WO2016035705A1 - Procédé de production d'un alliage de carbone contenant de l'azote, alliage de carbone contenant de l'azote et catalyseur pour pile à combustible - Google Patents

Procédé de production d'un alliage de carbone contenant de l'azote, alliage de carbone contenant de l'azote et catalyseur pour pile à combustible Download PDF

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WO2016035705A1
WO2016035705A1 PCT/JP2015/074426 JP2015074426W WO2016035705A1 WO 2016035705 A1 WO2016035705 A1 WO 2016035705A1 JP 2015074426 W JP2015074426 W JP 2015074426W WO 2016035705 A1 WO2016035705 A1 WO 2016035705A1
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nitrogen
carbon alloy
containing carbon
group
carbon
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PCT/JP2015/074426
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Japanese (ja)
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順 田邉
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富士フイルム株式会社
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for producing a nitrogen-containing carbon alloy, a nitrogen-containing carbon alloy, and a fuel cell catalyst. Specifically, the present invention relates to a method for producing a nitrogen-containing carbon alloy including a step of firing a precursor containing a nitrogen-containing organic compound, a porous skeleton material, and an inorganic metal salt or an organometallic complex. Furthermore, the present invention relates to a nitrogen-containing carbon alloy and a fuel cell catalyst using the nitrogen-containing carbon alloy.
  • a noble metal catalyst using platinum (Pt), palladium (Pd), etc. is used as a catalyst having a high oxygen reduction activity, for example, for a solid polymer electrolyte fuel cell used in automobiles, household electric heat supply systems, etc.
  • Pt platinum
  • Pd palladium
  • noble metal-based catalysts are expensive, it is difficult to further spread them. For this reason, technological development of a catalyst in which platinum is greatly reduced or a catalyst formed without using platinum is being promoted.
  • Patent Document 1 discloses a polymer electrolyte fuel cell catalyst comprising a composite of an s-triazine ring derivative and a metal.
  • Patent Document 2 discloses a nitrogen-containing carbon alloy catalyst produced by firing a nitrogen-containing heterocyclic compound having a molecular weight of 60 to 2000 and an inorganic metal or inorganic metal salt.
  • Patent Documents 3 and 4 disclose a nitrogen-containing carbon alloy catalyst produced by firing a mixture of a porous material such as a nitrogen-containing heterocyclic compound, a metal complex, and MOF (Metal-Organic frameworks).
  • a porous material such as a nitrogen-containing heterocyclic compound, a metal complex, and MOF (Metal-Organic frameworks).
  • TPTZ 2,4,6-tri (2-pyridyl) -1,3,5-triazine
  • Patent Document 3 phthalonitrile-based compounds and pyridine-based compounds are listed as nitrogen-containing organic compounds, but these compounds are only listed as non-limiting examples.
  • Patent Document 4 lists 6- (2-pyridyl) -1,3,5-triazine-2,4-diamine as a nitrogen-containing heterocyclic compound.
  • the nitrogen-containing carbon alloy catalyst containing a nitrogen-containing organic compound can exhibit catalytic activity without using platinum.
  • recent applications such as fuel cells are required to have higher oxygen reduction activity, and the oxygen reduction activity of conventional carbon catalysts may be insufficient. For this reason, it has been desired to produce a nitrogen-containing carbon alloy that can exhibit higher oxygen reduction activity.
  • the yield is poor, and further improvement in productivity has been demanded.
  • the present inventor has studied for the purpose of producing a nitrogen-containing carbon alloy having higher oxygen reduction activity and high production efficiency. Advanced.
  • the present inventor has a nitrogen-containing organic compound having a specific structure, at least one selected from a covalent organic skeleton material and a metal organic skeleton material, By calcining a precursor containing at least one selected from an inorganic metal salt or an organic metal complex to produce a nitrogen-containing carbon alloy, a nitrogen-containing carbon alloy having sufficiently enhanced oxygen reduction activity can be obtained. I found. Furthermore, the present inventor has found that the nitrogen-containing carbon alloy produced in this way has high production efficiency and a sufficient yield can be obtained, and has completed the present invention. Specifically, the present invention has the following configuration.
  • At least one selected from nitrogen-containing organic compounds represented by the following general formula (1), tautomers of nitrogen-containing organic compounds, salts of nitrogen-containing organic compounds, and hydrates of nitrogen-containing organic compounds And production of a nitrogen-containing carbon alloy comprising a step of firing a precursor comprising at least one selected from a covalently bonded organic skeleton material and a metal organic skeleton material and at least one selected from an inorganic metal salt and an organometallic complex Method;
  • Q represents an atomic group composed of at least one 5- to 7-membered aromatic ring or 5- to 7-membered heteroaromatic ring, and R represents a halogen atom, a substituted or
  • an unsubstituted alkyl group or a substituent represented by the following general formulas (2) to (5) is represented and Q does not include a nitrogen-containing heteroaromatic ring, at least one R is represented by the following general formula (2 ) To (5).
  • n an integer of 1 to 4.
  • * represents a bond to Q.
  • R 1 to R 8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
  • R 1 and R 2 , R 3 and R 4 , R 7 and R 8 may be bonded to each other to form a ring.
  • * Represents a bond to Q.
  • Q is a 5- to 7-membered nitrogen-containing heteroaromatic ring
  • R is a substituted or unsubstituted alkyl group, or a substituent represented by the general formula (2)
  • the method for producing a nitrogen-containing carbon alloy according to [4], wherein [6] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [5], wherein the metal organic framework material is a zeolite type imidazole framework material.
  • the inorganic metal salt is an inorganic metal chloride.
  • [15] The method for producing a nitrogen-containing carbon alloy according to [14], wherein the firing step includes a step of holding the precursor at 700 to 1050 ° C. for 1 second to 100 hours.
  • the method for producing a nitrogen-containing carbon alloy according to any one of [1] to [16] further comprising a step of pulverizing the fired nitrogen-containing carbon alloy and a step of re-firing after the firing step. .
  • a nitrogen-containing carbon alloy having a sufficiently high oxygen reduction activity can be obtained.
  • the nitrogen-containing carbon alloy obtained by the production method of the present invention can be used as a carbon catalyst, and such a carbon catalyst is preferably used for a fuel cell or an environmental catalyst.
  • the yield of a nitrogen-containing carbon alloy can be raised and productivity can be improved.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the substituent in the present invention may be any group that can be substituted.
  • a halogen atom fluorine atom, chloro atom, bromine atom or iodine atom
  • hydroxyl group cyano group
  • aliphatic group aralkyl group, cyclohexane Alkyl group, including active methine group, etc.
  • aryl group garding the position of substitution
  • heterocyclic group (regardless of the position of substitution)
  • acyl group aliphatic oxy group (alkoxy group or alkyleneoxy group, Ethyleneoxy group or a group containing a propyleneoxy group unit repeatedly), aryloxy group, heterocyclic oxy group, aliphatic carbonyl group, arylcarbonyl group, heterocyclic carbonyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, Heterocyclic oxycarbonyl group, carbamoyl group, sulfony
  • the present invention relates to at least one selected from nitrogen-containing organic compounds having a specific structure, tautomers of nitrogen-containing organic compounds, salts of nitrogen-containing organic compounds, and hydrates of nitrogen-containing organic compounds, and covalent bonding.
  • the present invention relates to a method for producing a nitrogen-containing carbon alloy including a step of firing a precursor containing at least one selected from an organic skeleton material and a metal organic skeleton material and at least one selected from an inorganic metal salt and an organometallic complex.
  • a nitrogen-containing organic compound having an after-mentioned structure and an inorganic metal salt or organometallic complex are mixed with a porous material (MOF (Metal-organic framework) or COF (Covalent organic framework). ) Etc.) in the reaction space field, a nitrogen-containing organic compound is coordinated to an inorganic metal salt or an organometallic complex using a pore shape as a template to form a nitrogen-containing carbon alloy having porosity.
  • MOF Metal-organic framework
  • COF Covalent organic framework
  • Q in the general formula (1) is composed of an atomic group composed of a 5- to 7-membered aromatic ring or a 5- to 7-membered heteroaromatic ring, whereby thermal decomposition of the atomic group is performed. It can be easily advanced. Thereby, formation of an oxygen reduction reaction (ORR) active site can be promoted, and a higher activity nitrogen-containing carbon alloy can be obtained.
  • ORR oxygen reduction reaction
  • the nitrogen-containing organic compound, the covalently bonded organic skeleton material, the metal organic skeleton material, the inorganic metal salt, and the organometallic complex will be described in detail.
  • the nitrogen-containing organic compound used in the method for producing a nitrogen-containing carbon alloy of the present invention is represented by the general formula (1).
  • a tautomer of the nitrogen-containing organic compound represented by the general formula (1), a salt of the nitrogen-containing organic compound or a hydrate of the nitrogen-containing organic compound is used. May be.
  • the nitrogen-containing organic compound represented by the general formula (1), the tautomer of the nitrogen-containing organic compound, the salt of the nitrogen-containing organic compound, and the hydrate of the nitrogen-containing organic compound may be used alone. Two or more kinds may be used.
  • Q represents an atomic group composed of at least one 5- to 7-membered aromatic ring or 5- to 7-membered heteroaromatic ring
  • R represents a halogen atom, a substituted or
  • an unsubstituted alkyl group or a substituent represented by the following general formulas (2) to (5) is represented and Q does not include a nitrogen-containing heteroaromatic ring
  • at least one R is represented by the following general formula (2 ) To (5).
  • n represents an integer of 1 to 4.
  • R 1 to R 8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
  • R 1 and R 2 , R 3 and R 4 , R 7 and R 8 may be bonded to each other to form a ring. * Represents a bond to Q.
  • the nitrogen-containing organic compound is an organic compound represented by the general formula (1), and is an organic compound having at least a carbon atom and a nitrogen atom in the molecule.
  • the nitrogen-containing carbon alloy obtained by firing such a nitrogen-containing organic compound and other materials is considered to generate active sites having high oxygen reduction activity consisting of carbon atoms, nitrogen atoms and metals.
  • Q represents an atomic group composed of at least one 5- to 7-membered aromatic ring or 5- to 7-membered heteroaromatic ring.
  • Q is preferably an atomic group composed of only a 5- to 7-membered aromatic ring or a 5- to 7-membered heteroaromatic ring, and a 5- to 7-membered aromatic ring or 5- to 7-membered ring.
  • a heteroaromatic ring is more preferable.
  • Q may be a condensed ring composed of a 5- to 7-membered aromatic ring or a 5- to 7-membered heteroaromatic ring, or a 5- to 7-membered aromatic ring or 5 to 7 It may be an atomic group in which membered heteroaromatic rings are directly connected. That is, the atomic group may be composed of at least one 5- to 7-membered aromatic ring or 5- to 7-membered heteroaromatic ring, and the atomic group includes a 5- to 7-membered aromatic ring.
  • a condensed ring composed of a 5- to 7-membered heteroaromatic ring, a 5- to 7-membered aromatic ring, or a 5- to 7-membered heteroaromatic ring, and a 5- to 7-membered aromatic ring
  • a linking ring in which a 5- to 7-membered heteroaromatic ring is directly connected is included.
