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• • 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
  • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
  • C30B29/02—Elements
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/65—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing carbon
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
  • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
• • 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

Definitions

• the present invention relates to single-crystal spherical carbon nanoparticles.
• Carbon nanoparticles are nanoparticles made of carbon atoms, and those with a particle diameter of less than 10 nm are also called carbon quantum dots.
• Quantum dots that are formed from metal elements such as CdSe and CdTe and exhibit fluorescence are known as quantum dots. However, these quantum dots are not suitable for use within the human body, and efforts have been made to find alternative materials.
• carbon nanoparticles can be produced by top-down or bottom-up methods.
• a top-down method for producing carbon nanoparticles for example, carbon nanoparticles are produced from at least micron-sized carbon materials such as graphite, carbon nanotubes, and diamonds using laser ablation, arc discharge, and electrochemical methods. method is known.
• bottom-up methods for producing carbon nanoparticles include, for example, a method of heat-treating pure water or an organic solvent under high temperature and high pressure conditions known as a hydrothermal method, and a chemical vapor deposition method (CVD). It is known how to use
• Claim 1 of Patent Document 1 describes a carbon nanoparticle phosphor containing carbon atoms, oxygen atoms, nitrogen atoms, and optionally hydrogen atoms. Since carbon nanoparticle phosphors have CN bonds and C-O bonds, they can be dispersed in an aqueous solution.
• the carbon nanoparticle phosphor is prepared by dissolving an organic substance selected from the group consisting of citric acid, benzoic acid, glucose, fructose, and sucrose, amines, and one or more selected from inorganic acids and acetic acid in a water-soluble solvent.
• Claim 9 of Patent Document 1 discloses that the method is produced by a method including a step of hydrothermally synthesizing a solution obtained by adding a carbon dioxide.
• the spatial lattice which is the structural information of the carbon nanoparticle phosphor, is not disclosed.
• Patent Document 2 describes a carbon composite for an oxygen reduction catalyst (Claim 1) that includes nanosheet-like graphene oxide or its reduced product and carbon quantum dots.
• Carbon quantum dots are carbon obtained by a conventional hydrothermal reaction, for example, by heating an aqueous solution containing a carbon source compound such as citric acid and a nitrogen source compound such as ethylenediamine at a temperature higher than the boiling point of water. Good things are described (Claim 6, [0031], etc.). These carbon quantum dots are different from the single crystal spherical carbon nanoparticles of the present invention, and it is not disclosed that the carbon nanoparticle phosphor is single crystal and spherical.
• Patent Document 3 describes a method for producing luminescent nanocarbon (Claim 1, [0013]) comprising a reaction step of reacting a raw material solution containing a carbon source compound and a nitrogen source compound by a solvothermal synthesis method or the like. ing.
• This luminescent nanocarbon is produced by hydrothermal synthesis similar to the production method of Patent Document 1, but it is not disclosed that the carbon nanoparticle phosphor is single crystal and spherical.
• Patent Document 4 discloses a method for forming carbon dots, comprising: (a) mixing carbon powder with sulfuric acid and nitric acid to form a carbon powder mixture; (b) refluxing the carbon powder mixture; heating to form a refluxed carbon powder mixture, and then (c) cooling said refluxed carbon powder mixture; (d) neutralizing said refluxed carbon powder mixture to form a neutralized carbon powder containing solubilized carbon dots.
• a method is described (Claim 1, [0036]) comprising forming a mixture and the like.
• acid in this step (a) the carbon powder is oxidized to a quantum size of 1.5 to 6 nm ([0037], [0038]).
• the carbon dots prepared by the above formation method have abundant carboxyl groups on the surface and may have negative charges on the carboxyl groups ([0048]). Carbon dots are different from the single crystal spherical carbon nanoparticles of the present invention because they have abundant carboxyl groups on their surfaces. Further, Patent Document 4 does not disclose that the carbon nanoparticle phosphor is single crystal and spherical.
• Patent Document 5 filed by the applicant of the present application, describes a method for manufacturing semiconductor particles (Claim 1) using a fluid treatment device equipped with relatively rotating processing surfaces that can approach and separate. ing.
• the semiconductor element it is described that it is an element selected from the group consisting of silicon, germanium, carbon, and tin ([0037]).
• the semiconductor element is carbon.
• single crystal spherical carbon nanoparticles cannot be obtained.
• Patent Document 6 filed by the applicant of the present application, discloses a method for producing crystals made of fullerene (Claim 1) using a fluid processing device equipped with relatively rotating processing surfaces that can approach and separate. Are listed. This production method uses fullerene as a raw material in advance and recrystallizes it, and is not a method for producing fullerene itself. As mentioned above, Patent Document 6 does not disclose that the carbon nanoparticle phosphor is single crystal and spherical.
• Non-Patent Document 1 describes carbon quantum dots that are obtained by reducing carbon tetrachloride with a hydride reducing agent such as lithium aluminum hydride, and then reacting with an arylamine in the presence of a platinum catalyst to produce amine-terminated carbon quantum dots. It is stated that the dots were combined. Since the carbon quantum dots of Non-Patent Document 1 have NH 2 groups on the surface, they are different from the single crystal spherical carbon nanoparticles of the present invention. Furthermore, it is not disclosed that the carbon quantum dots are single crystal and spherical.
• the object of the present invention is to generate fluorescence from blue to red depending on excitation wavelengths ranging from ultraviolet light to visible light, and to be able to be used as a fluorescent marker that can be injected into living organisms as drug delivery with almost no toxicity.
• the object of the present invention is to provide carbon nanoparticles that can be filled with materials at high density.
