining the structure of a film forming apparatus for producing an endohedral fullerene by a plasma irradiation method.
  • 301 is a vacuum chamber
  • 302 is a vacuum pump
  • 303 is an electromagnetic coil
  • 304 and 308 are ovens
  • 305 and 309 are nozzles
  • 306 is a heating substrate
  • 307 is a plasma flow
  • 310 is a deposition substrate
  • 311 is a composite.
  • 312 indicates a bias voltage applying device
  • 313 indicates a heating filament.
  • the vacuum chamber 301 is made of a corrosion-resistant metal such as stainless steel, has a cylindrical shape that is long in the lateral direction and has a circular or rectangular cross section as shown in FIG. 6, and is provided with a lid at both openings of the cylinder.
  • the structure is provided with an openable / closable lid that is not shown for replacement and maintenance of components in the vacuum chamber 301.
  • the heating filament 313 is made of a thin wire wound in a coil shape of a refractory metal such as tungsten, and heats the heating substrate 306 described later from the left side shown in FIG. 6 to, for example, about 2700 ° C. in a vacuum. Power is supplied from a power source (not shown) from a lid 301 via a current introduction terminal (not shown).
  • the heating substrate 306 is a plate having heat resistance and corrosion resistance due to a refractory metal such as tungsten or rhenium. As shown in FIG. 6, the central axis of the vacuum chamber 301 is inside the vacuum chamber 301 with respect to the heating filament 313. The plate surface is disposed so as to be substantially orthogonal to the plate.
  • the deposition substrate 310 is a plate having a smooth surface made of stainless steel or the like, and is disposed with the smooth surface facing the heating substrate 306 as shown in FIG. A desired film is formed on the smooth surface of the deposition substrate 310.
  • the bias voltage applying device 312 applies a negative voltage to the deposition substrate 310 so as to give acceleration energy to ions of inclusion target atoms guided to the vicinity of the deposition substrate 310 by a plasma flow 307 to be described later.
  • One end is connected to the deposition substrate 310 and the other end is grounded via a current introduction terminal (not shown) from the right lid shown in FIG.
  • the vacuum pump 302 reduces the internal pressure of the vacuum chamber 301 to about 10 ⁇ 4 Pa, facilitates plasma generation, increases the mean free path of desired molecules in the gas state, and allows molecules to reach the deposition substrate 310. Many are secured.
  • a rotary pump is used as a roughing pump, a diffusion pump, a turbo molecular pump, or the like is used as an auxiliary pump.
  • the electromagnetic coil 303 is a large coil in which the outer periphery of the vacuum chamber 301 is wound with a metal wire such as copper having a relatively large current capacity and good electrical conductivity.
  • a current source not shown
  • a magnetic field B in the direction of the arrow shown in FIG.
  • the ovens 304 and 308 are in close contact with the nozzles 305 and 309 provided with heaters (not shown) that cover the opening and have a bent tube as shown in FIG. 6 on the opening side of the vaporizer that stores the material to be vaporized. It is fixed.
  • the nozzles 305 and 309 of the ovens 304 and 308 are exposed to the inside of the vacuum chamber 301, and the center axis of the nozzle tip is provided toward the approximate center of the heating substrate 306 and the deposition substrate 310.
  • the film forming apparatus 300 is provided with an air supply pipe provided with an opening / closing valve such as nitrogen gas for returning the vacuum chamber 301 to the atmospheric pressure.
  • lithium as an inclusion target atom (hereinafter referred to as “Li”) is supplied to the oven 304 in advance and, for example, C60 powder or the like is supplied to the oven 308.
  • the inside of the vacuum chamber 301 is depressurized to, for example, 10 ⁇ 4 Pa by the vacuum pump 302, and then the heating substrate 306 is heated to about 2700 ° C. by supplying power to the heating filament 313 from a power source (not shown).
  • the heaters (not shown) of the oven 304 and the oven 308 are energized and heated to such an extent that lithium and C60 do not vaporize.
  • the vacuum evacuation is continued until the vacuum chamber 301 reaches a predetermined pressure.
  • the nozzles 305 and 309 are also heated by a heater (not shown).
  • a bias voltage is applied to the deposition substrate 310 by the application device 312. Then, the electromagnetic coil 303 is fed from a current source (not shown) to generate a magnetic field (2 to 7 kG) substantially parallel to the axis L in the vacuum chamber 301.
  • the oven 304 to which lithium is supplied is reset to 500 to 550 ° C., which is higher than the boiling point under reduced pressure, and heated to vaporize lithium, and the oven 308 to which C60 is supplied is changed to a sublimation temperature. Re-set to a higher 400-650 ° C. and heat to vaporize C60.
