WO2015199125A1 - Procédé de fabrication d'alliage au carbone contenant de l'azote, alliage au carbone contenant de l'azote et catalyseur pour pile à combustible - Google Patents

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

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WO2015199125A1
WO2015199125A1 PCT/JP2015/068180 JP2015068180W WO2015199125A1 WO 2015199125 A1 WO2015199125 A1 WO 2015199125A1 JP 2015068180 W JP2015068180 W JP 2015068180W WO 2015199125 A1 WO2015199125 A1 WO 2015199125A1
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nitrogen
group
carbon alloy
containing carbon
aromatic group
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順 田邉
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Fujifilm Corp
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • 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 heteroaromatic ring compound having a nitrogen-containing aromatic group and an inorganic metal salt, a nitrogen-containing carbon alloy, and a nitrogen-containing compound. The present invention relates to a fuel cell catalyst using 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.
  • a carbon catalyst is known as a catalyst that can be formed without using platinum, and a nitrogen-containing carbon alloy obtained by heat-treating a nitrogen-containing compound is used as a carbon catalyst.
  • 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.
  • Non-Patent Document 1 discloses a non-platinum catalyst for a fuel cell prepared by heating and firing a mixture of 2- pyridyltriazine Fe complex [Fe (TPTZ) 2 ] supported on carbon.
  • TPTZ 2- pyridyltriazine Fe complex
  • it has been proposed to fire a mixture of 2-pyridyltriazine and a metal complex, and there is no description about using an inorganic metal or firing an inorganic metal.
  • 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). .
  • Patent Document 3 discusses the use of TPTZ (2,4,6-tri (2-pyridyl) -1,3,5-triazine) as a nitrogen-containing heterocyclic compound.
  • 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 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 obtained a heteroaromatic ring compound having a nitrogen-containing aromatic group having a specific structure, a covalently bonded organic skeleton material, and a metal organic skeleton material.
  • a precursor containing at least one selected from at least one selected from inorganic metal salts or organometallic complexes to produce a nitrogen-containing carbon alloy.
  • the oxygen-reducing activity is sufficiently enhanced. It has been found that a nitrogen carbon alloy can be obtained.
  • 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.
  • the present invention has the following configuration.
  • a heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the following general formula (1), a salt thereof and a hydrate thereof, a covalent organic skeleton material, and a metal organic skeleton A method for producing a nitrogen-containing carbon alloy comprising a step of firing a precursor containing at least one selected from materials and at least one selected from inorganic metal salts and organometallic complexes;
  • A represents an atomic group composed of a 5- to 11-membered non-fused heteroaromatic ring
  • L represents a single bond or a (x + 1) -valent linking group
  • B represents a hydrogen atom, a substituted or Represents an unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of the nitrogen-containing aromatic groups , Any one or both of the ring skeleton constituent atoms at
  • the number of heteroatoms in the non-fused heteroaromatic ring of A is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of B.
  • x and y each independently represents an integer of 1 or more.
  • a method for producing a nitrogen-containing carbon alloy according to [1] or [2], wherein the heteroaromatic ring compound having a nitrogen-containing aromatic group is represented by the following general formula (2);
  • Q 1 to Q 3 each independently represent a hetero atom or a carbon atom, at least one of Q 1 to Q 3 is a nitrogen atom, b1 to b3 are each independently a hydrogen atom, Represents a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of b1 to b3 is a substituted or unsubstituted nitrogen-containing aromatic group, and a nitrogen-containing aromatic group
  • one or both of the ring skeleton constituent atoms at the 3-position and the 4-position with respect to the binding site are nitrogen atoms.
  • the number of heteroatoms in the non-fused heteroaromatic ring containing Q 1 to Q 3 is the same as or larger than the number of heteroatoms per nitrogen-containing aromatic group of b1 to b3.
  • A represents an atomic group composed of a 5- to 11-membered non-fused heteroaromatic ring
  • L represents a single bond or a (x + 1) -valent linking group
  • B represents a hydrogen atom, substituted Or an unsubstituted aromatic group or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of the nitrogen-containing aromatic groups
  • any one or both of the ring skeleton constituting atoms at the 3rd and 4th positions relative to the bonding site with L are nitrogen atoms.
  • the number of heteroatoms in the non-fused heteroaromatic ring of A is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of B.
  • x represents an integer of 1 or more.
  • the method for producing a nitrogen-containing carbon alloy according to [1] or [2], wherein the heteroaromatic ring compound having a nitrogen-containing aromatic group is a compound selected from the following compound group.
  • [16] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [15], wherein the firing step is a step of firing the precursor at 400 ° C. or higher.
  • 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 present invention is selected from a heteroaromatic ring compound having a nitrogen-containing aromatic group having a specific structure, a salt thereof and a hydrate thereof, a covalent organic skeleton material, and a metal organic skeleton material.
  • 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 the group consisting of inorganic metal salts and organometallic complexes.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group, the covalent organic skeleton material and the metal organic skeleton material, the inorganic metal salt, and the organometallic complex will be described in detail.
  • Heteroaromatic ring compound having nitrogen-containing aromatic group used in the method for producing a nitrogen-containing carbon alloy of the present invention is represented by the following general formula (1). Note that the heteroaromatic ring compound having a nitrogen-containing aromatic group includes salts thereof or hydrates thereof.
  • A represents an atomic group composed of a 5- to 11-membered non-condensed heteroaromatic ring, and L represents a single bond or a (x + 1) -valent linking group.
  • B represents a hydrogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group.
  • the nitrogen-containing aromatic groups one or both of the ring skeleton constituting atoms at the 3-position and the 4-position with respect to the bonding site with L are nitrogen atoms.
  • the number of heteroatoms in the non-fused heteroaromatic ring of A is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of B.