• the present inventors found that single crystal spherical carbon nanoparticles that are single crystal, spherical, and have an average particle diameter of 1 nm to 30 nm reduce luminous efficiency. Because it is a single crystal with no grain boundaries, it can produce high fluorescence quantum efficiency by excitation with light in a wide range of wavelengths from ultraviolet light to visible light, and can be used as a fluorescent marker for drug delivery and for secondary batteries.
• the present invention has been completed by discovering that electrode materials can be packed with high density. That is, the present invention is as follows.
• [5] Shows an absorption peak in the wave number range of 2800 cm -1 to 2950 cm -1 in the IR absorption spectrum,
• the area of the absorption peak of 1000 cm -1 to 1100 cm -1 obtained by waveform separation of the wave number range of 900 cm -1 to 1900 cm -1 is 15 % of the total area of the wave number range of 900 cm -1 to 1900 cm -1 .
• the single crystal spherical carbon particles according to any one of [1] to [4] below.
• the area of the absorption peak of 1300 cm -1 to 1400 cm -1 obtained by waveform separation of the wave number range of 900 cm -1 to 1900 cm -1 is the same as that of the wave number range of 900 cm -1 to 1900 cm -1 .
• the single-crystal spherical carbon nanoparticles of the present invention are single crystals without grain boundaries that reduce fluorescence efficiency, they generate fluorescence with high fluorescence quantum efficiency when excited by light with a wide wavelength range from ultraviolet light to visible light. It is possible to increase the fluorescence quantum efficiency of conventionally known carbon nanoparticles to 10% or more. Further, the single crystal spherical carbon nanoparticles of the present invention can be used for drug delivery because they do not have the toxicity to living organisms that compound semiconductors made of cadmium, selenium, tellurium, etc. have.
• the single crystal spherical carbon nanoparticles of the present invention are spherical, they can be densely packed with electrode materials for solar cells and secondary ion batteries, and can be used as negative electrodes for lithium ion batteries and electrodes for solar cells. Can be used as a material.
• Example 1-1 A TEM observation image of single crystal spherical carbon nanoparticles produced in Example 1-1 is shown. This is an IR spectrum at wave numbers of 2700 cm ⁇ 1 to 3050 cm ⁇ 1 of single crystal spherical carbon nanoparticles produced in Example 1-2. 2 shows the waveform separation of the IR spectrum at wave numbers of 900 cm ⁇ 1 to 1900 cm ⁇ 1 of the single-crystal spherical carbon nanoparticles produced in Example 1-2.
• the normalized fluorescence spectrum of the single-crystal spherical carbon nanoparticles produced in Example 1-3 that is, the normalized fluorescence spectrum in which the maximum intensity is set to 1.0 and the excitation wavelength is changed from 300 nm to 750 nm in steps of 40 nm.
• 5 is a diagram showing the relationship between excitation wavelength and fluorescence peak wavelength, prepared based on the results of FIG. 4.
• FIG. 2 shows the excitation wavelength dependence of the fluorescence peak wavelength of single-crystal spherical carbon nanoparticles of Examples 1-3.
• the Raman scattering spectrum of the single crystal spherical carbon nanoparticles produced in Example 1-3 at wave numbers from 1250 cm ⁇ 1 to 1700 cm ⁇ 1 is shown.
• the X-ray diffraction patterns at diffraction angles (2 ⁇ ) of 42° to 46° of the single crystal spherical carbon nanoparticles produced in Examples 1-1 to 1-3 are shown.
• the X-ray diffraction patterns of single crystal spherical carbon nanoparticles produced in Examples 3-1 to 3-3 are shown at diffraction angles (2 ⁇ ) of 42° to 46°.
• the normalized fluorescence spectrum of the single crystal spherical carbon nanoparticles produced in Example 3-3 that is, the normalized fluorescence spectrum with the maximum intensity set to 1.0 and the excitation wavelength varied from 240 nm to 360 nm.
• the single-crystal spherical carbon nanoparticles of the present invention are single-crystal, spherical, and have an average particle diameter of 1 nm to 30 nm. When the average particle diameter is 30 nm or more, when single-crystal spherical carbon nanoparticles are used as a negative electrode material for a secondary battery, it becomes difficult to achieve high-density packing.
• Single crystal spherical carbon nanoparticles are hexagonal. This hexagonal space lattice can have a simple lattice structure or a rhombohedral lattice structure.
• Single-crystal spherical carbon nanoparticles are preferably calculated using the formula: 4 ⁇ S/Z 2 using the perimeter (Z) and area (S) of a projected image of single-crystal spherical carbon nanoparticles observed by a transmission electron microscope.
• the average value of circularity is 0.9 or more, more preferably 0.92 or more, still more preferably 0.95 or more.
• the average particle diameter of the single crystal spherical carbon nanoparticles is preferably 1.2 nm to 10 nm, more preferably 1.5 nm to 7 nm. , more preferably 2 nm to 5 nm.
• One method for this purpose is to cut the bonding region of carbon atoms with sp 2 hybridized orbitals in the graphene layer and bond with carbon atoms or elements other than carbon atoms to generate carbon with sp 3 hybridized orbitals. It is the introduction of atomic bonds. Bonding of carbon atoms having sp 3 hybrid orbitals can generate C—H bonds and C—O bonds by bonding hydrogen and oxygen to the edges of the graphene layer. Therefore, it is possible to obtain carbon particles having a stacked structure of graphene layers in which C--H bonds are present in the graphene layer constituting the single-crystal spherical carbon nanoparticles and C--O bonds are present at the ends of the graphene layers. preferable.
• the presence of C-O bonds in single-crystal spherical carbon nanoparticles indicates that, for example, in the IR absorption spectrum, the wave number region of 2800 cm -1 to 2950 cm -1 , which is attributed to the stretching vibration of C-H bonds, and the C-O bond This can be confirmed by the presence of absorption in the wave number region of 1000 cm -1 to 1100 cm -1 , which is attributed to the stretching vibration.
