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WO2009113195A1 - Matériau catalyseur pour produire une nanostructure de carbone en forme de goupillon, procédé de fabrication du matériau catalyseur, nanostructure de carbone en forme de goupillon et son procédé de fabrication - Google Patents

Matériau catalyseur pour produire une nanostructure de carbone en forme de goupillon, procédé de fabrication du matériau catalyseur, nanostructure de carbone en forme de goupillon et son procédé de fabrication Download PDF

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Publication number
WO2009113195A1
WO2009113195A1 PCT/JP2008/066576 JP2008066576W WO2009113195A1 WO 2009113195 A1 WO2009113195 A1 WO 2009113195A1 JP 2008066576 W JP2008066576 W JP 2008066576W WO 2009113195 A1 WO2009113195 A1 WO 2009113195A1
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WIPO (PCT)
Prior art keywords
catalyst
layer
brush
metal
producing
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PCT/JP2008/066576
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English (en)
Japanese (ja)
Inventor
喜萬 中山
徹 坂井
岳志 長坂
成司 秋田
整郎 山口
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Nippon Sanso Holdings Corp
Osaka Metropolitan University
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Osaka Prefecture University PUC
Nippon Sanso Holdings Corp
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Priority claimed from PCT/JP2008/054672 external-priority patent/WO2008111653A1/fr
Application filed by Osaka Prefecture University PUC, Nippon Sanso Holdings Corp filed Critical Osaka Prefecture University PUC
Priority to JP2010502690A priority Critical patent/JPWO2009113195A1/ja
Publication of WO2009113195A1 publication Critical patent/WO2009113195A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/395—Thickness of the active catalytic layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density

Definitions

  • the present invention relates to a catalyst body for producing brush-like carbon nanostructures and a method for producing the same, and more specifically, a catalyst body for producing brush-like carbon nanostructures, a production method therefor, and a brush produced using the catalyst body
  • the present invention relates to a method for producing the structure using a CNT structure and a catalyst body.
  • the carbon nanostructure of the present invention is a nano-sized substance composed of carbon atoms.
  • CNT carbon nanotubes
  • CNT carbon nanocoils
  • CNC CNTs with beads in which beads are formed on CNTs
  • cup-stacked nanotubes formed by laminating cup-shaped graphene with no bottom, and the like are known.
  • a nano-sized carbon substance is formed in a brush shape, such as a brush-like CNT in which CNCs and CNTs are concentrated in a brush shape, or a carbon nanohorn in which a large number of CNTs whose tips are rounded in a square shape are radially concentrated.
  • the carbon nanostructure is referred to as a brush-like carbon nanostructure.
  • CNT is a pipe-like carbon material having a diameter of about 0.5 to 10 nm and a length of about 1 ⁇ m, and is a new carbon material discovered by Mr. Iijima in 1991. Since CNT has a very fine structure, it is difficult to perform observation and manipulation with the naked eye of CNT, and attempts have been made to produce a CNT aggregate in order to improve its handleability and workability. Yes. For example, it is possible to manufacture a CNT aggregate that can be visually recognized with the naked eye. As described in detail below, a rope-shaped CNT aggregate manufactured using a CNT structure formed in a so-called brush shape. There is a body (hereinafter referred to as “rope-like CNT”).
  • FIG. 16 is a schematic diagram for explaining a conventional method for manufacturing a rope-like CNT 152.
  • a brush-like CNT 148 is formed on the surface of the base 132 so as to be oriented substantially perpendicular to the base 132, and as shown in (16B), a bundle of a plurality of adjacent CNTs 146 are intertwined.
  • the rope-like CNT 152 can be manufactured.
  • the manufacturing process of an aggregate composed of a plurality of CNTs 146, so-called rope-like CNTs 152 is (1) a chemical vapor deposition (CVD) process for forming a plurality of CNTs 146 oriented in a direction perpendicular to the base 132 on the base; (2) Cleaving step of cleaving the substrate 132, (3) Tensile step of pulling a plurality of CNT 146 or bundled CNT aggregates 150 to form rope-like CNTs 152.
  • CVD chemical vapor deposition
  • Patent Document 1 includes a rope-like CNT which is a bundle-like assembly in which a plurality of CNTs are entangled with each other and this rope-like CNT (referred to as “CNT rope” in Patent Document 1). Is a method for producing a “CNT sheet” which is a CNT aggregate assembled in a planar manner.
  • Non-Patent Document 1 discloses that in the process of heating the iron catalyst, the iron catalyst in the helium gas atmosphere changes from the iron element state to magnetite (Fe 3 O 4 ) in the process from room temperature to the CNT structure growth temperature (700 ° C.). ) State, and at 700 ° C., a technical explanation of phase transition to an iron oxide state such as hematite (Fe 2 O 3 ) is shown.
  • (16A) in FIG. 17 is an atomic force microscope (AFM) image of iron catalyst particles formed on the surface of a conventional silicon substrate described in Non-Patent Document 1
  • (17B) is a dotted line in (17A). Is an enlarged image of the region indicated by (500 nm in both vertical and horizontal directions).
  • the enlarged catalyst particles in which the iron particles are aggregated to grow to a catalyst particle diameter of about 100 nm are formed, which exceeds the particle diameter suitable for the growth of CNTs. Furthermore, the density of the iron catalyst particles is greatly reduced by forming the enlarged catalyst particles.
  • FIG. 18 is a schematic diagram showing the structure of the conventional catalyst body 101 and brush-like CNT 148 and the production method thereof, and explains the formation process of the enlarged catalyst particles shown in FIG.
  • a catalyst layer 140 made of an iron film is formed on the surface of the conventional silicon substrate 132 shown in (18A).
  • the iron catalyst is formed from the catalyst layer 140 by heat treatment in an inert gas atmosphere. Particles 142 are formed.
  • the conventional silicon substrate 132 has a high affinity with a catalytic metal such as iron, and silicidated particles 143 with iron silicide formed on the interface with the silicon substrate 132 grow and adhere to the substrate to form a hemisphere. A phenomenon was observed in which the CNT did not grow. Furthermore, as shown in FIG.
  • Patent Document 1 describes rope-like CNTs.
  • continuous rope-like CNTs having a predetermined length or more are manufactured from conventional brush-like CNTs, reproducibility is low and a large amount is produced.
  • the conditions for stable production have not been clarified.
  • the present invention can efficiently produce brush-like carbon nanostructures such as high-density brush-like CNTs that can be used for producing CNT aggregates such as rope-like CNTs, and It is an object of the present invention to provide a catalyst body for producing brush-like carbon nanostructures that can be produced.
  • the present invention has been made to solve the above problems, and a first embodiment of the present invention comprises a substrate, a reaction preventing layer formed on the surface of the substrate, and a catalyst layer on the reaction preventing layer,
  • the catalyst body is a catalyst body for producing a brush-like carbon nanostructure, which is composed of a catalyst metal layer on the reaction preventing layer and an aggregation suppressing layer formed on the surface of the catalyst metal layer.
  • the second aspect of the present invention is the function of the first aspect, wherein the aggregation suppressing layer is formed of a metal compound having a melting point higher than that of the catalytic metal layer, and the catalyst layer is prevented from melting and aggregating during heating. It is a catalyst body for brush-like carbon nanostructure manufacture which has this.
  • the catalyst body for producing a brush-like carbon nanostructure according to the first or second aspect, wherein the aggregation suppressing layer is formed from a metal oxide of a metal element constituting the catalytic metal layer.
  • the substrate is heat-treated to form a reaction preventing layer made of an oxide on the surface of the substrate, and a catalytic metal layer is formed on the surface of the reaction preventing layer, and 80 ° C. ⁇ T ⁇ 300 ° C.
  • a coagulation suppression layer made of a metal oxide on the surface of the catalytic metal layer, and heated at a rate of temperature increase of 10 ° C./sec or more from the catalytic metal layer and the aggregation suppression layer.
  • the average particle diameter D of the metal-based catalyst particles is in the range of 0.5 nm ⁇ D ⁇ 80 nm
  • the individual particle diameter d of the metal-based catalyst particles is The ratio ⁇ D / D of the half-value width ⁇ D to the average particle diameter D is 0 ⁇ D / D, where ⁇ D is a half-value width of the particle size distribution of the metal-based catalyst particles within the range of the average particle diameter D.
