WO2006077890A1 - Procede de production de fines particules spheriques d'oxyde metallique monodispersees et fines particules d’oxyde metallique - Google Patents

Procede de production de fines particules spheriques d'oxyde metallique monodispersees et fines particules d’oxyde metallique Download PDF

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WO2006077890A1
WO2006077890A1 PCT/JP2006/300656 JP2006300656W WO2006077890A1 WO 2006077890 A1 WO2006077890 A1 WO 2006077890A1 JP 2006300656 W JP2006300656 W JP 2006300656W WO 2006077890 A1 WO2006077890 A1 WO 2006077890A1
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fine particles
metal oxide
oxide fine
metal
compound
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Japanese (ja)
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Shinpei Yamamoto
Mikio Takano
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Kyoto University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • the present invention relates to a method for producing monodispersed spherical metal oxide fine particles and metal oxide fine particles.
  • Submicron monodisperse spherical metal oxide fine particles can be used in many technical fields such as pigments, catalysts, raw materials for advanced ceramics, and opal-based photonic crystals (photocrystals). It has been actively researched as a new material, and there have been many reports on its production method.
  • a method for producing metal oxide fine particles by hydrolysis of metal alkoxide in a homogeneous solution is one of effective methods for producing spherical metal oxide fine particles with a narrow particle size distribution. It is.
  • This hydrolysis method is generally performed by subjecting the metal alkoxide to hydrolysis (condensation) slowly (at least several hours or more) in a homogeneous solution.
  • Monodispersed spherical metal oxide fine particles can be produced by the hydrolysis method using only a relatively inert metal alkoxide, such as silicon, titanium, zirconium, tantalum, etc. l: Ogiwara, T., Ikemoto, T "See Mizutani.N., Kato.M., Mitani.Y., J.Mater.Sci. 1986, 21, 2771.) Acids and their acids A few examples have been reported for mixtures of metal, but only! / ⁇ Hydrolysis of metal alkoxides other than these metals usually forms gels or aggregates.
  • a relatively inert metal alkoxide such as silicon, titanium, zirconium, tantalum, etc.
  • tantalum is reported in Reference 1, but the tantalum oxide fine particles synthesized by hydrolysis of tantalum alkoxide are not completely spherical.
  • the particle size distribution of the tantalum oxide fine particles is large and cannot be said to be monodispersed spherical fine particles of sufficient purity.
  • documents 3 and 4 only the example of formation of VO ⁇ ⁇ xerogel has been reported in the method described for the hydrolysis of vanadium alkoxide in a homogeneous solution.
  • Document 2 reports on silver vanadate oxide fine particles having a small particle size distribution produced by laser pyrolysis of a mixture of vanadium oxide and a silver compound.
  • the particle size distribution of the obtained fine particles is reported that the particle size of 95% is larger than about 40% of the average diameter and smaller than about 160%, and the particle size distribution is sufficient. It's not narrow.
  • the laser pyrolysis production method consumes more energy than the hydrolysis method and requires a large-scale apparatus.
  • the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to hydrolyze a metal alkoxide that has heretofore been difficult to synthesize monodispersed spherical metal oxide fine particles. Accordingly, an object of the present invention is to provide a method for producing monodispersed spherical metal oxide fine particles and metal oxide fine particles.
  • the method for producing monodispersed spherical metal oxide fine particles according to the present invention comprises a group of metal forces belonging to groups 3 to 5 and 3 to 5 in the periodic table. At least one metal alkoxide selected from the following general formulas (1), (2), (3) and (4)
  • R 2 , R 3 and R 4 independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the method includes a hydrolysis step for hydrolysis.
  • the method for producing metal oxide fine particles according to the present invention at least one selected from the group consisting of the compounds represented by the general formulas (1), (2), (3) and (4).
  • the particle diameter of the monodispersed spherical metal oxide fine particles can be controlled in the range of 200 nm or more and 800 nm or less.
  • the organic solvent is at least one general formula (5).
  • R 1 and R 2 independently represent a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the metal oxide fine particles according to the present invention are at least one metal selected from the group consisting of metals belonging to Groups 3A to 5A and Groups 3B to 5B of the periodic table.