  • X and y each independently represents an integer of 1 or more.
  • A represents an atomic group composed of a 5- to 11-membered non-condensed heteroaromatic ring.
  • the non-fused heteroaromatic ring is a heteroaromatic ring having no fused ring, and the atomic group composed of such a non-fused heteroaromatic ring has at least one non-fused heteroaromatic ring.
  • the atomic group composed of a non-fused heteroaromatic ring may be composed of two or more non-fused heteroaromatic rings, but is preferably composed of one non-fused heteroaromatic ring.
  • the number of members of one non-condensed heteroaromatic ring may be 5 to 11, preferably 5 to 10, more preferably 5 to 8, and still more preferably 5 or 6.
  • hetero atom constituting the 5- to 11-membered non-condensed heteroaromatic ring examples include 1 to 3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
  • the non-fused heteroaromatic ring examples include a pyridine ring, a pyrimidine ring, a triazine ring, an imidazole ring, a pyrroline ring, an imidazole group, a furan ring, and a thiophene ring.
  • a pyridine ring, a pyrimidine ring, and a triazine ring Preferred examples include an imidazole ring and a pyrroline ring.
  • L represents a single bond or a (x + 1) -valent linking group.
  • the (x + 1) -valent linking group includes a substituted or unsubstituted aromatic group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted cycloalkylene X-1 groups from the group, —CO—, —CO 2 —, —O—, —NH—, —SO—, —SO 2 —, —S—, —CONH—, —NHCO—, or a combination thereof.
  • the aromatic group preferably has 6 to 20 carbon atoms, more preferably a phenylene group, a biphenylene group, or a naphthylene group, further preferably a phenylene group or a biphenylene group, and more preferably a phenylene group. Particularly preferred.
  • the alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • the alkenylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
  • the alkynylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
  • the cycloalkylene group preferably has 4 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, still more preferably 5 to 12 carbon atoms, and particularly preferably 5 to 10 carbon atoms.
  • the substituent When having a substituent, the substituent includes a halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), hydroxy group, cyano group, aliphatic group (aralkyl group, cycloalkyl group, active methine group, etc.
  • halogen atom fluorine atom, chloro atom, bromine atom or iodine atom
  • hydroxy group cyano group
  • aliphatic group aralkyl group, cycloalkyl group, active methine group, etc.
  • a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), a vinyl group, an allyl group, an acetylenyl group, an aryl group (regarding the position of substitution) and an amino group are preferable as a substituent.
  • L represents a single bond or a divalent linking group
  • L represents a trivalent linking group.
  • divalent linking group examples include a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, an alkynylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted group.
  • Examples of the trivalent linking group include, for example,>CH—,> N—, a group obtained by removing one hydrogen atom from a group having a substituent among the groups listed as examples of the divalent linking group, and the like. Can be mentioned.
  • L may be a group obtained by combining two or more of the above linking groups. For example, a combination of two or more substituted or unsubstituted alkylene groups, alkenylene groups, and alkynylene groups, or a combination of two or more substituted or unsubstituted alkylene groups, alkenylene groups, alkynylene groups, and substituted or unsubstituted phenylene groups. It can be based.
  • the plurality of L may be the same or different.
  • the (x + 1) -valent linking group include a phenylene group, an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, an alkynylene group having 2 to 6 carbon atoms, —CO 2 —, —CONH—, — O— or a combination of x + 1 valences in which x ⁇ 1 arbitrary hydrogen atoms are removed from a combination thereof, a phenylene group, an alkylene group having 1 to 4 carbon atoms, and an alkenylene group having 2 to 6 carbon atoms Further, an alkynylene group having 2 to 6 carbon atoms, —CONH—, or a combination of x + 1 valent groups in which any hydrogen atom of x-1 is removed from a combination thereof is more preferable.
  • B represents a hydrogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group
  • the nitrogen-containing aromatic group means a group having a nitrogen atom as a constituent atom of the aromatic group.
  • at least one of the Bs may be a substituted or unsubstituted nitrogen-containing aromatic group, but it is preferable that all Bs are substituted or unsubstituted nitrogen-containing aromatic groups.
  • the nitrogen-containing aromatic group is preferably a pyridyl group, a pyrimidyl group, a triazyl group, or an imidazolyl group.
  • a plurality of B may be the same or different.
  • B is preferably a hydrogen atom, a phenyl group, a pyridyl group, a pyrimidyl group, a triazine group, or an imidazolyl group.
  • the number of carbon atoms is preferably 6 to 14, more preferably 6 to 10, and particularly preferably a phenyl group.
  • At least one B is a nitrogen-containing aromatic group, and in this case, it is preferably 5 to 11 members, more preferably 5 to 8 members, more preferably 5 or 6 members, and a pyridyl group , A pyrimidyl group, a triazine group, or an imidazolyl group is particularly preferable.
  • aromatic group or nitrogen-containing aromatic group represented by B has a substituent
  • preferable substituents include a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), a hydroxy group, and a cyano group.
  • Aliphatic groups including aralkyl groups, cycloalkyl groups, active methine groups, etc.
  • vinyl groups including aralkyl groups, cycloalkyl groups, active methine groups, etc.
  • vinyl groups allyl groups, acetylenyl groups, aryl groups (regardless of the position of substitution), acyl groups, aliphatic oxy groups (alkoxy groups) Or an aryloxy group, a heterocyclic oxy group, an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, an aliphatic oxycarbonyl group.
