WO2014126296A1 - Procédé de formation de particules contenant du métal au moyen de matériau de carbone poreux - Google Patents

Procédé de formation de particules contenant du métal au moyen de matériau de carbone poreux Download PDF

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WO2014126296A1
WO2014126296A1 PCT/KR2013/003527 KR2013003527W WO2014126296A1 WO 2014126296 A1 WO2014126296 A1 WO 2014126296A1 KR 2013003527 W KR2013003527 W KR 2013003527W WO 2014126296 A1 WO2014126296 A1 WO 2014126296A1
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metal
carbon material
containing precursor
porous carbon
particles
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Korean (ko)
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곽근재
하경수
전기원
이진우
황종국
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한국화학연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles

Definitions

  • the present invention relates to a method for producing metal-containing particles using pores of a porous carbon material as a template.
  • Nanoparticles are particles with a large surface area ranging in size from several nm to hundreds of nm, and are required for commercialization of various fields of technology including nanocatalysts, biosensors, next generation display phosphors, terabit hard drives, solar cells, and nanoelectronics. It is a key material. Reactivity of particles through introduction of a reactive functional group that chemically bonds to the surface of the particle, introduction of ligands, change of surface charge type, introduction of a self-assembled monolayer, and an appropriate particle size and size distribution for a desired purpose. Its functionality can be improved.
  • Nanoparticles using one chemical species but also composite nanoparticles using two or more inorganic materials, and core-shell structured nanoparticles having different materials between the core and the shell may be used in various applications. It is expected to be the next generation functional material in the field. Nanoparticles from inorganic materials exhibit bulk properties and other unique physical properties and new functions. Because of its unique properties in light, electricity, and magnetism due to quantum size effects, research on the synthesis and application of nanoparticles has attracted great attention as the research field of advanced materials science leading the 21st century. .
  • Nanoparticle synthesis methods vary widely.
  • Neutralization Emulsification Process is a method of self-emulsification without surfactants by introducing functional organic groups that ionize into polymers, and chemically binding to coating polymers pre-polymerized with organic acids (-COOH).
  • the nanoparticles are formed by the repulsive force of organic acids. This method is mainly used when producing urethane dispersion particles.
  • Synthesis method of nanoparticles through a polymer electrolyte is well known as a method of forming nanoparticles of inorganic material such as metal or semiconductor.
  • Adsorption of linear polymer electrolytes with opposite charges to the metal ions of the ionized metal precursors in the solvent encloses the polymer electrolyte with nanoparticles of a certain size with a surface energy determined by the concentration of the polymer electrolyte or metal ion.
  • Nanoparticle growth does not occur and is formed of nanoparticles of constant size.
  • Subsequent reduction reactions are then transferred to semiconductor nanoparticle assemblies or one-dimensional metals.
  • it may be formed by a cationic chain (PVP: Polyvinylpyrrolidone) or an anion (PdCl 4 2- ), and may form a nanoparticle assembly by a hydrophilic block copolymer.
  • PVP Polyvinylpyrrolidone
  • PdCl 4 2- anion
  • Nanowires and nanotubes provide a harder and structured support compared to polymer electrolytes and biomolecules.
  • the surface and inside of the nanowires and hollow carbon nanotubes (CNTs) are used as templates for the assembly of nanoparticles.
  • Synthesis of semiconductor nanoparticles or metal on the template surface by chemical vapor deposition (PVD) or physical vapor deposition (PVD: physical vapor deposition, ex. Thermal evaporation, Sputtering etc.) or metal complexes on the nanowire surface
  • PVD chemical vapor deposition
  • PVD physical vapor deposition
  • aqueous solution including a spontaneously arranged polymer and a nanoparticle precursor
  • the polymer spontaneously forms a layer and the aqueous solution is isolated between the layers.
  • the particles dissolved in the aqueous solution are aggregated to form particles of a specific shape.
  • This method is a method of synthesizing nanoparticles by self-assembly, and the size and shape of the metal and semiconductor nanoparticles prepared at this time can be controlled by the type and concentration of the surfactant used.