  • the catalyst body for producing brush-like carbon nanostructures wherein the number of the metal-based catalyst particles forming the catalyst layer per unit area is set to 1 ⁇ 10 8 / cm 2 or more It is a manufacturing method.
  • the catalyst body for producing brush-like carbon nanostructures according to the first, second or third aspect is disposed in a reaction chamber, and the reaction chamber is heated to form the catalyst metal layer and the agglomerate.
  • a catalyst layer made of a suppression layer is made into particles, a catalyst particle layer made of metal-based catalyst particles mainly composed of a catalyst metal is formed on the surface of the reaction prevention layer, and at least a raw material gas is circulated in the heated reaction chamber
  • a brush-like carbon nanostructure manufacturing method in which a large number of carbon nanostructures are grown in a brush shape on the surface of the catalyst particle layer of the catalyst body for manufacturing the brush-like carbon nanostructure.
  • a brush-like carbon nanostructure production catalyst produced by the production method of the fourth or fifth aspect is disposed in a reaction chamber, and the reaction chamber is heated and heated.
  • An eighth aspect of the present invention is a carbon nanotube structure manufactured by the method for manufacturing a brush-like carbon nanostructure according to the seventh aspect, wherein the bulk density of the structure is 20 mg / cm 3 or more, This is a brush-like carbon nanostructure having an average height of carbon nanotubes of 50 ⁇ m or more.
  • the catalyst layer is composed of the catalyst metal layer on the reaction preventing layer and the aggregation suppressing layer formed on the surface of the catalyst metal layer.
  • the metal catalyst particles formed by the catalyst metal layer being agglomerated are aggregated and become larger than a predetermined particle size suitable for the growth of carbon nanostructures such as CNT and CNC. Can be suppressed.
  • the catalyst body according to the present invention is composed of a portion composed of a catalyst substance and other members (base, reaction prevention layer), and the shape of the base is a substrate, a multilayer substrate, a cylinder, There are various forms such as polyhedrons, pellets, and powders.
  • the catalyst layer of the first form is a precursor of the catalyst particle layer, and the catalyst particle layer is formed from the catalyst layer by heat treatment for synthesizing carbon nanostructures such as CNT and CNC. That is, the particle formation of the catalyst layer and the growth of the carbon nanostructure are performed sequentially or continuously or continuously and simultaneously during the heat treatment.
  • the catalyst layer composed of the catalyst metal layer and the aggregation suppression layer formed on the surface of the catalyst metal layer may increase the amount of heat necessary for the formation of the catalyst layer by forming the aggregation suppression layer.
  • the catalyst layer is prevented from being granulated at a relatively low temperature, and the granulation is started at a predetermined temperature or higher. Can be prevented.
  • the aggregation suppressing layer a substance having a higher melting point than the catalyst metal layer or a substance that raises the melting temperature of the catalyst layer by a reaction with the catalyst metal layer can be used. Furthermore, when using a substance in which a part of the constituent elements of the aggregation suppression layer diffuses and reacts with the catalyst metal layer during heating, the catalyst layer can be prevented from being particleized.
  • the aggregation suppressing layer is made of an oxide
  • the oxide is formed on the surface of the catalytic metal layer, and suppresses excessive oxidation of the catalytic metal and functions as an oxidizing agent for the catalytic metal,
  • the melting temperature is increased and particle formation at a relatively low temperature is suppressed.
  • the catalyst layer is aggregated at a relatively low temperature and formed into particles by holding the aggregation suppression layer.
  • the aggregation suppressing layer is preferably formed so as to uniformly cover the entire surface of the catalytic metal layer.
  • the aggregation suppressing layer can set the metal oxide component contained in the metal-based catalyst particles to a suitable amount so that the catalyst metal layer can suppress oxidation during the particle formation process. it can.
  • the catalyst body for producing the brush-like carbon nanostructure is composed of a base, a reaction preventing layer formed on the surface of the base, and a catalyst layer on the reaction preventing layer.
  • the metal-based catalyst particles are formed by forming the catalyst layer into particles, which can prevent the base and the catalyst metal from reacting in the temperature rising process during the synthesis of the CNT or CNP.
  • the catalytic function can be maintained.
  • the reaction-preventing layer is formed from an oxide or a heat-resistant resin that has a very low reactivity with the catalyst metal, and even if the catalyst body for producing a brush-like carbon nanostructure according to the present invention is heated at a high temperature, Bonding between the catalyst metal and the base material can be prevented.
  • a reaction preventing layer made of silicon nitride, silicon carbide, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, zirconium oxide or the like is formed.
  • the substrate is a silicon substrate
  • the surface of the substrate can be heated as the reaction preventing layer to form a silicon oxide layer, and the reaction preventing layer can be formed relatively easily.
  • the catalytic metal is prevented from reacting with the substrate and forming a metal silicide.
  • the silicon substrate is a preferable material as a substrate material because it can form a smooth surface with high accuracy and can be manufactured at low cost.
  • the thickness of the reaction preventing layer is preferably 10 nm or more, and the reaction between the catalyst layer and the substrate can be more reliably prevented.
  • the base material When the thickness of the reaction preventing layer is less than 10 nm, the base material may be diffused into the reaction preventing layer by heat treatment, and a reaction with the catalyst metal may be caused.
  • the present inventors conducted a test on the effect of the reaction preventing layer under the growth temperature of CNT. When the thickness of the reaction preventing layer is 10 nm or more, the reaction between the catalyst layer and the substrate is reliably prevented. I have confirmed that. If the thickness of the reaction preventing layer is 10 nm or more, it can be appropriately set according to the use of the brush-like CNT, the structure of the substrate, and the like.
  • the catalyst metal can be appropriately selected from iron, tin, indium, cobalt, nickel, alloys thereof, oxides thereof, and the like, and metal catalyst particles containing any catalyst metal as a main component are formed. Even in this case, the reaction-preventing layer can prevent the metal-based catalyst particles from reacting with the substrate by heat treatment.
  • the metal-based catalyst particles are made of one or more kinds of iron oxides, brush-like CNTs in which CNTs are densely formed are formed, and selected from tin, indium, cobalt, nickel, and alloys thereof other than iron oxides.
  • the aggregation suppressing layer is formed of a metal compound having a melting point higher than that of the catalytic metal layer, and it is suppressed that the catalytic layer melts and aggregates during heating.
  • the particle size suitable for the growth of the carbon nanostructure is small, and relatively uniform metal-based catalyst particles can be formed.
  • the fluidization start temperature of the metal or metal compound falls from the fluidization start temperature of the bulk metal. The temperature may be set higher than the fluidization start temperature of the lowered catalyst metal layer.
  • the fluidization start temperature includes a temperature at which a part of the solid begins to fluidize, such as surface melting, and means a lower limit temperature at which the fluidization of the solid starts.
  • the melting point in this specification refers to the fluidization Includes the onset temperature.
  • the aggregation suppressing layer is made of a metal oxide of a metal element constituting the catalytic metal layer, and is relatively easily aggregated by subjecting the surface of the catalytic metal layer to an oxidation treatment.
  • a suppression layer can be formed.
  • the compatibility with a catalyst metal layer is good, and the said aggregation suppression layer can be formed more efficiently.
  • the metal oxide forming the aggregation suppressing layer according to the present invention has a melting point higher than that of the catalyst metal layer.
  • the catalyst metal layer that has been granulated aggregates due to surface melting or the like, and becomes larger than a predetermined particle size suitable for CNT growth.
  • Speed can be reduced.
  • the metal oxide has a higher melting point than the catalyst metal layer, and can oxidize part or all of the catalyst metal layer to increase the melting temperature of the catalyst layer.
  • the aggregation suppressing layer can prevent the catalyst metal from being excessively oxidized during the heat treatment process when the catalyst particle layer is formed.
  • the aggregation suppressing layer when a part of the constituent elements of the aggregation suppressing layer diffuses and reacts with the catalytic metal layer during heating, an oxide is formed on the surface of the catalytic metal layer to suppress excessive oxidation of the catalytic metal, It functions as an oxidizing agent for the catalytic metal, increases the melting temperature of the entire catalyst layer, and suppresses particle formation at a relatively low temperature. More specifically, when the catalytic metal layer is composed of iron, tin, indium, cobalt, or nickel, the aggregation suppressing layer is formed of FeO, Fe 2 O 3 , Fe 3 O 4 , SnO 2 , and CoO, respectively. Alternatively, it is formed from NiO.