• the single-crystal spherical carbon nanoparticles of Example 1-2 have absorption peaks due to C-H bonds at 2925 cm -1 and 2852 cm -1 , and absorption peaks due to C-O bonds at 1097 cm -1 .
• the presence of an absorption peak allows confirmation of a structural change that contributes to the generation of a band gap due to the presence of a carbon atom having an sp 3 hybridized orbital.
• the single crystal spherical carbon particles preferably exhibit an absorption peak in the wave number range of 2800 cm -1 to 2950 cm -1 in the IR absorption spectrum, and have an absorption peak of 1000 cm - obtained by waveform separation of the wave number range of 900 cm -1 to 1900 cm -1 .
• the area of the absorption peak from 1 to 1100 cm -1 (stretching vibration of C-O bond) is 15% or less of the total area in the wave number range of 900 cm -1 to 1900 cm -1 (ratio of C-O bond), More preferably, it is 2% or more and 15% or less, still more preferably 2% or more and 10% or less, and even more preferably 2% or more and 8.5% or less.
• the single crystal spherical carbon particles preferably have a Raman scattering spectrum in which the intensity of the peak between 1650 cm -1 and 1550 cm -1 is I G and the intensity of the peak between 1250 cm -1 and 1350 cm -1 is I D.
• the single-crystal spherical carbon particles are preferably single-crystal spherical carbon nanoparticles that exhibit a fluorescence maximum in the wavelength range of 400 nm to 600 nm in the fluorescence spectrum.
• the single-crystal spherical carbon particles have an IR absorption spectrum in which the area of the absorption peak of 1300 cm -1 to 1400 cm -1 obtained by waveform separation of the wave number range of 900 cm -1 to 1900 cm -1 is 900 cm -1 to 1400 cm -1 .
• Examples include single-crystal spherical carbon nanoparticles that are 10% or less (CN bond ratio), more preferably 8% or less, even more preferably 6.5% or less, with respect to the total area in the wavenumber range of 1900 cm -1 . It will be done.
• the single-crystal spherical carbon nanoparticles of the present invention exhibit fluorescence through the synergistic action of (A) quantum effect mechanism and (C) oxygen-mediated mechanism. arise.
• the mechanism is different from the amino group-terminated carbon nanoparticles of Non-Patent Document 1, which uses (A) a quantum effect mechanism and (B) a surface modification mechanism.
• the single crystal spherical carbon nanoparticles of the present invention preferably produce a fluorescence maximum in the wavelength range of 400 nm to 600 nm.
• the single-crystal spherical carbon nanoparticles of the present invention can be produced by, for example, two processes that are arranged facing each other and can be approached and separated, at least one of which rotates relative to the other.
• Manufactured by mixing a liquid containing raw materials for single-crystal spherical carbon nanoparticles (Liquid B) and a reducing liquid containing metallic lithium and a condensed aromatic compound (Liquid A) in a thin film fluid formed between the surfaces. can do.
• the raw material for single-crystal spherical carbon nanoparticles is not particularly limited as long as it is a substance that can precipitate single-crystal spherical carbon nanoparticles by reduction.
• the raw material includes carbon tetrahalide, more preferably carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, and the like. More preferable examples include carbon tetrachloride and carbon tetrabromide.
• the solvent includes ether, and more preferably tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane (DME), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl ether, polyethylene glycol dimethyl ether, or a mixture thereof. etc., and more preferably THF, DME and the like.
• the reducing agent contained in the single crystal spherical carbon nanoparticle reducing solution can reduce the raw material for single crystal spherical carbon nanoparticles contained in the single crystal spherical carbon nanoparticle raw material solution and precipitate it as single crystal spherical carbon nanoparticles.
• the reducing agent include a combination of metallic lithium and a condensed aromatic compound.
• condensed aromatic compound examples include compounds that can transfer one electron from metallic lithium to the condensed aromatic compound to generate lithium ions and condensed aromatic compound anions (radical anions).
• a fused aromatic compound anion that has one electron transferred has one electron in the lowest unoccupied molecular orbital (LUMO) of the fused aromatic compound.
• LUMO unoccupied molecular orbital
• the potential is a value relative to silver (Ag)/silver chloride (AgCl) as a standard electrode (reference electrode).
• condensed aromatic compounds with a potential lower than -1.9V include naphthalene (-2.53V), DBB (-2.87V), biphenyl (-2.68V), and 1,2-dihydronaphthalene (-2 .57V), phenanthrene (-2.49V), anthracene (-2.04V), pyrene (-2.13V), or a mixture thereof, preferably naphthalene, DBB, biphenyl, etc.
• tetracene (-1.55V) and azulene (-1.62V) are not suitable for reducing carbon tetrachloride.
• the molar ratio of metallic lithium to the condensed aromatic compound is, for example, 1:1 to 1:5, preferably 1:1 to 1:1.2, more preferably 1:1 to 1:15. Can be mentioned.
• the molar ratio between metallic lithium and the raw material for the single crystal spherical carbon nanoparticles is, for example, 10:1 to 1.2:1, preferably 7:1 to 1.5:1, and more preferably 5:1. Examples include 1 to 3:1. It is preferable to use metallic lithium in excess of the raw material for the single crystal spherical carbon nanoparticles. By using an excess amount, single crystal spherical carbon nanoparticles can be prepared.
• the concentration of metallic lithium in the single-crystal spherical carbon nanoparticle reducing solution is not particularly limited, but is determined according to the molar ratio of the above-mentioned metallic lithium and the raw material for the single-crystal spherical carbon nanoparticles.