  • Substituents containing unsaturated groups are more preferred, vinyl group, allyl group, acetylenyl group, aryl group (phenyl group, naphthyl group, phenanthrene group, anthracenyl group, triphenyl group, pyrenyl group, perylenyl group, benzhydryl group, benzyl group. Group, cinamyl group, cumenyl group, methicyl group, phenylethyl group, styryl group, tolyl group, trityl group, xylyl group). These substituent groups may be further substituted, and examples of the further substituent include groups selected from the substituents and heteroaromatic groups described above (regardless of the position of substitution).
  • either one or both of the ring skeleton constituting atoms at the 3-position and the 4-position with respect to the bonding site with L are nitrogen atoms.
  • either one or both of the ring skeleton constituting atoms at the 3-position and the 4-position with respect to the bonding site with L may be a nitrogen atom.
  • the ring skeleton constituting atom at the 3rd or 4th position with respect to the bonding position with L is a nitrogen atom, but the ring skeleton constituting atom other than the corresponding site is a nitrogen atom. May be.
  • the ring skeleton constituent atoms at the 3rd and 1st positions relative to the bond position with L are nitrogen atoms
  • the ring skeleton constituent atoms at the 3rd and 2nd positions are nitrogen atoms
  • the ring skeleton constituent atom may be a nitrogen atom.
  • the ring skeleton constituting atom at the 3rd or 4th position is a nitrogen atom, for example, it is preferred that one or both of the ring skeleton constituting atoms at the 3rd and 4th positions are nitrogen atoms.
  • the atomic group composed of the non-condensed heteroaromatic ring includes a triazine ring, it is preferable that the ring skeleton constituent atom at the 2-position in the nitrogen-containing aromatic group is not a nitrogen atom.
  • the number of heteroatoms in the non-condensed heteroaromatic ring of A is the same as or larger than the number of heteroatoms per one nitrogen-containing aromatic group of B.
  • the number of heteroatoms per all nitrogen-containing aromatic groups satisfies the above condition.
  • the atomic group of A is composed of two or more non-fused heteroaromatic rings
  • the number of heteroatoms in the non-fused heteroaromatic ring of A represents the number of heteroatoms per one non-fused heteroaromatic ring. .
  • x and y each independently represent an integer of 1 or more.
  • x is preferably an integer of 1 to 6, more preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and still more preferably an integer of 1 to 3. 1 or 2 is particularly preferable.
  • y is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, more preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. Further preferred.
  • a heteroaromatic ring compound having a nitrogen-containing aromatic group having the structure described above and an inorganic metal salt or an organometallic complex are made of a porous material (MOF, COF, etc.).
  • a nitrogen-containing aromatic group 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.
  • ORR oxygen reduction reaction
  • the thermal decomposition of the non-fused heteroaromatic part (central atomic group) 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 coordination between the inorganic metal salt or organometallic complex and the nitrogen-containing aromatic group is any one of the ring skeleton constituent atoms at the 3-position and the 4-position with respect to the bonding position with L in the nitrogen-containing aromatic group or It progresses more easily when both are nitrogen atoms.
  • the central atomic group includes a triazine ring
  • the atom at the 2-position of the ring skeleton is preferably not a nitrogen atom.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group is preferably one represented by the following general formula (2).
  • Q 1 to Q 3 each independently represent a hetero atom or a carbon atom, at least one of Q 1 to Q 3 is a nitrogen atom, b1 to b3 are each independently a hydrogen atom, Represents a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of b1 to b3 is a substituted or unsubstituted nitrogen-containing aromatic group, In at least one, one or both of the ring skeleton constituent atoms at the 3-position and the 4-position with respect to the binding site are nitrogen atoms.
  • the number of heteroatoms in the non-fused heteroaromatic ring containing Q 1 to Q 3 is the same as or larger than the number of heteroatoms per nitrogen-containing aromatic group of b1 to b3.
  • the binding site of b1 to b3 refers to a binding site of b1 to b3 and a linking group between non-condensed heteroaromatic rings containing Q 1 to Q 3 .
  • Q 1 to Q 3 each independently represents a hetero atom or a carbon atom, and at least one of Q 1 to Q 3 represents a nitrogen atom.
  • Q 1 to Q 3 are each independently preferably a nitrogen atom, a sulfur atom, or a carbon atom, particularly preferably a nitrogen atom or a carbon atom, and any one is a nitrogen atom.
  • the atoms in Q 1 to Q 3 may be ionized.
  • it is preferable that at least one of Q 1 ⁇ Q 3 is a nitrogen atom, and more preferably all of Q 1 ⁇ Q 3 is a nitrogen atom.
  • B1 to b3 in the general formula (2) have the same meaning as B in the general formula (1), and the preferred range is also the same.
  • b1 to b3 preferably represent a substituted or unsubstituted nitrogen-containing aromatic group, and b1 to b3 are preferably 5 or 6 membered rings, preferably 6 membered rings. Is more preferable.
  • substituents that can be taken by b1 to b3 include the same substituents as those that can be taken by B in the general formula (1).
  • b1 to b3 are preferably a pyridyl group, a pyrimidyl group or a triazyl group, and more preferably a pyridyl group or a pyrimidyl group.
  • either one or both of the ring skeleton constituting atoms at the 3-position and the 4-position with respect to the bonding site with L are nitrogen atoms.
  • the ring skeleton constituting atom at the 2-position with respect to the binding site is preferably not a nitrogen atom.
  • Q 1 and Q 3 are preferably carbon atoms
  • Q 1 And Q 2 are preferably carbon atoms.
  • Q 2 and Q 3 are preferably carbon atoms. That is, the distance between the nitrogen atom constituting the central atomic group and the nitrogen atom of the nitrogen-containing aromatic group represented by b1 to b3 is preferably a certain distance or more, and the distance between the nitrogen atoms of the nitrogen-containing aromatic group Is preferably 4 atoms or more.