  • the vaporized lithium is ejected from the nozzle 305 and collides with the high-temperature heating substrate 306.
  • the lithium atoms in the vapor phase that collide with the high-temperature heating substrate 306 and are in thermal contact are supplied with larger thermal energy in addition to the kinetic energy accompanying vaporization, and the lithium atoms themselves release electrons and become positive ions.
  • Macroscopically neutral plasma is formed with nearby electrons (thermal contact ionization).
  • the magnetic field B is formed in the longitudinal direction in the vacuum chamber 301, it is limited that lithium ions having a positive charge are spread by receiving a force from the magnetic field B.
  • lithium ions and electrons that have been thermally contact-ionized on the heating substrate 306 move in pairs, but the electrons are overwhelmed by lithium ions having a large mass. Due to the force that suppresses the spread by the magnetic field B received by the lithium ions, the movement direction of the lithium ion / electron pair after the collision is substantially the longitudinal direction of the vacuum chamber 301, and the plasma flow 307 moves to the right side shown in FIG. Is generated. The flow velocity of this plasma is about the speed of sound and can be said to be extremely low.
  • the vaporized C60 is ejected from the nozzle 309 toward the deposition substrate 310 in the vacuum chamber 301.
  • the ejected molecules form a high concentration C60 atmosphere in the vicinity of the deposition substrate 310. Since the deposition substrate 310 is applied so as to have a small negative potential, an extremely thin ion sheath is formed in the vicinity of the deposition substrate 310. Then, lithium ions are accelerated only in the vicinity of the deposition substrate 310 where C60 is densely present, and lithium atoms are included without destroying C60. As a result, a reaction product film containing the endohedral fullerene is sequentially generated on the deposition substrate 310.
  • the plasma flow 307 is formed by a relatively small magnetic field, and the lithium ions themselves are weakly accelerated by the electric field in the vicinity of the deposition substrate 310. Therefore, the interaction of lithium ions with C60 molecules is not physical but chemical. The reaction is the main one. As a result, decreases the ratio of C 60 itself is destroyed on impact, it becomes more can highly endohedral synthesis yield.
  • FIG. 7 shows the mass analysis result of the film thus formed on the deposition substrate 310 by LDI-TOF-MS (laser desorption ionization time-of-flight mass spectrum), and the mass indicating the presence of empty C 60.
  • LDI-TOF-MS laser desorption ionization time-of-flight mass spectrum
  • the inventors of the present invention encapsulate fullerenes such as atoms to be encapsulated by the above-described plasma irradiation method, a method for producing a compound containing fullerene encapsulating target atoms, and this compound as a solvent.
  • the fullerene base material also referred to as “TCE”
  • TCE fullerene base material
  • the method for producing a fullerene base material disclosed in Patent Document 2 includes a first treatment for removing at least an inclusion target atom and a compound of an inclusion target atom that have not been included in an aqueous solvent from a synthetic product containing an inclusion fullerene, and an inclusion fullerene.
  • the molecular cluster containing the endohedral fullerene is separated and purified by performing a second treatment for extracting the fullerene into the solvent and a third treatment for removing empty fullerene by the reprecipitation method.
  • the separation and purification of the endohedral fullerene is performed by a combined process consisting of at least an unreacted inclusion target atom removal process, an endohedral fullerene solvent extraction process, and an empty fullerene removal process by reprecipitation.
  • separation and purification of the endohedral fullerene which has been insufficient only by solvent extraction, is performed with high purity, and the yield of the endohedral fullerene that can be purified and recovered from the synthesized product is improved.
  • Patent Document 2 shows a product obtained by measuring the particle size distribution of a product in a solution by a dynamic light scattering method. From the particle size distribution in a C 60 solution, the diameter size of C 60 is 0. It has a peak at 7 nm, and the particle size distribution in the chloronaphthalene solution states that the particle size in this solution has a peak at 4 to 6 nm.
  • Patent Document 3 IS503 Isolated Encapsulated Fullerene Patent
  • Patent Document 3 instead of the treatment described in Patent Document 2, a fullerene base material that forms a cluster structure by cutting the binding force between empty fullerene and encapsulated fullerene is used. Further separation and purification were performed.
  • Patent Document 3 discloses a technique for producing an isolated endohedral fullerene, and the endohedral fullerene generally has the following steps. That is, (A) a step of introducing a material having a cluster structure composed of an endohedral fullerene and a plurality of empty fullerenes surrounding the inner fullerene into a solvent; (B) a step of decomposing the cluster structure of the material in this solvent and forming an endohedral fullerene cation; (C) a step of precipitating a salt of an endohedral fullerene cation, (D) a step of separating the solvent and the salt of the encapsulated fullerene cation
  • the present inventors succeeded in loosening the cluster structure by deelectron oxidation reaction and obtaining lithium-encapsulated C 60 fullerene as a cation salt.