  • the catalyst layer composed of the catalyst metal layer and the aggregation suppressing layer is formed into a relatively uniform particle at a high temperature rise of 10 ° C./sec or more, and the metal system is uniformly and densely formed.
  • a catalyst body for producing brush-like carbon nanostructures in which catalyst particles are distributed can be produced with high efficiency.
  • the reaction preventing layer made of an oxide is formed on the surface of the substrate by heat treatment, it is possible to prevent the catalyst metal from reacting with the substrate in the formation of particles of the catalyst layer by the heat treatment.
  • the catalyst layer is heat-treated in a temperature range of 80 ° C. ⁇ T ⁇ 300 ° C.
  • an aggregation suppression layer made of a metal oxide on the surface of the catalyst metal layer It is possible to suppress the metal-based catalyst particles from agglomerating and becoming larger than a predetermined particle size suitable for CNT growth. It has been experimentally confirmed that when the temperature of the catalyst layer is 300 ° C. or higher, the particle formation of the catalyst layer proceeds rapidly.
  • the aggregation suppressing layer can prevent the catalytic metal from being excessively oxidized during the formation of the catalyst particle layer, thereby reducing the function as a catalyst for producing CNTs. Therefore, according to the production method of the present invention, it is possible to provide a catalyst body capable of producing high-density and uniform brush-like CNTs with high efficiency.
  • the average particle diameter D of the metal catalyst particles is in the range of 0.5 nm ⁇ D ⁇ 80 nm, and the individual particle diameter d of the metal catalyst particles is the average particle diameter. Since it is set within the range of D, it is possible to provide a catalyst body for producing brush-like carbon nanostructures that grows brush-like carbon nanostructures with high efficiency.
  • the metal-based catalyst particles preferably contain a metal element serving as a catalyst, that is, a catalyst metal as a main component, and contain an oxide of the catalyst metal, thereby imparting suitable catalyst performance.
  • a metal element serving as a catalyst that is, a catalyst metal as a main component
  • the metal-based catalyst particles preferably contain an oxide of the catalyst metal, thereby imparting suitable catalyst performance.
  • the average particle diameter D is less than 0.5 nm, most of the metal-based catalyst particles have a diameter equal to or smaller than the CNT diameter, and the function as a catalyst for growing the CNT is lost.
  • the average particle diameter D exceeds 80 nm, most of the metal-based catalyst particles are larger than the CNT diameter, and the number of metal-based catalyst particles for growing CNTs is greatly reduced. Therefore, according to the catalyst body manufactured according to the fifth embodiment of the present invention, the average particle diameter D and the individual particle diameters d are set within the above range, whereby brush-like CNTs are manufactured with high efficiency. can do.
  • the particle diameter d of the metal-based catalyst particles is made uniform.
  • a catalyst body for producing brush-like carbon nanostructures for growing uniform brush-like CNTs and the like with high efficiency can be provided.
  • the particle size distribution is such that the half width ⁇ D is within a range of 0 ⁇ D / D ⁇ 0.7 with respect to the average particle size D, and the particle size d Are concentrated in the vicinity of the average particle diameter D, the uniformity of the metal-based catalyst particles is maintained, and brush-like carbon nanostructures such as brush-like CNTs can be grown with high efficiency. High uniformity is achieved with CNTs.
  • the ratio ⁇ D / D exceeds 0.7, the particle size distribution is widened, so that the diameter of the growing brush-like CNTs becomes non-uniform, making it difficult to produce the rope-like CNTs, and the predetermined diameter is the total length.
  • the number of the metal catalyst particles forming the catalyst layer per unit area is 1 ⁇ 10 8 particles / cm 2 or more, and the metal catalyst having a particle diameter capable of growing CNT as described above. Since the particles are uniformly formed, high-density and uniform brush-like CNTs can be produced with high efficiency. When the CNT density of the brush-like CNTs is less than 1 ⁇ 10 8 pieces / cm 2 , it has been confirmed that the production of rope-like CNTs is almost impossible.
  • the density of the metal-based catalyst particles is , At least 1 ⁇ 10 8 / cm 2 or more is required. Considering that it is difficult to grow CNT from all metal catalyst particles, the number of the metal catalyst particles per unit area is more preferably 1 ⁇ 10 9 particles / cm 2 or more.
  • the catalyst body for producing the brush-like carbon nanostructure according to the first, second or third aspect is disposed in the reaction chamber and heated, the catalyst metal layer and the aggregation suppression are performed. It is possible to produce a catalyst body for producing brush-like carbon nanostructures in which metal catalyst particles are uniformly distributed at a high density by making particles of the catalyst layer relatively uniform into particles. That is, the catalyst layer is agglomerated at a relatively low temperature by holding the agglomeration suppression layer until the temperature approaches a predetermined temperature or a relatively high temperature at which the brush-like carbon nanostructure is generated, or only its surface is melted. Therefore, uniform and fine metal catalyst particles can be formed by forming particles at a relatively high temperature in a short time. Furthermore, since a catalyst particle layer composed of metal-based catalyst particles containing a catalyst metal as a main component is formed on the surface of the reaction preventing layer, it is possible to prevent the catalyst metal from reacting with the substrate by heating.
  • the catalyst body of the first or second aspect is disposed in the reaction chamber, and a large number of carbon nanostructures such as CNTs are grown in a brush shape on the surface of the catalyst particle layer. Therefore, a brush-like carbon nanostructure having a high density and a more uniform shape such as a CNT diameter can be produced.
  • a catalyst body for producing brush-like carbon nanostructures such as a catalyst body for producing brush-like CNTs has metal catalyst particles having a suitable particle size and catalytic activity formed uniformly, and has a high density.
  • the brush-like CNTs can be provided, and rope-like CNTs and a large amount of CNTs having a uniform diameter can be obtained from the brush-like CNTs.
  • organic gas such as hydrocarbon gas, sulfur containing organic gas, and phosphorus containing organic gas
  • Hydrocarbons include alkane compounds such as methane and ethane, alkene compounds such as ethylene and butadiene, alkyne compounds such as acetylene, aryl hydrocarbon compounds such as benzene, toluene and styrene, and condensed rings such as indene, naphthalene and phenanthrene.
  • Aromatic hydrocarbons such as cyclopropane and cyclohexane, cycloolefin compounds such as cyclopentene, and alicyclic hydrocarbon compounds having a condensed ring such as steroids can be used. It is also possible to use a mixed hydrocarbon gas in which two or more of the above hydrocarbon compounds are mixed.
  • a mixed hydrocarbon gas in which two or more of the above hydrocarbon compounds are mixed.
  • hydrocarbons low molecules such as acetylene, arylene, ethylene, benzene, and toluene are preferable, and acetylene gas C 2 H 2 is inexpensive and easily available, has a triple bond, and is reactive with catalyst particles. Therefore, it can be used as a raw material gas capable of generating a carbon nanostructure such as CNT in the lowest temperature range.
  • the bulk density of the structures is 20 mg / cm 3 or more
  • Brush-like CNTs having an average CNT height of 1 ⁇ m or more can be easily produced.
  • the present inventors have clarified from experiments that the rope-like CNTs are formed when the average height of the CNTs constituting the brush-like CNTs is about 1 ⁇ m or more and the CNTs have a predetermined density or more, and the present invention is completed. I arrived.
  • the predetermined density is reached when the bulk density is 20 mg / cm 3 or more, and rope-like CNTs can be produced from the brush-like CNTs.
  • rope-like CNTs suitable for high efficiency can be manufactured.
  • FIG. 2 is a surface of a catalyst body for producing brush-like CNTs of Example 1 and an AFM image of a comparative example.
  • FIG. 3 is a view showing a surface of a catalyst body for producing brush-like CNTs of Example 2 and an AFM image of a comparative example.
  • 3 is a particle size distribution diagram of iron-based catalyst particles produced by the same method as in Example 2.
  • FIG. 6 is an AFM image of Comparative Example 1 and Comparative Examples 3 to 5 shown in order to compare the effect of the pre-oxidation treatment and the treatment temperature.
  • 4 is a scanning electron microscope (SEM) image obtained by observing the brush-like CNTs of Example 3 and Comparative Example 6.
  • FIG. 10 is an SEM image obtained by observing the brush-like CNTs of Comparative Examples 7 to 9.