• Alkali metals can be dissolved in ether organic solvents in the presence of condensed aromatic compounds, but if the dissolution temperature is 0°C or higher, the condensed aromatic compound anions become unstable, and the condensed aromatic compounds and alkali metal atoms become unstable. There was a problem in that the effectiveness of the reducing solution was impaired due to the occurrence of a chemical reaction. For example, when naphthalene (molecular formula: C 10 H 8 ) is used as the condensed aromatic compound and lithium (Li) is used as the alkali metal, a compound such as C 10 H 7 Li is produced, which acts as a reducing agent.
• naphthalene molecular formula: C 10 H 8
• Li lithium
• the condensed aromatic compound anion produced by the electron transfer of metallic lithium to the condensed aromatic compound can bond with the metallic lithium cation produced by electron transfer through Coulomb force.
• the reducing power may change due to reverse electron transfer from the fused aromatic compound anion once generated to the lithium cation. Fluctuations in reducing power affect the particle size distribution of the resulting single-crystal spherical carbon nanoparticles. Therefore, in order to suppress fluctuations in reducing power due to reverse electron transfer, lithium cations and condensed aromatic compound anions must interact with solvent molecules. This is possible by having a bonding form based on the Coulomb force.
• mediated by a solvent means that a solvated cation and a solvated anion exist in which the lithium cation and the condensed aromatic compound anion are each surrounded by solvent molecules, and the two solvents are in contact with each other. It means. Since such a solvent can intervene and create a state in which the cation and anion are in contact with each other in the solution, the condensed aromatic compound anion can exist stably, and the reverse conversion from the condensed aromatic compound anion to the lithium cation can occur. Electron transfer can be suppressed.
• the solution state of a solution prepared in advance with such a solution structure is a reducing solution prepared at a temperature of 0°C or higher without sufficient solvation or with a distribution in the solvation state. Even if the carbon nanoparticles are prepared at a low temperature, solvation does not necessarily occur completely, which causes variations in the reducing power and causes a distribution of the particle size of the carbon nanoparticles inside the solution. In a state of equilibrium where ions are directly bonded to each other by Coulomb force at a low temperature, even if the carbon nanoparticles are cooled to a low temperature during preparation, the solvent molecules can overcome the Coulomb force and enter between the cation and anion. It is difficult to do so. Therefore, the temperature during liquid preparation is important.
• the single-crystal spherical carbon nanoparticles of the present invention can be produced, for example, in a thin film fluid formed between two processing surfaces disposed oppositely that can be approached and separated, at least one of which rotates relative to the other. It can be produced by mixing a liquid containing raw materials for single-crystal spherical carbon nanoparticles (liquid B) and a reducing liquid (liquid A) containing metallic lithium and a condensed aromatic compound.
• liquid B liquid containing raw materials for single-crystal spherical carbon nanoparticles
• liquid A reducing liquid
• the device used in the manufacturing method of the present invention include the fluid treatment device described in Japanese Patent Application Laid-open No. 2009-112892 proposed by the applicant of the present application.
• the device includes a stirring tank having an inner peripheral surface having a circular cross-sectional shape, and a stirring tool attached with a slight gap from the inner peripheral surface of the stirring tank, and the stirring tank includes at least It is equipped with two fluid inlets and at least one fluid outlet, and from one of the fluid inlets, a first to-be-treated fluid containing one of the reactants among the to-be-treated fluids is introduced into the stirring tank.
• a second fluid to be treated containing one of the reactants different from the above-mentioned reactants is introduced from one point other than the above among the fluid inlets through a flow path different from that of the first fluid to be treated. It is introduced into a stirring tank.
• At least one of the stirring tank and the stirring tool rotates at a high speed relative to the other to form a thin film of the fluid to be treated, and in this thin film, the reactants contained in at least the first fluid to be treated and the second fluid to be treated are removed. It causes them to react with each other.
• devices based on the same principle as the fluid treatment devices described in Patent Documents 6 and 7 may be mentioned.
• single-crystal spherical carbon nanoparticles are produced by mixing a liquid containing a raw material for the single-crystal spherical carbon nanoparticles (liquid B) and the reducing liquid (liquid A) in the thin film fluid.
• Single-crystal spherical carbon nanoparticles are manufactured in two steps: first, a graphene layer is formed as the core of the single-crystal spherical carbon nanoparticles, and then single-crystal spherical carbon nanoparticles are grown by stacking them on top of each other. .
• a single-crystal spherical carbon nanoparticle reducing solution (liquid A )
• the temperature include -30°C to 25°C, preferably -10°C to 25°C, and more preferably 0°C to 25°C.
• the temperature of liquid A at 17 ° C., it was possible to manufacture single crystal spherical carbon nanoparticles that were single crystal, spherical, and emitted fluorescence with high fluorescence quantum efficiency.
• Single-crystal spherical carbon nanoparticle raw material solution Liquid B
• the temperature include -10°C to 25°C, preferably 0°C to 25°C, and more preferably 10°C to 25°C.
• the temperature of liquid B at 23 ° C., it was possible to manufacture single crystal spherical carbon nanoparticles that were single crystal, spherical, and emitted fluorescence with high fluorescence quantum efficiency.
• Ta Single-crystal spherical carbon nanoparticle raw material solution
• lithium chloride is produced as a by-product. Since lithium chloride has high solubility in the reaction solvent, it can be easily separated from single crystal spherical carbon nanoparticles by centrifugation.
• the single-crystal spherical carbon nanoparticles of the present invention can be used, for example, in light-emitting elements, light-emitting materials that generate fluorescence, negative electrodes of lithium ion batteries, electrode materials for solar cells, and bonding materials to substrates of semiconductor devices. etc. can be used as
• TEM observation A transmission electron microscope JEM-2100 (manufactured by JEOL Ltd.) was used for TEM observation of single-crystal spherical carbon nanoparticles.