  • Q is preferably a 5- to 7-membered aromatic ring or a 5- to 7-membered heteroaromatic ring, preferably a 5- or 6-membered aromatic ring or a 5- or 6-membered ring.
  • the heteroaromatic ring is more preferable.
  • Q is more preferably a benzene ring, a pyridine ring or an imidazole ring.
  • Q since Q has an unsaturated bond, it becomes easy to form a carbon alloy skeleton by various interactions described later.
  • the 5- or 6-membered aromatic ring or the 5- or 6-membered heteroaromatic ring represented by Q is represented by the following general formulas (A-1) to (A-20).
  • a structure is preferred.
  • R 51 ⁇ R 56 represents a linking portion between the R in the general formula (1), the R of the R 51 ⁇ R 56 Groups other than the linking part each independently represent a hydrogen atom or a substituent, and adjacent substituents may be bonded to each other to form a 5- or 6-membered ring.
  • the substituent represented by R 51 to R 56 is not limited as long as it is a substitutable group, but is preferably an aliphatic group, aryl group, heterocyclic group, hydroxyl group, acyl group, aliphatic oxycarbonyl group, substituted A carbamoyl group which may have a group, an ureido group which may have a substituent, an acylamino group, a sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group or a sulfonyl group, and more Preferably, a halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), aliphatic group, aryl group, heterocyclic group, hydroxyl group, aliphatic oxycarbonyl group, carbamoyl group which may have a substituent, Examples thereof include a ureido group and an aliphatic
  • the substituents represented by R 51 to R 56 are alkyl groups (methyl group, ethyl group, t-butyl group, etc.), aryl groups (phenyl group, naphthyl group, etc.), halogen atoms (chlorine atom, bromine atom). , Fluorine atoms, etc.) and heteroaryl groups (pyridyl groups, etc.) are preferred.
  • R 51 to R 56 groups other than the linkage with R are more preferably a hydrogen atom.
  • the number of hydrogen atoms represented by R 51 to R 56 is preferably 1 to 4, more preferably 2 to 4.
  • Q is preferably a 5- to 7-membered nitrogen-containing heteroaromatic ring, more preferably a 5- or 6-membered nitrogen-containing heteroaromatic ring.
  • the nitrogen-containing heteroaromatic ring may contain a heteroatom in addition to a nitrogen atom, but preferably contains only a nitrogen atom as a heteroatom.
  • R in the general formula (1) represents a halogen atom, a substituted or unsubstituted alkyl group, or a substituent represented by the following general formulas (2) to (5), and Q includes a nitrogen-containing heteroaromatic ring.
  • at least one R represents a substituent represented by the following general formulas (2) to (5).
  • Q does not contain a nitrogen-containing heteroaromatic ring
  • Q is an atomic group composed of a 5- to 7-membered aromatic ring, or Q is a 5- to 7-membered heteroaromatic ring.
  • This is an atomic group composed of a ring and a group composed of a heteroaromatic ring in which a nitrogen atom is not a ring constituent atom.
  • R 1 to R 8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
  • R 1 and R 2 , R 3 and R 4 , R 7 and R 8 may be bonded to each other to form a ring. * Represents a bond to Q.
  • At least one R represents a substituent represented by the following general formulas (2) to (5).
  • the nitrogen-containing organic compound includes a structure represented by the general formulas (2) to (5), so that a CN bond is generated in the decomposition product, and the CN and metal interact with each other. Nitrogen is retained until carbonization. Therefore, it is preferable because nitrogen is easily introduced into the graphene of carbon alloy and the oxygen reduction reaction activity can be enhanced.
  • R is a halogen atom. It represents an atom, a substituted or unsubstituted alkyl group, or a substituent represented by the following general formulas (2) to (5).
  • nitrogen is introduced into the heteroaromatic ring, which is more preferable because nitrogen atoms are uniformly introduced into the nitrogen-containing graphene skeleton constituting the carbon alloy and the oxygen reduction reaction activity can be enhanced.
  • R 1 to R 8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
  • R 1 and R 2 , R 3 and R 4 , R 7 and R 8 may be bonded to each other to form a ring.
  • R 1 to R 8 are groups having a substituent, examples of the substituent include the specific examples described above.
  • R 1 to R 4 are preferably each independently a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • R 5 and R 6 are preferably each independently a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • R 7 and R 8 are preferably each independently a hydrogen atom or an alkyl group.
  • R 1 and R 2 , R 3 and R 4 , R 7 and R 8 may be bonded to each other to form a ring.
  • Examples of the ring formed by combining R 1 and R 2 , R 3 and R 4 , R 7 and R 8 with each other include, for example, a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a pyrrole ring, Examples include a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, an oxadiazole ring, a thiazole ring, a thiadiazole ring, a furan ring, a thiophene ring, a selenophene ring, a silole ring, a gelmol ring, a phosphole ring, and a pyrrolidone ring.
  • the ring formed by bonding R 7 and R 8 to each other includes pyrrolidone ring, benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring.
  • a pyrrole ring or a pyrrolidone ring is more preferable.
  • the ring formed by combining R 1 and R 2 , R 3 and R 4 , R 7 and R 8 may further have a substituent.
  • R is preferably a substituent represented by general formula (2).
  • Q is preferably a 5- to 7-membered nitrogen-containing heteroaromatic ring.
  • at least one R is a substituted or unsubstituted alkyl group, or the general formula (2 It is preferable that it is a substituent represented by.
  • the nitrogen-containing organic compound is a compound represented by the general formula (1) in JP2011-225431A. Can be mentioned.
  • n represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.
  • Q represents an atomic group composed of at least one 5- to 7-membered aromatic ring or 5- to 7-membered heteroaromatic ring.
  • a linking ring in which a 5-membered aromatic ring or a 5- to 7-membered heteroaromatic ring is directly connected is included. That is, the nitrogen-containing organic compound represented by the general formula (1) may be a dimer or more multimer in which the general formula (7) or (8) is connected by a single bond.
  • n1 represents an integer of 1 to 5
  • n2 represents an integer of 1 to 6.
  • n1 is preferably 1 to 4, more preferably 2 to 4, and even more preferably 2.
  • n2 is preferably from 1 to 4, more preferably from 2 to 4, and even more preferably 2.
  • the compound represented by the general formula (7) or (8) may have a substituent other than a cyano group, but preferably has only a cyano group.
  • the nitrogen-containing organic compound used in the present invention is a salt of the nitrogen-containing organic compound represented by the general formula (1)
  • the salt of the nitrogen-containing organic compound represented by the general formula (1) 9).
  • Q n + represents, for example, an organic cation represented by the following general formulas (A-21) to (A-24)
  • Y m ⁇ represents an m-valent anion
  • n and m Each independently represents a natural number, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, particularly preferably 1 or 2, and particularly preferably 1.
  • R 61 to R 63 each independently represents a hydrogen atom or an alkyl group.
  • the alkyl group of R 61 to R 63 may have a substituent, and examples of the substituent include the above-described substituents, and a cyano group and a vinyl group can be given as preferable examples. .
  • an alkyl group having 1 to 8 carbon atoms is preferable.
  • a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a hexadecyl group, an octadecyl group Group and allyl group are more preferable, and methyl group, ethyl group, propyl group and butyl group are particularly preferable.
  • R 61 to R 63 may be the same or different, but when the molecule has two or more substituents represented by R 61 to R 63, it may contain at least two kinds of alkyl groups. In this case, it is preferable that any one of R 61 to R 63 represents a methyl group, and the other represents one of an ethyl group, a propyl group, and a butyl group.
  • [Y] n m- in the general formula (9) is a halogen anion (Cl ⁇ , Br ⁇ , F ⁇ , I ⁇ ), BF 4 ⁇ , PF 6 ⁇ , an imide anion [N (SO 2 CF 3 ) 2 ⁇ , N (COCF 3 ) (SO 2 CF 3 ) ⁇ , N (CN) 2 — etc.], Carbanion [C (CN) 3 — etc.], R 21 OSO 3 ⁇ , R 21 SO 3 ⁇ , FeCl 4 ⁇ CoCl 4 2- and the like.
  • R 21 each independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. Further, R 21 is preferably fluorine as a substituent of the alkyl group, more preferably a trifluoroalkyl group, and particularly preferably a trifluoromethyl group.
  • the nitrogen-containing organic compound is preferably a nitrogen-containing crystalline organic compound from the viewpoint of crystallinity that the molecules are easily arranged regularly.
  • the nitrogen-containing crystalline organic compound is preferably other than a nitrogen-containing metal complex. Nitrogen-containing metal complexes are difficult to purify and the composition ratio of nitrogen-containing ligands and metal complexes is constant, so when decomposed during firing, the decomposition rate of nitrogen-containing ligands and the vaporization of coordination metal complexes The speed cannot be controlled and it is difficult to obtain the target nitrogen-containing carbon alloy.
  • the nitrogen-containing metal complex and the low-molecular organic compound are mixed, the nitrogen-containing metal complex crystal is decomposed and the metal is directly reduced, so that the generated adjacent metals are easily aggregated and crystallized. Since the metal is removed by acid cleaning, the obtained nitrogen-containing carbon alloy becomes non-uniform, and there is a fear that the required function may be reduced.
  • the nitrogen-containing crystalline organic compound preferably forms a crystal structure by two or more bonds or interactions selected from ⁇ - ⁇ interaction, coordination bond, charge transfer interaction, and hydrogen bond.
  • the crystal structure here refers to the arrangement and arrangement of molecules in the crystal.
  • the crystal structure consists of a repeating structure of unit cell, and the molecules are arranged at any position in the unit cell and oriented. In the crystal, the molecules have a uniform appearance. That is, since the arrangement of functional groups in the crystal is uniform, each molecular interaction is the same inside or outside the unit cell.
  • aromatic rings for example, in the case of a nitrogen-containing organic compound having a laminated structure, aromatic rings, heterocyclic rings, condensed polycyclic rings, condensed heterocyclic polycyclic rings, unsaturated groups (C ⁇ N group, vinyl group, allyl group, acetylene group), etc.
  • Action for example, an aromatic ring is face-to-face and has a ⁇ - ⁇ interaction ( ⁇ - ⁇ stack)).
  • Stacking is performed by SP 2 orbits of carbons derived from unsaturated bonds in these rings and groups being overlapped regularly at equal intervals between molecules to form a stacked column structure.
  • the nitrogen-containing organic compound is preferably a low-molecular compound, has crystallinity, and is preferably heat-resistant by being relaxed by phonons (quantized lattice vibration) against heat. Therefore, the decomposition temperature is maintained up to the carbonization temperature, the vaporization of the decomposition product is reduced and carbonized, and a carbon alloy skeleton is formed.
  • a crystalline compound is preferable because the orientation can be controlled at the time of firing, so that it becomes a uniform carbon material.
  • the nitrogen-containing organic compound preferably has a melting point of 25 ° C. or higher.
  • the melting point is 25 ° C. or higher, an air layer that contributes to heat resistance during firing exists, boiling or bumping can be suppressed, and a good carbon material can be obtained.