  • FIG. 1 is a schematic diagram showing a production process of a catalyst body 1 for producing a brush-like carbon nanostructure according to the present invention.
  • the base 32 is disposed in a processing chamber (not shown), and an oxidizing gas is supplied to the surface of the base 32 to perform heat treatment.
  • the substrate 32 various materials having a smooth surface can be used, but a silicon substrate is suitable because it can be easily and inexpensively manufactured using conventional processing techniques.
  • a reaction preventing layer 34 made of an oxide is formed on the surface of the base 32 heat-treated in an oxidizing gas atmosphere.
  • the reaction preventing layer 34 to have a thickness of more than T S 10 nm, the catalyst metal layer 36 and the substrate 32 to be formed later is prevented from reacting upon heating. Further, when the reaction preventing layer 34 is an oxide, the catalytic metal layer 36 is reduced by the catalytic metal at a high temperature rise (about 80 ° C./sec) in the pre-oxidation treatment process or the CVD process. Oxygen may move to the catalytic metal layer 36. Therefore, when a strong affinity is generated between the substrate and the catalyst metal layer, catalyst particles are not formed in the particle formation process described later, and as a result, a phenomenon in which the growth probability of CNT decreases is observed.
  • reaction prevention layer 34 By forming the reaction preventing layer 34 that is not reduced by the catalyst metal layer 36, that is, by using the reaction preventing layer 34 that is stable to various conditions such as temperature and pressure and is completely unreacted with the catalyst metal layer 36, High density and high probability of CNT growth can be realized. However, the reaction prevention layer 34 is appropriately selected because of the problem of manufacturing cost.
  • a catalytic metal layer 36 made of a catalytic metal element suitable for the growth of CNTs is formed on the surface of the reaction preventing layer 34.
  • the formation of the catalytic metal layer 36 includes various film forming methods for forming a metal film or a metal powder layer, a so-called coordination compound in which metal atoms are surrounded by atomic groups called ligands, or metal ions. It is possible to use a catalyst metal salt solution containing, a coating method of a gaseous, liquid or solid organometallic compound at room temperature and normal pressure. Ar sputtering, electron beam evaporation, dip coating, spin coating, and the like can be used, but it is important that the catalytic metal layer 36 with a thickness of nanometer order can be formed uniformly.
  • the surface of the catalyst metal layer is 80 ° C. to 300 ° C., preferably 80 ° C. to 300 ° C. in an oxidizing gas atmosphere.
  • An oxidation treatment is performed by heating in a temperature range below, and an aggregation suppression layer 38 made of a metal oxide is formed on the surface of the catalytic metal layer 36, which is used for producing brush-like CNTs as a catalyst body for producing brush-like carbon nanostructures.
  • the catalyst body 1 (hereinafter also referred to as “catalyst body 1”) is completed.
  • the heating temperature in the oxidation treatment is more preferably about 150 ° C., and the aggregation suppressing layer 38 having a suitable thickness is formed by heating for about 10 minutes.
  • the catalyst layer 40 of the catalyst body 1 is a precursor of a later-described catalyst particle layer composed of the catalyst metal layer 36 and the aggregation suppressing layer 38, and is formed into particles by heat treatment during the synthesis of CNTs.
  • the coating film heating treatment for drying the solvent of the solution needs to be performed in a temperature range of 50 ° C. to 300 ° C. in an inert gas atmosphere and / or in a vacuum state.
  • the temperature is 80 ° C. to 300 ° C. It is necessary to perform oxidation treatment by heating to a temperature range. In the case of a catalyst layer obtained by a wet process, it is more preferable that the oxidation treatment is performed in a temperature range of 600 ° C to 700 ° C.
  • the catalyst layer 40 made of the precursor as shown in FIG. 1D is also defined as the catalyst body 1 for producing brush-like CNTs according to the present invention.
  • the oxidizing gas water, oxygen, acetone, alcohol, DMF (dimethylformamide), CO 2 , CO, O 3, H 2 O 2 or the like is used.
  • FIG. 2 is a schematic view showing a process of manufacturing the brush-like CNT 48 from the catalyst body 1 according to the present invention.
  • the catalyst layer 40 is made into particles, and as shown in (2B), catalyst particles 42 made of the catalyst metal and its oxide are formed.
  • a particle layer 44 is formed.
  • the particle formation temperature is about 800 ° C.
  • the catalyst layer is set to a particle size suitable for the growth of CNTs while being uniformly formed into particles. This is considered to be due to the fact that the aggregation suppression layer 38 prevents fluidization of the catalyst metal layer 36 and aggregation of metal particles in the heat treatment, and suppresses the enlargement of the metal catalyst particles 42.
  • the aggregation suppressing layer in (2A) is preferably formed from iron oxide.
  • the oxygen of the iron oxide is the catalyst metal. It diffuses into the layer and granulates simultaneously or afterwards. Further, even when heat treatment is performed at a high temperature rise of 10 ° C./sec or more, enlargement of the metal-based catalyst particles 42 is suppressed, and a uniform catalyst particle layer 44 suitable for CNT growth is formed. A suitable catalyst particle layer 44 can be formed even at a high temperature rise of about / sec.
  • CNT 46 grows by heating the catalyst body 1 while supplying the raw material gas from the metal-based catalyst particles 42, and brush-like CNTs 48 are formed.
  • FIG. 3 is a schematic view schematically showing CNTs 46 grown from the metal-based catalyst particles 42 according to the present invention.
  • the metal-based catalyst particles 42 are iron-based catalyst particles mainly composed of iron and contain an iron oxide component.
  • the metal-based catalyst particles 42 that can form the CNTs 46 are not necessarily spherical as shown in the figure, and may have a particle size of 0.5 nm to 80 nm.
  • acetylene gas is supplied as a source gas, it has been found that the synthesis reaction of CNT 46 has growth by a two-stage reaction of initial rapid growth and slow growth while generating amorphous carbon.
  • the source gas is acetylene will be described, the same mechanism is used for other source gases.
  • the initial rapid reaction is a reaction in which the reaction itself based on the following formulas 1 and 2 on the surface of the metal catalyst particles 42 is rate-limiting.
  • Fe 3 O 4 + C 2 H 2 ⁇ FeO + 2FeC + H 2 O + O 2 (Formula 2)
  • the rapid first-stage growth is stopped when the amount of oxygen retained by the catalyst is consumed by the reaction, and the catalyst surface is usually covered with excess amorphous carbon supplied from the raw material gas. It becomes difficult to contact the raw material gas and eventually the reaction is stopped.
  • the oxygen held by the metal-based catalyst particles 42 is approximately the same, the length of the CNTs 46 is almost the same, so that the reproducibility and the length of the CNTs 46 depend on the amount of oxygen retained in the initial catalyst. Can be understood as determined.
  • a multilayer layer 46a constituting the wall of the CNT 46 is formed on the surface of the carbide.
  • CNTs are formed by the amorphous carbon produced by the reaction between the metal catalyst particles 46 and the raw material gas pushing out the multilayer layer 46a.
  • the arrows in the figure indicate the direction of carbon diffusion.
  • a reaction preventing layer is formed, and the affinity is extremely reduced.
  • the carbon layer may extend vertically to some extent, the catalyst may float against the force pushed out by the diffusion of carbon, and may exist at an intermediate point in the length direction of the CNT 46.
  • the carbon component generated by the reaction of Formula 3 and Formula 4 is supplied by burning and removing oxygen and moisture contained in the carrier gas and / or raw material gas on the catalyst surface by the metal catalyst particles, Generation is possible.
  • the formation of the catalytic metal layer 36 includes a complex so-called coordination compound in which metal atoms are surrounded by atomic groups called ligands, in addition to film forming methods such as physical vapor deposition and chemical vapor deposition.
  • a catalyst metal salt solution containing metal ions or the like is used as a catalyst layer, a method of applying a solution containing a catalyst metal by a spin coating method or a dip coating method can be used.
  • FIG. 4 is a production process diagram in which a catalyst metal layer is formed by the method of applying a catalyst metal salt solution according to the present invention, and brush-like CNTs are produced from the obtained catalyst body.
  • the formation of the catalyst metal layer used for CNT production is prepared by preparing a catalyst metal salt solution in which the catalyst metal salt is dispersed or dissolved in a solvent having good wettability with the reaction preventing layer (catalyst metal salt solution adjustment step S1), The catalyst metal salt solution is applied onto the reaction preventing layer (catalyst metal salt solution application treatment step S2).