• the above sample for TEM observation was used as a sample.
• the observation conditions were an accelerating voltage of 200 kV and an observation magnification of 10,000 times or more.
• the particle diameter is calculated from the distance between the maximum outer circumferences of single crystal spherical carbon nanoparticles observed by TEM, and the average value (average particle diameter) of the results of measuring the diameter of single crystal spherical carbon nanoparticles for 50 particles is calculated. did.
• IR absorption spectrum The IR absorption spectrum of the single crystal spherical carbon nanoparticles was measured by the attenuated total reflection (ATR) method using a Fourier transform infrared spectrophotometer FT/IR-6600 (manufactured by JASCO Corporation). The measurement conditions were a resolution of 4.0 cm ⁇ 1 and 128 integrations, a diamond prism (FT/IR-6600 accessory ATR PRO470-H), and an incident angle of 45°. The number of integrations was 128. A diamond prism (PKS-D1F) (wide area) (refractive index 2.4) was incorporated into the ATRPRO ONE accessory of FT/IR-6600, and the incident angle was set to 45°.
• the infrared (IR) absorption spectra measured for the single-crystal spherical carbon nanoparticles produced in Examples and the polycrystalline carbon nanoparticles produced in Comparative Examples are referred to as IR spectra.
• fluorescence spectrum The fluorescence spectrum of the single crystal spherical carbon nanoparticles was measured using a spectrofluorometer FT-6500 (manufactured by JASCO Corporation). The above sample for TEM observation was used as a sample.
• a sample liquid dispersed in THF was placed in a quartz cell (light path length: 1 cm) in a glove box with an argon atmosphere, the top of the cell was sealed tightly, and the cell was taken out from the glove box and measured.
• the measurement conditions were an excitation band width of 3 nm, a fluorescence band width of 3 nm, a response of 0.1 seconds, a scanning speed of 100 nm/min, and a data acquisition interval of 0.5 nm.
• the fluorescence spectrum of 9,10-diphenylanthracene as a reference material for relative fluorescence quantum efficiency was measured under the same conditions.
• Waveform separation of fluorescence spectrum The measured fluorescence spectrum of the single crystal spherical carbon nanoparticles was waveform separated to calculate the relative fluorescence quantum efficiency to that of 9,10-diphenylanthracene, and the area percentage of the fluorescence spectrum showing a peak at 430 nm was calculated. Calculated. Waveform separation was performed using the waveform separation software built into the FT/IR-6600 used in the IR absorption spectrum measurement.
• the fluorescence quantum efficiency of a fluorescent substance can be evaluated by the efficiency of fluorescence generated in response to excitation light.
• the fluorescence quantum efficiency of single-crystal spherical carbon nanoparticles was calculated as the fluorescence quantum efficiency, which is a relative value to the fluorescence quantum efficiency of 9,10-diphenylanthracene as a reference substance, which is 1.0.
• 9,10-diphenylanthracene has a fluorescence quantum efficiency of 1.0 at a fluorescence peak wavelength of 430 nm.
• the relative fluorescence quantum efficiency was calculated using the following formula (1).
• ⁇ x ⁇ s (F x /F s ) (A s /A x ) (I s /I x ) (n x 2 / ns 2 )...(1) [In the formula, x means single-crystal spherical carbon nanoparticles. s means 9,10-diphenylanthracene. ⁇ x is the relative fluorescence quantum efficiency of single crystal spherical carbon nanoparticles. ⁇ s is the quantum efficiency of 9,10-diphenylanthracene. F is the area of the fluorescence spectrum. A is the absorbance at the excitation wavelength. I is the intensity of excitation light. n is the refractive index of the solvent used.
• the reference substance 9,10-diphenylanthracene and single-crystal spherical carbon nanoparticles have a bandpass width of excitation light, a fluorescence bandpass width, which is the measurement condition of a spectrofluorometer that measures fluorescence. Since the scanning speed, data acquisition interval, and measurement sensitivity are all constant, and the same solvent THF is used, (I s /I x )(n x 2 /n s 2 ) in equation (1) is 1 .0.
• UV-vis absorption spectrum measurement The UV-vis (ultraviolet-visible) absorption spectrum of single-crystal spherical carbon nanoparticles was measured using an ultraviolet-visible near-infrared spectrophotometer (product name: V-770, manufactured by JASCO Corporation). The measurement range was 200 nm to 900 nm, the sampling rate was 0.2 nm, and the measurement speed was low. A quartz cell for liquid with a thickness of 10 mm was used for the measurement.
• Circularity was calculated as an index for evaluating the sphericity of single-crystal spherical carbon nanoparticles as follows.
• the circularity of single-crystal spherical carbon nanoparticles was determined by approximating an image obtained by TEM observation as an ellipse using TEM image software iTEM (manufactured by Olympus Soft Imaging Solutions GmbH).
• TEM image software iTEM manufactured by Olympus Soft Imaging Solutions GmbH.
• the major axis (D), perimeter (Z), and area (S) of an ellipse which is a projected image of the single-crystal spherical carbon nanoparticle, were determined from the analysis results of TEM image analysis software.
• X-ray diffraction X-ray diffraction
• EMPYREAN powder X-ray diffraction measuring device manufactured by Spectris Corporation, Malvern Panalytical Division
• the measurement conditions were: measurement range: 10 to 100 [°2 ⁇ ], Cu anticathode, tube voltage 45 kV, tube current 40 mA, and scanning speed 0.013°/min.
• the Raman scattering spectrum of single-crystal spherical carbon nanoparticles was measured using a JASCO PR-1w palmtop Raman spectrophotometer.