  • the nitrogen-containing organic compound preferably has a molecular weight of 60 to 2000, more preferably 100 to 1500, and still more preferably 130 to 1000. By making the molecular weight within the above range, purification before firing becomes easy.
  • the metal content in the nitrogen-containing organic compound is preferably 10 ppm or less.
  • the metal content in the nitrogen-containing organic compound means a content other than the inorganic metal salt described later.
  • the nitrogen content of the nitrogen-containing organic compound is preferably from 0.1 to 55% by mass, more preferably from 1 to 30% by mass, and even more preferably from 4 to 20% by mass.
  • the nitrogen-containing organic compound is preferably a hardly volatile compound having a ⁇ TG of ⁇ 95% to ⁇ 0.1% at 400 ° C. in a nitrogen atmosphere, and is hardly volatile having a ⁇ 95% to ⁇ 1%. More preferably, the compound is -90% to -5%.
  • the nitrogen-containing organic compound is preferably a hardly volatile compound that is carbonized without being vaporized during firing.
  • ⁇ TG is 10 ° C./min from 30 ° C. to 1000 ° C. under a flow of 100 mL / min in a TG-DTA measurement (simultaneous measurement of differential heat-thermogravimetry) of a mixture of a nitrogen-containing organic compound and an inorganic metal salt. Refers to the mass reduction rate at 400 ° C. based on the mass at room temperature (30 ° C.).
  • At least one selected from the nitrogen-containing organic compound represented by the general formula (1), a tautomer of the nitrogen-containing organic compound, a salt of the nitrogen-containing organic compound, and a hydrate of the nitrogen-containing organic compound is
  • the content of the precursor is preferably more than 0.5% by mass, more preferably 1 to 95% by mass, and still more preferably 5 to 70% by mass.
  • the nitrogen-containing organic compound is also preferably a pigment having a structure represented by the general formula (1).
  • the pigment has a stacked column structure due to ⁇ - ⁇ interaction between molecules. Since hydrogen bonding or van der Waals interaction occurs between the stacked columns, the stacked column structure has a uniform structure with a defined intermolecular distance. For this reason, it has the effect that the heat transfer in a crystal
  • the pigment is a low-molecular compound, it has crystallinity and has heat resistance because the vibration is reduced by phonons (quantized lattice vibration) against heat.
  • pigments include isoindoline pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, oxazine pigments, phthalocyanine pigments, quinophthalone pigments, and latent pigments or dyes made from the above pigments.
  • metal ions such as diketopyrrolopyrrole pigments, quinacridone pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, and latin pigments obtained by latinizing the above pigments.
  • the benzonitrile (Ph-CN) skeleton which is decomposed and formed, becomes a reactive species, and a carbon alloy catalyst having higher oxygen reduction reaction activity is generated.
  • the metal species (M) coexists, a complex of Ph—CN... M is formed, and a carbon alloy that is more active in high oxygen reduction reaction is generated.
  • Covalent organic framework materials and metal organic framework materials Preparation of the precursor in the method for producing a nitrogen-containing carbon alloy of the present invention includes at least selected from a covalent organic framework material (COF) and a metal-organic framework material (MOF).
  • COF covalent organic framework material
  • MOF metal-organic framework material
  • the covalent organic skeleton material (COF) and the metal organic skeleton material (MOF) are porous materials, and there are innumerable pores of several nm in the structure.
  • the porous material may be a structure having pores therein, and an organic skeleton material or a metal organic skeleton material can be preferably used.
  • the pore diameter of the porous material used in the present invention is preferably from 0.1 to 100 nm, and more preferably from 0.2 to 10 nm.
  • the porous material preferably has one or more of micropores having a pore diameter of 2 nm or less, 2 to 50 nm mesopores, and 50 nm to macropores, and more preferably mesopores.
  • the pore diameter is in this range, it is preferable because the number of action points increases and the generated water is easily discharged. Further, it is preferable because the internal pores of the porous material have a pore volume and easily interact with oxygen.
  • an inorganic metal salt or an organometallic complex and a nitrogen-containing organic compound are formed inside the pores of the added material.
  • a covalent organic framework material COF
  • MOF metal organic framework material
  • an inorganic metal salt or an organometallic complex and a nitrogen-containing organic compound are formed inside the pores of the added material.
  • At least one selected from a covalent organic skeleton material and a metal organic skeleton material is preferably included in an amount exceeding 5% by mass with respect to the total mass of the precursor, and is included in an amount of 10 to 95% by mass.
  • the content is more preferably 20 to 70% by mass.
  • Covalent organic skeletal material is a material having a crystalline porous structure using only an organic skeleton.
  • the porous structure is formed from a two-dimensional or three-dimensional network of organic compounds linked by covalent bonds.
  • the covalent organic framework material (COF) preferably contains at least one atom of an element other than carbon, such as hydrogen, oxygen, nitrogen, silicon, phosphorus, selenium, fluorine, boron or sulfur.
  • covalent organic skeleton material for example, Science, 2005, 310, 1166. J. et al. Am. Chem. Soc. 2007, 129, 12914. , Science, 2007, 316, 268. , J .; Am. Chem. Soc. , 2009, 131, 4570. Chem. Matter, 2006, 18, 5296. , Angew. Chem. , Int. Ed. 2008, 47, 8826.
  • Covalent organic skeletal materials (COF) described in US Patent Publication No. US2006 / 015480780A1 and JP-T 2010-516869 are preferably used.
  • a metal organic framework material is a material having a porous structure utilizing a coordinate bond between a metal ion and an organic substance.
  • an organic compound coordinated to at least one metal ion forms a porous structure.
  • the metal ions constituting the metal organic framework material (MOF) can be almost any metal of the periodic table, but among them, it is preferable to be Co 2+ , Ni 2+ , Cu 2+ , Fe 2+ , Fe 3+ or Zn 2+. Zn 2+ is more preferable.
  • Examples of organic substances that form a coordinate bond with a metal ion include 3-pyridyltriazine, 4-pyridyltriazine, alkylimidazole, bipyridine, terephthalic acid, 2,6-naphthalenedicarboxylic acid, or 1,3,5-benzenetricarboxylic acid.
  • 3-pyridyltriazine, 4-pyridyltriazine, alkylimidazole, or bipyridine is more preferable
  • 3-pyridyltriazine, 4-pyridyltriazine, or alkylimidazole is particularly preferable.
  • the metal organic framework material (MOF) is particularly preferably an equi-reticular metal organic framework material (IRMOF) or a zeolite type imidazole framework material (ZIF).
  • the metal ion becomes the core of the metal organic framework material (MOF), and the core is linked using a linking ligand or a linking moiety.
  • the core refers to a repeating unit (single or plural) found in the skeleton.
  • Such a skeleton may include a uniform repeating core structure or a non-uniform repeating core structure.
  • the core includes a metal or metal cluster and a connecting portion, and a skeleton is defined by a plurality of cores connected to each other.
  • the metal cluster is a combination of two or more metal atoms.
  • the linking moiety refers to a monodentate or multidentate compound that bonds a metal or a plurality of metals through a linking cluster.
  • the linking moiety includes a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aryl group.
  • the linking part may contain nitrogen, oxygen, sulfur, boron, phosphorus, silicon or aluminum in addition to the carbon atom.
  • a linking cluster refers to one or more condensable reactive species containing atoms that can form a bond between a linking moiety and a metal, or between a linking moiety and another linking moiety. .
  • Examples of such species are preferably selected from the group consisting of boron, oxygen, carbon, nitrogen, and phosphorus atoms.
  • the linked cluster includes, for example, —COOH, —CS 2 H, —NO 2 , —SO 3 H, —Si (OH) 3 , —Ge (OH) 3 , —Sn (OH) 3 , —Si (SH) 4.
  • R is an alkyl group having 1 to 20 carbon atoms or an aryl group.
  • metal organic framework materials examples include US Pat. No. 5,648,508, US Pat. No. 7,196,210, European Patent Publication No. EP 0790253 A2, O'Keeff et al. Sol. State Chem. , 152 (2000), pages 3 to 20, H .; Li et al., Nature 402, (1999), p. Edaudi et al., Topics, in, Catalysis 9 (1999), pp. 105-111; Chen et al., Science 291, (2001), pages 1021-1023, German Patent Publication DE10111230 A1, European Patent Publication EP1785428A1, International Publication WO2007 / 045481, International Publication WO2005 / 044982 and International Publication WO2007.
  • the materials described in Japanese Patent No. 023134 can be used. Among these, ZIF-8 (Zn (2-Methylimidazole)) is preferable.
  • metal organic framework material As the metal organic framework material (MOF), a restricted framework material having a polyhedral structure in which the porous structure does not expand infinitely may be used. Such materials are formed by special selection of organic compounds. For example, A.I. C. Sudik et al. Am. Chem. Soc. 127 (2005), 7110-7118 describes such a specific skeletal material and is specifically called a metal organic polyhedron (MOP). In the present invention, such a metal organic polyhedron (MOP) is also preferably used.
  • MOP metal organic polyhedron
  • Inorganic metal salts and organometallic complexes For the preparation of the precursor in the method for producing a nitrogen-containing carbon alloy of the present invention, at least one selected from inorganic metal salts and organometallic complexes is used.
  • the inorganic metal salt is not particularly limited, but hydroxide, oxide, nitride, sulfite, sulfide, sulfonate, carbonylate, nitrate, nitrite, halide and the like can be used.
  • the counter ion is a halogen ion or a nitrate ion.
  • the counter ion is a halide or nitrate in which a halogen ion, a nitrate ion or a sulfate ion is used, because the specific surface area can be increased by binding to carbon on the carbon surface generated during the thermal decomposition.
  • the inorganic metal salt is preferably a halide, and particularly preferably an inorganic metal chloride.
  • the inorganic metal salt can contain crystal water, and the inorganic metal salt is preferably a hydrated salt. Since the inorganic metal salt contains crystal water, the thermal conductivity is improved, which is preferable in that it can be uniformly fired.
  • the inorganic metal salt containing crystal water for example, cobalt chloride (III) hydrate salt, iron chloride (III) hydrate salt, cobalt chloride (II) hydrate salt, iron chloride (II) hydrate salt is preferably used. it can.
  • the metal species of the inorganic metal salt is preferably at least one of Fe, Co, Ni, Mn and Cr, more preferably Fe or Co, and even more preferably Fe.
  • Fe, Co, Ni, Mn, and Cr salts are excellent in forming a nano-sized shell structure that improves the catalytic activity of the carbon catalyst, and in particular, Co and Fe form a nano-sized shell structure. It is preferable because it is particularly excellent.
  • Co and Fe contained in the carbon catalyst can improve the oxygen reduction activity of the catalyst in the carbon catalyst. Most preferably, it is Fe as a transition metal.
  • the Fe-containing nitrogen-containing carbon alloy has a high rising potential, has a higher number of reaction electrons than Co, and can relatively improve the durability of the fuel cell.
  • elements other than transition metals for example, B, alkali metals (Na, K, Cs), alkaline earths (Mg, Ca, Ba), lead, tin, indium, thallium, etc. ) May be included in one or more types.