  • the pre-oxidation treatment is a process in which metal ions are converted into metal oxide mainly by the reaction formulas shown in (Expression 7) and (Expression 8).
  • Fe 2- + 1 / 2O 2 ⁇ FeO (Formula 7)
  • 3FeO + 1 / 2O 2 ⁇ Fe 3 O 4 (Formula 8)
  • the aggregation preventing layer 38 is formed on the surface of the catalytic metal layer 36 by pre-oxidation treatment.
  • the catalyst layer 40 is a so-called coordination compound in which a metal atom is surrounded by an atomic group called a ligand or a catalyst metal salt solution containing a metal ion, the solution containing the catalyst metal is spun.
  • a coating method such as a coating method or a dip coating method, a metal catalyst layer is formed from the state of metal ions on the substrate.
  • a metal catalyst layer that is thinner than a metal catalyst layer (minimum thickness 4 nm) that is generally carefully industrially deposited by Ar sputtering such as physical vapor deposition or chemical vapor deposition, or electron beam vapor deposition.
  • Ar sputtering such as physical vapor deposition or chemical vapor deposition, or electron beam vapor deposition.
  • the metal catalyst layer is thin, in the pre-oxidation treatment, the aggregation suppression layer 38 is heated to 80 ° C./300° C. in a high temperature range of 80 ° C. to 300 ° C. in an atmosphere containing an oxidizing component such as air. It has been found that it is necessary to form an agglomeration suppression layer 38 that can withstand a high temperature rise of about sec. Thereafter, as shown in FIG. 2 and FIG.
  • the catalyst body on which the catalyst particle layer 44 is formed is introduced into a brush-like CNT manufacturing apparatus described later and grown by thermal CVD (CNT growth processing step: S5).
  • CNT growth processing step: S5 CNT growth processing step: S5
  • spin coating is used as a coating method when the catalyst layer is a so-called coordination compound in which a metal atom is surrounded by an atomic group called a ligand or a catalytic metal salt solution containing a metal ion in the coating treatment step S2. Method or dip coating method is used.
  • FIG. 5 is a chart showing the relationship between the passage of time and the temperature change in the reaction chamber in the production process of the brush-like CNTs according to the present invention.
  • a catalyst body for producing brush-like CNTs which is heated at a heating temperature of 80 ° C. to 300 ° C., preferably about 150 ° C. by pre-treatment (pre-oxidation treatment), and on which the aggregation suppression layer is formed is introduced Is done.
  • the heating step P2 is heated by a rapid temperature increase of more than 10 ° C. / sec of the initial temperature T 1h to the growth temperature T h2 of CNT.
  • the growth temperature Th2 is about 800 ° C.
  • the brush-like CNT catalyst body is maintained at the reaction temperature and brought into a complete thermal equilibrium state, and then the raw material gas is supplied in the reaction step P4. .
  • Supply time t 2 of the raw material gas is about several 10 seconds to several minutes.
  • an inert gas such as Ar gas
  • purge time t 3 is about several 10 seconds to several minutes.
  • the temperature in the reaction chamber is lowered, and the substrate on which the brush-like CNTs are synthesized is taken out. Fast heating, it is possible to shorten the time t 0 until the next term.
  • FIG. 6 is a schematic diagram of the configuration of the brush-like CNT manufacturing apparatus according to the present invention.
  • This brush-like CNT manufacturing apparatus is a manufacturing apparatus that synthesizes brush-like CNTs 48 by a CVD method.
  • the reaction chamber 4 is heated by the reaction heater 2, and the catalyst body 1 is disposed in the reaction chamber 4.
  • the catalyst particle layer of the catalyst body 1 is formed from iron-based catalyst particles containing iron element and iron oxide, and a brush-like CNT manufacturing apparatus will be described in detail below.
  • the source gas various organic gases suitable for the production of CNTs such as hydrocarbons, sulfur-containing organic gases, and phosphorus-containing organic gases can be selected as described above.
  • acetylene gas is inexpensive and easily obtained. Both have triple bonds, are highly reactive with the iron-based catalyst particles, and are suitable raw material gases when the brush-like CNTs 48 are grown on the iron-based catalyst particles.
  • a gas discharge line 3 is connected to one end of the reaction chamber 4, and a flow path connected to the gas discharge line 3 is connected to a carrier gas container (not shown) via open / close valves 5 and 7. ing.
  • a carrier gas a mixed gas of helium He and argon Ar is used.
  • an inert gas such as neon, N 2 , CO 2, krypton, xenon, or a mixed gas thereof is used as the carrier gas.
  • the carrier gas is a gas that carries the raw material gas, and the raw material gas is consumed by the reaction, whereas the carrier gas has no reaction and is not consumed.
  • a source gas is supplied from a source gas container (not shown) to the reaction chamber 4 through a source gas inlet 9 provided at the other end of the reaction chamber 4, and the source gas in the source gas container is predetermined by a regulator (not shown).
  • the pressure is reduced to the pressure.
  • the low-pressure raw material gas is adjusted to a predetermined flow rate by a raw material gas flow controller 8 comprising a mass flow controller (MFC).
  • MFC mass flow controller
  • the raw material gas flow rate controller 8 is provided in an inflow passage communicating with the raw material gas inflow passage 9, and the raw material gas is supplied through the electromagnetic three-way valves 10 and 12 and the opening / closing valve 11.
  • the carrier gas is supplied from the carrier gas container, and the carrier gas is supplied so as to merge with the raw material gas inflow passage 9 through two channels provided with the gas flow rate controllers 22 and 23 as described later. .
  • the brush-like CNT manufacturing apparatus manufactures brush-like CNTs 48 in which the catalyst body 1 is disposed in a reaction chamber 4, and carbon nanostructures are grown by the catalyst body 1 while supplying a raw material gas and flowing it through the reaction chamber 4. Before supplying the raw material gas and circulating it to the reaction chamber 4, an oxidizing gas is supplied to the reaction chamber 4 together with the carrier gas to convert the catalyst body 1 into magnetite. Further, also in the growth process of the brush-like CNTs by the catalyst body 1, the source gas and the oxidizing gas are circulated through the reaction chamber 4.
  • the oxidizing gas contains 0.05 ppm to 3% moisture and 0.01 ppb to 1% oxygen.
  • An oxygen cylinder (not shown) filled to a predetermined concentration by a gravimetric method is adjusted to a predetermined flow rate by an oxygen flow rate controller 13 having a mass flow controller (MFC).
  • the oxygen flow rate controller 13 is provided in the inflow path communicating with the source gas inflow path 9, and oxygen is supplied to the reaction chamber 4 through the electromagnetic three-way valve 14 and the opening / closing valve 11.
  • An oxygen analyzer 21 is provided in the carrier gas introduction path in front of the opening / closing valve 11, and oxygen from the oxygen cylinder is also introduced into the oxygen analyzer 21, so that an appropriate concentration of oxygen is introduced into the reaction chamber 4. It is monitored to be supplied.
  • the water addition device 15 is composed of a water container equipped with a heater, and a purified carrier gas such as He or Ar is introduced into the warmed water of the water addition device 15 via the gas flow rate controller 16 to mix the flow rate.
  • a mixed gas of moisture and carrier gas to which moisture has been added by the method is supplied to the reaction chamber 4 via the electromagnetic three-way valve 18 and the open / close valve 11.
  • the carrier gases are also joined and mixed via the gas flow controller 20 on the outlet side of the moisture addition device 15.
  • a moisture analyzer 17 is provided in a monitoring bypass path 19 provided in the mixed gas introduction path of moisture and carrier gas, and monitoring is performed so that moisture of an appropriate concentration is supplied to the reaction chamber 4 by the moisture analyzer 17. is doing.
  • the carrier gas includes inert gases such as He, neon, argon, N 2 , CO 2, krypton, and xenon.
  • He and Ar are particularly inexpensive and easily available. it can.
  • the G2 grade contains oxygen ( ⁇ 1 ppm), moisture ( ⁇ 2.6 ppm), and the G1 grade contains oxygen ( ⁇ 0.05 ppm).
  • oxygen scavenger generally include Pd, Ni, Mn, Zr, and Ti metals
  • adsorbent include a purification method using synthetic zeolite, alumina, silica gel, and the like.