• the wavelength of the excitation laser light was 785 nm
• the output of the laser light was 5 mW
• the measurement wave number was 200 cm -1 to 3000 cm -1 .
• Example 1 In Example 1, a THF solution of carbon tetrachloride (CCl 4 ) as a raw material (single-crystal spherical carbon nanoparticle raw material solution) was converted to a THF solution of metallic lithium dissolved in naphthalene (single-crystal spherical carbon nanoparticle reduction solution). By reduction, single crystal spherical carbon nanoparticles were produced. Table 1 shows the formulations of Examples 1-1 to 1-4.
• Example 1 The solvent used in Example 1 was ultra-dehydrated tetrahydrofuran (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) with a residual water content of 10 ppm or less.
• a single crystal spherical carbon nanoparticle reducing solution (liquid A) and a single crystal spherical carbon nanoparticle raw material solution (liquid B) were prepared.
• the single-crystal spherical carbon nanoparticle reduction solution of solution A is prepared at a temperature of -5°C, and is added to a THF solution in which naphthalene is dissolved at a concentration of 0.4 mol/L.
• a liquid was prepared by dissolving metallic lithium using a glass-coated magnetic stirrer to give a concentration of .
• carbon tetrachloride which is a raw material for single-crystal spherical carbon nanoparticles in Solution B, was dissolved in THF, and then stirred for at least 60 minutes using a glass-coated magnetic stirrer.
• CCl 4 is carbon tetrachloride (manufactured by Kanto Chemical Co., Ltd.), Li is metallic lithium (manufactured by Kishida Chemical Co., Ltd.), and C 10 H 8 is naphthalene (manufactured by Kishida Chemical Co., Ltd.). Kanto Kagaku Co., Ltd.).
• the prepared single crystal spherical carbon nanoparticle reduction liquid (liquid A) and the single crystal spherical carbon nanoparticle raw material liquid (liquid B) were mixed.
• the fluid treatment device described in Patent Document 6 is the device described in FIG. A concentric ring shape surrounding the central opening of the use surface 2 was used. Specifically, a single crystal spherical carbon nanoparticle reduction liquid or a single crystal spherical carbon nanoparticle raw material liquid, which is liquid A, is introduced between the processing surfaces 1 and 2 from the first introduction part d1, and the processing part 10 is rotated.
• a second liquid which is different from the liquid sent as liquid A, of the single crystal spherical carbon nanoparticle raw material liquid as liquid B or the single crystal spherical carbon nanoparticle reduction liquid is added.
• the monocrystalline spherical carbon nanoparticle raw material liquid and the single-crystalline spherical carbon nanoparticle reduction liquid are introduced between the processing surfaces 1 and 2 from the introduction part d2, and mixed in a thin film fluid. , single-crystal spherical carbon nanoparticles were precipitated.
• a discharged liquid containing single-crystal spherical carbon nanoparticles was discharged from between processing surfaces 1 and 2 of the fluid processing device.
• the discharged single crystal spherical carbon nanoparticle dispersion was collected into a beaker via a vessel.
• Table 2 shows the operating conditions of the fluid treatment device of Example 1.
• the introduction temperature (liquid feeding temperature) and introduction pressure (liquid feeding pressure) of liquid A and liquid B shown in Table 2 are based on the introduction temperature (liquid feeding temperature) and introduction pressure (liquid feeding pressure) shown in Table 2. It was measured using a thermometer and a pressure gauge provided in the second introduction part d2), and the introduction temperature of liquid A shown in Table 2 is the actual temperature under the introduction pressure in the first introduction part d1.
• the temperature of liquid A and the introduction temperature of liquid B are the actual temperature of liquid B under the introduction pressure in the second introduction section d2.
• a wet cake sample was prepared from the single crystal spherical carbon nanoparticle dispersion discharged from the fluid processing device and collected in a beaker.
• the production method was carried out according to a conventional method, and the discharged single-crystal spherical carbon nanoparticle dispersion was collected, and the single-crystal spherical carbon nanoparticles were sedimented from the collected liquid by centrifugation (30,190 G for 2 hours). , the supernatant was separated. Thereafter, ultrasonic cleaning with THF and sedimentation were repeated, and the finally obtained single crystal spherical carbon nanoparticles were dried at -0.10 MPaG and 25° C. for 20 hours to form a dry powder.
• FIG. 1 shows a TEM image of single-crystal spherical carbon nanoparticles of Example 1-1. Similar results were confirmed for the single crystal spherical carbon nanoparticles of Examples 1-2 to 1-4. Since lattice fringes were observed in one direction, it was confirmed that it was a single crystal.
• FIG. 2 shows the results of IR spectrum measurement of the single crystal spherical carbon nanoparticles of Example 1-2 in the wave number range of 2700 cm ⁇ 1 to 3050 cm ⁇ 1 . Since the absorption peaks at 2855 cm ⁇ 1 and 2920 cm ⁇ 1 were attributed to stretching vibrations of C—H bonds, it was confirmed that the single crystal spherical carbon nanoparticles were hydrogenated. The same confirmation was made for Examples 1-1, 1-3, and 1-4.
• FIG. 3 shows the results of IR spectrum measurement of the single-crystal spherical carbon nanoparticles of Example 1-2 in the wave number region of 900 cm ⁇ 1 to 1900 cm ⁇ 1 and then waveform separation performed. The peak wave number of each band after waveform separation and the relative area ratio are shown in parentheses. Waveform separation was performed using waveform separation software built into FT/IR-6600.
• the IR spectrum in FIG. 3 is divided into 10 parts by waveform separation, and absorption in the wave number region of 1000 cm -1 to 1100 cm -1 is attributed to the C--O bond.