  • the number of heteroatoms in the non-condensed heteroaromatic ring containing Q 1 to Q 3 is the same as or larger than the number of heteroatoms per one nitrogen-containing aromatic group of b1 to b3.
  • the number of heteroatoms per one nitrogen-containing aromatic group satisfies the above condition.
  • the number of heteroatoms in the non-fused heteroaromatic ring represents the number of heteroatoms per one non-fused heteroaromatic ring.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group is preferably the following compound (3) or compound (4).
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group may be a compound represented by the following general formula (5).
  • A represents an atomic group composed of a 5- to 11-membered non-fused heteroaromatic ring
  • L represents a single bond or a (x + 1) -valent linking group
  • B represents a hydrogen atom, substituted Or an unsubstituted aromatic group or a substituted or unsubstituted nitrogen-containing aromatic group, and at least one B is a substituted or unsubstituted nitrogen-containing aromatic group, and at least one of the nitrogen-containing aromatic groups
  • any one or both of the ring skeleton constituting atoms at the 3rd and 4th positions relative to the bonding site with L are nitrogen atoms.
  • the number of heteroatoms in the non-fused heteroaromatic ring of A is the same as or more than the number of heteroatoms per one nitrogen-containing aromatic group of B.
  • x represents an integer of 1 or more.
  • a in the general formula (5) is the same as A in the general formula (1), and the preferred range is also the same.
  • L in General formula (5) is the same as L in General formula (1), and its preferable range is also the same.
  • B represents a hydrogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted nitrogen-containing aromatic group
  • at least one B is a substituted or unsubstituted nitrogen-containing aromatic group
  • the nitrogen-containing aromatic group means a group having a nitrogen atom as a constituent atom of the aromatic group.
  • at least one of the Bs may be a substituted or unsubstituted nitrogen-containing aromatic group, but it is preferable that all Bs are substituted or unsubstituted nitrogen-containing aromatic groups.
  • the nitrogen-containing aromatic group is preferably a pyridyl group, a pyrimidyl group, a triazyl group, or an imidazolyl group.
  • one or both of the ring skeleton constituting atoms at the 3-position and 4-position with respect to the bonding site with L are nitrogen atoms. is there.
  • the preferred configuration is the same as B in the general formula (1).
  • the number of heteroatoms in the non-condensed heteroaromatic ring of A is the same as or larger than the number of heteroatoms per one nitrogen-containing aromatic group of B.
  • the number of heteroatoms per all nitrogen-containing aromatic groups satisfies the above condition.
  • x represents an integer of 1 or more.
  • x is preferably an integer of 1 to 6, more preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and still more preferably an integer of 1 to 3. 1 or 2 is particularly preferable.
  • heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the general formula (1) include the following compounds. However, the present invention is not limited to the following specific examples.
  • the nitrogen-containing aromatic group of a terminal part corresponds to the non-condensed heteroaromatic ring represented by A of General formula (1), and the connection part containing a benzene ring is common. It corresponds to the linking group represented by L in formula (1).
  • heteroaromatic ring compound having a nitrogen-containing aromatic group represented by the general formula (1) the following compounds are preferably used among the above compounds.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group described above forms a crystal structure by two or more bonds or interactions selected from ⁇ - ⁇ interaction, coordination bond, charge transfer interaction and hydrogen bond. It is preferable. This is because the use of a low-molecular compound having a crystal structure can improve the intermolecular interaction and suppress vaporization during firing when obtaining a nitrogen-containing carbon alloy.
  • the crystal structure here refers to the arrangement and arrangement of molecules in the crystal. In other words, 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.
  • each molecular interaction is the same inside or outside the unit cell.
  • a heteroaromatic compound having a nitrogen-containing aromatic group having a laminated structure an aromatic ring, a heterocyclic ring, a condensed polycyclic ring, a condensed heterocyclic polycyclic ring, an unsaturated group (nitrile group, vinyl group, allyl group, acetylene) Group) and the like (for example, an aromatic ring is a face-to-face ⁇ - ⁇ 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 adjacent stacked columns have a uniform structure in which the intermolecular distance is defined by hydrogen bonding or van der Waals interaction. For this reason, it has the effect that the heat transfer in a crystal
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group used in the present invention preferably has crystallinity.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group is preferable because the crystallinity is crystallinity, and the compound can be controlled in orientation during firing, so that it becomes a uniform carbon material.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group preferably further has a melting point of 25 ° C. or higher.
  • the melting point is 25 ° C. or higher, there is an air layer that contributes to heat resistance during firing, boiling or bumping can be prevented from the relationship between temperature and vapor pressure, and a carbon material can be easily obtained.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group is not particularly limited, but is preferably at least one selected from low molecular compounds, oligomers and polymers, and at least one selected from low molecular compounds and oligomers. More preferably, it is a low molecular weight compound.
  • the molecular weight of the heteroaromatic ring compound having a nitrogen-containing aromatic group is not limited, but in the case of a low molecular compound or oligomer, it is preferably 60 to 2000, more preferably 100 to 1500, and 130 to 1000. Is particularly preferred. By making the molecular weight within the above range, purification before firing becomes easy.
  • the number average molecular weight is preferably from 2,000 to 1,000,000, and more preferably from 2,000 to 100,000.
  • the measurement method of weight average molecular weight and number average molecular weight includes Japanese Industrial Standards (JIS K 7252 (how to determine the average molecular weight and molecular weight distribution of a polymer by plastic size exclusion chromatography), and size exclusion chromatography (SEC).
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group may be a polymer such as Poly (4-VinylPyridine), a low molecular compound or an oligomer in the above exemplary compounds.
  • the degree of polymerization n is preferably 20 to 1.0 ⁇ 10 4 , more preferably 20 to 1.0 ⁇ 10 3 , and further preferably 20 to 1.0 ⁇ 10 2. preferable.