  • the present invention there is an advantage that it is not necessary to uniformly disperse the nitrogen-containing organic compound and the inorganic metal salt in the organic material before firing. That is, when the nitrogen-containing organic compound is decomposed by firing, if the decomposition product is in contact with a vaporized substance such as an inorganic metal salt, it is considered that an active species having oxygen reduction reaction activity is formed. The oxygen reduction reaction activity of the carbon alloy is not affected by the mixed state of the nitrogen-containing organic compound and the inorganic metal salt.
  • the particle diameter of the inorganic metal salt is preferably 0.001 to 100 ⁇ m. More preferably, it is 0.01 to 10 ⁇ m. By making the particle size of the inorganic metal salt within this range, it becomes possible to uniformly mix with the nitrogen-containing organic compound, and the nitrogen-containing organic compound is likely to form a complex when decomposed.
  • the precursor contains at least one selected from inorganic metal salts and organometallic complexes.
  • organometallic complexes include compounds described in the Basic Complex Engineering Study Group, Coordination Chemistry-Fundamentals and Latest Topics, and Kodansha Scientific (1994).
  • a compound in which a ligand is coordinated can be preferably exemplified, and at least one selected from a metal acetate complex, a ⁇ -diketone metal complex, and a salen complex can be preferably used.
  • the organometallic complex may be a derivative of the above-described metal complex.
  • the organometallic complex can take the coordination number of various ligands, may be a coordination geometric isomer, and may have different valences of metal ions.
  • the organometallic complex may be an organometallic compound having a metal-carbon bond.
  • Preferred as metal ions are Fe, Co, Ni, Mn and Cr ions.
  • Preferable ligands include monodentate ligands (halide ions, cyanide ions, ammonia, pyridine (py), triphenylphosphine, carboxylic acid, etc.), bidentate ligands (ethylenediamine (en), ⁇ - Diketonate (acetylacetonate (acac), pivaloylmethane (DPM), diisobutoxymethane (DIBM), isobutoxypivaloylmethane (IBPM), tetramethyloctadione (TMOD)), trifluoroacetylacetonate (TFA), bipyridine (Bpy), phenanthrene (phen), etc.), polydentate ligands (ethylenediaminetetraacetate ion (edta), N, N′-bis (salicylidene) ethylenediamine (sal
  • the metal complex examples include the ⁇ -diketone metal complex (bis (acetylacetonato) iron (II) [Fe (acac) 2 ], tris (acetylacetonato) iron (III) [Fe ( acac) 3 ], bis (acetylacetonato) cobalt (II) [Co (acac) 2 ], tris (acetylacetonato) cobalt (III) [Co (acac) 3 ], bis (dipivaloylmethane) iron (II) [Fe (DPM) 2 ], tris (dipivaloylmethane) iron (III) [Fe (DPM) 3 ], tris (dipivaloylmethane) cobalt (III) [Co (DPM) 3 ] , bis (diisobutoxyphenyl methane) iron (II) [Fe (DIBM) 2], tris (diisobutoxyphen
  • ⁇ -diketone metal complexes bis (acetylacetonato) iron (II) [Fe (acac) 2 ], tris (acetylacetonato) iron (III) [Fe (acac) 3 ], bis (dipivaloyl) Methane) iron (II) [Fe (DPM) 2 ], bis (diisobutoxymethane) iron (II) [Fe (DIBM) 2 ], bis (isobutoxypivaloylmethane) iron (II) [Fe (IBPM) 2 ], bis (tetramethyloctadione) iron (II) [Fe (TMOD) 2 ]), N, N′-ethylenediaminebis (salicylideneaminato) iron (II) [Fe (salen)], tris (2,2'-bipyridine) iron (II) chloride [Fe (bpy) 3] Cl 2, iron
  • the organometallic complex preferably contains a ⁇ -diketone metal complex.
  • a ⁇ -diketone metal complex may be used alone, or a ⁇ -diketone metal complex and another organometallic complex may be mixed and used.
  • the ⁇ -diketone metal complex represents a compound represented by the following general formula (10) and tautomers thereof.
  • M represents a metal
  • R 1 and R 3 each independently represents a hydrocarbon group which may have a substituent
  • R 2 has a hydrogen atom or a substituent.
  • the hydrocarbon group which may be carried out is shown.
  • R 1 , R 2 and R 3 may be bonded to each other to form a ring.
  • n represents an integer of 0 or more
  • m represents an integer of 1 or more.
  • the ⁇ -diketone or its ion is coordinated or bonded to the atom or ion of the metal M.
  • Preferred metals include Fe, Co, Ni, Mn and Cr, more preferably Fe and Co, and still more preferably Fe.
  • examples of the “hydrocarbon group” in the hydrocarbon group which may have a substituent of R 1 , R 2 , and R 3 include an aliphatic hydrocarbon group and an alicyclic hydrocarbon.
  • Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, and hexyl groups (C 1-6 alkyl groups); An alkenyl group ( C2-6 alkenyl group etc.) etc. are mentioned.
  • Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl and cyclohexyl groups (3 to 15-membered cycloalkyl groups and the like); cycloalkenyl groups such as cyclohexenyl groups (3 to 15-membered cycloalkenyl groups and the like) ); A bridged carbocyclic group such as an adamantyl group (such as a bridged carbocyclic group having about 6 to 20 carbon atoms).
  • Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group (aryl group) having about 6 to 20 carbon atoms such as a phenyl group and a naphthyl group.
  • Heterocyclic (heterocyclic) hydrocarbon groups include, for example, nitrogen-containing five-membered hydrocarbon groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing six-membered pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl groups Member ring hydrocarbon group; pyrrolidinyl group, indolizinyl group, isoindolyl group, isoinindolinyl group, indolyl group, indazolyl group, purinyl group, quinolidinyl group, quinolinyl group, naphthyridinyl group, phthalazinyl group, quinoxalinyl group, cinnolinyl group, pteridinyl group Nitrogen-containing condensed bicyclic hydrocarbon groups such as carbazolyl group, ⁇ -carbolinyl group, phenanthridinyl group, a
  • Examples of the substituent that the hydrocarbon group may have include, for example, a halogen atom such as fluorine, chlorine, bromine atom; an alkoxy group such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy, t-butyloxy group (C 1-4 alkoxy group etc.); hydroxyl group; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups (C 1-4 alkoxy-carbonyl group etc.); acyl groups such as acetyl, propionyl and benzoyl groups (C 1- 1 10 acyl group); cyano group; nitro group and the like.
  • a halogen atom such as fluorine, chlorine, bromine atom
  • an alkoxy group such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy, t-butyloxy group (C 1-4 alkoxy
  • R 1 , R 2 , and R 3 are each bonded to each other to form a ring of, for example, a 5- to 15-membered cyclohexane such as a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, or a cyclohexene ring.
  • a 5- to 15-membered cyclohexane such as a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, or a cyclohexene ring.
  • Examples include an alkane ring and a cycloalkene ring.
  • R 1 and R 3 in the general formula (10) are an alkyl group (C 1-6 alkyl group etc.), an alkenyl group (C 2-6 alkenyl group etc.), a cycloalkyl group (3 to 15 membered cycloalkyl group). Etc.), cycloalkenyl groups (3- to 15-membered cycloalkenyl groups, etc.), aryl groups (C 6-15 aryl groups, etc.), substituted aryl groups (p-methylphenyl groups, p-hydroxyphenyl groups, etc.) C 6-15 aryl group having a substituent, etc.) are preferred.
  • R 2 includes a hydrogen atom, an alkyl group (C 1-6 alkyl group, etc.), an alkenyl group (C 2-6 alkenyl group, etc.), a cycloalkyl group (3-15 membered cycloalkyl group, etc.), a cycloalkenyl group. (3- to 15-membered cycloalkenyl group etc.), aryl group (C 6-15 aryl group etc.), aryl group having a substituent (C 6 having a substituent such as p-methylphenyl group, p-hydroxyphenyl group) -15 aryl group, etc.) are preferred.
  • the valence n of the metal may be any of 0, 1, 2, 3 and the like, but is usually divalent or trivalent.
  • the ⁇ -diketone coordinates as the corresponding anion, ⁇ -diketonate.
  • the coordination number m is usually the same.
  • a solvent or the like may be axially coordinated with the metal. In that case, the valence n and the coordination number m of the metal may be different. Examples of the solvent that may be axially coordinated include pyridine, acetonitrile, alcohol, and the like, but are not particularly limited as long as they are axially coordinated.
  • ⁇ -diketone iron complex As the ⁇ -diketone iron complex, a commercially available product may be used as it is or after purification, or it may be prepared and used. It can also be generated and used in a reaction system. When it is generated in the reaction system, for example, iron chloride, hydroxide and ⁇ -diketone such as acetylacetone may be added. At this time, a base such as ammonia, amines, alkali metal or alkaline earth metal hydroxides, carbonates or carboxylates can be added as necessary.
  • a base such as ammonia, amines, alkali metal or alkaline earth metal hydroxides, carbonates or carboxylates can be added as necessary.
  • At least one selected from an inorganic metal salt and an organometallic complex is preferably contained in an amount exceeding 0.1% by mass, and 0.5 to 85% by mass with respect to the total mass of the precursor. More preferably, the content is 0.5 to 70% by mass.
  • a carbon alloy having higher oxygen reduction activity can be generated by interaction with a nitrogen atom.
  • at least one selected from inorganic metal salts and organometallic complexes may be 0.1 to 10% by mass relative to the total mass of the precursor.
  • a nitrogen-containing organic compound having a specific structure in combination with a covalent organic skeleton material and a metal organic skeleton material at least one selected from inorganic metal salts and organometallic complexes is used. Even when the content is kept low, a carbon alloy having high oxygen reduction activity can be generated.
  • the oxygen reduction activity can be measured as an ORR activity value by obtaining a potential by the method described in detail in Examples.
  • ORR activity it is preferred high value of the potential at the time of oxygen reduction, specifically, the potential at a current density value -2 mA / cm 2 in the electrode coating amount of 0.5 mg / cm 2, 0 .67V or more is preferable, 0.70V or more is more preferable, and 0.73V or more is more preferable.
  • the coating amount and the current density increase linearly, but as the coating amount increases, the current density decreases from the assumed straight line due to an increase in resistance between carbon alloy particles, an increase in diffusion resistance of oxygen and water, and the like.
  • the coating amount and the potential are similarly deviated from the straight line in the relationship between the coating amount and the potential.
  • the value of the potential at 0.5 mg / cm 2 is a value that takes into account the potential of the catalyst activity at 0.05 mg / cm 2 and the conductivity of the carbon alloy. By making this potential range, the conductivity is excellent. This is particularly preferable.
  • the nitrogen-containing organic compound By firing an organic material containing a nitrogen-containing organic compound, the nitrogen-containing organic compound is decomposed, and the generated decomposition product forms a nitrogen-containing carbon alloy catalyst in the gas phase. At that time, if a metal is present in the vicinity of the gas phase, the decomposition product interacts with the metal (forms a complex), and the performance of the nitrogen-containing carbon alloy catalyst is further improved.