• the ratio of Band 9 and Band 10, which were waveform-separated in this wavenumber region, to the total area (ratio of C—O bonds) was 10.7%.
• the ratio of C-O bonds is preferably 2% or more and 15% or less. If it is less than 2%, it will be difficult to disperse single-crystal spherical carbon nanoparticles in an aqueous solution, and if it exceeds 15%, it will be difficult to disperse single-crystal spherical carbon nanoparticles in an aqueous solution. This is because when the circularity becomes 0.9 or less and the distance from the spherical shape increases, there is an inconvenience that the relative fluorescence quantum efficiency decreases.
• the C-O bonds of single-crystal spherical carbon nanoparticles are formed when single-crystal spherical carbon nanoparticles are produced by a reduction reaction in ultra-dehydrated THF, which is a grade specified with residual moisture of 10 ppm or less in tetrahydrofuran (THF). can be generated by controlling the moisture content to always be 10 ppm or less.
• THF tetrahydrofuran
• the graphene layer is easily reactive, so the single-crystal spherical carbon nanoparticles can be protected by a mild oxidation reaction caused by a certain amount of moisture.
• This washing and recovery basically requires dissolving the residual organic matter once in a THF solvent and then washing with pure water, but some oxidation reaction progresses during this washing and recovery operation.
• CN bond The CN bond is generated by reacting with the outermost surface of the graphene layer that was not protected by oxygen when exposed to the atmosphere during cleaning and recovery of single-crystal spherical carbon nanoparticles.
• C--N bonds are generated after the reaction of single-crystal spherical carbon nanoparticles because no nitrogen-containing raw materials or solvents are used in the reduction reaction of single-crystal spherical carbon nanoparticles. Although this does not have a major effect on the fluorescence properties, it also makes it possible to terminate defects with nitrogen.
• the C-N bond has absorption in the wavenumber region of 1300 cm -1 to 1400 cm -1 , so band 7 with a peak wave number of 1357 cm -1 corresponds to the relative area ratio (of the C-N bond). ratio) is 6.2%.
• the ratio of CN bonds is preferably 10% or less, since CN bonds, together with C--O bonds, have the effect of terminating defects where bonds of carbon atoms in the graphene layer are broken. This C—N bond may not be detected if a C—O bond terminates a carbon atom bond defect.
• the single-crystal spherical carbon nanoparticles confirmed in FIG. 2 can make the surface of the single-crystal spherical carbon nanoparticles hydrophobic, the single-crystal spherical carbon nanoparticles can be well dispersed in an organic solvent. However, according to the results shown in FIG. 2, it was confirmed that dispersibility in aqueous solvents was also possible due to the coexistence of C—O bonds.
• FIG. 4 shows the fluorescence spectrum of the single-crystal spherical carbon nanoparticles of Examples 1-3. This is a fluorescence spectrum normalized by setting the maximum intensity of the fluorescence spectrum obtained for each excitation wavelength as 1.0, and is the result of changing the excitation wavelength every 20 nm from 320 nm to 580 nm. From the results shown in FIG. 4, it was confirmed that the fluorescence of the single-crystal spherical carbon nanoparticles of Example 1-3 showed a maximum peak at 400 nm to 600 nm, depending on the excitation wavelength.
• Figure 5 is a diagram showing the relationship between excitation wavelength and fluorescence peak wavelength, created based on the results of Figure 4. It shows the excitation wavelength dependence of the fluorescence peak wavelength of the single crystal spherical carbon nanoparticles of Examples 1-3. It is known that as the particle size of single crystal spherical carbon nanoparticles increases, the fluorescence peak wavelength shifts to the longer wavelength side, so it is believed that fluorescence is obtained from nanoparticles whose particle size has been increased little by little.
• the change in the fluorescence peak wavelength in this single crystal spherical carbon particle is explained by (A) quantum effect among the three mechanisms (A) to (C) above. That is, the fluorescence peak wavelength of the single-crystal spherical carbon nanoparticles is thought to be shifted to the shorter wavelength side because the band gap increases as the particle size of the single-crystal spherical carbon nanoparticles decreases. (A) This is a result due to the quantum effect mechanism. Furthermore, the single-crystal spherical carbon nanoparticles of the present invention are not surface-modified with alkyl groups, amino groups, etc., and do not have the surface modification mechanism (B) among the three mechanisms described above. It is thought that the fluorescence is produced by a synergistic effect of (C) an oxygen-mediated mechanism due to the bonding of oxygen to the particles and (A) a quantum effect mechanism.
• FIG. 6 shows the Raman scattering spectrum of the single crystal spherical carbon nanoparticles of Examples 1-3.
• the Raman scattering spectrum of graphite shows a peak called the IG band only in the wave number region from 1650 cm -1 to 1550 cm -1 , but when the bonds in the graphene layer are disrupted and defects occur in the graphite, the peak from 1300 cm -1 to 1300 cm -1 . Since a peak called the I D band appears at 1450 cm ⁇ 1 , defects in the carbon material can be estimated based on the value of I D /I G , which is the spectral intensity ratio between the two.
• FIG. 6 shows the Raman scattering spectrum of the single crystal spherical carbon nanoparticles of Examples 1-3.
• the Raman scattering spectrum of graphite shows a peak called the IG band only in the wave number region from 1650 cm -1 to 1550 cm -1 , but when the bonds in the graphene layer are disrupted and defects occur in the graph
• Example 6 shows the results of a relative comparison of the I D band intensity with the I G band intensity of each carbon particle being 100, and shows the I D /I of the single crystal spherical carbon particles manufactured in Example 1-3.
• the G ratio was 0.23, and it was confirmed that there were few bonding defects.
• FIG. 7 shows XRD patterns of single crystal spherical carbon particles of Examples 1-1, 1-2, and 1-4.