  • the degree of polymerization n is preferably 2 to 20, and more preferably 4 to 10.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group is a polymer, the nitrogen-containing aromatic group is arranged by a covalent bond.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group is a low-molecular compound or oligomer
  • the nitrogen-containing aromatic group is bonded by a covalent bond.
  • the aromatic group is preferred because it is oriented with the metal, the nitrogen-containing aromatic group is easily arranged, and vacancies are easily formed.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group is preferably contained in an amount exceeding 0.5% by mass relative to the total mass in the precursor, more preferably 1 to 95% by mass. Preferably, it is contained in an amount of 5 to 70% by mass.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group may be used alone or in combination of two or more. Moreover, it is preferable that the metal content in the hetero aromatic ring compound which has nitrogen-containing aromatic groups other than the inorganic metal salt mentioned later is 10 ppm or less.
  • the nitrogen content of the heteroaromatic ring compound having a nitrogen-containing aromatic group is preferably 0.1 to 55% by mass, more preferably 1 to 30% by mass, and further 4 to 20% by mass. It is particularly preferred.
  • a compound containing a nitrogen atom (N) within the above range, there is no need to introduce a separate nitrogen source compound, the nitrogen atom and metal are regularly positioned uniformly on the crystal edge, and the nitrogen and metal are It becomes easy to interact. Thereby, the composition ratio of nitrogen atom and metal can be a composition ratio having higher oxygen reduction activity.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group is preferably a hardly volatile compound having a ⁇ TG of ⁇ 95% to ⁇ 0.1% at 400 ° C. in a nitrogen atmosphere, and is ⁇ 95% to ⁇ It is more preferably a hardly volatile compound of 1%, particularly preferably -90% to -5%.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group is preferably a hardly volatile compound that is carbonized without being vaporized during firing.
  • ⁇ TG is at least one selected from a heteroaromatic ring compound having a nitrogen-containing aromatic group, 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.
  • TG-DTA TG-DTA measurement of the mixture, when the temperature was raised from 30 ° C. to 1000 ° C. at 10 ° C. per minute under a flow of 100 mL per minute, the mass decreased at 400 ° C. based on the mass at room temperature (30 ° C.) Refers to the rate.
  • the heteroaromatic ring compound having a nitrogen-containing aromatic group is also preferably a pigment having a structure represented by the general formula (1).
  • the pigment forms a stacked column structure by ⁇ - ⁇ interaction between molecules, and has a uniform structure with a defined intermolecular distance by hydrogen bonds or van der Waals interactions between the stacked columns. It has the effect that heat transfer is easily achieved. In addition, it has crystallinity, and is vibration-reduced and heat-resistant by phonon (quantized lattice vibration) against heat. Therefore, the decomposition temperature is maintained up to the carbonization temperature, and there is an effect that the vaporization of the decomposition product is reduced and the carbonization is achieved.
  • isoindoline pigments isoindolinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, oxazine pigments, phthalocyanine pigments, quinophthalone pigments, and latent pigments or dyes obtained by converting the above pigments into
  • a pigment such as a lake pigment pigmented with a metal ion is preferred, and a diketopyrrolopyrrole pigment, a quinacridone pigment, an isoindoline pigment, an isoindolinone pigment, a quinophthalone pigment, and a latent pigment obtained by laminating the above pigment ( (Described later) is more preferable.
  • Covalent organic framework materials and metal organic framework materials For the preparation of the precursor in the method for producing a nitrogen-containing carbon alloy of the present invention, 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 within 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 aromatic group are present in the pores of the added material. It is possible to form a porous nitrogen-containing carbon alloy with a heteroaromatic ring compound having a coordination with a pore shape as a template.
  • At least one selected from a covalent organic skeleton material and a metal organic skeleton material is preferably included in an amount of more than 5% by mass with respect to the total mass in the precursor, and 10 to 95% by mass is included.
  • 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 is, 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.
  • a restricted framework material having a polyhedral structure may be used instead of an infinite porous structure.
  • Such materials are formed by special selection of organic compounds.
  • 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).
  • MOP metal organic polyhedron
  • such a metal organic polyhedron (MOP) is also preferably used.
  • Inorganic metal salts and organometallic complexes For the preparation of the precursor in the method for producing the 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, and hydroxides, oxides, nitrides, sulfites, sulfides, sulfonates, carbonylates, nitrates, nitrites, halides, 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, and more preferably Fe or Co.
  • 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 heteroaromatic ring compound having a nitrogen-containing aromatic group and the inorganic metal salt do not need to be uniformly dispersed in the organic material before firing. That is, when a heteroaromatic ring compound having a nitrogen-containing aromatic group undergoes calcination decomposition, if the decomposition product is in contact with a vaporized product such as an inorganic metal salt, an active species having oxygen reduction reaction activity is formed. Therefore, the oxygen reduction reaction activity of the carbon alloy is not affected by the mixed state of the heteroaromatic ring compound and the inorganic metal salt at room temperature.
  • 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 heteroaromatic ring compound having a nitrogen-containing aromatic group, and the heteroaromatic ring compound is likely to form a complex when it is 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, Complex Chemistry-Fundamentals and Latest Topics-, Kodansha Scientific (1994).
  • a compound in which a ligand is coordinated can be preferably exemplified, and a metal acetate complex or a ⁇ -diketone metal complex can be preferably used.
  • 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.), multidentate ligands (ethylenediaminetetraacetate ion (edta), etc.).
  • 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
  • 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 (6) 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.
  • 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.
  • ⁇ -diketone or its ion is coordinated or bonded to the atom or ion of 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 optionally having a substituent for R 1 , R 2 , and R 3 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. , Heterocyclic (heterocyclic) hydrocarbon groups, and groups in which a plurality of these are bonded.