  • the electromagnetic three-way valve 10 is controlled to a cut-off state and a supply state by the action of an automatic valve controller (not shown). That is, when the source gas is shut off, the source gas is exhausted to the exhaust side, and when the source gas is supplied, the source gas is supplied to the injection side, and the source gas is mixed with the carrier gas at the junction that reaches the opening / closing valve 11. Is done.
  • an automatic valve controller not shown
  • the switching is performed by electromagnetic action, the switching is performed instantaneously without pressure fluctuations, and there is no slow rise of the source gas, and the source gas at a predetermined flow rate is supplied at once. Even when the raw material gas is switched from the supply state to the shut-off state, the flow rate of the raw material gas can be instantaneously switched to zero without electromagnetic pressure fluctuation by the electromagnetic action of the automatic valve controller, and there is no slow falling of the raw material gas.
  • the supply and shutoff of the raw material gas to the reaction chamber 4 can be instantaneously performed, and there is no fluctuation in the flow rate in the changing process. Therefore, if the total flow rate is constant, the gas pressure inside the reaction chamber 4 is constant. Since the source gas is decomposed while the total pressure (gas pressure) is constant, pressure fluctuation does not occur in the reaction chamber 4 and the growth of the brush-like CNT 48 is promoted.
  • the carrier gas and the raw material gas are mixed at the junction, and then supplied to the reaction chamber 4 as a mixed flow from a gas supply nozzle (not shown) provided at the tip of the raw material gas inflow passage 9.
  • the reaction chamber 4 is heated to a temperature range where carbon nanostructures are most easily generated, and the raw material gas is thermally decomposed in the vicinity of the catalyst body 1, and brush-like CNTs 48 grow from the decomposition product on the surface of the catalyst body 1.
  • a thermal decomposition method is used to decompose the raw material gas.
  • a laser beam decomposition method, an electron beam decomposition method, an ion beam decomposition method, a plasma decomposition method, and other decomposition methods can be used.
  • Kabrush-like CNTs 48 are formed on the surface of the catalyst body 1 from these decomposition products.
  • brush-like CNTs are synthesized from a part of the raw material gas, and the unreacted raw material gas that has not contributed to the reaction is purged from the gas discharge line 3 together with the carrier gas.
  • Example 1 In the catalyst body for producing brush-like CNTs of Example 1, a silicon oxide layer was formed as the reaction-preventing layer on the Si (001) surface of a disk-like silicon substrate (diameter 6 inches) by oxidation treatment. SiO 2 ) substrate. The thickness of the silicon oxide layer is set to about 10 nm. On the surface of the SiO 2 substrate, a pure iron film having a thickness of 4 nm is formed as a catalytic metal layer by electron beam evaporation, and is heated at 150 ° C. for 10 minutes in an oxygen atmosphere as a pretreatment before CNT synthesis. Pre-oxidation treatment is performed.
  • an aggregation suppressing layer made of iron oxide is formed, and then heated to about 800 ° C., which is the reaction temperature at the time of CNT synthesis, at a high temperature increase of 80 ° C./sec as a pre-stage of CVD.
  • the catalyst layer formed from the catalyst metal layer and the aggregation suppressing layer is made into particles, and a catalyst particle layer of iron-based catalyst particles is formed, and the catalyst body for producing brush-like CNTs of Example 1 is obtained.
  • AFM measurement of the surface of the catalyst body for producing brush-like CNTs is performed, and an AFM image obtained from the measurement is shown.
  • AFM Atomic Force Microscope
  • AFM is a method of evaluating the sample surface shape by tracing the sample surface using a cantilever probe with a sharp tip and measuring the displacement of the cantilever in the vertical direction. AFM is commonly used to measure the shape of the microparticles on the substrate.
  • DFM Dynamic Force Microscope
  • tapping mode is performed, and the probe is moved up and down so that the surface of the sample jumps off the surface of the sample. Measuring.
  • the AFM measurement was performed using Seiko Instruments' model SPI-3800N and using the DFM mode. The scanning frequency was set to 1 Hz, measurement was performed in the atmosphere, and a CNT probe was used as the cantilever probe.
  • FIG. 7 is an AFM image of the surface of the catalyst body for producing brush-like CNTs of Example 1 and a comparative example.
  • (7A) shows an AFM image of Example 1
  • (7B) shows, as Comparative Example 1, a pure iron film having a thickness of 4 nm on the Si (001) surface of a silicon substrate on which no reaction preventing layer is formed.
  • An AFM image of the surface of a catalyst body for producing brush-like CNTs on which a catalyst metal layer is formed and heated at a high speed of 80 ° C./sec without performing a prior oxidation treatment to form a catalyst particle layer is shown.
  • the average particle diameter D in Example 1 (7A) was 12 nm, and the range of individual particles was in the range of 0.5 nm to 80 nm. Furthermore, in (7C), as Comparative Example 2, a reaction preventing layer (SiO 2 layer: 10 nm) was formed on the Si (001) surface of the silicon substrate, and a catalytic metal layer (pure iron film: 4 nm) was formed. An AFM image of the surface of a catalyst body for producing brush-like CNTs that is heated at a high speed of 80 ° C./sec without performing pre-oxidation treatment and has a catalyst particle layer formed thereon is shown.
  • (7D) shows, as Comparative Example 3, an AFM image of the surface of the catalyst body for producing brush-like CNTs when pre-oxidation is performed by the production method of Comparative Example 1.
  • a silicon oxide (SiO 2 ) layer as a reaction preventing layer
  • Table 1 shows manufacturing conditions of Examples and Comparative Examples.
  • ⁇ Reaction preventing layer the effect of the SiO 2 layer>
  • Comparative Example 1 of (7B) the density of the iron-based catalyst particles is low, the size is enlarged, the particle size exceeds 80 nm, and many enlarged particles that cannot grow CNT are formed.
  • Comparative Example 2 of (7C) the formation of the SiO 2 layer as the reaction preventing layer increases the particle density of the iron-based catalyst particles and decreases the average particle size. This difference is due to the fact that iron silicide is formed at the interface with the silicon substrate, the contact area with the substrate is large, and a large number of enlarged hemispherical silicidation particles are generated.
  • Example 1 of (7A) and Comparative Example 3 of (7D) after a pure iron film is formed as a catalytic metal layer, a prior oxidation treatment is performed by heating at 150 ° C. for 10 minutes. An aggregation suppressing layer made of iron oxide is formed before the temperature raising process that is performed and heated to the reaction temperature during CNT synthesis.
  • (7A) and (7C) and (7B) and (7D) are compared, enlargement of the iron-based catalyst particles is remarkably suppressed by performing the prior oxidation treatment.
  • Comparative Example 2 of (7C) uses a substrate (SiO 2 substrate) on which an SiO 2 layer is formed as an aggregation suppression layer as in Example 1, but the particle diameter of the iron-based catalyst particles is 50 It is difficult to produce a high-density brush-like CNT because it is about ⁇ 100 nm and contains many catalyst particles that are not suitable for CNT growth. This is considered to be due to the fact that the aggregation suppression layer suppresses fluidization of the iron film and aggregation of the metal particles in the heat treatment, and suppresses the enlargement of the iron-based catalyst particles.
  • the catalyst particle layer can be densified and homogenized by the synergistic effect of the formation of the aggregation suppressing layer by the pre-oxidation treatment and the reaction preventing layer. It can be seen that the enlargement of is greatly suppressed.
  • Example 2 In the catalyst body for producing brush-like CNTs of Example 2, as in Example 1, silicon oxide having a thickness of 10 nm was used as the reaction preventing layer on the Si (001) surface of a disk-like silicon substrate (diameter 6 inches). A pure iron film having a thickness of 4 nm is formed as a catalyst metal layer by an electron beam evaporation method.
  • the prior oxidation treatment is not performed, and the formation of the aggregation suppressing layer and the particle formation are performed almost simultaneously during the temperature rising process.
  • the rate of temperature increase in the preceding stage of CVD is 0.3 ° C./sec
  • Example 2 is a catalyst body for producing brush-like CNTs for growing brush-like CNTs at 700 ° C.
  • FIG. 8 shows the surface of the catalyst body for producing brush-like CNTs of Example 2 and the AFM image of Comparative Example 2.
  • the temperature rising rate and the heating temperature are changed. I am letting.
  • (8A) is an AMF image of Example 2 heated to 700 ° C. at a rate of temperature increase of 0.3 ° C./sec in the preceding stage of CVD, and Comparative Example 2 shown in (8B)
  • the catalyst body for producing brush-like CNTs when the temperature raising rate is set to 80 ° C./sec and heated to 800 ° C.