  • pores mean that a material has a myriad of holes, and according to the size of the hole, it is classified into microporous, mesoporous and macroporous materials.
  • Nanoporous material refers to a microporous material and a mesoporous material which is the center of the present invention.
  • the mesoporous material can control the pore size in various ways, selectively adsorb or separate the appropriate molecules according to the size, and can be used in petrochemical through its inherent surface properties and support of catalytically active materials. .
  • These mesoporous materials are introduced to a variety of materials due to their wide application, and is expanding the application.
  • mesoporous materials are synthesized by hydrothermal reaction using organic molecules such as surfactants or amphiphilic polymers as structural materials.
  • Surfactants or amphiphilic polymers consist of hydrophilic heads and hydrophobic tails to form micelles or liquid crystals of various structures through self-assembly in aqueous solutions.
  • the macromolecules thus formed are used as templates to synthesize mesoporous materials of the desired form.
  • Mesoporous materials are currently used in various fields such as catalysts, nanocatalyst supports, adsorption and separation, and sensors. The most important feature of this application is that the pore size and structure can be adjusted according to the purpose.
  • Materials with one-dimensional pore structures such as MCM-41 are suitable for use as templates for producing 0- and 1-dimensional nanomaterials such as metal nanowires and conductive polymers, and nanopores are arranged in regular hexagonal arrangements.
  • the form SBA-15 is used to make another material, CMK-3, a mesoporous material made of carbon.
  • MSU-F-Silca a mesocellular foam material, is used as a template to synthesize MSU-F-C, a mesoporous form of carbon, another material. Since the surfactant may exist in various structures depending on the concentration or temperature of the aqueous solution, it is possible to synthesize mesoporous materials having different structures or pore sizes.
  • the easiest way to control the pore size is to vary the length of the surfactant hydrophobic tail, and the longer the hydrophobic tail, the larger the pore size.
  • the shape and shape of the pores vary depending on the length of the hydrophobic tail, and this method can be used to produce mesoporous materials of various structures.
  • mesoporous carbon synthesized using template material was first reported by the Knox group (JH Knox, B. Kaur, GR Millward, Journal of Chromatography 352, 3, 1986), and mesoporous synthesized using mesoporous silica as a template. Carbon was first reported by Yuryong et al. In 2001 (Korea Patent Publication 2002-0084372). Unlike conventional commercial carbon materials, mesoporous carbon materials have not only micropores but also uniform mesoporous pores, which play an important role in the diffusion of reactants and products when used as a catalyst support. Although soft template method by surfactant is used, it is mainly synthesized using nano-replication method.
  • a hard template method Since it uses hard mesoporous silica as a template, it is called a hard template method. It is a method of synthesizing mesoporous carbon bodies by removing a template through carbonization by adding a carbon precursor into silica pores.
  • nanoparticles are formed on the surface of the mesoporous silica having an amino (-NH 2 ) functional group formed by capillary action (Jing-Yue Fang, Shi-Qiao Qin, Sheng-Li Chang, Xue). -Ao Zhang, Microporous and Mesoporous Materials 145, 205, 2011), there is a technique of forming palladium nanoparticles on the surface of SBA-15 mesoporous silica to use as a heterogeneous catalyst.
  • the conventional nanoparticle forming techniques are difficult to selectively remove the template because the nanoparticles are included in the mesoporous material used as a template to form nanoparticles in the mesoporous material.
  • the template removal method by high temperature heat treatment is used, the formed nanoparticles are recombined by sintering to form large particles or chemical reaction and bonding with the mesoporous material used as a support.
  • nanoparticles having a chemical composition other than nanoparticles are formed.
  • the template is removed by a chemical etching method, it is difficult to select an etchant according to the etching rate, and even if the selective etching is performed, the etchant may affect the surface structure of the nanoparticles or may be accompanied by chemical contamination. There is. In particular, when it is necessary to form and use only intact nanoparticles, in order to extract the nanoparticles inside the mesoporous structure material, there are disadvantages that at least two separate processes are required, such as forming the nanoparticles and removing the template.