• As the lattice a simple lattice and a rhombohedral lattice can be formed.
• the peaks at diffraction angles 2 ⁇ of 42.2° and 44.6° appear due to a simple lattice of hexagonal structure, whereas the peaks at 2 ⁇ of 43.3° appear due to a rhombohedral lattice.
• Table 3 shows the average particle diameter, average circularity, crystal structure, average lattice spacing of the graphene layer, and C- The ratio of O bonds, the I D /I G ratio obtained from the Raman scattering spectrum and the relative fluorescence quantum efficiency are shown.
• Comparative example 1 The recipe of Comparative Example 1 was the same as that of Example 1 shown in Table 1, but as shown in Table 4, the disk rotation speed was lowered to 600 rpm and 500 rpm to produce single crystal spherical carbon nanoparticles. Table 5 shows the results for the single crystal spherical carbon particles obtained. By reducing the disk rotation speed to less than 700 rpm, no change was observed in the crystal structure, but the average circularity became less than 0.9, and the I D / I G ratio increased from 1.0. Since the number of defects increased more than in Example 1, the relative fluorescence quantum efficiency became a low value of 5% or less.
• Example 2 shows the results of single-crystal spherical carbon nanoparticles produced when the single-crystal spherical carbon particle reducing solution was prepared at ⁇ 10° C. and 10° C. below 0° C., and the disk rotation speed was 5000 rpm and 3500 rpm.
• the compositions of the single crystal spherical carbon nanoparticle reducing solution and the single crystal spherical carbon nanoparticle raw material solution were the same as in Example 1, and they were produced under the conditions shown in Table 1.
• Table 6 shows the manufacturing conditions of Example 2, and the results of the obtained single crystal spherical carbon nanoparticles are as shown in Table 7.
• Comparative example 2 The prescription of Comparative Example 2 was the same as that of Example 1 shown in Table 1, but as shown in Table 8, the disk rotation speed was lowered to 700 rpm, and the temperature of the single crystal spherical carbon nanoparticle reduction solution of Solution A was lowered. Single crystal spherical carbon particles were produced at -10°C and 10°C. Table 9 shows the results for the produced single crystal spherical carbon nanoparticles. The average circularity of the single-crystal spherical carbon nanoparticles produced at a lower disk rotation speed of 700 rpm and a liquid A temperature of 10° C. or less is less than 0.9, which indicates the abundance ratio of defects calculated by Raman scattering spectrum ID / Since the IG ratio increased to 1.0 or more, the relative fluorescence quantum efficiency became a low value of 5% or less.
• Example 3 the formulations of liquids A and B were the same as those in Table 1, and the flow rate ratio of liquid B, single crystal spherical carbon nanoparticle raw material liquid, to liquid A, single crystal spherical carbon nanoparticle reducing liquid, was changed. Crystalline spherical carbon nanoparticles were fabricated. Table 10 shows the manufacturing conditions for single crystal spherical carbon nanoparticles. Table 11 shows the results for the obtained single crystal spherical carbon nanoparticles.
• FIG. 8 shows an XRD pattern of single-crystal spherical carbon nanoparticles obtained in Example 3.
• Example 3-1 a diffraction peak with a diffraction angle 2 ⁇ of 43.25° due to the hexagonal and rhombohedral space lattice and a diffraction peak at 44.6° due to the hexagonal and simple lattice are observed.
• Example 3-2 and Example 3-3 a diffraction peak with a diffraction angle 2 ⁇ of 43.25° due to the rhombohedral space lattice was observed, and results were obtained that suggested that the space lattice was almost a rhombohedral lattice.
• Example 3-3 a peak was also observed at 43.5°, which was determined to be due to the rhombohedral lattice.
• FIG. 9 shows the fluorescence spectrum of single-crystal spherical carbon nanoparticles produced in Example 3-3.
• the fluorescence peak wavelength measured at an excitation wavelength of 240 nm to 360 nm was 420 nm, indicating no dependence on excitation wavelength.
• the fluorescence peak wavelength of Examples 1-3 shown in FIG. 4 shows excitation light dependence, and as the excitation wavelength becomes longer, the fluorescence peak wavelength also shifts to the longer wavelength side.
• the structure of single-crystal spherical carbon nanoparticles corresponds to a hexagonal structure in which a simple lattice and a rhombohedral lattice coexist, as shown in FIG.
• Example 3-3 results were obtained only for the rhombohedral lattice, so it is considered that the difference in the excitation light dependence of the fluorescence peak wavelength is due to the difference in the spatial lattice of the single crystal spherical carbon particles.
• the effect of increasing the flow rate of the single-crystal spherical carbon nanoparticle reducing solution of solution A than the flow rate of the single-crystal spherical carbon nanoparticle raw material solution of solution B is to increase the reduction reaction rate.
• these fine graphene layers are stacked on each other in the c-axis direction, thereby making it possible to manufacture smaller single-crystal spherical carbon nanoparticles.
• the single-crystal spherical carbon nanoparticles of the present invention are single crystals without grain boundaries that reduce fluorescence efficiency, they generate fluorescence with high fluorescence quantum efficiency when excited by light with a wide wavelength range from ultraviolet light to visible light. It is possible to increase the fluorescence quantum efficiency of conventionally known carbon nanoparticles to 10% or more. Further, the single crystal spherical carbon nanoparticles of the present invention can be used for drug delivery because they do not have the toxicity to living organisms that compound semiconductors made of cadmium, selenium, tellurium, etc. have.
• the single crystal spherical carbon nanoparticles of the present invention are spherical, they can be densely packed with electrode materials for solar cells and secondary ion batteries, and can be used as negative electrodes for lithium ion batteries and electrodes for solar cells. Can be used as a material.

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