  • the nitrogen atom (N) is immobilized on the surface of the carbon catalyst at a high concentration due to the catalytic action of a specific transition metal compound added to the nitrogen-containing organic compound containing the nitrogen atom (N) as a constituent element.
  • carbon fine particles containing a transition metal compound that forms a nitrogen carbon alloy and interacts with the nitrogen atom (N) are formed.
  • the transition metal compound which interacted with some nitrogen atoms (N) by the acid treatment mentioned later may drop off.
  • a conductive additive may be added to the precursor and fired, or may be added to the carbon alloy. Since a conductive support agent is disperse
  • a conductive support agent For example, Norrit (made by NORIT), Ketjen black (made by Lion), Vulcan (made by Cabot), black pearl (made by Cabot), acetylene black (Chevron) Carbon black such as (manufactured) (all are trade names), graphite, and carbon materials such as fullerenes such as C60 and C70, carbon nanotubes, carbon nanohorns, and carbon fibers.
  • the addition rate of the conductive auxiliary is preferably 0.01 to 50% by mass, more preferably 0.1 to 20% by mass, and more preferably 1 to 10% by mass with respect to the total mass of the precursor. More preferably it is.
  • the method for producing the nitrogen-containing carbon alloy of the present invention comprises: (1) A precursor is prepared by mixing a nitrogen-containing organic compound, at least one selected from a covalent organic skeleton material and a metal organic skeleton material, and at least one selected from an inorganic metal salt and an organometallic complex. Process, (2) a temperature raising step of raising the temperature of the precursor from 1 to 2000 ° C. per minute from room temperature to the carbonization temperature under an inert atmosphere; (3) a carbonization step of holding at 400 to 2000 ° C. for 1 second to 100 hours; (4) It is preferable to include a cooling step of cooling from the carbonization temperature to room temperature.
  • the manufacturing method of the nitrogen-containing carbon alloy of the present invention is the firing step, (6) It preferably includes a step of washing the baked nitrogen-containing carbon alloy with an acid, (7) More preferably, after the acid cleaning step, a step of refiring the acid-cleaned nitrogen-containing carbon alloy is included.
  • the steps (1) to (7) will be described in order with respect to the method for producing a nitrogen-containing carbon alloy of the present invention.
  • Precursor preparation step In the precursor preparation step, the above-mentioned nitrogen-containing organic compound, at least one selected from a covalent organic skeleton material and a metal organic skeleton material, an inorganic metal salt and an organometallic complex are used.
  • a precursor is prepared by mixing at least one selected.
  • the precursor prepared in the production process of the nitrogen-containing carbon alloy is then fired, but preferably further includes a step of pulverizing the precursor before the firing step.
  • the pulverization method can be any method known to those skilled in the art, for example, using ball mill, agate pulverization, mechanical pulverization, etc. And can be crushed.
  • the mechanical pulverization method is preferably used.
  • the specific surface area of the produced nitrogen-containing carbon alloy is increased, and high oxygen reduction activity (ORR activity) is obtained.
  • ORR activity oxygen reduction activity
  • machine pulverization for example, X-TREME MX1200XTM manufactured by Waring Co., Ltd. can be used.
  • mixing is preferably performed at a rotating blade rotation speed of 80 to 30000 rpm, more preferably 300 to 25000 rpm, and even more preferably 1300 to 20000 rpm.
  • the rotation method can be performed by continuous rotation, intermittent rotation, or a combination of continuous and intermittent rotation.
  • the pulverization time is preferably from 0.1 seconds to 15 minutes, and the pulverization frequency is preferably at least once.
  • the stop time of the rotary blade is preferably 0.1 to 100 times, more preferably 1 to 50 times, and further preferably 2 to 30 times the pulverization time.
  • the pulverization time is 10 seconds or less
  • the rotary blade stop time is 0.1 times or more
  • the number of pulverizations is 2 times or more
  • decomposition of the precursor mixture by heat is reduced, and the precursor mixture Since the mixing can be made uniform, the oxygen reduction reaction activity can be increased more effectively.
  • the pulverization time by continuous pulverization is 30 seconds or more
  • the precursor mixture generates heat, and at least one kind of pores selected from a covalently bonded organic skeleton material and a metal organic skeleton material has a nitrogen-containing organic compound and a nitrogen-containing organic compound.
  • the oxygen reduction reaction activity can be increased.
  • the nitrogen-containing organic compound having a specific structure, its tautomer, its salt and its hydrate The precursor containing at least one selected from the group consisting of at least one selected from the group consisting of a covalent organic skeleton material and a metal organic skeleton material and at least one selected from inorganic metal salts and organometallic complexes is heated to a carbonization temperature. After the heat treatment, it is preferable to cool to room temperature.
  • the temperature may be raised in multiple stages in the temperature raising process of the temperature raising process and the re-baking process described later.
  • the latter stage of the temperature raising process may be carried out by holding the temperature after the completion of the preceding temperature raising process or by raising the temperature as it is.
  • the temperature may be raised and a subsequent temperature increase process may be performed.
  • the sample after a process may be grind
  • the metal may be removed by acid cleaning of the sample after the treatment in (6) acid cleaning step described later.
  • the sample before treatment may be inserted from the normal temperature to a predetermined temperature after being inserted into the carbonization apparatus, or the temperature may be increased by inserting the sample before treatment into the carbonization apparatus at the predetermined temperature. May be warm.
  • the temperature of the sample before processing is raised from room temperature to a predetermined temperature.
  • the rate of temperature increase is preferably 1 to 2000 ° C./min, more preferably 1 to 1000 ° C./min, and 1 to 500 ° C./min. Is more preferable.
  • the pre-treatment of the organic material containing the nitrogen-containing organic compound, the covalently bonded organic skeleton material or the metal organic skeleton material, the inorganic metal salt, etc. is performed at a relatively low temperature. Preferably it is done. In such a low temperature treatment, a constant temperature may be maintained. As a result, only the heat-stable structure can be maintained, and unstable impurity components, solvents, and the like can be removed.
  • the temperature of the organic material containing the nitrogen-containing organic compound and the inorganic metal salt is preferably raised to 100 to 1500 ° C., more preferably raised to 150 to 1050 ° C., More preferably, the temperature is raised to 200 to 1000 ° C. Thereby, a uniform preliminary carbide is obtained.
  • the inert atmosphere refers to a gas atmosphere such as a nitrogen gas or a rare gas atmosphere. Note that even if oxygen is contained, the atmosphere may be any atmosphere in which the amount of oxygen is limited to such an extent that the workpiece is not combusted.
  • the inert atmosphere may be either a closed system or a distribution system for circulating a new gas, and is preferably a distribution system. In the case of a circulation system, it is preferable to circulate a gas of 0.01 to 2.0 liter / min per 36 mm ⁇ inner diameter, and a gas of 0.05 to 1.0 liter / min per 36 mm ⁇ inner diameter. More preferably, it is particularly preferable to circulate a gas of 0.1 to 0.5 liter / min per 36 mm ⁇ inside diameter.
  • the temperature holding time is 1 second to 100 hours, preferably 1 minute to 50 hours, and more preferably 5 minutes to 10 hours. Even if the carbonization treatment is performed for more than 100 hours, an effect corresponding to the treatment time may not be obtained.
  • the heating device used in the above temperature raising treatment is not particularly limited, but is a tubular furnace (Kantar wire furnace, imaging furnace), muffle furnace, vacuum gas replacement furnace, rotary furnace (rotary kiln), roller hearth kiln, pusher kiln, multistage It is preferable to use a furnace, a tunnel furnace, a fluidized firing furnace or the like, and it is more preferable to use a tubular furnace (a cantal wire furnace, an imaging furnace), a muffle furnace, a rotary furnace (rotary kiln), a fluidized firing furnace, a tubular furnace (a cantal wire) Furnaces, imaging furnaces) and muffle furnaces are particularly preferred.
  • the portions of the temperature rise treatment are collectively referred to as an infusible treatment.
  • an infusible treatment a nitrogen-containing organic compound having a specific structure in the previous stage, at least one selected from a covalent organic skeleton material and a metal organic skeleton material, and an inorganic metal salt and an organometallic complex are selected.
  • the subsequent temperature raising treatment is continuously performed following the temperature raising treatment of the precursor containing at least one kind.
  • the residual heat of the previous stage can be utilized, the decomposition reaction and the carbonization reaction of the organic material can be continuously performed, and the decomposition product and the metal interact with each other, so that the metal is more active. It can be stabilized with.
  • the subsequent temperature increase treatment is preferably performed in an inert atmosphere
  • the inert atmosphere may be either a closed system or a distribution system for circulating a new gas, and is preferably a distribution system.
  • a circulation system it is preferable to circulate a gas of 0.01 ml to 2.0 liter / min per 36 mm ⁇ inner diameter, and a gas of 0.02 ml to 1.0 liter / min per 36 mm ⁇ inner diameter. More preferably, a gas of 0.05 milliliter to 0.5 liter / min is circulated per 36 mm ⁇ inside diameter.
  • the downstream gas flow rate may be different from the upstream gas flow rate.
  • the temperature holding time is 1 second to 100 hours, preferably 1 minute to 50 hours, and more preferably 5 minutes to 10 hours. Even if the carbonization treatment is performed for more than 100 hours, an effect corresponding to the treatment time may not be obtained.
  • the heating device used in the above temperature raising treatment is not particularly limited, but is a tubular furnace (Kantar wire furnace, imaging furnace), muffle furnace, vacuum gas replacement furnace, rotary furnace (rotary kiln), roller hearth kiln, pusher kiln, multistage It is preferable to use a furnace, a tunnel furnace, a fluidized firing furnace or the like, and it is more preferable to use a tubular furnace (a cantal wire furnace, an imaging furnace), a muffle furnace, a rotary furnace (rotary kiln), a fluidized firing furnace, a tubular furnace (a cantal wire) Furnaces, imaging furnaces) and muffle furnaces are particularly preferred.
  • the firing temperature of the carbonization treatment of the precursor containing a nitrogen-containing organic compound having a specific structure and an inorganic metal salt is not particularly limited as long as the nitrogen-containing organic compound is thermally decomposed and carbonized.
  • the upper limit of is required to be 2000 ° C.
  • the lower limit of the reaction temperature is preferably 400 ° C, more preferably 500 ° C, and even more preferably 600 ° C. 700 ° C. is even more preferable.
  • reaction temperature is 2000 degrees C or less, nitrogen will remain in carbon skeleton and it can be set as desired N / C atomic ratio, and sufficient oxygen reduction reaction activity will be obtained.
  • the firing temperature is preferably 600 to 1500 ° C., more preferably 700 to 1200 ° C., and particularly preferably 700 to 1050 ° C.
  • carbonization treatment is performed within this range, the yield of carbon alloy may be reduced, but the crystallite size of the obtained carbon alloy is uniform, so that the metal is uniformly distributed and the state of high activity is maintained. The As a result, it becomes possible to produce a carbon alloy having excellent oxygen reduction performance. Further, by performing the carbonization treatment within the above range, nitrogen easily remains in the carbon skeleton due to the action of the generated inorganic metal, and the oxygen reduction reaction activity can be enhanced.