  • a technique for synthesizing desired nanoparticles using a surfactant does not require a separate template.
  • most nano nanoparticles are surface-stabilizing surfactants that are chemically adsorbed onto the surface of nanoparticles in a three-dimensional structure. Particle active points are blocked.
  • a separate surfactant must be removed for use as a nanocatalyst, and in order to utilize the electronic material, since the electrical contact with the electrode material may be degraded, the surfactant needs to be removed. Since the high temperature heat treatment is required to remove the surfactant, there is a possibility that the sintering of the nanoparticles and the change of chemical composition may be caused.
  • the present inventors have been studying a method for preparing nanoparticles by a simple process while avoiding sintering and chemical reaction of the nanoparticles, and using a porous carbon material as a template to prepare metal-containing particles.
  • a metal-containing precursor that generates oxidizing gas upon decomposition it was confirmed that nanoparticle generation and carbon material template removal can be simultaneously performed and high purity nanoparticles can be obtained.
  • the first step of preparing a porous carbon material is applied in the pores of the metal-containing precursor is produced when the oxidation gas is decomposed; Heat-treating the prepared porous carbon material at or above the decomposition temperature of the metal-containing precursor under an oxidizing atmosphere, thereby forming carbon particles and forming particles from the metal-containing precursor while simultaneously removing carbon material. It is providing the manufacturing method of metal containing particle
  • Another object of the present invention is to prepare a porous carbon material to which the metal-containing precursor is applied in the pores; By heat-treating the prepared porous carbon material at a temperature above the decomposition temperature of the metal-containing precursor to less than the thermal decomposition temperature of the carbon material under an inert atmosphere, the pores of the porous carbon material as a template without removing the porous carbon material are contained in the pores. It provides a method for producing metal-containing particles comprising a second step of forming particles from a precursor.
  • Still another object of the present invention is to prepare a carbon material to which a metal-containing precursor to which an oxidizing gas is generated when decomposed is prepared; And a second step of heat-treating the prepared carbon material to the decomposition temperature of the metal-containing precursor under an oxidizing atmosphere, to provide a method for removing the carbon material below the thermal decomposition temperature of the carbon material.
  • Another object of the present invention is to provide a porous carbon material in which a metal-containing precursor, which is decomposed to produce an oxidizing gas, is applied in pores.
  • oxidizing gas is a gas having an oxidizing power for oxidizing other substances.
  • oxidizing gases include oxygen or oxygen-containing mixtures as well as oxygen generating materials, halogen gases such as F 2 , Cl 2 , Br 2 , I 2 .
  • oxygen-generating materials include HNO 3 , H 2 SO 4 , KMnO 4 , H 2 O 2 , and the like.
  • an oxidizing gas may be formed by metal ions having a high valence such as FeCl 3 and SnCl 4 .
  • the present invention uses a metal-containing precursor that generates an oxidizing gas when it is decomposed, and when heat-treated under an oxidizing atmosphere, the carbon material is removed at a lower temperature than the existing temperature, that is, the thermal decomposition temperature of the carbon material by the oxidizing gas generated from the metal-containing precursor. Based on finding something
  • the first aspect of the present invention is a first step of preparing a porous carbon material is applied in the pores of the metal-containing precursor is produced when the oxidation gas is decomposed; Heat-treating the prepared porous carbon material at or above the decomposition temperature of the metal-containing precursor in an oxidizing atmosphere, thereby forming carbon particles and forming particles from the metal-containing precursor while simultaneously removing carbon material. It provides a method for producing metal-containing particles comprising a.
  • the first step is preparing a porous carbon material to which a metal-containing precursor, which is decomposed when oxidized gas is generated, is applied in the pores.
  • Metal-containing precursors that produce oxidizing gas upon decomposition include water-soluble precursors or fat-soluble precursors of all metal elements capable of generating oxidizing gas upon decomposition.