  • the lithium-encapsulated C 60 fullerene cation (Li @ C 60 + ) salt shown as an example is a kind of atomic-encapsulated fullerene salt.
  • a salt is generally a compound in which a cation (cation) and an anion (anion) are ion-bonded.
  • the atomic inclusion fullerene salt refers to a salt containing a cation (cation) or an anion (anion) of the atomic inclusion fullerene.
  • an isolated endohedral fullerene represented by M @ C 2n was obtained, and the peak of other endohedral fullerene with respect to the peak intensity of this endohedral fullerene in LDI-TOF-MS was obtained.
  • the intensity ratio was 0.5% or less in the positive mode and 50% or less in the negative mode. “Isolated” was used in the meaning of a state giving a single peak when viewed in a mass spectrum, or a state of being separated almost alone having a peak overwhelming others.
  • Patent Document 4 discloses a technique for separating or purifying a desired endohedral fullerene from a material containing the endohedral fullerene using HPLC (High Performance Liquid Chromatography).
  • HPLC High Performance Liquid Chromatography
  • this HPLC is a kind of column chromatography and uses a liquid pressurized to a high pressure as a mobile phase.
  • Column chromatography is one of the methods for purifying compounds and utilizes the distribution of substances between two different phases (solid phase and liquid phase).
  • a cylindrical container (column) is filled with a packing material (stationary phase) such as silica gel, and a reaction mixture (eluent) dissolved in a solvent is poured into it, and the compound has an affinity for the packing material and molecular size. Separation of the mixture is performed by utilizing the difference in length.
  • a packing material such as silica gel
  • eluent dissolved in a solvent
  • the separation here depends on the degree of partitioning between both phases of each molecule (or ion) in the sample. And the smaller the particle size of the stationary phase that is the filler in the container, the higher the number of theoretical plates, but the greater the flow resistance.
  • the number of theoretical plates is an index that represents the performance of an apparatus that separates substances using the difference in the distribution ratio of substances between two phases, and is also used as an index that represents the performance of a column. If this value is high, it is said to be a high-performance column, that is, a column with good separation performance.
  • HPLC a method of flowing the eluent at high speed using a high-pressure pump and a method of recording a chart on recording paper using a detector greatly increase the time required for analysis and sorting. Can be shortened.
  • Patent Document 4 discloses an efficient and selective extraction method for metal-encapsulated fullerenes, which has improved the disadvantages of conventional methods for extracting metal-encapsulated fullerenes.
  • the extraction method of metal fullerene disclosed in Patent Document 4 for example, a soot-like mixture containing metal-encapsulated fullerene and empty fullerene, a solvent (A) having a donor number of 25 or more and a donor number of less than 25, And it extracts with a mixed solvent with the solvent (B) whose dielectric constant is larger than 10.
  • the content of metal-encapsulated fullerene in the mixture can be increased by selectively extracting the metal-encapsulated fullerene from the mixture containing the metal-encapsulated fullerene and the empty fullerene. For this reason, by using extraction with a mixed solvent as a pretreatment for separation work using HPLC, the time required for HPLC treatment and the elution solvent are reduced, and efficient and selective extraction of metal-encapsulated fullerenes is achieved. It is supposed to contribute to.
  • the solvent (A) is selected from amine solvents such as tritylamine and ethylamine, dimethyl sulfoxide and the like, and the solvent (B) is a ketone such as acetone and cyclohexane.
  • System solvents, nitrile solvents such as acetonitrile, ether solvents such as tetrahydrofuran and 1,2-dimethoxyethane, and others are used.
  • HPLC it is considered that the above mixed solvent was used as the eluent.
  • Patent Document 5 a technique relating to such a manufacturing method of the fullerenes were encapsulated guest elements such as copper have been disclosed in the interior of the fullerene molecules such as C 60.
  • the method for producing an endohedral fullerene disclosed in Patent Document 5 includes a step of causing a guest element supply source and a fullerene molecule supply source to exist in a plasma generation chamber, and a guest element from the supply source in the plasma generation chamber. And a step of causing the fullerene molecules to collide with each other under plasma excitation to introduce guest elements into the fullerene molecules, and purify the endohedral fullerenes obtained.
  • the purification process of the endohedral fullerene includes a process of extracting a soluble part of the deposit with a solvent, a process of filtering unnecessary precipitates, and a process of separating the target product by HPLC.
  • Non-Patent Document 1 the presence / generation of Li @ C 60 has been confirmed by electromagnetic spectrum observation and mass spectrometry.