  • 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 groups, ⁇ -carbolinyl groups, phenanthridinyl groups, 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.); hydroxy 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 group
  • Examples of the ring formed by combining R 1 , R 2 , and R 3 with each other include, for example, a 5- to 15-membered cycloalkane ring or cycloalkene ring such as a cyclopentane ring, cyclopentene ring, cyclohexane ring, cyclohexene ring, etc. Is mentioned.
  • R 1 and R 3 include 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.
  • 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 any solvent that can be axially coordinated may be used.
  • ⁇ -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 a total of a heteroaromatic ring compound having a nitrogen-containing aromatic group and an inorganic metal salt or an organometallic complex contained in the precursor (however, the total Is preferably contained in an amount exceeding 0.1% by mass, more preferably 0.5 to 85% by mass, and 1 to 70% by mass. Further preferred.
  • a carbon alloy having higher oxygen reduction activity can be generated by interaction with a nitrogen atom.
  • 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 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 heteroaromatic ring compound By firing an organic material containing a heteroaromatic ring compound having a nitrogen-containing aromatic group, the heteroaromatic ring 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. Further, due to the catalytic action of a specific transition metal compound added to a heteroaromatic ring compound having a nitrogen-containing aromatic group containing a nitrogen atom (N) as a constituent element, the nitrogen atom (N) is increased on the carbon catalyst surface.
  • a conductive additive may be added to the precursor and baked, or may be added to the carbon alloy. Since the conductive auxiliary agent is uniformly dispersed, it is preferable to add a conductive auxiliary agent and fire.
  • 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. If too much conductive additive is added, the aggregation / growth of the metal produced from the inorganic metal salt in the system becomes non-uniform and the desired porous nitrogen-containing carbon cannot be obtained, which is not suitable.
  • the step of firing the precursor is as follows: (1) A heteroaromatic ring compound having a nitrogen-containing aromatic group, 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 are mixed And preparing a precursor, (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.
  • 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-described heteroaromatic ring compound having a nitrogen-containing aromatic group, at least one selected from a covalently bonded organic skeleton material and a metal organic skeleton material, and inorganic A precursor is prepared by mixing at least one selected from metal salts and organometallic complexes.
  • 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.
  • a heteroaromatic ring compound having a nitrogen-containing aromatic group having a specific structure, and a covalently bonded organic skeleton A precursor containing at least one selected from a material and a metal-organic framework material and at least one selected from an inorganic metal salt and an organometallic complex is heated to a carbonization temperature and cooled to room temperature after the heat treatment. Is preferred.
  • 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 into a carbonization device and then heated from room temperature to a predetermined temperature, or may be increased by inserting the sample before treatment into a carbonization device or the like at a 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.
  • Preliminary carbide In order to obtain a preliminary carbide having pores, it is preferable to perform the previous treatment of the organic material containing a heteroaromatic ring compound having a nitrogen-containing aromatic group and an inorganic metal salt at a relatively low temperature. In such a low temperature treatment, a constant temperature may be maintained. By doing so, only a heat-stable structure can be maintained, and unstable impurity components, solvents, and the like can be removed.
  • the temperature raising treatment performed at a relatively low temperature it is preferable to raise the temperature of an organic material containing a heteroaromatic ring compound having a nitrogen-containing aromatic group and an inorganic metal salt to 100 ° C. to 1500 ° C., preferably 150 ° C. to 1050 ° C. It is more preferable to raise the temperature to 200 ° C to 1000 ° C. By doing so, 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.
  • the gas flow rate is preferably 0.01 to 2.0 liters / min per 36 mm ⁇ inner diameter, and the gas flow rate is 0.05 to 1.0 per 36 mm ⁇ inner diameter. It is more preferable to circulate a liter / min gas, and it is particularly preferable that the gas flow rate is 0.1 to 0.5 liter / min gas per an inner diameter of 36 mm ⁇ .
  • the temperature holding time is 0.1 to 100 hours, preferably 0.2 to 10 hours, and more preferably 0.5 to 5 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.
  • an infusible treatment In the heat treatment up to the carbonization temperature, the portions of the temperature rise treatment are collectively referred to as an infusible treatment.
  • a heteroaromatic ring compound having a nitrogen-containing aromatic group having a specific structure in the preceding stage, at least one selected from a covalently bonded organic skeleton material and a metal organic skeleton material, and an inorganic metal Subsequent to the temperature raising treatment of the precursor containing at least one selected from a salt and an organometallic complex, it is preferable to perform the subsequent temperature raising treatment continuously.
  • 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.
  • the gas flow rate is preferably 0.01 ml to 2.0 liters / min per 36 mm ⁇ inside diameter, and the gas flow rate is 0.02 ml to 1 per 36 mm ⁇ inside diameter. More preferably, a gas of 0.0 liter / min is circulated, and the flow rate of the gas is particularly preferably 0.05 to 0.5 liter / min.
  • the downstream gas flow rate may be different from the upstream gas flow rate.
  • the temperature holding time is 0.1 to 100 hours, preferably 0.2 to 10 hours, and more preferably 0.5 to 5 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 heteroaromatic ring compound having a nitrogen-containing aromatic group having a specific structure and an inorganic metal salt is the same as that of the heteroaromatic ring compound having a nitrogen-containing aromatic group.
  • the upper limit of the carbonization temperature needs to be 2000 ° C., although it is not particularly limited as long as it is a temperature to be converted.
  • 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 By setting the reaction temperature within the above range, carbon alloy having high catalytic performance due to advanced carbonization can be obtained. Moreover, if 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.