  • the metal-containing precursor is a water-soluble precursor oxide oxide, oxyhydroxide salt, chloride salt, carbonate, acetate, citrate, nitosilonitrate, nitrate. Hydroxide salts.
  • the metal-containing precursor may be an oxide, hydroxide, oxyhydroxide, nitrate, chloride, carbonate, acetate, oxalate, citrate, sulfate, nitrosylnitrate (NO (NO 3 ) 2 ), or mixtures thereof, of the metal.
  • the metal-containing precursor may include all metals of alkali metal, alkaline earth metal, group IB, group IIB, group IIIB, group IVB, group VB, group VIB, group VIIB and group VIIIB.
  • the metal in the metal-containing precursor is preferably a metal used in the metal catalyst or metal oxide catalyst, non-limiting examples of cobalt (Co), nickel (Ni), copper (Cu), iron (fe), zinc ( Zn), ruthenium (Ru), molybdenum (Mo), tungsten (W), bismuth (Bi), reniche (Re), rhodium (Rh), palladium (Pd), silver (Ag), platinum (Pt) or its May be a combination.
  • Porous materials are divided into microporous and mesoporous materials according to the pore size of the material. In general, when the pore size is 2 nm or less, the microporous and the pore size are between 2 and 50 nm. It is called.
  • the porous carbon material of the present invention is not limited to the pore size, but is preferably a mesoporous carbon material for preparing nano-level metal-containing particles.
  • the porous carbon material of the present invention has a pore average particle diameter of 1 to 50 nm and a surface area of 100 m 2 g ⁇ 1 to 2000 m 2 g ⁇ 1 , but the larger the surface area, the larger the content of nanoparticles. If the pore average particle size is smaller than 1 nm, the pore size is only molecular level, and thus there is a disadvantage that it cannot be used for applications of larger sized molecules. In addition, when the pore average particle diameter is larger than 50 nm, the size of the resulting metal-containing particles becomes large, which is not preferable.
  • the porous material may be, but is not limited to, carbon nanotubes, CMK-3, CMK-8, MSU-F-C, activated carbon, graphite fibers, activated carbon fibers or mixtures thereof.
  • the "carbon nanotube” may be a cylindrical carbon crystal having a diameter of 0.5 nm to 10 nm, in which carbons connected by hexagonal rings have a long shape.
  • the carbon nanotubes may be single-walled carbon nanotubes or multi-walled carbon nanotubes.
  • CMK-3 is synthesized from SBA-15, which is mesoporous silica, and is a porous carbon material having hexagonal pores and a long cylindrical shape in the axial direction.
  • CMK-8 is synthesized from KIT-6, a silica mesoporous silica, and is a porous carbon material having a cubic structure in which two kinds of mesopores are independently connected three-dimensionally.
  • MSU-FC is synthesized from "MSU-F-silica” which is mesoporous silica, and has a mesocellular structure of porous carbon having a small pore of 4 to 8 nm between a large pore of about 30 nm and a pore structure. It is a substance.
  • Activated carbon is a highly adsorptive material, and most of the components are carbonaceous materials. It is composed of amorphous carbon in which graphite planar crystallites are intricately combined and is porous. The average radius of pores is 1 mm to 2 mm, and the specific surface area is 800 m 2 / g to 1500 m 2 / g.
  • the present invention is preferably used to produce metal-containing particles of nanoscale size.
  • the size of the particles produced according to the invention may be similar to or slightly larger than the pore size of the porous carbon material used as the template. The reason why the nanoparticles are slightly larger than the pore size is that some sintering has been performed to reduce the surface energy of the nano-sized particles having high surface energy.
  • the size of the metal-containing particles produced according to the present invention depends on the pore size of the porous carbon material used, and the average diameter may be between 1 and 50 nm, but is not limited thereto.
  • the porous carbon material to which the metal-containing precursor, in which the oxidizing gas is generated when decomposed, is applied in the pores may be prepared by impregnating the metal-containing precursor solution in the pores of the porous carbon material and then drying.