  • the endohedral fullerene in the composite is a so-called clustered state in which empty C 60 fullerene is wrapped around, and it is not a cluster structure but an isolated pure one.
  • Li @ C 60 could not be obtained stably in the amount (milligram order by weight), and the properties were not measured and evaluated in detail.
  • Patent Document 1 is a purification method based on a solubility difference method using a clear difference in chemical characteristics between empty fullerenes and encapsulated fullerenes, both of which are in solution or insoluble, respectively. This is effective when there is no interaction in the object. This is not a bond decomposition method in the case where different fullerenes form a bonded state (cluster state) as in the processing object in the present application described later.
  • lithium-encapsulated C 60 fullerene cation (Li @ C 60 + ) salt is a kind of atomic-encapsulated fullerene salt.
  • an atomic inclusion fullerene salt is a salt containing a cation (cation) or anion (anion) of an atomic inclusion fullerene, and Li @ C 60 PF 6 (Li @ C 60 + PF 6 - and also referred), such as Li @ C 60 SbCl 6 is a specific representative examples.
  • Li @ C 60 SbCl 6 which is a typical example of the atom-encapsulated fullerene salt obtained by deelectronization described in Patent Document 3, the present inventors tried a sublimation method or an HPLC method. . However, it did not get enough results. In other words, Li @ C 60 SbCl 6 was easily decomposed, and it was found that purification by heating sublimation was inappropriate. Moreover, when the HPLC method conventionally used for the production of endohedral fullerene was applied as it was, the Li @ C 60 salt and the same cation were not discharged from the column. This is presumed to be because the Li @ C 60 salt and the same cation were held strongly adsorbed on the stationary phase in the HPLC column and were not easily desorbed.
  • Patent Document 3 Although the Li @ C 60 salt was successfully separated and purified by the solubility difference method, the obtained atomic-encapsulated fullerene salt has a low purity and a low recovery rate. There was an inconvenience. That is, the above-described method has not yet been sufficiently separated and purified, and the impurities have not been sufficiently removed and the purity has been low. In addition, because the difference in solubility was not sufficiently secured, problems such as low recovery due to leakage of the target product into the liquid on the impurity side or loss due to adhesion to containers and jigs remained. .
  • the present invention is an inexpensive and simple method that can solve the above-mentioned disadvantages of the solubility difference method and achieve high purity and high recovery rate as a method for separating and purifying atomic inclusion fullerene salts.
  • the HPLC method is one of well-known methods for separation / purification of various organic substances including fullerenes, and is simple and highly efficient. (High separation rate, high purification rate, low process loss), so it is widely used.
  • the present invention overcomes the problem that the endohedral fullerene salt or ion (cation or anion), which is a disadvantage of the conventional HPLC method, is not adsorbed by the HPLC column packing material and discharged from the column. Proposes a novel HPLC method in which is separated from other components and easily discharged from the column.
  • Chromatography is one of the techniques (techniques) used to separate gases, liquids, and solutes.
  • a straight glass tube packed with an adsorbate such as alumina or diatomaceous earth was used as a column.
  • a sample is poured from the top of the column to be adsorbed, and then a new solvent is continuously dropped from above (“development” operation).
  • development operation
  • those that are easily dissolved in the solvent move to the liquid side and descend in the column.
  • each component is separated from the sample in the order of the distribution ratio of the adsorbent and the solvent, so that it elutes from the lower end of the column.
  • Each component can be separated by separating each fraction.
  • HPLC High Pressure Liquid Chromatography
  • Chromatography refers to the use of substance distribution between two different phases (stationary phase and mobile phase). Separation by this distribution is the separation of each molecule (or ion) in a sample. Depends on the degree of distribution between the two phases.
  • Column chromatography in the previous chlorophyll is typical of what is called “adsorption” chromatography, in which the sample is adsorbed onto an adsorption medium such as alumina.
  • partition chromatography a liquid (for example, water) is included in the stationary phase, and another liquid that does not mix with the liquid is used as the mobile phase. In this case, it is the distribution of the solute between the two liquid phases that influences the separation.
  • the HPLC system includes units such as an eluent bottle, a degassing device, a pump, an injector, a column and a column thermostat, a detector, and a recording device.
  • units such as an eluent bottle, a degassing device, a pump, an injector, a column and a column thermostat, a detector, and a recording device.
  • each unit will be described.
  • a) Deaeration device This is used to remove oxygen and other gases mixed in the eluent, which become noise during detection by the detector and cause baseline instability.
  • b) Pump The pump is installed in the uppermost stream of the HPLC system and sends the eluent in the eluent bottle to the system.
  • Various devices have been devised to reduce periodic pressure fluctuations (called pulsations) as much as possible and to flow the eluent at a constant flow rate under any conditions without affecting the measurement. As a result, a very small amount of sample can be analyzed with high sensitivity.