  • Oxide fine particles, wherein the metal alkoxide of the metal is represented by the following general formulas (1), (2), (3) and (4)
  • R 2 , R 3 and R 4 independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the metal oxide may be V 2 O.
  • the method for producing metal oxide fine particles useful in the present invention is at least one selected from the group consisting of metal forces belonging to groups 3A-5A and 3B-5B of the periodic table.
  • a metal metal alkoxide is converted into at least one compound selected from the group having the compound power represented by the general formulas (1), (2), (3) and (4), water, an organic solvent ( However, in the case where the metal is vanadium, a lower alcohol is excluded.), A composition including a hydrolysis step for hydrolysis is included. The effect is that the dispersed spherical metal oxide fine particles can be easily synthesized.
  • FIG. 1 Figures l (a), (b), (c) and (d) show the transmission type of V ⁇ fine particles obtained by hydrolysis of vanadium alkoxide at various pyridine concentrations (C). Observation by electron microscope
  • Figure 1 (a), (b), (c), and (d) show the VO generated under the conditions of pyridine concentration (C) of 2.5 wt%, 5 wt%, 10 wt%, and 20 wt%, respectively.
  • FIG. 25 is a diagram showing the observation results.
  • Fig. 2 shows the average particle size of monodispersed spherical V 2 O fine particles (D, unit: nm, ⁇ in Fig. 2)
  • Fig. 25 is a diagram showing an FTIR spectrum of a fine particle.
  • Fig. 4 shows monodispersed spherical V O fine particles formed under the condition of a pyridine concentration (C) of 10 wt%.
  • Figure 5 shows the average particle diameter (D, unit: nm) of monodispersed spherical V 2 O fine particles and the relative standard.
  • the present inventors have made this by hydrolyzing the metal alkoxide in an organic solvent containing a metal alkoxide, pyridine, and water. Even for powerful metals for which monodisperse spherical metal oxide fine particles could not be obtained by the hydrolysis method up to 1, monodisperse spherical particles with a relative standard deviation of the particle size of 10% or less. For the first time, it was found that metal oxide fine particles can be synthesized, and the present invention has been completed.
  • the conventional hydrolysis method is generally performed by hydrolyzing metal alkoxide in a homogeneous solution for at least several hours.
  • the method for producing metal oxide fine particles according to the present invention is a monodisperse spherical metal oxide having a monodispersion (relative standard deviation of particle size of 10% or less), which has not been conventionally synthesized.
  • This is a novel method that enables simple and extremely rapid mass synthesis of fine particles.
  • the particle size can be reduced to 200 ⁇ while maintaining a narrow particle size distribution! It was also found that it can be changed freely in the range of ⁇ 800 nm. This makes it possible to synthesize monodispersed spherical metal oxide fine particles having a desired particle size.
  • monodispersed is not particularly limited as long as the metal oxide fine particles have the same particle size in the system in which the metal oxide fine particles are dispersed.
  • the relative standard deviation of the narrow particle diameter is preferably 10% or less, more preferably 7% or less.
  • the particle size means the particle diameter of spherical metal oxide fine particles.
  • R 2, R 3 and R 4 are not particularly limited as long as they are independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, but among them, a hydrogen atom, a methyl group , An ethyl group, a propyl group, or a butyl group.
  • the metal oxide refers to a metal oxide belonging to groups 3A to 5A and groups 3B to 5B of the periodic table or a mixture of two or more of these metal oxides.
  • metals include Sc, Y, Ga, In, T1, Ti, Zr, Si, Ge, Sn, Pb, V, Nb, Ta, As, Sb, and Bi.
  • the metal is more preferably vanadium, niobium, tantalum or the like, and these oxides are preferably VO, Ta 2 O, Nb 2 O, or the like.
  • the method for producing monodispersed spherical metal oxide fine particles useful in the present invention comprises at least one metal metal selected from the group consisting of metals belonging to groups 3A-5A and 3B-5B of the periodic table.
  • An alkoxide is a solution containing at least one compound selected from the group consisting of compounds represented by the general formulas (1), (2), (3) and (4), water, and an organic solvent. Among them, it includes a hydrolysis step for hydrolysis.
  • the method for producing monodispersed spherical metal oxide fine particles includes a periodic table.