  • the solvent used for the metal-containing precursor solution is not limited as long as it can evaporate below the temperature at which the oxidizing gas is decomposed from the metal-containing precursor without chemical reaction with the metal-containing precursor.
  • Non-limiting examples of such solvents include C1 to C6 alcohols (eg ethanol), water, ether series, ketones (eg acetone), chain hydrocarbons (eg n-hexane) and the like.
  • the impregnation may be carried out at room temperature.
  • the capillary force is used to the maximum, and if impregnation is difficult, a vacuum atmosphere or an ultrasonic treatment may be used as necessary.
  • the amount of impregnation may be increased because the air or moisture contained in the material is completely removed by the vacuum.
  • the metal-containing precursor solution may have a mass ratio of metal in the metal-containing precursor to 1% to 500% with respect to the porous carbon material.
  • impregnation may be performed in one step or through two or more impregnation steps, but is not limited thereto.
  • the drying temperature after the impregnation may be 100 °C to 150 °C.
  • the drying temperature depends on the solvent used in the metal containing precursor solution.
  • the oxidizing atmosphere may be heat treatment with an oxidizing gas or a mixed gas composed of a combination of an oxidizing gas and an inert gas, but is not limited thereto.
  • the oxidizing gas may be oxygen, nitric oxide (NO, NO 2 ), air, or a combination thereof, but is not limited thereto.
  • the inert gas may be nitrogen, helium, argon or a combination thereof, but is not limited thereto.
  • the inert gas serves as a carrier gas for promoting the movement of the mixed gas and at the same time serves to adjust the concentration of the oxidizing gas.
  • the heat treatment temperature may be 250 °C to 450 °C. This is lower than 550 ° C., which is a thermal decomposition temperature of general carbon materials.
  • 550 ° C. is a thermal decomposition temperature of general carbon materials.
  • the carbon material can be removed at 250 ° C. to 450 ° C., which is lower than the existing pyrolysis temperature.
  • a metal-containing precursor that generates an oxidizing gas when decomposed and fired in an oxidizing atmosphere can remove the carbon material at a temperature lower than the pyrolysis temperature of the carbon. Prevent sintering of particles and interactions with chemicals, chemical and physical changes.
  • the manufacturing method according to the present invention can be carried out at the same time to produce the metal-containing particles and the carbon material removal step can reduce the cost and time.
  • the flow rate of the oxidizing gas treated during the heat treatment is measured by the gas hourly space velocity (GHSV) and is preferably 0 hr -1 to 10000 hr -1 .
  • 0 hr -1 means an atmosphere of a state having no constant flow rate and a stagnant oxidizing gas atmosphere. Even in such a stagnant atmosphere, the metal particles and the carbon support in the oxidized state can be removed. If the flow rate of the oxidizing gas exceeds 10000 hr ⁇ 1 , the contact time with the carbon material may be insufficient and the carbon material may not be sufficiently removed.
  • the particles formed in the second step is a metal oxide, after which the metal oxide may be reduced to form metal particles.
  • the reduction treatment is an optional process, and reduction may be performed using conventional methods known to those skilled in the art.
  • the metal containing particles may be a catalyst for Fischer-Tropsch synthesis or a precursor thereof.
  • the step of applying the metal-containing precursor to the porous carbon material (first step) and the heat treatment under the oxidation atmosphere (second step) may be performed simultaneously.
  • the metal-containing particles prepared according to the present invention may be subjected to conventional impregnation, coprecipitation, deposition, or the like.
  • the ratio of surface oxygen absorbed oxygen to lattice oxygen is lower than that of particles produced by the present invention. This reduction in the surface oxygen ratio improves the reducibility of the particles and enables the reduction of the particles at lower temperatures.
  • the metal-containing particles prepared according to the present invention are metal oxides
  • oxidation deficiency is induced on the surface of the particles due to the reducing action of the porous carbon material, so that the metal oxides are reducible at low temperatures, thereby reducing the metal particles.