  • Example 2 and Comparative Example 2 since the reaction preventing layer made of SiO 2 is formed with a thickness of 10 nm, the catalyst particle size are both uniformly aligned.
  • the iron-based catalyst particles are uniformly formed with a particle size of 20 to 30 nm.
  • the particle diameter of the iron-based catalyst particles is about 50 to 100 nm, and a large number of catalyst particles that are not suitable for CNT growth are contained, so that high-density brush-like CNTs are produced.
  • the temperature rising rate is preferably 0.3 ° C./sec or less. In other words, when the rate of temperature increase is set to 80 ° C./sec or higher, as in Example 1 shown in (7A) of FIG.
  • a catalyst body for producing brush-like CNTs can be produced, and the production efficiency can be significantly improved.
  • FIG. 9 is a particle size distribution diagram of iron-based catalyst particles produced by the same method as in Example 2.
  • the plot (square mark: ⁇ ) shows the number (Number) with respect to the particle size d (Particle diameter) estimated from the AFM image, and the particle size distribution indicated by the solid line is obtained by fitting a distribution function.
  • the average particle diameter D is about 34 nm, and the half width ⁇ D of the distribution function is 23 nm. That is, the ratio ⁇ D / D of the half-value width ⁇ D to the average particle diameter D is 0.68. It has been confirmed that rope-like CNTs can be produced from the brush-like CNTs produced using the catalyst body for producing brush-like CNTs having the particle size distribution shown in the figure.
  • the homogenization is improved by forming the aggregation suppressing layer by the prior oxidation treatment, and the ratio ⁇ D / D can be further reduced.
  • the more uniform the layer the more uniform brush-like CNTs can be produced.
  • FIG. 10 is an AFM image of Comparative Example 1 and Comparative Examples 3 to 5 shown in order to compare the effect of the pre-oxidation treatment and the treatment temperature.
  • Comparative Example 1 of (10A) Comparative Example 4 of (10B), Comparative Example 3 of (10C), and Comparative Example 5 of (10D)
  • a catalytic metal layer made of a pure iron film is formed on a silicon substrate.
  • the effect of the pre-oxidation treatment is more clarified.
  • the heating rate in the heating process in which the catalyst metal layer is granulated is 80 ° C./sec, and is heated to 800 ° C.
  • Comparative Example 1 of (10A) as described above, the prior oxidation treatment is not performed, and the enlargement and non-uniformity of the iron-based catalyst particles are remarkable.
  • Comparative Example 4 of (10B) an oxidation treatment was performed at 80 ° C. for 10 minutes in an oxidizing gas atmosphere to form an aggregation suppression layer, and then the temperature was raised to 800 ° C. corresponding to the reaction temperature of the CNTs. Is particleized.
  • Comparative Example 3 of (10C) the pre-oxidation treatment is performed at 150 ° C. for 10 minutes
  • Comparative Example 5 of (10D) the pre-oxidation treatment is performed at 300 ° C. for 10 minutes.
  • Comparative Example 4 of (10B) the effect of the pre-oxidation treatment is not sufficient, the catalyst particles are enlarged, and at least the heating temperature in the oxidation treatment is preferably set higher than 80 ° C.
  • Comparative Example 3 of (10C) the iron-based catalyst particles are deformed in some places by pre-oxidation treatment at 150 ° C. for 10 minutes, but the particle size is smaller than that of (10B), and the particle size of 30 to 50 nm is small. Observed.
  • Comparative Example 5 of (10D) the shape changed to iron-based catalyst particles, and an angular lump was observed. This is considered to be because the formation of catalyst particles does not occur well if the proportion of the oxidized aggregation suppressing layer is too large compared to the catalytic metal layer.
  • Example 3 is a brush-like CNT produced using the catalyst body for producing brush-like CNTs of Example 1, using acetylene as a raw material gas and setting the reaction temperature to 800 ° C. by a CVD method, and brush-like CNTs Is manufactured. Further, He gas is used as the carrier gas.
  • FIG. 11 is a scanning electron microscope (SEM) image obtained by observing the brush-like CNTs of Example 3 and Comparative Example 6.
  • the brush-like CNT of Comparative Example 6 is a brush-like CNT produced using the catalyst body of Comparative Example 2 (see (8B) in FIG. 8) under the same conditions.
  • the brush-like CNT of Comparative Example 6 had a low CNT density, an average brush-like CNT height of 40 ⁇ m, and a bulk density of 16.0 mg / CC. That is, when the pre-oxidation treatment is performed at 150 ° C. for 10 minutes, the result is that the bulk density of the CNTs is remarkably increased. From the brush-like CNTs of Example 3, rope-like CNTs are produced. Has been confirmed.
  • FIG. 12 is an SEM image obtained by observing the brush-like CNTs of Comparative Examples 7 to 9.
  • acetylene is used as the source gas, and the reaction temperature is set to 800 ° C.
  • the brush-like CNT of Comparative Example 7 shown in (12A) is manufactured using the catalyst body for producing brush-like CNT of Comparative Example 1 (see (7B) in FIG. 7) (no pre-oxidation treatment, no reaction prevention layer). Brush-like CNT.
  • the average height of the brush-like CNTs is 64 ⁇ m, but because of the low density, the bulk density of the CNTs is 10.8 mg / CC.
  • the brush-like CNT of Comparative Example 8 shown in (12B) is a brush-like CNT produced using the brush-like CNT production catalyst body of Comparative Example 4 (see (10B) of FIG. 10), and the height of the CNT However, the bulk density is as low as 8.3 mg / CC. As described above, the reaction preventing layer was not formed, and further, the formation of the aggregation suppressing layer was insufficient because the heating temperature in the pre-oxidation treatment was as low as 80 ° C., and the catalyst particle layer This is due to the low density of.
  • the brush-like CNT of Comparative Example 9 shown in (12C) is a brush-like CNT produced using the brush-like CNT production catalyst body of Comparative Example 3 (see (10B) in FIG.
  • FIG. 13 shows the relationship between the temperature rising rate in the temperature rising process in which the catalyst layer according to the present invention is granulated and the average particle diameter D of the metal-based catalyst particles to be formed.
  • the metal catalyst particles are iron catalyst particles.
  • Line A is a pre-oxidation treatment in which the catalyst metal layer is heated to 150 ° C. in an oxidizing gas atmosphere and subjected to an oxidation treatment for 10 minutes (pre-oxidation treatment: 150 ° C. ⁇ 10 min) to form an aggregation suppression layer. After that, the relationship between the heating rate and the average particle diameter D when the catalyst particle layer is formed in the heating process is shown.
  • Line B represents the case where the catalytic metal layer was pre-oxidized at 80 ° C.
  • Line C was not pre-oxidized and the metal catalyst particles were formed in the temperature rising process.
  • the relationship between the heating rate and the average particle size C is shown. Lines A to C are estimated from actually measured values plotted in the graph. Further, the region G where the gradient is applied indicates that CNTs are hardly manufactured gradually.
  • the average particle diameter D is 30 nm or less even when the inclination is relatively small and the temperature rising rate increases to reach 80 ° C./sec.
  • Metal-based catalyst particles are formed to constitute a catalyst metal layer.
  • the inclination becomes larger than that of the line A, and when the temperature rising rate exceeds 80 ° C./sec, the average particle diameter D is a region where CNT is difficult to be manufactured. It overlaps with G.
  • the metal catalyst particles have an average particle diameter D suitable for the growth of CNTs at least up to about 10 ° C./sec. In the above, it is preferable to perform a pre-oxidation process.
  • the metal-based catalyst particle layer is made of iron or iron oxide, it is formed from Fe 2 O 3 composite particles containing at least Fe 2 O 3 .
  • the Fe 2 O 3 composite particles contain Fe 2 O 3 together with Fe 2 O 3 .
  • the structure has the structure of the catalyst body shown in FIG.
  • Example 3 shows the production conditions and characteristics of the brush-like CNTs of Examples 4 to 7 manufactured using a catalyst body in which the reaction preventing layer is formed of a silicon nitride film.
  • the catalyst bodies used in the manufacture of Example 4 and Example 5 are Si substrates (silicon wafers) cut into 1 cm ⁇ 1 cm and 3 cm ⁇ 3 cm, respectively, as substrates.