  • the alkoxide is hydrolyzed in an organic solvent containing at least one compound selected from the group consisting of compounds represented by formula (I) and water, and the relative standard deviation in particle size is 10% or less. It is preferable to include a hydrolysis step for obtaining a dispersion of monodispersed spherical metal oxide fine particles.
  • the metal alkoxide is not particularly limited as long as it is a metal alkoxide of at least one metal selected from the group consisting of metals belonging to Groups 3A to 5A and Groups 3B to 5B of the periodic table.
  • at least one metal selected from the group consisting of metals belonging to groups 3A to 5A and 3B to 5B in the periodic table is the same as the metal described in the description of the metal oxide.
  • R in the above general formula is not particularly limited as long as it is an organic group that is non-reactive to hydrolysis and does not interfere with monodispersion. It is preferably a linear or branched alkyl group of ⁇ 8.
  • metal alkoxide examples include, for example, VO (OCH 3) 2, VO (OC 2 H
  • Nb (OC H), Nb (0-isoC H), Nb (0—nC H), Nb (0—isoC H), N
  • Niobium alkoxides such as b (0—nC H) and Nb (OCH 3) can be mentioned. This
  • the metal alkoxide is VO (OCH), VO (OC H), VO (0-is
  • the metal alkoxide may be a part of the alkoxy group that is substituted with a part of the alkoxy group (one C1) or the like. Furthermore, as the metal alkoxide, one type of metal alkoxide may be used alone, or two or more types of metal alkoxide may be mixed and used.
  • the hydrolysis step is performed in the presence of at least one compound selected from the group consisting of compounds represented by the general formulas (1), (2), (3) and (4). Do. That is, the hydrolysis step is performed in the presence of a single compound represented by the general formula (1), (2), (3) or (4) alone or a mixture of two or more compounds.
  • equation (1), (2), (3) and (4) in, R ⁇ R 2, R 3 and R 4 are independently a hydrogen atom or a linear or branched alkyl having 1 to 4 carbon atoms Although it is not particularly limited as long as it is a group, it is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group.
  • the compound of the compound and the previous organic solvent in a solution containing the compound, water, and the organic solvent is 100 wt%
  • the compound of the compound and the previous organic solvent It is preferable that the ratio to the total weight of 2.5 wt% or more is 4 wt% or more It is more preferable that The upper limit of the proportion of the compound in the solution is not particularly limited, but is preferably 35 wt%, more preferably when the total weight of the compound and the organic solvent is 100 wt%. Is 30wt%.
  • the particle size is reduced to 200 ⁇ while maintaining a narrow particle size distribution. It can be changed freely within the range of ⁇ 800nm.
  • V O vanadium pentoxide
  • the concentration of the product (pyridine) When the concentration of the product (pyridine) is higher than the concentration at which the relative standard deviation of particle size is 10% or less, the particle size gradually increases from about 200 nm to 250 nm until it reaches a certain concentration, and exceeds a certain concentration. And increases in proportion to the concentration of the compound from about 250 nm to about 800 nm.
  • the compound of the compound and the previous organic solvent when the total weight of the compound and the previous organic solvent in a solution containing the compound, water, and the organic solvent is 100 wt%, the compound of the compound and the previous organic solvent By changing the ratio to the total weight, the particle size is reduced to 200 ⁇ while maintaining a narrow particle size distribution! It can be changed freely within the range of ⁇ 800nm. For example, hydrolyzing nonadium alkoxide to synthesize vanadium pentoxide (V O) fine particles
  • the concentration of the above compound (pyridine) when the concentration of the above compound (pyridine) is higher than the concentration at which the relative standard deviation of particle size is 10% or less, Is about 200 ⁇ ! It gradually increases from ⁇ 250 nm, and increases above a certain concentration in proportion to the concentration of the compound from about 250 nm to about 800 nm.
  • the organic solvent is not particularly limited, and it is preferable to use an ether, ester, alcohol, ketone or the like which can be used.
  • a ketone when the metal is vanadium, a ketone can be particularly preferably used.
  • the ketone is not particularly limited, but among them, at least one general formula (5)
  • the ketone represented by (5) can be preferably used.
  • R 1 and R 2 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms.
  • organic solvents include acetone, 2-butanone, 3-pentanone, methyl isopropyl ketone, methyl n-propyl ketone, 3-hexanone, and methyl n-butyl ketone.