  • a second aspect of the invention provides a method for preparing a porous carbon material to which a metal-containing precursor is applied in a pore;
  • the prepared porous carbon material under an inert atmosphere Heat-treating at a temperature above the decomposition temperature of the metal-containing precursor to below the thermal decomposition temperature of the carbon material, thereby forming particles from the metal-containing precursor in the pores by using pores of the porous carbon material as a template without removing the carbonaceous material; It provides a method for producing a metal-containing particles comprising a.
  • the metal-containing precursor may be a metal-containing precursor that generates an oxidizing gas when decomposed.
  • the inert atmosphere is made of an inert gas, the inert gas may be nitrogen, helium, argon or a combination thereof, but is not limited thereto.
  • the temperature above the decomposition temperature of the metal-containing precursor to below the thermal decomposition temperature of the carbon material means a temperature of less than about 550 degrees, which is the thermal decomposition temperature of the carbon material.
  • the decomposition temperature of the metal containing precursor may vary depending on the temperature of the precursor used.
  • the metal-containing particles according to the manufacturing method are obtained in a form supported on the pores of the carbon material without removing the carbon material support.
  • the metal-containing particles supported on the carbon material have a constant nano size and high dispersibility similar to the pore size of the carbon material, and thus may be usefully used for catalysts, adsorption and / or separation.
  • the third aspect of the present invention provides a method for preparing a carbon material to which a metal-containing precursor to which an oxidizing gas is generated when decomposed is prepared; And a second step of heat-treating the prepared carbon material to the decomposition temperature of the metal-containing precursor under an oxidizing atmosphere, thereby providing a method of removing the carbon material below the thermal decomposition temperature of the carbon material.
  • the carbon material is not limited to a specific structure. Any structure that can apply a metal-containing precursor can be used without limitation.
  • the carbon material may be a porous structure, and a metal containing precursor may be impregnated into the porous structure.
  • the fourth aspect of the present invention provides a porous carbon material in which a metal-containing precursor, which is decomposed to generate an oxidizing gas, is applied in the pores.
  • the porous carbon material may be an intermediate used in the metal-containing particle production method or the carbon material removal method according to the present invention.
  • the pores of the carbon material support may be formed as a template through low temperature heat treatment to form metal-containing particles and to effectively remove the carbon material.
  • the method for preparing metal-containing particles according to the present invention enables the production of highly purified nanoparticles by a simple process, while avoiding sintering and chemical reaction with the support by removing the carbon material support by low temperature heat treatment.
  • Figure 1a shows the nitrogen adsorption and desorption isotherm characteristics of the mesoporous carbon material CMK-3, MSU-F-C used as a template for the production of nanoparticles.
  • Figure 1b shows the pore size distribution of mesoporous carbon material calculated from nitrogen isotherm using the Barrett-Joyner-Halenda (BJH) method.
  • Figure 2a shows the result of thermogravimetric analysis of mesoporous carbon material CMK-3 used as a template in Comparative Example 1.
  • Figure 2b shows the thermogravimetric analysis of the mesoporous carbon material MSU-F-C used as a template in Comparative Example 2.
  • Figure 3 shows the results of thermogravimetric analysis of the physical mixture of mesoporous carbon material CMK-3 and cobalt oxide used as a template prepared in Comparative Examples 3 and 4.
  • Figure 4 shows the results of thermogravimetric analysis of the dried mesoporous carbon material loaded with cobalt precursor prepared in Examples 1, 3 and 4.
  • Figure 5a shows an electron scanning micrograph (TEM) of the mesoporous carbon material CMK-3 used as a template for nanoparticle generation.
  • Figure 5b shows a transmission electron micrograph (TEM) of the mesoporous carbon material MSU-F-C used as a template for the production of nanoparticles.
  • TEM transmission electron micrograph
  • Figure 6a shows a transmission electron micrograph (TEM) of the cobalt oxide nanoparticles produced from the CMK-3 template prepared in Example 1.
  • Figure 6b shows a transmission electron micrograph (TEM) of the cobalt oxide nanoparticles produced from the MSU-F-C template prepared in Example 2.