  • a silicon nitride layer (Si X N Y ) having a thickness of about 11.5 nm was formed on the silicon oxide film by using a sputtering apparatus (RFS-200 manufactured by ULVAC). Layer).
  • the silicon nitride layer is made of Si 3 N 4, but the silicon composition ratio X and the nitrogen composition ratio Y vary depending on the fabrication conditions. Therefore, the reaction preventing layer is composed of a SiO 2 layer and a Si 3 N 4 layer formed thereon.
  • a pure iron film having a thickness of about 4 nm was formed as a catalytic metal layer on the surface of the reaction preventing layer by an electron beam evaporation method.
  • the brush-like carbon nanostructure used in the manufacture of Examples 4 and 5 is formed by heating at 150 ° C. for 10 minutes to form an oxide film layer that functions as an aggregation suppression layer on the surface of the pure iron film.
  • the product manufacturing catalyst body is completed.
  • Example 4 it was confirmed that brush-like CNTs having an average CNT height of 119 ⁇ m and a bulk density of 49.1 mg / cc (mg / cm 3 ) were formed on the substrate composed of the base and the reaction preventing layer. .
  • Example 5 even if the average height was 119 ⁇ m, rope-like CNTs could be stably drawn out if the bulk density was about 50 mg / cc (mg / cm 3 ).
  • the average CNT height on the substrate was 167 ⁇ m, and the bulk density was 27.6 mg / cc (mg / cm 3 ).
  • the bulk density is small and does not reach about 50 mg / cc (mg / cm 3 ), so the yield of rope-like CNTs is slightly reduced, but rope-like CNTs can be produced from Example 5. It was confirmed.
  • a silicon nitride layer (Si 3 N 4 layer) as a reaction preventing layer on a 6-inch diameter Si substrate (silicon wafer) serving as a substrate. Is formed.
  • the Si 3 N 4 layer is formed by a CVD method using an apparatus manufactured by E & M, and the film thickness is set to about 310 nm.
  • a pure iron film having a thickness of 4 nm is formed as a catalytic metal layer by an electron beam evaporation method.
  • the oxide film layer is formed as an aggregation suppression layer on the surface of the pure iron film by heating at 150 ° C.
  • Example 6 even if the CNT average height on the substrate is 182 ⁇ m, the bulk density is 30.1 mg / cc (mg / cm 3 ), and the bulk density is about 30 mg / cc (mg / cm 3 ). If the average height is about 180 ⁇ m, it has been confirmed that rope-like CNTs can be pulled out stably.
  • Example 7 the average CNT height on the substrate was 119 ⁇ m, the bulk density was 49.1 mg / cc (mg / cm 3 ), and the bulk density was 50 mg / cc (mg / cm 3 ) even if the average height was 119 ⁇ m. If it is about cm 3 ), it has been confirmed that rope-like CNTs can be pulled out stably.
  • FIG. 14 is an explanatory diagram for considering the conditions under which rope-like CNTs can be produced from the relationship between the bulk density and average height of brush-like CNTs.
  • the average CNT height ( ⁇ m) against the bulk density (mg / cc) of Examples 4 to 7 is plotted.
  • a rope-like CNT is manufactured by pulling out an aggregate of CNTs from a brush-like CNT, a suitable region is becoming clear regarding the relationship between the bulk density and the average height. From this research by the present inventors, it is considered that this region is in the range of the diagonal line surrounded by the one-dot chain line including Examples 4 to 7 or includes these ranges in FIG.
  • Table 4 shows evaluations of brush-like CNTs produced by the catalyst body according to the present invention obtained using a catalytic metal salt solution in which iron nitrate or iron nitrate nonahydrate is dissolved in a solvent. As shown. That is, Table 4 shows a catalyst for producing brush-like CNTs obtained using a mixed solution of ethanol and ⁇ -terpineol or a solution (solution concentration 0.6% by weight) obtained by dissolving a catalyst metal salt in a solvent composed of ethanol. It is evaluated based on whether or not brush-like CNTs can be produced by the medium. In the table, when the brush-like CNT grows, a circle is attached.
  • the solvent preferably has a property rich in wettability with the reaction preventing layer, and the particle diameter of the catalyst particles can be reduced by forming a thinner catalyst metal layer.
  • various iron complexes etc. can be used as a metal salt, for example, an acetylacetonato iron complex, a DMF (dimethylformamide) iron complex, a halogeno iron complex, a cyano iron complex etc. can be used.
  • FIG. 15 shows the conditions of oriented CNTs that can produce rope-like CNTs from the relationship between CNT bulk density and catalyst particle diameter.
  • Plot E shows the catalyst body for producing brush-like CNTs of Example 1
  • region F shows the optimum range in which rope-like CNTs can be produced.
  • rope-like CNT can be produced easily, so that a bulk density increases.
  • the conditions for producing the rope-like CNTs are that the CNT bulk density is 20 mg / cm 3, preferably about 40 mg / cm 3 or more, and the average particle diameter D of the metal-based catalyst particles is preferably in the range of about 20 nm to 30 nm.
  • the catalyst body for producing brush-like carbon nanostructures according to the present invention it is possible to produce CNTs with high efficiency, and at the same time, it is indispensable for producing so-called rope-like CNTs, which are aggregates of CNTs.
  • Brush-like CNTs of brush-like carbon nanostructures having a long CNT length can be produced. That is, high-density and long highly oriented CNTs can be produced.
  • the rope-like CNTs produced using the brush-like CNTs according to the present invention are ultralight and high-strength fibers, and can be used as carbon wires and various carbon materials.

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Abstract

L'invention porte sur une nanostructure de carbone en forme de goupillon hautement dense qui peut être utilisée pour fabriquer un produit composé de nanotubes de carbone (CNT) rassemblés ensemble, par exemple, des CNT sous forme de cordon, qui est produite à un rendement élevé. L'invention porte également sur un matériau catalyseur qui permet à la nanostructure de carbone en forme de goupillon d'être fabriquée. Le matériau catalyseur (1) pour fabriquer une nanostructure de carbone en forme de goupillon comprend une base (32), une couche empêchant une réaction (34) formée sur une surface de la base et une couche de catalyseur (40) superposée sur la couche empêchant une réaction (34). La couche de catalyseur (40) est composée d'une couche de métal catalytique (36) superposée sur la couche empêchant une réaction (34) et d'une couche empêchant l'agglomération (38) formée sur la surface de la couche de métal catalytique (36). De plus, l'invention porte sur : un procédé pour la fabrication du matériau catalyseur ; une nanostructure de carbone en forme de goupillon fabriquée avec le matériau catalyseur ; et un procédé de fabrication de la nanostructure de carbone en forme de goupillon.
PCT/JP2008/066576 2007-03-14 2008-09-12 Matériau catalyseur pour produire une nanostructure de carbone en forme de goupillon, procédé de fabrication du matériau catalyseur, nanostructure de carbone en forme de goupillon et son procédé de fabrication Ceased WO2009113195A1 (fr)

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PCT/JP2008/054672 WO2008111653A1 (fr) 2007-03-14 2008-03-13 Corps catalyseur permettant la production d'une nanostructure de carbone en forme de brosse, procédé de production du corps catalyseur, nanostructure de carbone en forme de brosse et son procédé de production
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JP2011137230A (ja) * 2009-12-29 2011-07-14 Univ Of Tokyo 凝集現象による自己組織化されたナノ構造薄膜の製造方法
JP2014231446A (ja) * 2013-05-29 2014-12-11 日立造船株式会社 カーボンナノチューブの製造方法
JP2015212084A (ja) * 2015-05-07 2015-11-26 ニッタ株式会社 Ｆｅ微粒子保持構造、ＣＮＴ、ＣＮＴ生成用触媒、ＣＮＴ製造方法およびＦｅ微粒子保持構造の製造方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011137230A (ja) * 2009-12-29 2011-07-14 Univ Of Tokyo 凝集現象による自己組織化されたナノ構造薄膜の製造方法
JP2014231446A (ja) * 2013-05-29 2014-12-11 日立造船株式会社 カーボンナノチューブの製造方法
JP2015212084A (ja) * 2015-05-07 2015-11-26 ニッタ株式会社 Ｆｅ微粒子保持構造、ＣＮＴ、ＣＮＴ生成用触媒、ＣＮＴ製造方法およびＦｅ微粒子保持構造の製造方法

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