  • a strong organic solvent it is possible to synthesize monodispersed spherical metal oxide particles.
  • 1 type of a powerful ketone may be used independently, and multiple may be used in mixture.
  • the organic solvent further contains other organic solvents such as ethers, esters, alcohols and the like as long as monodispersed spherical metal oxide fine particles can be obtained. Also good.
  • the metal is vanadium, it is preferable to use a lower alcohol having 1 to 4 carbon atoms because metal oxide fine particles cannot be obtained.
  • the hydrolysis step is carried out in the presence of water necessary for hydrolysis.
  • the amount of water to be coexisted may be appropriately selected according to the type of metal oxide fine particles to be synthesized.
  • the amount of water is preferably 2 to 4 mol with respect to 1 mol of the metal alkoxide. By coexisting a strong amount of water, it is possible to synthesize monodispersed spherical metal oxide fine particles.
  • the water necessary for hydrolysis may be supplied by water contained in the reagent used, water contained in the atmosphere, or the like.
  • the metal alkoxide and at least one compound selected from the group consisting of the compound forces represented by the general formulas (1), (2), (3) and (4), Water and organic The method of mixing these substances is not particularly limited as long as the alkoxide is hydrolyzed in a solution containing a medium.
  • the organic solvent and the general formulas (1), (2) ), (3) and (4) are preferred to be a mixture of at least one compound selected from the group consisting of the compound strengths, wherein the metal alkoxide is covered in a solution containing moisture. Can be used.
  • the organic solvent and the compound power represented by the general formulas (1), (2), (3) and (4) are selected from the group consisting of
  • the reaction temperature for the hydrolysis is not particularly limited, but can be, for example, in the range of 5 to 50 ° C, preferably in the range of 15 to 40 ° C.
  • spherical metal oxide fine particles monodispersed in a short reaction time of 30 to 60 seconds can be synthesized.
  • the atmosphere for carrying out the hydrolysis is not particularly limited, and it can be carried out in the atmosphere, but of course, it may be carried out in an inert gas atmosphere such as nitrogen or argon.
  • the method for producing monodispersed spherical metal oxide fine particles according to the present invention preferably further includes a drying step of separating and drying the metal oxide fine particles from the dispersion obtained in the hydrolysis step. . Thereby, monodispersed spherical metal oxide fine particles can be obtained.
  • a method for separating the metal oxide fine particles to obtain dried monodispersed spherical metal oxide fine particles is not particularly limited, and various conventionally known methods can be used. As such a method, for example, a method in which the metal oxide fine particles are separated by vacuum separation, sedimentation separation or the like and vacuum-dried can be suitably used. In addition, a method of distilling an organic solvent can be used.
  • metal oxide fine particles in addition to obtaining dried metal oxide fine particles by a drying step, metal oxide fine particles dispersed in different solvents by solvent substitution. A dispersion of fine particles can also be obtained.
  • the metal oxide fine particles useful in the present invention are metal oxide fine particles of at least one metal selected from the group consisting of metal forces belonging to groups 3A-5A and 3B-5B of the periodic table,
  • the metal metal alkoxide comprises at least one compound selected from the group consisting of compounds represented by the general formulas (1), (2), (3) and (4), water, an organic solvent, Monodispersed spherical metal oxide fine particles having a relative standard deviation of particle size of 10% or less, obtained by hydrolysis in a solution containing.
  • the metal oxide fine particles useful in the present invention may be those composed of the metal oxide of the metal.
  • the general formula (1) It may comprise at least one compound selected from the group consisting of the compounds represented by (2), (3) and (4) and water.
  • the produced metal oxide fine particles can contain the compound and water.
  • the contained compound and water can be removed by heat treatment.
  • the temperature of the intense heat treatment is preferably 250 ° C. or higher and 600 ° C. or lower, more preferably 350 ° C. or higher and 500 ° C. or lower.
  • the heat treatment temperature is 600 ° C. or lower, the compound and water can be removed without impairing the perfect spherical shape of the metal oxide fine particles.
  • the heat treatment temperature is 250 ° C. or higher, the compound and water can be suitably removed.
  • the atmosphere in which the heat treatment is performed is not particularly limited, and can be performed in an atmosphere, but of course, it may be performed in an inert gas atmosphere such as nitrogen or argon.