  • c) Injector The injector is installed next to the pump, and a sample to be analyzed is injected into the eluent through a syringe called a syringe. Note that when a large number of samples are continuously injected at regular intervals, an autoinjector (autosampler) is often used.
  • ⁇ / RTI> HPLC configured in this way purifies compounds using the distribution of substances between two different phases (solid and liquid phases) as described above.
  • the affinity with the packing material and the molecular size differ depending on the compound. To separate the mixture.
  • the separation here depends on the degree of partitioning between both phases of each molecule (or ion) in the sample. And the smaller the particle size of the stationary phase that is the filler in the container, the higher the number of theoretical plates, but the greater the flow resistance.
  • the number of theoretical plates is an index that represents the performance of an apparatus that separates substances using the difference in the distribution ratio of substances between two phases, and is also used as an index that represents the performance of a column. If this value is high, it is said to be a high-performance column, that is, a column with good separation performance.
  • liquid chromatography including HPLC is classified as adsorption chromatography, distribution chromatography, ion exchange chromatography, gel filtration chromatography, etc., based on the difference in the degree of partitioning between phases as described above. Then, it is not limited to the HPLC of a specific aspect.
  • the method for separating / purifying the endohedral fullerene salt of the present invention is based on the HPLC method using a solution to which an electrolyte is added as a mobile phase.
  • the method for separating and purifying an atomic inclusion fullerene salt of the present invention since the HPLC method using a solution with an electrolyte added as a mobile phase is adopted, the atomic inclusion fullerene salt or the same ion is easily discharged from the column that is a stationary phase. Separation / purification becomes possible. That is, as a result of the inventors' trials, an organic solvent solution obtained by adding a soluble electrolyte to a mobile phase and dissolving it in an organic solvent that is usually used as a mobile phase is used as a mobile phase in HPLC.
  • the endohedral fullerene salt or ions can be easily discharged from the stationary phase column, allowing separation and purification. I found out.
  • the mechanism by which the endohedral fullerene ions and other components (impurities) are separated is based on the difference between the interaction between the binder phase and the endohedral fullerene ions and the interaction between the binding phase and other components (impurities). It is based on the separation mechanism of a normal HPLC method.
  • Fullerene is a group of carbons represented by the general formula C 2n (2n ⁇ 60), which consists of 12 five-membered rings and two or more six-membered rings, and is actually closed into a spherical shell with a size of C 60 or more.
  • a general term for molecules include, but are not limited to, C 60 , C 70 , C 76 , C 82 , C 90 , C 96 and the like.
  • Fullerenes are three-dimensional closed spherical molecules consisting of five- and six-membered rings of carbon atoms.
  • Atomic endohedral fullerene is a generic name for molecules represented by the general formula M @ C 2n (2n ⁇ 60) having a structure in which atoms (hereinafter referred to as M) are confined in the spherical shell of fullerene.
  • M is a single atom or a plurality of atoms or an atomic group containing them, and is not necessarily a single atom.
  • a salt is a compound in which a cation (cation) and an anion (anion) are ion-bonded.
  • a familiar representative example is sodium chloride (chemical symbol NaCl, also referred to as Na + Cl ⁇ to emphasize that it is an ion-bonded compound or salt).
  • the atomic inclusion fullerene salt is a salt containing a cation (cation) or an anion (anion) of the atomic inclusion fullerene.
  • the valence of the ion is 1 or 1 or more.
  • Li @ C 60 PF 6 (emphatically Li @ C 60 + PF 6 that the salt - also referred to as a), Li @ the like C 60 SbCl 6 is a specific representative example, limited to is not.
  • the target substance is an atom-encapsulated fullerene salt.
  • the present invention that is, a separation / purification method using an HPLC method using an electrolyte-added mobile phase is applicable without being limited to the atom-encapsulated fullerene salt. It is.
  • An electrolyte is a substance that ionizes into a cation (cation) and an anion (anion) when dissolved in a solvent. Generally, it is a substance such as an acid, a base or a salt.
  • the material used in the present application may be any substance (electrolyte) that is soluble in the solvent of the mobile phase and dissolves and ionizes into a cation and an anion.
  • electrolyte any substance that is soluble in the solvent of the mobile phase and dissolves and ionizes into a cation and an anion.
  • Typical examples of the electrolyte are combinations of cations and anions listed below. Although it is a thing, it is not particular about it.
  • the electrolyte is not particularly limited as long as it is soluble in the mobile phase solvent.
  • examples of cations (cations) and anions (anions) constituting the electrolyte are specifically listed, but are not limited thereto.