  • the temperature raising treatment is preferably performed under a flow of an inert gas or a non-oxidizing gas, and these atmospheres may be either a closed system or a flow system through which a new gas is circulated. is there.
  • the gas flow rate is preferably 0.01 to 2.0 liters / min per 36 mm ⁇ inner diameter, and 0.02 to 1.0 liter / min per 36 mm ⁇ inner diameter. Is more preferable, and it is particularly preferably 0.05 to 0.5 liter / min per 36 mm ⁇ inside diameter. It is preferable for the flow rate to be within this range because the desired nitrogen-containing carbon alloy can be suitably obtained.
  • the treatment time for the carbonization treatment is 1 second to 100 hours, preferably 1 minute to 50 hours, and more preferably 1 hour to 10 hours.
  • the oxygen reduction reaction activity can be enhanced.
  • a nitrogen-containing organic compound present outside the pores of the covalently bonded organic skeleton material or the metal organic skeleton material, a tautomer of the nitrogen-containing organic compound, Of the salt of the nitrogen-containing organic compound, the hydrate of the nitrogen-containing organic compound, the inorganic metal salt, and the organometallic complex, unnecessary substances that have not been used in the carbonization reaction can be volatilized.
  • the holding time to 1 to 10 hours, the decomposition product of the precursor mixture can be removed, and the oxygen reduction reaction activity can be enhanced more effectively.
  • the heating device used in the above temperature raising treatment is not particularly limited, but is a tubular furnace (Kantar wire furnace, imaging furnace), muffle furnace, vacuum gas replacement furnace, rotary furnace (rotary kiln), roller hearth kiln, pusher kiln, multistage It is preferable to use a furnace, a tunnel furnace, a fluidized firing furnace or the like, and it is more preferable to use a tubular furnace (a cantal wire furnace, an imaging furnace), a muffle furnace, a rotary furnace (rotary kiln), a fluidized firing furnace, a tubular furnace (a cantal wire) Furnaces, imaging furnaces) and muffle furnaces are particularly preferred.
  • the carbon alloy may be cooled to room temperature and then crushed.
  • the pulverization treatment can be performed by any method known to those skilled in the art.
  • the pulverization can be performed using a ball mill, agate pulverization, mechanical pulverization, or the like.
  • the method for producing a nitrogen-containing carbon alloy of the present invention may include an acid washing process for washing the fired nitrogen-containing carbon alloy with an acid after the firing process.
  • the ORR activity can be improved by acid cleaning of the metal on the surface of the produced carbon alloy catalyst.
  • any aqueous Bronsted (proton) acid including a strong acid or a weak acid having a pH of 7 or less can be used in the acid cleaning step.
  • an inorganic acid (mineral acid) or an organic acid can be used.
  • Suitable acids include HCI, HBr, HI, H 2 SO 4 , H 2 SO 3 , HNO 3 , HClO 4 , [HSO 4 ] ⁇ , [HSO 3 ] ⁇ , [H 3 O] + , H 2 [C 2 O 4 ], HCO 2 H, HCIO 3 , HBrO 3 , HBrO 4 , HIO 3 , HIO 4 , FSO 3 H, CF 3 SO 3 H, CF 3 CO 2 H, CH 3 CO 2 H, B (OH) 3 , etc. (including any combination thereof), but are not limited to these. Further, the method described in JP-T-2010-524195 can also be used in the present invention.
  • the manufacturing method of the nitrogen-containing carbon alloy of this invention further includes the process of grind
  • a refiring step By such a refiring step, the potential can be improved with an increase in the coating amount when the nitrogen-containing carbon alloy is applied to the electrode, and the ORR activity can be improved.
  • MOF decomposes and the metal is volatilized and desorbed from the carbon material, so that it can be made porous and the specific surface area can be increased. Can be increased.
  • the calcining temperature in the refiring process is preferably 500 to 2000 ° C, and preferably 600 to 1500 ° C. Is more preferable, and a temperature of 1000 to 1500 ° C. is even more preferable.
  • firing may be performed in a pressurized state during the reaction.
  • the gas discharge port may be trapped with water and fired in a state where back pressure is applied.
  • the pressure in the carbonization step is 0.01 to 5 MPa, preferably 0.05 to 1 MPa, more preferably 0.08 to 0.3 MPa, and particularly preferably 0.09 to 0.15 MPa.
  • the method of the refiring step is not particularly limited, but preferably a tubular furnace, a rotary furnace (rotary kiln), a roller hearth kiln, a pusher kiln, a multi-stage furnace, a vacuum gas replacement furnace, a tunnel furnace, a fluidized firing furnace, and the like are more preferable.
  • a rotary furnace rotary kiln
  • a vacuum gas replacement furnace a vacuum gas replacement rotary furnace (rotary kiln)
  • a tunnel furnace and a fluidized firing furnace
  • a vacuum gas replacement rotary furnace vacuum gas replacement rotary furnace
  • the apparatus used for deaeration is not particularly limited as long as it can be deaerated, but it is preferable to use a vacuum gas replacement furnace or a vacuum gas replacement rotary furnace (rotary kiln).
  • the pressure at the time of vacuum deaeration is not particularly limited, but is preferably 4 ⁇ 10 4 Pa or less, more preferably 4 ⁇ 10 3 Pa or less, and particularly preferably 2 ⁇ 10 2 Pa or less.
  • the apparatus used at this time is not particularly limited as long as it can flow the carbon alloy, but it is preferable to use a rotary furnace (rotary kiln), a vacuum gas replacement rotary furnace (rotary kiln), or a fluidized firing furnace.
  • a rotary furnace (rotary kiln) or a vacuum gas replacement rotary furnace (rotary kiln) the sample tube is rotated during firing, but the rotational speed, speed change, etc. are not particularly limited.
  • the rotation speed is preferably 10 rpm or less, more preferably 5 rpm or less. By setting the rotation speed within this range, rubbing occurs between the tube wall and the preparatory carbon, and the carbon alloy is further refined and made porous. Therefore, the oxygen reduction reaction activity can be enhanced more effectively.
  • the method for producing a nitrogen-containing carbon alloy of the present invention it is preferable to perform a carbonization treatment in the presence of an activator (activation step).
  • an activator activation step
  • the pores of the carbon alloy develop and the surface area increases, and the exposure of the metal on the surface of the carbon alloy improves, thereby improving the performance as a catalyst.
  • the surface area of the carbide can be measured by the N 2 adsorption amount.
  • the activator that can be used is not particularly limited.
  • carbon dioxide, ammonia gas, water vapor, air, oxygen gas, hydrogen gas, carbon monoxide gas, methane gas, alkali metal hydroxide, zinc chloride, and phosphoric acid At least one selected from the group consisting of carbon dioxide, ammonia gas, water vapor, air, and oxygen gas can be used, more preferably at least one selected from the group consisting of:
  • the gas activator is preferably diluted with an inert gas.
  • the inert gas to be diluted include nitrogen gas and rare gases (for example, argon gas, helium gas, and neon gas).
  • the gas activator may be contained in the atmosphere of carbonization treatment in an amount of 2 to 80 mol%, preferably 10 to 60 mol%. By including the gas activator so as to be within the above range, a sufficient activation effect can be obtained.
  • the solid activator such as alkali metal hydroxide may be mixed with the carbonized substance in a solid state, or after being dissolved or diluted with a solvent such as water, impregnated with the carbonized substance or in a slurry state. And may be kneaded into the article to be carbonized. The liquid activator may be diluted with water or the like and then impregnated with the carbonized material or kneaded into the carbonized material.
  • the pressure in the gas phase may be any of normal pressure, pressurization, and reduced pressure, but is preferably pressurized at a high temperature.
  • the gas may be stationary or distributed, but is preferably distributed from the viewpoint of discharging generated impurities.
  • Nitrogen atoms can be introduced after carbonization.
  • a liquid phase doping method a gas phase doping method, or a gas phase-liquid phase doping method can be used.
  • nitrogen atoms can be introduced into the surface of the carbon catalyst by heat treatment by maintaining the carbon alloy in an ammonia atmosphere as a nitrogen source at 200 to 1200 ° C. for 5 to 180 minutes.
  • the present invention relates to a nitrogen-containing carbon alloy produced by the above-described method for producing a nitrogen-containing carbon alloy.
  • the nitrogen-containing carbon alloy of the present invention obtained by firing the precursor is a nitrogen-containing carbon alloy into which nitrogen has been introduced.
  • the nitrogen-containing carbon alloy of the present invention preferably contains graphene, which is an aggregate of carbon atoms having a hexagonal network structure in which carbon is chemically bonded by sp 2 hybrid orbitals and spreads in two dimensions.
  • the content of surface nitrogen atoms in the carbon catalyst is more preferably 0.02 to 0.3 in terms of atomic ratio (N / C) to surface carbon.
  • N / C atomic ratio
  • strength of the carbon skeleton of a carbon alloy can be raised by making atomic ratio (N / C) of a nitrogen atom and a carbon atom into the said range, and the fall of electrical conductivity can be suppressed.
  • the skeleton of the carbon alloy may be formed of at least carbon atoms and nitrogen atoms, and may contain hydrogen atoms, oxygen atoms, and the like as other atoms.
  • the atomic ratio ((other atoms) / (C + N)) of other atoms to carbon atoms and nitrogen atoms is preferably 0.3 or less.
  • carbon alloy is put in a predetermined container, cooled to liquid nitrogen temperature (-196 ° C), nitrogen gas is introduced into the container and adsorbed, and the adsorption amount of single molecules and adsorption parameters are determined from the adsorption isotherm.
  • BET Brunauer-Emmett-Teller
  • the pore shape of the carbon alloy is not particularly limited, and for example, pores may be formed only on the surface, or pores may be formed not only on the surface but also inside.
  • pores may be tunnel-shaped, and it has a shape in which polygonal cavities such as spherical or hexagonal columns are connected to each other. It may be.
  • the specific surface area of the carbon alloy is preferably at 90m 2 / g or more, more preferably 350 meters 2 / g or more, and particularly preferably 560 m 2 / g or more.
  • the catalytically active site metal coordination product or configuration space (field) having at least C, N, and metal ions as constituents
  • the specific surface area of the carbon alloy is preferably 3000 m 2 / g or less, and preferably 2000 m 2 / g or less. More preferably, it is particularly preferably 1500 m 2 / g or less.
  • the shape of the nitrogen-containing carbon alloy of the present invention is not particularly limited as long as it has oxygen reduction reaction activity.
  • a large distorted structure such as a sheet shape, a fiber shape, a plate shape, a column shape, a block shape, a particle shape, many ellipses other than a spherical shape, a flat shape, a square shape, and the like can be given.
  • it is preferably a block shape or a particle shape.
  • a slurry described later is applied and dried, it is preferably a fiber shape, a plate shape, or a column shape from the viewpoint of imparting thixotropy.
  • the slurry containing a carbon alloy can be produced by dispersing the nitrogen-containing carbon alloy of the present invention in a solvent.
  • a slurry in which a carbon alloy is dispersed in a solvent is applied to a support material, baked, and dried, so that an arbitrary shape is obtained. It is possible to form a carbon catalyst that has been processed into Thus, by making a carbon alloy into a slurry, the workability of the carbon catalyst is improved and it can be easily used as an electrode catalyst or an electrode material.