  • the metal oxide has a layer structure, and the compound is a layer of the metal oxide. It is shown that there is an inter force between layers in the structure. Therefore, according to the method for producing monodispersed spherical metal oxide fine particles of the present invention, the substance that is desired to be inter-forced in the metal oxide fine particles is present during the reaction, so It is considered that the metal oxide fine particles that are force-rated can be produced by a one-step reaction.
  • the metal oxide fine particles that are useful in the present invention may be those which have been subjected to such a material force and an S force.
  • Such substances include at least one compound selected from the group consisting of compound powers represented by the above general formulas (1), (2), (3) and (4).
  • the above compounds which are not limited to these, It is thought that substances other than the above compounds can be interspersed by allowing substances other than the above compounds to exist during the reaction.
  • the composition of the substance that is inter-forced is preferably in the range of greater than 0 and less than or equal to 2 with respect to the metal oxide 1 in terms of mol ratio.
  • Monodispersed spherical V 2 O fine particles with various particle sizes are mixed with acetone.
  • V 0 isoC H (0.06 ml (2.55 X 10 _4 mol), Nichia Chemical Co., Ltd.) in a solution of acetone / pyridine mixture (total weight 8 g) with vigorous stirring in air. Industrial Co., Ltd.)
  • the amount was 01 wt% or less (pyridine, Wako Pure Chemical Industries) and 0.4 wt% or less (acetone, Nacalai Testa Co., Ltd.).
  • the hydrolysis was performed at room temperature (about 20 ° C).
  • the amount of pyridine is 2.5 wt% or more and 30 wt% or less when the total weight of the mixture with acetone is 8 g and the total weight of the acetone Z pyridine mixture is 100 wt%. (Hereinafter, when the total weight of the acetone Z pyridine mixture is 100 wt%, the ratio (wt%) of pyridine in the acetone Z pyridine mixture is expressed as “pyridine concentration (C ) ".
  • V O fine particles are collected by centrifugation for 12 hours in a vacuum.
  • one of the features of the production method of the present invention is a significantly faster monodispersed spherical shape.
  • the generation of VO fine particles are at most 30 seconds long and could be faster
  • V o fine particles The shape of the obtained V o fine particles, the presence or absence of aggregates, and the particle size were observed with a transmission electron microscope.
  • Fig. 1 shows transmission electron microscope observations of V O fine particles obtained at various pyridine concentrations.
  • Figure 1 (a), (b), (c), and (d) show VO fine particles produced under the conditions of pyridine concentration (C) of 2.5 wt%, 5 wt%, 10 wt%, and 20 wt%, respectively. Observation results
  • V O fine particles obtained as shown in Fig. 1 (a) to (d) are almost completely spherical.
  • the fine particles have a uniform particle size around 200 nm in Fig. 1 (a), around 220 nm in Fig. 1 (b), around 240 nm in Fig. 1 (c), and around 400 nm in Fig. L (d). It was confirmed that! /
  • FIG. 2 shows the average particle diameter (D, unit: nm, ⁇ in FIG. 2) of spherical VO fine particles monodispersed at each pyridine concentration, measured by observation with a transmission electron microscope. )When,
  • the relative standard deviation (c .v, unit:..%, Shown in FIG. 2 ⁇ ) and a graph plotted against pyridine concentration (C).
  • the average particle size and the relative standard deviation of the particle size were obtained by measuring 300 fine particles or more for samples at each pyridine concentration.
  • the average particle size and the relative standard deviation of the particle size were obtained from the following formula.
  • the relative standard deviation is a value that expresses the standard deviation ⁇ ⁇ as a percentage based on the average value of the observed population.
  • the relative standard deviation is less than 10%.
  • the relative standard deviation is about 7% when the pyridine concentration (C)> about 4 wt%.
  • the amount of pyridine used for 3 7 3 was about 19 mol.
  • the pyridine concentration (C) 30 wt%
  • the pyridine used for VO (0-isoC H) lmol is about 119 mol
  • the pyridine concentration (C) 30 wt%
  • the amount of pyridine used for VO (0—isoC H) lmol is about 139 mol.
  • reaction solution containing 2 5 2 5 particles was used as a sample, it is considered that the same result can be obtained for dried Vo fine particles by drying the sample under observation under high vacuum.