  • the concentration of the electrolyte added to the mobile phase solvent is desirably 1 mmol (1 mmol / l) or more with respect to 1 L (liter) of the solvent.
  • a saturation solubility (saturation concentration) by a combination of an electrolyte and a solvent is a standard.
  • the solvent of the mobile phase may be any solvent that can be dissolved without altering the target substance to be separated and purified and can be used as a mobile phase for HPLC.
  • a solvent having a relative dielectric constant of 10 or more is selected.
  • the target substance for separation / purification is an atomic inclusion fullerene salt, which is easily dissolved in a highly polar solvent, that is, a solvent having a large relative dielectric constant.
  • a solvent having a large relative dielectric constant Several examples of solvents having a relative dielectric constant of 10 or more are listed below (numerical values are relative dielectric constants), but are not limited thereto.
  • AN acetonitrile
  • ODCB o-dichlorobenzene C 6 H 4 Cl 2
  • a mixed solvent composed of two or more kinds of solvents may be used.
  • FIG. 1 is a schematic diagram of a typical molecular structure of a Li @ C 60 salt obtained by the present invention.
  • (A) is an SbCl 6 salt and
  • (b) is a PF 6 salt. It is a graph which shows the electrolyte addition effect in the HPLC chromatogram of Li @ C 60 salt.
  • Li lithium as contained target atoms
  • Li @ C 60 cation was synthesized, separated and purified according to the process shown in FIG.
  • S1 Synthesis (S11: (Cluster material) synthesis)
  • a production apparatus having a structure shown in FIG. 6 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 301 was evacuated to a vacuum degree of 4.2 ⁇ 10 ⁇ 4 Pa, and a magnetic field with a magnetic field strength of 0.044 T was generated by the electromagnetic coil 303.
  • Encapsulated atom sublimation oven 304 was filled with solid Li and heated to a temperature of 400 to 600 ° C. to sublimate Li to generate Li gas.
  • the generated Li gas was introduced through a gas introduction tube heated to 500 ° C. and sprayed onto the thermoionization plate 306 heated to 2500 ° C.
  • Li vapor was ionized on the surface of the thermoionization plate 306, and a plasma flow composed of Li positive ions and electrons was generated.
  • V Further, C 60 vapor heated and sublimated to 610 ° C. in a chimney type fullerene oven 308 was introduced into the generated plasma flow.
  • the deposition substrate mounting portion in the apparatus was opened from the inside of the glove bag, the inside substrate was taken out, put in a desiccator, covered with a lid, shut off from outside air, and the substrate mounting / extraction port of the apparatus was closed.
  • the desiccator in which the deposition substrate was accommodated in a state of being shielded from the outside air in an anaerobic gas by argon was taken out.
  • a desiccator containing a deposition substrate was placed in a collection glove box in an anaerobic atmosphere with argon gas, and the composite on the substrate was scraped off with a spatula and collected on an aluminum foil.
  • a recovered material which is a composition containing Li @ C 60 having a cluster structure and a plurality of empty fullerenes, is added to a solvent (mixed solvent of first and second solvents) together with an oxidizing reagent.
  • a solvent mixed solvent of first and second solvents
  • an oxidizing reagent Li @ C 60 , empty fullerene, and other components are released and exist in the solution by a chemical reaction of deelectron oxidation.
  • I In a glove box made an anaerobic atmosphere with argon gas, 42.45 g of the recovered product and an aminium salt as an oxidizing reagent were charged into a 1 L eggplant-shaped flask.
  • the input amount of the aminium salt is larger than the calculated expected amount of Li @ C60, and lithium atoms that are not circumscribed or encapsulated with the C60 fullerene contained in the composition (free lithium) ) was also removed.
  • the glove box used was manufactured by Miwa Seisakusho with an internal volume of 6 m 3 and had a moisture content of 2 ppm (corresponding to a dew point of ⁇ 75 ° C.) and an oxygen content of 60 ppm.
  • the aminium salt that is an oxidizing reagent is described as “aminium A” according to the following chemical formula.
  • aminium A in this example, compound name: hexachloroantimonate tris (4-bromophenyl) aminium, rational formula: (4-BrC 6 H 4 ) is 3 NSbCl 6 That Is.
  • this aminium A a reagent manufactured by Aldrich was used.
  • ODCB o-dichlorobenzene
  • AN acetonitrile
  • the purpose was to facilitate precipitation of Li @ C 60 cations in the next step S31 by distilling off AN from the suspension after the oxidation reaction.
  • the eggplant-shaped flask containing the suspension was taken out from the glove box and connected to an evaporator.
  • the eggplant-shaped flask was immersed in a high-temperature water tank maintained at 70 ° C., and the pressure was reduced to 75 hPa or less with a diaphragm pump to distill off AN.