  • 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. More preferably, it is particularly preferable to circulate a gas of 0.05 ml 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 0.1 to 100 hours, preferably 0.2 to 10 hours, and more preferably 0.5 to 5 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 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. Without being bound by any theory, it is expected that a porous nitrogen-containing carbon alloy having optimum porosity can be obtained by this acid cleaning treatment.
  • 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
  • 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 high-pressure treatment is not preferable because it has a diamond structure composed of sp 3 orbitals.
  • 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
  • a vacuum gas replacement rotary furnace rotary kiln
  • the sample tube is rotated at the time of firing, but is not limited to the rotational speed, speed change, and the like.
  • the rotation speed is preferably 10 rpm or less, more preferably 5 rpm or less.
  • 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%. If it is 2 mol% or more, a sufficient activation effect can be obtained, while if it exceeds 80 mol%, the activation effect becomes remarkable and the yield of carbide is remarkably reduced, making it impossible to produce carbide efficiently. There is a fear.
  • 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.
  • the atomic ratio (N / C) of the nitrogen atom to the carbon atom is less than 0.02, the number of effective nitrogen atoms bonded to the metal is reduced, and sufficient oxygen reduction catalyst characteristics cannot be obtained.
  • the atomic ratio (N / C) of nitrogen atoms to carbon atoms exceeds 0.3, the strength of the carbon skeleton of the carbon alloy is lowered, and the electrical conductivity is lowered.
  • 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 of 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. And direct-current power generate
  • 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”.
  • (3-Py) 3 -TAz was prepared with reference to FIG. 10 g of 3-cyanopyridine, 10 g of 18-crown-6, 225 mg of KOH, and 10 mL of decalin were mixed and stirred at 200 ° C. for 5 hours. After air cooling to room temperature, the reaction product was filtered and washed by boiling with pyridine. The obtained solid was dissolved in 1N hydrochloric acid, the solid was precipitated with aqueous ammonia, filtered, washed with water and dried to obtain (3-Py) 3 -TAz in a yield of 4.1 g.
  • 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. Further, 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 0.2048 g of acid-washed carbon material (1E).
  • 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
  • the nitrogen-containing carbon alloy dispersion is placed on the carbon electrode so that the nitrogen-containing carbon alloy is 0.50 mg / cm 2. It was applied and dried at room temperature to obtain a carbon alloy coated electrode.
  • (4-Py) 3 -TAz was prepared with reference to FIG. 10 g of 3-cyanopyridine, 10 g of 18-crown-6, 225 mg of KOH, and 10 mL of decalin were mixed and stirred at 200 ° C. for 5 hours. After air cooling to room temperature, the reaction product was filtered and washed by boiling with pyridine. The obtained solid was dissolved in 1N hydrochloric acid, the solid was precipitated with aqueous ammonia, filtered, washed with water and dried to obtain (4-Py) 3 -TAz in a yield of 4.1 g.
  • the obtained carbon precursor (2B) 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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then allowed to stand overnight to obtain 0.1849 g of acid-cleaned carbon material (2E).
  • 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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.2785 g of an acid cleaned carbon precursor (3C).
  • the 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. Further, 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 0.1156 g of acid-washed carbon material (3E). The obtained acid cleaned carbon material (3E) was used as the nitrogen-containing carbon alloy of Example 3.
  • the obtained carbon precursor (4B) 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. Further, 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 0.2692 g of acid-washed carbon precursor (4C).
  • the carbon material (4D) 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. Further, 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 0.0979 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. Further, 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 0.3186 g of an acid cleaned carbon precursor (5C).
  • the carbon material (5D) 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 0.1364 g of acid-cleaned carbon material (5E). The obtained acid-washed carbon material (5E) was used as the nitrogen-containing carbon alloy of Example 5.
  • the obtained carbon precursor (6B) 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. Further, 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 0.3558 g of an acid cleaned carbon precursor (6C).
  • 0.2350 g of the above carbon precursor (6C) was measured on a quartz boat and placed in the center of a 4.0 cm ⁇ (inner diameter 3.6 cm ⁇ ) quartz tube inserted in a vacuum gas replacement furnace, and nitrogen was added at 200 mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of the tube was evacuated to 3.0 ⁇ 10 1 Pa with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour.
  • the carbon material (6D) 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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and left overnight as it was to obtain 0.1668 g of acid-washed carbon material (6E). The obtained acid cleaned carbon material (6E) was used as the nitrogen-containing carbon alloy of Example 6.
  • 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. Further, 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 0.7437 g of an acid cleaned carbon precursor (7C).
  • the carbon material (7D) was pulverized in an agate mortar, washed with water, filtered and air-dried. Further, 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 0.4693 g of acid-washed carbon material (7E). The obtained acid cleaned carbon material (7E) was used as the nitrogen-containing carbon alloy of Example 7.
  • the carbon material (7D) described above 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. Further, 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 0.4667 g of acid-washed carbon material (8E). The obtained acid cleaned carbon material (8E) was used as the nitrogen-containing carbon alloy of Example 8.
  • 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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and then left overnight to obtain 0.4517 g of an acid cleaned carbon precursor (9C).
  • the carbon material (9D) 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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.0745 g of acid-washed carbon material (9E). The obtained acid cleaned carbon material (9E) was used as the nitrogen-containing carbon alloy of Example 9.
  • the carbon material (10D) 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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.0754 g of acid-cleaned carbon material (10E). The obtained acid cleaned carbon material (10E) was used as the nitrogen-containing carbon alloy of Example 10.
  • the obtained carbon precursor (11B) 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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.3117 g of acid-washed carbon precursor (11C).
  • the carbon material (11D) 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. Further, 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 0.1251 g of acid-cleaned carbon material (11E). The obtained acid cleaned carbon material (11E) was used as the nitrogen-containing carbon alloy of Example 11.