  • the FTIR measurement was performed using an FTS 6000 Fourier transform infrared spectrometer (BioRad) and monodispersed spherical V O of various particle sizes produced under different pyridine concentrations (C).
  • C pyridine concentration
  • Lysine is 350 at atmospheric pressure in an argon gas atmosphere containing 5% H. C-500. Heat at C for 1 hour
  • Figure 7 shows the results of observing the V 2 O fine particles with a scanning electron microscope after heat treatment.
  • VO fine particles from which water and pyridine have been completely removed are completely spheres.
  • X-ray diffraction of dried VO fine particles obtained through hydrolysis and drying processes went.
  • X-ray diffraction was performed using Rigaku RINT2500 (manufactured by Rigaku Corporation) on monodispersed spherical VO fine particles with various particle sizes produced under different pyridine concentrations (C).
  • Figure 4 shows the X-ray diffraction pattern of monodispersed spherical V 2 O particles produced under a pyridine concentration (C) of 10 wt%.
  • V ⁇ fine particles are V ⁇ ⁇ ⁇ ⁇ xerogel
  • the distance between the layers is about 1.05 nm, which is related to the particle size of monodispersed spherical V ⁇ fine particles.
  • V O ⁇ ⁇ ⁇ Xerogels are used in many organic molecules.
  • Ethanol was used in the same manner as in Example 1 except that ethanol was used instead of acetone. Hydrolysis of VO (0-isoC H) was performed with the ratio of pyridine in the ethanol Z pyridine mixture being 12.5 wt% when the total weight of the Z pyridine mixture was ioowt%.
  • VO octanol
  • Average particle size (D, unit: nm) and relative standard deviation (v., Unit:%) of the fine particles are determined based on the water concentration (the ratio of water when the total reaction solution weight is 100 wt%, Draft plotted against (unit: wt%).
  • Example 1 there are two possible sources of H 2 O in the hydrolysis of VO (0—isoC H).
  • the concentration of is preferably 0.3 wt% or less (4.3 mol or less with respect to VO (0—iso C H) lmol) when the weight of the total reaction solution is 100 wt%.
  • the method for producing metal oxide fine particles according to the present invention provides monodispersed spherical metal oxide fine particles having a relative standard deviation of the particle size of 10% or less.
  • R 2 , R 3 and R 4 independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the metal alkoxide is hydrolyzed in an organic solvent containing at least one compound selected from the group represented by It may include the following hydrolysis step for obtaining a dispersion of monodispersed spherical metal oxide fine particles.
  • the method for producing metal oxide fine particles according to the present invention includes a drying step of further separating and drying the dispersion of the metal oxide fine particles obtained in the hydrolysis step. Is preferred.
  • At least one compound selected from the group consisting of the compound forces represented by the general formulas (1), (2), (3) and (4) is based on lmol of the metal alkoxide of the metal. lOmol or more is preferable. It is more preferable to use 19 mol or more.
  • the method for producing metal oxide fine particles according to the present invention is selected from the group consisting of the compounds represented by the general formulas (1), (2), (3) and (4). It is preferable that the particle size of the monodispersed spherical metal oxide fine particles can be controlled in the range of 200 nm or more and 800 nm or less by changing the amount of at least one compound.
  • the organic solvent is at least one general formula (5)
  • R 1 and R 2 independently represent a linear or branched alkyl group having 1 to 4 carbon atoms.) Are preferred.
  • the method for producing metal oxide fine particles useful for the present invention produces monodispersed spherical metal oxide fine particles having a relative standard deviation of the particle size of 10% or less.
  • the composition includes a hydrolysis step for obtaining a dispersion of monodispersed spherical metal oxide fine particles
  • the monodispersed spherical metal oxide which was conventionally impossible to synthesize, is as follows. The effect is that the fine particles can be synthesized easily.
  • the metal oxide fine particles according to the present invention are monodispersed spherical metal oxide fine particles having a relative standard deviation of the particle size of 10% or less, and are 3A to 3A in the periodic table.
  • the metal oxide fine particles of at least one metal selected from metals belonging to Group 5A and Group 3B-5B represented by the general formulas (1), (2), (3) and (4) Compound power Since it has a composition comprising at least one selected compound and water, it can be used for pigments, catalysts, advanced ceramic materials, opal-based photonic crystals (photocrystals), etc. It can be used in many technical fields.