  • the guideline for the completion of the AN distillation was the point at which foaming from the solution surface was no longer observed visually.
  • the residue solid content obtained by repeated filtration up to “Filtration 3” is the filtration residue solid content that is the second composition.
  • the amount of AN used in the salt removal treatment was 300 ml for “Filtration 1”, 300 ml for “Filtration 2”, and 150 ml for “Filtration 3”, for a total of 750 ml.
  • empty fullerene (C 60 ) is dissolved and removed from the filtration residue solid content of the second composition using a fifth solvent (toluene).
  • a fifth solvent a good solvent for empty fullerene and a solvent that does not substantially dissolve the endohedral fullerene cations are selected.
  • a filtration residue solid of the second composition and a filter were placed in a 500 ml eggplant-shaped flask, and 300 ml of toluene as the fifth solvent was poured therein so that they were immersed.
  • the encapsulated fullerene cation is dissolved and extracted from the solid residue of the filtration residue, which is the third composition, using a sixth solvent (ODCB and AN).
  • a sixth solvent a good solvent for the endohedral fullerene cation is selected.
  • the third composition filtration residue solid and the filter were placed in a eggplant-shaped flask having a capacity of 500 ml, and ODCB 40 ml and AN 40 ml, which were sixth solvents, were poured therein so that they were immersed.
  • ODCB is a special grade ODCB (manufactured by Aldrich)
  • AN is a special grade AN (manufactured by Wako Pure Chemical Industries, Ltd.)
  • Filtration filter is a membrane filter (Nihon Millipore omnipore membrane filter, model number JGWP09025, specification pore size 0.2 ⁇ m, A diameter of 90 mm ⁇ and a thickness of 65 ⁇ m) was used.
  • ODCB 1: 1 volume ratio of mixed solvent OxAm-C 1mg mixed solvent 1.5ml
  • the above solution was filtered using a 0.2 ⁇ m filter with a diaphragm pump suction filter to obtain 40.36 ml of filtrate.
  • the target product Li @ C 60 cation is dissolved in the filtrate.
  • the solid content of the filtration residue remaining on the filter is an insoluble impurity.
  • Other 3 lots of OxAm-C 26.4 mg, 19.0 mg, and 16.5 mg were also dissolved by the above treatment method, and the 4 lot solution was combined to obtain 130.5 ml of filtrate.
  • HPLC preparative conditions were as follows. Mobile phase: ODCB / AN 1: 2 50 mmol / l electrolyte TBAPF 6 added flow rate: 6.0 ml / min
  • Detection UV wavelength 380 nm HPLC fractionation was performed under the above conditions to obtain 429 ml of a fraction from 130.5 ml of the filtrate of S41.
  • AN distillation As part of solidification of Li @ C60 salt precipitation, AN (acetonitrile), one component of the mixed solvent, was distilled to reduce the amount of solvent and concentrate the Li @ C60 salt. Left. 492 ml of the preparative liquid obtained in the above step S42 was put into a 1 L eggplant type flask and connected to an evaporator. The concentrated eggplant-shaped flask was immersed in a high-temperature water tank maintained at 35 ° C., and the pressure was reduced to 75 hPa or less with a diaphragm pump to distill off AN. The guideline for the completion of the AN distillation was the point at which foaming from the solution surface was no longer observed visually.
  • step S52-2 The solid on the filter obtained in step S52-2 was wrapped in an aluminum foil, placed in a glass desiccator at room temperature, and dried under reduced pressure for 15 hours with a diaphragm pump. (S52-4: Recovery) The solid on the filter after drying was removed from the filter using a spatula.
  • Li analysis Li content (Li determination) and carbon / hydrogen / nitrogen content (CHN determination)
  • Li analysis was performed by ICP-OES method using a RIS-AP type apparatus of JARRELL-ASH, adjusting the analysis sample by wet ashing method.
  • a CHN analyzer MT-6 manufactured by YANACO was used for the C, H, and N analysis. The results of analytical measurement are shown below.
  • Li content Li quantitative Li [wt.%]; 0.728 CHN content (CHN determination) C [wt.%]; 81.913 H [wt.%]; 0.244 N [wt.%]; 0.244
  • the theoretical content of Li @ C 60 PF 6 is Li [wt.%]; 0.80 C [wt.%]; 82.59 H [wt.%]; 0.0 N [wt.%]; 0.0
  • a small amount of residual solvent or H and N which are considered to be derived from the residual electrolyte, have been observed, the desired product having a purity of 90% or more was obtained.
  • the peak of the target substance is not observed (that is, it is not separated), but as the electrolyte concentration increases, the peak appears and the peak itself is also separated into multiple peaks. Become so.