  • the obtained carbon precursor (12B) 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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.2651 g of acid-washed carbon precursor (12C).
  • the carbon material (12D) 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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and left overnight as it was to obtain 0.1011 g of acid-washed carbon material (12E). The obtained acid cleaned carbon material (12E) was used as the nitrogen-containing carbon alloy of Example 12.
  • the obtained carbon precursor (13B) 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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and allowed to stand overnight to obtain 0.1870 g of an acid cleaned carbon precursor (13C).
  • the carbon material (13D) was pulverized with an agate mortar, washed with water, filtered and air-dried. Further, 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 0.0729 g of the acid-washed carbon material (13E). The obtained acid-washed carbon material (13E) was used as the nitrogen-containing carbon alloy of Example 13.
  • 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. Further, 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 0.2237 g of acid-washed carbon material (C1-E).
  • the obtained carbon precursor (C2-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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain 0.2482 g of acid-washed carbon precursor (C2-C).
  • the carbon material (C2-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. Further, 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 0.1188 g of acid-washed carbon material (C2-E). The obtained acid-washed carbon material (C2-E) was used as the nitrogen-containing carbon alloy of Comparative Example 2.
  • ZIF8 (trade name: Basolite Z1200, manufactured by BASF) 2.0 g was measured in a quartz boat without crushing, and placed in the center of a 4.0 cm ⁇ (inner diameter 3.6 cm ⁇ ) quartz tube inserted into a tubular furnace. After degassing nitrogen substitution three times, nitrogen was circulated at 200 mL / min for 30 minutes at room temperature. The temperature was raised from 30 ° C. to 100 ° C. at a rate of 5 ° C. per minute, dried at 100 ° C. for 24 hours, and then cooled to room temperature over 12 hours to obtain ZIF8 (C3-E) of Comparative Example 3.
  • the obtained carbon precursor (C4-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. Further, 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 an acid cleaned carbon precursor (C4-C).
  • the above carbon precursor (C4-C) 0.2536 g was measured in 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 distributed at 200 mL / min for 1 minute at room temperature. Next, the inside of the tube was evacuated to 1.9 ⁇ 10 1 Pa with a vacuum pump, and nitrogen substitution was repeated three times. Thereafter, nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C.
  • the carbon material (C4-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. Further, 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 0.1837 g of acid-washed carbon material (C4-E). The obtained acid cleaned carbon material (C4-E) was used as the carbon material of Comparative Example 4.
  • the obtained carbon precursor (C5-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. Further, 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 0.4994 g of an acid cleaned carbon precursor (C5-C).
  • the carbon material (C5-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. Further, 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 an acid cleaned carbon material (C5-E). The obtained acid cleaned carbon material (C5-E) was used as the carbon material of Comparative Example 5.
  • 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.
  • 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.
  • the yield of a nitrogen-containing carbon alloy can be raised and productivity can be improved.
  • Such a carbon catalyst is preferably used for a fuel cell or an environmental catalyst and has high industrial applicability.

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Abstract

Cette invention concerne un procédé de fabrication d'un alliage au carbone contenant de l'azote qui présente une plus grande activité de réduction de l'oxygène, ledit alliage au carbone contenant de l'azote et un catalyseur pour pile à combustible. Le procédé de fabrication d'un alliage au carbone contenant de l'azote selon l'invention comprend une étape dans laquelle un précurseur contenant les éléments suivants est calciné ; un composé à noyau hétéro-aromatique contenant un groupe aromatique contenant de l'azote qui peut être représenté par la formule générale (1) ; une ou plusieurs espèces choisies parmi les matériaux à structure organique covalente et les matériaux à structure organométallique ; une ou plusieurs espèces choisies parmi les sels métalliques inorganiques et les complexes organométalliques. Dans la formule générale (1), A représente un groupe d'atomes comportant un noyau hétéro-aromatique à 5 à 11 chaînons non condensé ; L représente une liaison simple ou un groupe de liaison ayant une valence x +1 ; chaque B représente un atome d'hydrogène, un groupe aromatique substitué ou non substitué ou un groupe aromatique contenant de l'azote substitué ou non substitué ; au moins un B représente un groupe aromatique contenant de l'azote substitué ou non substitué ; dans au moins un groupe aromatique contenant de l'azote, au moins l'un des atomes formant la structure cyclique dans les troisième et quatrième positions par rapport au site de liaison à L est un atome d'azote. (1)
PCT/JP2015/068180 2014-06-27 2015-06-24 Procédé de fabrication d'alliage au carbone contenant de l'azote, alliage au carbone contenant de l'azote et catalyseur pour pile à combustible Ceased WO2015199125A1 (fr)

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CN110164716A (zh) * 2019-05-31 2019-08-23 上海交通大学 一种基于共价有机框架材料的薄膜电极的制备方法
CN116239779A (zh) * 2022-09-06 2023-06-09 武汉大学 一种用于碘化试剂的二维卤键有机框架材料、其制备方法及应用

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CN109180956A (zh) * 2018-08-27 2019-01-11 福建师范大学 亲水性寡聚物@疏水性金属有机框架的复合材料的制备方法
CN109180956B (zh) * 2018-08-27 2021-04-23 福建师范大学 亲水性寡聚物@疏水性金属有机框架的复合材料的制备方法
CN110164716A (zh) * 2019-05-31 2019-08-23 上海交通大学 一种基于共价有机框架材料的薄膜电极的制备方法
CN110164716B (zh) * 2019-05-31 2021-03-30 上海交通大学 一种基于共价有机框架材料的薄膜电极的制备方法
CN116239779A (zh) * 2022-09-06 2023-06-09 武汉大学 一种用于碘化试剂的二维卤键有机框架材料、其制备方法及应用

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