  • the coating amount after drying of the nitrogen-containing carbon alloy is preferably 0.01 mg / cm 2 or more, more preferably 0.02 to 100 mg / cm 2 , Particularly preferred is 0.05 to 10 mg / cm 2 .
  • the solvent a solvent used when producing an electrode catalyst for a fuel cell or an electrode material for a power storage device can be appropriately selected and used.
  • a solvent used for producing an electrode material for a power storage device diethyl carbonate (DEC), dimethyl carbonate (DMC), 1,2-dimethoxyethane (DME), ethylene carbonate (EC), ethyl methyl carbonate (EMC) ), N-methyl-2-pyrrolidone (NMP), propylene carbonate (PC), ⁇ -butyrolactone (GBL), etc.
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • DME 1,2-dimethoxyethane
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • NMP N-methyl-2-pyrrolidone
  • PC propylene carbonate
  • GBL ⁇ -butyrolactone
  • the use of the nitrogen-containing carbon alloy of the present invention is not particularly limited to structural materials, electrode materials, filtration materials, catalyst materials, etc., but is preferably used as electrode materials for power storage devices such as capacitors and lithium secondary batteries. More preferably, it is used as a carbon catalyst for a fuel cell, zinc-air battery, lithium-air battery or the like having reactive activity.
  • the catalyst can be included in the catalyst layer. Furthermore, the electrode membrane assembly can be provided in a fuel cell.
  • FIG. 1 shows a schematic configuration diagram of a fuel cell 10 using a carbon catalyst made of a nitrogen-containing carbon alloy of the present invention.
  • the carbon catalyst is applied to the anode electrode and the cathode electrode.
  • the fuel cell 10 includes a separator 12, an anode electrode catalyst (fuel electrode) 13, a cathode electrode catalyst (oxidant electrode) 15, and a separator 16 that are disposed so as to sandwich the solid polymer electrolyte 14.
  • a fluorine-based cation exchange resin membrane represented by a perfluorosulfonic acid resin membrane is used.
  • the fuel cell 10 provided with the carbon catalyst in the anode electrode catalyst 13 and the cathode electrode catalyst 15 is configured by bringing the carbon catalyst into contact with both the solid polymer electrolyte 14 as the anode electrode catalyst 13 and the cathode electrode catalyst 15.
  • The By forming the carbon catalyst described above on both sides of the solid polymer electrolyte, and adhering the anode electrode catalyst 13 and the cathode electrode catalyst 15 to both main surfaces of the solid polymer electrolyte 14 on the electrode reaction layer side by hot pressing, It integrates as MEA (Membrane Electrode Assembly).
  • a gas diffusion layer made of a porous sheet (for example, carbon paper) that also functions as a current collector is interposed between the separator and the anode and cathode electrode catalyst.
  • a carbon catalyst having a large specific surface area and high gas diffusibility can be used as the anode and cathode electrode catalyst.
  • the separators 12 and 16 support the anode and cathode electrode catalyst layers 13 and 15 and supply and discharge reaction gases such as fuel gas H 2 and oxidant gas O 2 .
  • a reaction gas is supplied to each of the anode and cathode electrode catalysts 13 and 15, a gas phase (reaction gas) and a liquid phase (solid) are formed at the boundary between the carbon catalyst provided on both electrodes and the solid polymer electrolyte 14.
  • a three-phase interface of a polymer electrolyte membrane) and a solid phase (a catalyst possessed by both electrodes) is formed.
  • Cathode side O 2 + 4H + + 4e ⁇ ⁇ 2H 2 O
  • Anode side H 2 ⁇ 2H + + 2e ⁇ H + ions generated on the anode side move in the solid polymer electrolyte 14 toward the cathode side, and e ⁇ (electrons) move to the cathode side through an external load.
  • oxygen contained in the oxidant gas reacts with H + ions and e ⁇ that have moved from the anode side to generate water.
  • the above-described fuel cell generates direct-current power from hydrogen and oxygen to generate water.
  • FIG. 2 shows a schematic configuration diagram of an electric double layer capacitor 20 using a carbon catalyst made of nitrogen-containing carbon alloy and having an excellent storage capacity.
  • the first electrode 21 and the second electrode 22 which are polarizable electrodes are opposed to each other through the separator 23, and are accommodated in the outer lid 24a and the outer case 24b. ing.
  • the first electrode 21 and the second electrode 22 are connected to the exterior lid 24a and the exterior case 24b via current collectors 25, respectively.
  • the separator 23 is impregnated with an electrolytic solution.
  • the electric double layer capacitor 20 is configured by caulking and sealing the outer lid 24a and the outer case 24b while being electrically insulated via the gasket 26.
  • the carbon catalyst made of the above-described nitrogen-containing carbon alloy can be applied to the first electrode 21 and the second electrode 22.
  • the electric double layer capacitor by which the carbon catalyst was applied to the electrode material can be comprised.
  • the above-described carbon catalyst has a fibrous structure in which nanoshell carbon is aggregated, and furthermore, since the fiber diameter is in a nanometer unit, the specific surface area is large, and the electrode interface where charges are accumulated in the capacitor is large.
  • the above-mentioned carbon catalyst is electrochemically inactive with respect to the electrolytic solution, and has appropriate electrical conductivity. For this reason, the electrostatic capacitance per unit volume of an electrode can be improved by applying as an electrode of a capacitor.
  • the above-described carbon catalyst can be applied as an electrode material composed of a carbon material, such as a negative electrode material of a lithium ion secondary battery. And since the specific surface area of a carbon catalyst is large, a secondary battery with a large electrical storage capacity can be comprised.
  • the nitrogen-containing carbon alloy of the present invention is used as a substitute for an environmental catalyst containing a noble metal such as platinum.
  • a catalyst for exhaust gas purification for removing pollutants contained in polluted air (mainly gaseous substances) etc. by decomposition treatment a catalyst material composed of noble metal materials such as platinum alone or in combination Environmental catalysts are used.
  • the above-mentioned carbon catalyst can be used as an alternative to these exhaust gas purifying catalysts containing noble metals such as platinum. Since the above-described carbon catalyst is provided with an oxygen reduction reaction catalytic action, it has a function of decomposing substances to be treated such as pollutants.
  • a low-cost environmental catalyst can be provided.
  • the specific surface area is large, the treatment area for decomposing the material to be treated per unit volume can be increased, and an environmental catalyst having an excellent decomposition function per unit volume can be constituted.
  • a noble metal-based material such as platinum used in conventional environmental catalysts is carried alone or in a composite, so that an environmental catalyst with more excellent catalytic action such as a decomposition function can be obtained.
  • the environmental catalyst provided with the above-mentioned carbon catalyst can also be used as a purification catalyst for water treatment as well as the above-described exhaust gas purification catalyst.
  • the nitrogen-containing carbon alloy of the present invention can be widely used as a catalyst for chemical reaction, and in particular, can be used as a substitute for a platinum catalyst. That is, the above-mentioned carbon catalyst can be used as a substitute for a general process catalyst for the chemical industry containing a noble metal such as platinum. For this reason, according to the above-mentioned carbon catalyst, a low-cost chemical reaction process catalyst can be provided without using expensive noble metals such as platinum. Furthermore, since the above-mentioned carbon catalyst has a large specific surface area, it can constitute a chemical reaction process catalyst excellent in chemical reaction efficiency per unit volume.
  • Such a carbon catalyst for chemical reaction is applied to, for example, a hydrogenation reaction catalyst, a dehydrogenation reaction catalyst, an oxidation reaction catalyst, a polymerization reaction catalyst, a reforming reaction catalyst, and a steam reforming catalyst. be able to. More specifically, it is possible to apply a carbon catalyst to each chemical reaction with reference to a catalyst related literature such as “Catalyst Preparation (Kodansha) by Takaho Shirasaki and Naoyuki Todo, 1975”.
  • Example 1 Synthesis of non-acid-washed carbon material (1E) of ZIF8, Fe (OAc) 2 added (2-mim) mixture> (Preparation of ZIF8, Fe (OAc) 2 addition (2-mim) mixture) 2-methylimidazole (2-mim) (manufactured by Aldrich) 0.10 g, ZIF8 (manufactured by BASF, Basolite Z1200) 0.90 g, Fe (OAc) 2 (manufactured by Aldrich, iron (II) acetate, purity 99.
  • the obtained carbon precursor (1B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.3463 g of acid-washed carbon precursor (1C).
  • the quartz tube was rotated at 2.0 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (1D) of non-acid washing
  • the carbon material (1D) was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.1381 g of non-acid washed carbon material (1E).
  • the obtained non-acid cleaned carbon material (1E) was used as the nitrogen-containing carbon alloy of Example 1.
  • Oxygen reduction reaction (ORR) activity of carbon alloy coated electrode preparation of carbon alloy coated electrode
  • ORR Oxygen reduction reaction activity of carbon alloy coated electrode
  • Nafion solution 5% alcohol aqueous solution
  • IPA 1-propanol
  • a nitrogen-containing carbon alloy dispersion was applied on the carbon electrode so that the nitrogen-containing carbon alloy was 0.50 mg / cm 2, and And dried to obtain a carbon alloy coated electrode.
  • the obtained carbon precursor (3B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.3225 g of acid-washed carbon precursor (3C).
  • the carbon material (3D) was pulverized in an agate mortar to obtain 0.1175 g of a non-acid-washed carbon material (3E).
  • the obtained non-acid cleaned carbon material (3E) was used as the nitrogen-containing carbon alloy of Example 3.
  • Example 4 ⁇ Synthesis of ZIF8, Fe (OAc) 2 addition (2-mim) mixture of acid washed carbon material (4E)> 0.0786 g of the above carbon material (3D) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight to obtain 0.0674 g of acid-washed carbon material (4E). The obtained acid-washed carbon material (4E) was used as the nitrogen-containing carbon alloy of Example 4.
  • the obtained carbon precursor (5B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.6244 g of acid-washed carbon precursor (5C).
  • the carbon material (5D) was pulverized in an agate mortar to obtain 0.3587 g of a non-acid-cleaned carbon material (5E).
  • the obtained non-acid cleaned carbon material (5E) was used as the nitrogen-containing carbon alloy of Example 5.
  • Example 6 ⁇ Synthesis of carbon material of ZIF8, Fe (acac) 2 addition (2-mim) mixture (6E)> (Continuous firing distribution furnace, pulverization)
  • the above-mentioned ZIF8, Fe (acac) 2 added 2-mim mixture (5A) (2.0666 g) was weighed into a quartz boat and installed in the center of a 4.0 cm ⁇ (inner diameter 3.6 cm ⁇ ) quartz tube inserted into a tubular furnace. Then, the nitrogen flow rate was set to 200 mL per minute, and the mixture was circulated at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 700 ° C. at 5 ° C. per minute, held at 700 ° C.
  • Example 6 The obtained carbon precursor (6B) was pulverized in an agate mortar to obtain 0.6206 g of an unacid-washed carbon precursor (6C).
  • the obtained non-acid cleaned carbon material (6E) was used as the nitrogen-containing carbon alloy of Example 6.