  • the concentration is such that the peaks are separated, the target product can be concentrated and obtained by HPLC using the retention time as a guide (HPLC preparative).
  • the TOF-MS diagram for the collected target product has already been described with reference to FIG. 3. However, in the case of using the solution with no electrolyte added, since there is no peak, it cannot be separated and cannot be measured. That is, a TOF-MS diagram cannot be obtained.
  • Fig. 7 (b) is 20 mmol / l with 20 mmol electrolyte for 1 l mobile phase
  • Fig. 7 (c) is 50 mmol concentration. / l
  • FIG. 7 (d) is a chromatogram at 100 mmol / l.
  • Tetrabutylammonium hexafluorophosphate (TBAPF6) was selected as a stable electrolyte that has sufficient solubility in organic solvents and is easily ionized.
  • the HPLC analysis conditions were as follows.
  • a high-purity atomic inclusion fullerene salt can be obtained easily and stably in a quantity to be obtained (milligram mg or more).
  • organic thin film solar cells and fiber solar cells are most promising.
  • applications as electronic materials and high-temperature superconducting materials are extensive.
  • blood pressure measuring devices and acoustic devices such as speakers are also promising fields in application as piezoelectric elements utilizing dielectric properties.

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Abstract

À l'heure actuelle, on ne connaît aucun procédé commode, efficace et à rendement élevé pour séparer et purifier à un niveau nécessaire et suffisant un sel de fullerène encapsulant un atome. Étant donné que la structure en agrégat d'un fullerène encapsulant un atome, après l'encapsulation, perturbe l'amélioration de la séparation et de la purification, un sel de fullerène encapsulant un atome, qui a été formé par oxydation par enlèvement d'un électron à partir d'un fullerène encapsulant un atome ayant cette structure d'agrégat, est séparé et purifié par la méthode HPLC, à l'aide d'une solution contenant un électrolyte en tant que phase mobile. Ainsi, le sel de fullerène encapsulant un atome, ou son ion, peut être aisément détaché d'une colonne utilisée en tant que phase stationnaire, ce qui en permet la séparation et la purification.
PCT/JP2010/062871 2009-09-01 2010-07-30 Procédé de séparation et de purification d'un sel de fullerène encapsulant un atome, à l'aide d'une phase mobile contenant un électrolyte WO2011027637A1 (fr)

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JP2014141410A (ja) * 2009-09-01 2014-08-07 Kaneko Hiroyuki 電解質を添加した移動相を用いた原子内包フラーレン塩の分離・精製方法
JP6283795B2 (ja) 2012-06-22 2018-02-28 国立大学法人東北大学 キャパシタ用電解質およびキャパシタ
WO2015005353A1 (fr) * 2013-07-08 2015-01-15 Matsuo Yutaka Sel de fullerène endoédrique et son procédé de production

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WO2004094309A1 (fr) * 2003-04-22 2004-11-04 Institute Of Tsukuba Liaison Co., Ltd. Procede de separation et d'epuration fullerene contenant du metal
JP2005504700A (ja) * 2001-10-01 2005-02-17 ティーディーエイ リサーチ インコーポレイテッド 金属内包フラーレン類及びその他のフラーレン類の化学的精製方法
JP2006036569A (ja) * 2004-07-26 2006-02-09 Takeshi Kodama 金属内包フラーレンの効率的かつ選択的抽出法
JP2006219364A (ja) * 2005-01-14 2006-08-24 Ideal Star Inc フラーレンベース材料の製造装置、及び、製造方法
WO2007123208A1 (fr) * 2006-04-20 2007-11-01 Ideal Star Inc. MATIÈRE À base de fullerÈne et PROCÉDÉ de fabrication d'une MATIÈRE À base de fullerÈne

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Publication number Priority date Publication date Assignee Title
JP2005504700A (ja) * 2001-10-01 2005-02-17 ティーディーエイ リサーチ インコーポレイテッド 金属内包フラーレン類及びその他のフラーレン類の化学的精製方法
WO2004094309A1 (fr) * 2003-04-22 2004-11-04 Institute Of Tsukuba Liaison Co., Ltd. Procede de separation et d'epuration fullerene contenant du metal
JP2006036569A (ja) * 2004-07-26 2006-02-09 Takeshi Kodama 金属内包フラーレンの効率的かつ選択的抽出法
JP2006219364A (ja) * 2005-01-14 2006-08-24 Ideal Star Inc フラーレンベース材料の製造装置、及び、製造方法
WO2007123208A1 (fr) * 2006-04-20 2007-11-01 Ideal Star Inc. MATIÈRE À base de fullerÈne et PROCÉDÉ de fabrication d'une MATIÈRE À base de fullerÈne

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