  • Figure 7a shows a transmission electron micrograph (TEM) of the cobalt oxide nanoparticles produced inside the CMK-3 template prepared in Example 5.
  • Figure 7b shows a transmission electron micrograph (TEM) of the cobalt oxide nanoparticles produced inside the MSU-F-C template prepared in Example 6.
  • CMK-3 synthesized from the SBA-15 framework and MSU-F-C synthesized from MSU-F-silica were used.
  • the pore size and BET surface area of the material are shown in Table 1.
  • CMK-3 has hexagonal pores and a cylinder shape that is long in the axial direction.
  • MSU-FC is a mesocellular structure having large pores of about 30 nm and small pores of 4 to 8 nm between the pore structures.
  • Cobalt nitrate Cobalt nitrate hexahydrate, Co (NO 3 ) 2 6H 2 O
  • ethanol was used as the solvent.
  • the carbon support Before using the carbon support, it was dried in an oven at 150 ° C. for 12 hours to remove foreign matter remaining in the surface and moisture that may be present in pores.
  • the mass of the mesoporous carbon support was 1.0 g and the cobalt precursor was 1.235 g.
  • the solvent was sufficiently evaporated in a vacuum evaporator for 2 hours or more at an internal temperature of 70 to 90 ° C.
  • the resulting mixture was dried in an electric oven at 110 ° C. for at least 12 hours.
  • the dried mixture was heated at a reaction temperature of 400 ° C. for 5 hours in a kiln in which air at a flow rate of 100 sccm was injected.
  • the nanoparticles prepared using the mesoporous carbon support having the pore size and surface area of Table 1 are 6 nm to 10 nm for CMK-3, and cobalt oxide having a composition of Co 3 O 4 at 10 nm to 16 nm for MSU-FC. It was confirmed that nanoparticles of were produced. Nanoparticles that are somewhat larger than the pore size were produced, which suggests that some nanosized particles with high surface energy have undergone some sintering to reduce the surface energy. Upon completion of firing, the mesoporous carbon support was completely removed, and it was confirmed that only nanoparticles in the oxidized state remained.
  • thermogravimetric analysis was used to investigate the causes of mesoporous carbon support removal. Unlike Examples 1 and 2, only the carbon support was used to check the change in weight due to pyrolysis while increasing the temperature in the air. The experimental results are shown in Table 2 below. In addition, the results of thermogravimetric analysis of Comparative Examples 1 to 4 are shown in FIGS. 2 (Comparative Example 1-2) and 3 (Comparative Example 3-4).
  • both of the CMK-3 and MSU-F-C started pyrolysis in air after 500 ° C., and completely decomposed at 630 ° C. (Comparative Examples 1 and 2).
  • the carbon support itself was not decomposed at the firing temperature of Examples 1 to 2, but when the nanoparticle precursor was supported, it was confirmed that the carbon support was decomposed and removed at a temperature lower than 300 ° C. below the actual thermal decomposition temperature of the carbon support itself.
  • Example 3-4 Formation of Nanoparticles Using Mesoporous Carbon and Cobalt Acetate or Cobalt Chloride
  • Example 1 except that the cobalt chloride (Cobalt chloride (II), CoCl 2 ), cobalt acetate tetrahydrate (Cobalt acetate tetrahydrate, Co (CH 3 COO) 2 4H 2 O) was supported on CMK-3 Nanoparticles were prepared by the same method as described above. At this time, 0.551 g of cobalt chloride precursor and 0.751 g of cobalt acetic acid precursor were supported on 1.0 g of mesoporous carbon support.
  • cobalt chloride (II), CoCl 2 ) cobalt acetate tetrahydrate
  • Co (CH 3 COO) 2 4H 2 O) Cobalt acetate tetrahydrate, Co (CH 3 COO) 2 4H 2 O
  • thermogravimetric analyzer The decomposition temperature through the thermogravimetric analyzer is shown in Table 3 and FIG. 4.