  • Submicron monodispersed spherical metal oxide fine particles are used in many technical fields such as pigments, catalysts, raw materials for advanced ceramics, and opal-based photonic crystals (photocrystals). Available. Monodispersed spherical VO particles are also used in automobile exhaust gas purification. It is an important material in many fields, such as catalysts for batteries, cathode materials for lithium ion batteries, electochromic devices, sensors, and actuators.
  • the present invention makes it possible to synthesize monodisperse spherical metal oxide fine particles that could not be synthesized conventionally.
  • spherical metal oxide fine particles having a uniform size can be synthesized very quickly, which is a great advantage for mass synthesis in the manufacturing industry.
  • the present invention is used not only in the chemical industry that supplies spherical metal oxide fine particles as a basic material, but also in the battery manufacturing industry, electronic component manufacturing industry, machinery / equipment manufacturing industry, electrical machinery / equipment manufacturing industry, and the like.
  • the power is also very useful.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Selon la présente invention, un alcoxyde métallique est hydrolysé dans un solvant organique contenant ledit alcoxyde métallique, de l’eau et un composé choisi dans le groupe constitué de composés représentés par les formules générales respectives (1), (2), (3) et (4) : [Formule chimique 1] (dans lesquelles R1, R2, R3 et R4 représentent chacun indépendamment un atome d'hydrogène ou un alkyle en C1-4 linéaire ou ramifié). On produit ainsi de fines particules sphériques monodispersées d’un oxyde métallique, dont les diamètres de particules ont un écart type relatif inférieur ou égal à 10 %. Il est ainsi possible de produire lesdites particules avec un diamètre voulu, même pour un métal dont il a jusque là été difficile de synthétiser un oxyde sous la forme de fines particules sphériques monodispersées.
PCT/JP2006/300656 2005-01-19 2006-01-18 Procede de production de fines particules spheriques d'oxyde metallique monodispersees et fines particules d’oxyde metallique WO2006077890A1 (fr)

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JP2008088505A (ja) * 2006-10-02 2008-04-17 Toyota Central R&D Labs Inc 絶縁皮膜、磁心用粉末及び圧粉磁心、並びにそれらの形成方法又は製造方法
WO2010090274A1 (fr) * 2009-02-09 2010-08-12 独立行政法人産業技術総合研究所 Fines particules, leur procédé de fabrication et matériau de revêtement, film et encre contenant chacun les fines particules
JP2017030994A (ja) * 2015-07-29 2017-02-09 公立大学法人首都大学東京 無機系単分散球形微粒子、電池用電極並びに電池

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JPS62278106A (ja) * 1986-05-26 1987-12-03 Tama Kagaku Kogyo Kk 金属アルコキシドの加水分解法
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JP2002356327A (ja) * 2001-03-28 2002-12-13 Samsung Sdi Co Ltd 球形のナノサイズバナジウム酸化物粒子の製造方法

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JPS62278106A (ja) * 1986-05-26 1987-12-03 Tama Kagaku Kogyo Kk 金属アルコキシドの加水分解法
JPH0222105A (ja) * 1987-10-29 1990-01-25 Fraunhofer Ges 単分散セラミック粉末の製造方法
JP2002356327A (ja) * 2001-03-28 2002-12-13 Samsung Sdi Co Ltd 球形のナノサイズバナジウム酸化物粒子の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008088505A (ja) * 2006-10-02 2008-04-17 Toyota Central R&D Labs Inc 絶縁皮膜、磁心用粉末及び圧粉磁心、並びにそれらの形成方法又は製造方法
WO2010090274A1 (fr) * 2009-02-09 2010-08-12 独立行政法人産業技術総合研究所 Fines particules, leur procédé de fabrication et matériau de revêtement, film et encre contenant chacun les fines particules
JP5598857B2 (ja) * 2009-02-09 2014-10-01 独立行政法人産業技術総合研究所 微粒子、その製造方法、ならびにそのような微粒子を含む塗料、フィルムおよびインク
JP2017030994A (ja) * 2015-07-29 2017-02-09 公立大学法人首都大学東京 無機系単分散球形微粒子、電池用電極並びに電池

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