  • Example 7 ⁇ Synthesis of carbon material of ZIF8, Fe (acac) 2 addition (2-mim) mixture (7E)> (Continuous firing, pulverization, acid cleaning treatment, first firing, distribution furnace)
  • the obtained carbon precursor (7B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.6257 g of acid-washed carbon precursor (7C).
  • Carbon material (7D) was pulverized in an agate mortar to obtain 0.3806 g of carbon material (7E) that was not acid-washed.
  • the obtained non-acid cleaned carbon material (7E) was used as the nitrogen-containing carbon alloy of Example 7.
  • Example 8 ⁇ Synthesis of carbon material of ZIF8, FeCl 2 .4H 2 O added (2-mim) mixture (8E)> (Preparation of ZIF8, FeCl 2 .4H 2 O addition (2-mim) mixture) 2-methylimidazole (2-mim) (Aldrich) 1.00 g, ZIF8 9.00 g (BASF, Basolite Z1200), FeCl 2 .4H 2 O 0.37 g (Wako Pure Chemical Industries, purity 99) 9%) was added to an X-TREME MX1200XTM container manufactured by Waring Co., purged with nitrogen, and mixed at 10,000 rpm for 40 seconds to obtain a 2-mim mixture (8A) containing ZIF8 and FeCl 2 .4H 2 O. It was.
  • the obtained carbon precursor (8B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.5412 g of an acid cleaned carbon precursor (8C).
  • Example 9 Carbon Material Synthesis of ZIF8, Fe (salen) Addition (2-Mim) Mixture (9E)> (Preparation of ZIF8, Fe (salen) addition (2-mim) mixture) 2-methylimidazole (2-mim) (manufactured by Aldrich) 1.00 g, ZIF8 (manufactured by BASF, Basolite Z1200) 9.00 g, N, N′-ethylenebis (salicylideneaminato) iron (II) ( Fe (salen)) (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.596 g was added to a Waring Co., Ltd. X-TREME MX1200XTM container, purged with nitrogen, mixed at 10,000 rpm for 40 seconds, and ZIF8 and Fe (salen) added. A 2-mim mixture (9A) was obtained.
  • the obtained carbon precursor (9B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.6795 g of acid-washed carbon precursor (9C).
  • Example 10 ⁇ Synthesis of carbon material of ZIF8, FeCl 2 ⁇ 4H 2 O added DCPy mixture (10E)> (Preparation of DCPy mixture containing ZIF8 and FeCl 2 .4H 2 O) 3,4-dicyanopyridine (DCPy, Aldrich) 1.00 g, ZIF8 (BASF, Basolite Z1200) 9.00 g, FeCl 2 .4H 2 O (Wako Pure Chemical Industries, purity 99.9%) 0.37 g was added to an X-TREME MX1200XTM container manufactured by Waring Co., purged with nitrogen, and mixed at 10,000 rpm for 40 seconds to obtain a DCPy mixture (10A) containing ZIF8 and FeCl 2 .4H 2 O.
  • DCPy mixture (10A) containing ZIF8 and FeCl 2 .4H 2 O.
  • Example 11 ⁇ Synthesis of carbon material of ZIF8 and FeCl 2 .4H 2 O added DCPy mixture (11E)> (Acid cleaning treatment) 0.8496 g of the above-mentioned non-acid cleaned carbon material (10B) was pulverized in an agate mortar, and concentrated hydrochloric acid cleaning, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.7923 g of acid-washed carbon material (11C).
  • Example 12 ⁇ Synthesis of carbon material of ZIF8 and FeCl 2 .4H 2 O added DCPN mixture (12E)> (Preparation of DCPN mixture containing ZIF8 and FeCl 2 .4H 2 O) 3,4-dichlorophthalonitrile (DCPN, manufactured by Aldrich) 1.00 g, ZIF8 (BASF, Basolite Z1200) 9.00 g, FeCl 2 .4H 2 O (Wako Pure Chemical Industries, purity 99.9%) ) 0.37 g was added to an X-TREME MX1200XTM container manufactured by Waring Co., and purged with nitrogen, followed by mixing at 10,000 rpm for 40 seconds to obtain a DCPN mixture (12A) containing ZIF8 and FeCl 2 .4H 2 O.
  • DCPN 3,4-dichlorophthalonitrile
  • the obtained carbon precursor (C1-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.1870 g of an acid cleaned carbon precursor (C1-C).
  • the carbon material (C1-D) was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.0540 g of non-acid washed carbon material (C1-E). The obtained non-acid cleaned carbon material (C1-E) was used as the nitrogen-containing carbon alloy of Comparative Example 1.
  • the obtained preliminary carbide (C4-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained preliminary carbide material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.2026 g of acid-cleaned preliminary carbide (C4-C).
  • the carbon material (C4-D) was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.1159 g of non-acid washed carbon material (C4-E). The obtained non-acid cleaned carbon material (C4-E) was used as the nitrogen-containing carbon alloy of Comparative Example 4.
  • the obtained carbon precursor (C6-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.4994 g of acid-washed carbon precursor (C6-C).
  • the carbon material (C6-D) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.2048 g of acid-washed carbon material (C6-E). The obtained acid cleaned carbon material (C6-E) was used as the carbon material of Comparative Example 6.
  • the obtained carbon precursor (C7-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and left overnight to obtain 0.2561 g of an acid cleaned carbon precursor (C7-C).
  • the carbon precursor (C7-B) was pulverized in an agate mortar, 0.1607 g was weighed into a quartz boat, and placed in the center of a 4.0 cm ⁇ (inner diameter 3.6 cm ⁇ ) quartz tube inserted into a vacuum gas displacement rotary furnace. It was installed and the nitrogen flow rate was 200 mL per minute and allowed to flow at room temperature for 1 minute. Next, the inside of a pipe
  • the carbon material (C7-D) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.1119 g of acid-cleaned carbon material (C7-E). The obtained acid cleaned carbon material (C7-E) was used as the carbon material of Comparative Example 7.
  • a 2-mim mixture (C8-A) containing Fe (acac) 2 and FeCl 2 .4H 2 O was calcined in the same manner as in Comparative Example 7, but only a very small amount of carbon material was obtained, and the specific surface area was measured by the BET method. In addition, the production of carbon alloy-coated electrodes and the measurement of oxygen reduction reaction (ORR) activity could not be performed.
  • thermocompression-bonded film was taken out from the two polyimide films, and the catalyst layer was transferred to both sides of the proton conducting film by peeling off the Teflon (registered trademark) sheet which is the base of the cathode coating film and the anode coating film.
  • Teflon registered trademark
  • An electrode composite membrane was obtained. This electrode composite membrane was immersed in a 0.5 mol / L sulfuric acid aqueous solution for 10 hours, washed with ion-exchanged water, and dried to obtain the desired electrode composite membrane.

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Abstract

La présente invention a pour objectif de fournir : un procédé de production d'un alliage de carbone contenant de l'azote ayant une plus grande activité de réduction de l'oxygène; un alliage de carbone contenant de l'azote; et un catalyseur de pile à combustible. Un procédé de production d'un alliage de carbone contenant de l'azote selon la présente invention comprend une étape de cuisson d'un précurseur qui contient : au moins une substance choisie parmi des composés organiques contenant de l'azote représentés par la formule générale (1), des tautomères des composés organiques contenant de l'azote, des sels des composés organiques contenant de l'azote et des hydrates des composés organiques contenant de l'azote; au moins une substance choisie parmi des charpentes moléculaires pouvant se lier de manière covalente (COF) et des solides hybrides poreux de type MOF (metal-organic framework); et au moins une substance choisie parmi les sels métalliques inorganiques et les complexes métalliques organiques.
PCT/JP2015/074426 2014-09-01 2015-08-28 Procédé de production d'un alliage de carbone contenant de l'azote, alliage de carbone contenant de l'azote et catalyseur pour pile à combustible WO2016035705A1 (fr)

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Cited By (6)

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JP2016178005A (ja) * 2015-03-20 2016-10-06 富士フイルム株式会社 複合体、複合体の製造方法及び燃料電池触媒
JP2020500096A (ja) * 2016-09-30 2020-01-09 コーロン インダストリーズ インク 担体、燃料電池用電極、膜−電極接合体及びこれを含む燃料電池
CN112827510A (zh) * 2021-02-08 2021-05-25 福州大学 一种用于催化合成碳酸丙烯酯的多孔复合材料及其制备方法
WO2021177359A1 (fr) * 2020-03-04 2021-09-10 国立大学法人東京大学 Procédé de décomposition d'ammoniac et pile à combustible l'utilisant
WO2022163752A1 (fr) * 2021-01-29 2022-08-04 国立大学法人東海国立大学機構 Procédé de production de matériau carboné, matériau carboné, procédé de production d'électrode, électrode et pile à combustible
CN116396489A (zh) * 2023-03-17 2023-07-07 西北农林科技大学 一种柔性金属有机框架材料的制备方法及应用

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WO2013125503A1 (fr) * 2012-02-20 2013-08-29 富士フイルム株式会社 Alliage de carbone contenant de l'azote, son procédé de fabrication, catalyseur en alliage de carbone et pile à combustible
JP2014512251A (ja) * 2011-02-08 2014-05-22 アンスティチュ ナショナル ド ラ ルシェルシュ シアンティフィーク 熱分解性多孔質担体を使用して製造される触媒

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JP2014512251A (ja) * 2011-02-08 2014-05-22 アンスティチュ ナショナル ド ラ ルシェルシュ シアンティフィーク 熱分解性多孔質担体を使用して製造される触媒
WO2013125503A1 (fr) * 2012-02-20 2013-08-29 富士フイルム株式会社 Alliage de carbone contenant de l'azote, son procédé de fabrication, catalyseur en alliage de carbone et pile à combustible

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016178005A (ja) * 2015-03-20 2016-10-06 富士フイルム株式会社 複合体、複合体の製造方法及び燃料電池触媒
JP2020500096A (ja) * 2016-09-30 2020-01-09 コーロン インダストリーズ インク 担体、燃料電池用電極、膜−電極接合体及びこれを含む燃料電池
WO2021177359A1 (fr) * 2020-03-04 2021-09-10 国立大学法人東京大学 Procédé de décomposition d'ammoniac et pile à combustible l'utilisant
WO2022163752A1 (fr) * 2021-01-29 2022-08-04 国立大学法人東海国立大学機構 Procédé de production de matériau carboné, matériau carboné, procédé de production d'électrode, électrode et pile à combustible
CN112827510A (zh) * 2021-02-08 2021-05-25 福州大学 一种用于催化合成碳酸丙烯酯的多孔复合材料及其制备方法
CN112827510B (zh) * 2021-02-08 2022-04-12 福州大学 一种用于催化合成碳酸丙烯酯的多孔复合材料及其制备方法
CN116396489A (zh) * 2023-03-17 2023-07-07 西北农林科技大学 一种柔性金属有机框架材料的制备方法及应用
CN116396489B (zh) * 2023-03-17 2024-04-12 西北农林科技大学 一种柔性金属有机框架材料的制备方法及应用

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