  • Nanoparticles were prepared in the same manner as in Examples 1 and 2, except that the mixture was calcined in an inert gas atmosphere. To be calcined in an inert gas atmosphere, the dried mixture was heated at a reaction temperature of 400 ° C. for 5 hours in a tubular reactor fed with nitrogen at 100 sccm flow rate.
  • composition of cobalt oxide nanoparticles produced in an inert gas atmosphere is stoichiometrically advantageous for CoO over Co 3 O 4 , the size of which is largely dependent on the size in the pores. It was confirmed that the cobalt oxide nanoparticles supported on the CMK-3 template had a size of 3 nm to 6 nm, and that the cobalt oxide nanoparticles supported on the MSU-FC had a size of 8 nm to 15 nm, and that particles were formed in pores. Confirmed.

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  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un procédé de production de particules contenant du métal, ce procédé comprenant une première étape consistant à préparer un matériau de carbone poreux dans les pores duquel est appliqué un précurseur contenant du métal, ce précurseur générant un gaz oxydant lorsqu'il est décomposé ; et une seconde étape consistant à soumettre le matériau de carbone poreux préparé à un traitement thermique à une température égale ou supérieure à la température de décomposition du précurseur contenant du métal sous une atmosphère d'oxydation, ce qui forme des particules à partir du précurseur contenant du métal à l'aide des pores du matériau de carbone poreux servant de moule, et à retirer simultanément le matériau de carbone. Dans le procédé de production de particules contenant du métal, selon la présente invention, des particules contenant du métal peuvent être formées et simultanément un support de matériau de carbone peut être efficacement retiré par un traitement thermique basse température alors que les pores du support du matériau de carbone sont utilisés comme moule. Également, dans le procédé de production de particules contenant du métal selon la présente invention, du fait que le support de matériau de carbone est retiré par traitement thermique à basse température, des nanoparticules de haute pureté peuvent être produites par un procédé simple tout en évitant le frittage des nanoparticules et une réaction chimique entre les nanoparticules et le support de matériau de carbone.
PCT/KR2013/003527 2013-02-12 2013-04-24 Procédé de formation de particules contenant du métal au moyen de matériau de carbone poreux WO2014126296A1 (fr)

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KR1020130015054A KR101675457B1 (ko) 2013-02-12 2013-02-12 다공성 탄소물질을 이용한 금속 함유 입자 형성방법

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CN110697680A (zh) * 2019-10-18 2020-01-17 龙岩学院 一种高比表面积的杂原子掺杂多孔碳材料及其制备方法

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KR102431688B1 (ko) * 2015-12-31 2022-08-11 엘지디스플레이 주식회사 내열성이 향상된 어레이 기판 및 이를 포함하는 표시장치
WO2019093553A1 (fr) * 2017-11-13 2019-05-16 주식회사 비비비 Procédé de fabrication d'électrode en carbone poreux
WO2024080811A1 (fr) * 2022-10-13 2024-04-18 한화솔루션(주) Méthode de modification de tamis moléculaire de carbone

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KR100838644B1 (ko) * 2007-01-29 2008-06-16 충남대학교산학협력단 탄소주형체를 이용한 속빈 금속 구 나노 구조체 및제조방법

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JPH07155587A (ja) * 1993-12-09 1995-06-20 Mitsubishi Gas Chem Co Inc 高吸着性炭素材料およびその製造方法
KR20020031447A (ko) * 2000-10-20 2002-05-02 이 병 길 메조포러스 탄소/금속산화물 복합물질과 이의 제조방법 및이를 이용한 전기 화학 캐패시터
JP2003313011A (ja) * 2002-04-23 2003-11-06 Toyota Motor Corp 金属酸化物の製造方法
KR20070057602A (ko) * 2005-12-01 2007-06-07 삼성전자주식회사 다공성 템플릿을 이용한 나노 와이어의 제조방법 및나노와이어 구조체
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110697680A (zh) * 2019-10-18 2020-01-17 龙岩学院 一种高比表面积的杂原子掺杂多孔碳材料及其制备方法

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