WO2016035705A1

WO2016035705A1 - Method for producing nitrogen-containing carbon alloy, nitrogen-containing carbon alloy and fuel cell catalyst

Info

Publication number: WO2016035705A1
Application number: PCT/JP2015/074426
Authority: WO
Inventors: 順田邉
Original assignee: 富士フイルム株式会社
Priority date: 2014-09-01
Filing date: 2015-08-28
Publication date: 2016-03-10
Also published as: JP6454350B2; JPWO2016035705A1

Abstract

The objective of the present invention is to provide: a method for producing a nitrogen-containing carbon alloy having higher oxygen reduction activity; a nitrogen-containing carbon alloy; and a fuel cell catalyst. A method for producing a nitrogen-containing carbon alloy according to the present invention comprises a step for firing a precursor that contains: at least one substance selected from among nitrogen-containing organic compounds represented by general formula (1), tautomers of the nitrogen-containing organic compounds, salts of the nitrogen-containing organic compounds and hydrates of the nitrogen-containing organic compounds; at least one substance selected from among covalently bondable organic framework materials and metal organic framework materials; and at least one substance selected from among inorganic metal salts and organic metal complexes.

Description

Method for producing nitrogen-containing carbon alloy, nitrogen-containing carbon alloy and fuel cell catalyst

The present invention relates to a method for producing a nitrogen-containing carbon alloy, a nitrogen-containing carbon alloy, and a fuel cell catalyst. Specifically, the present invention relates to a method for producing a nitrogen-containing carbon alloy including a step of firing a precursor containing a nitrogen-containing organic compound, a porous skeleton material, and an inorganic metal salt or an organometallic complex. Furthermore, the present invention relates to a nitrogen-containing carbon alloy and a fuel cell catalyst using the nitrogen-containing carbon alloy.

Conventionally, 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. Has been. However, since such 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.

Carbon catalysts are known as catalysts that can be formed without using platinum, and nitrogen-containing carbon alloys obtained by heat-treating nitrogen-containing organic compounds are used as carbon catalysts. For example, Patent Document 1 discloses a polymer electrolyte fuel cell catalyst comprising a composite of an s-triazine ring derivative and a metal. Patent Document 2 discloses a nitrogen-containing carbon alloy catalyst produced by firing a nitrogen-containing heterocyclic compound having a molecular weight of 60 to 2000 and an inorganic metal or inorganic metal salt.

Patent Documents 3 and 4 disclose a nitrogen-containing carbon alloy catalyst produced by firing a mixture of a porous material such as a nitrogen-containing heterocyclic compound, a metal complex, and MOF (Metal-Organic frameworks). . In Patent Document 3, TPTZ (2,4,6-tri (2-pyridyl) -1,3,5-triazine) is used as a nitrogen-containing heterocyclic compound. In Patent Document 3, phthalonitrile-based compounds and pyridine-based compounds are listed as nitrogen-containing organic compounds, but these compounds are only listed as non-limiting examples. Patent Document 4 lists 6- (2-pyridyl) -1,3,5-triazine-2,4-diamine as a nitrogen-containing heterocyclic compound.

JP 2007-175578 A JP 2011-225431 A US Patent Publication US2014 / 0099571 US Patent Publication US2011 / 0294658

As described above, the nitrogen-containing carbon alloy catalyst containing a nitrogen-containing organic compound can exhibit catalytic activity without using platinum. However, 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.
Moreover, in the conventional method for producing a nitrogen-containing carbon alloy using a nitrogen-containing compound, the yield is poor, and further improvement in productivity has been demanded.

Therefore, in order to solve such problems of the prior art, 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.

As a result of intensive studies to solve the above problems, the present inventor has a nitrogen-containing organic compound having a specific structure, at least one selected from a covalent organic skeleton material and a metal organic skeleton material, By calcining a precursor containing at least one selected from an inorganic metal salt or an organic metal complex to produce a nitrogen-containing carbon alloy, a nitrogen-containing carbon alloy having sufficiently enhanced oxygen reduction activity can be obtained. I found. Furthermore, the present inventor has found that the nitrogen-containing carbon alloy produced in this way has high production efficiency and a sufficient yield can be obtained, and has completed the present invention.
Specifically, the present invention has the following configuration.

[1] At least one selected from nitrogen-containing organic compounds represented by the following general formula (1), tautomers of nitrogen-containing organic compounds, salts of nitrogen-containing organic compounds, and hydrates of nitrogen-containing organic compounds And production of a nitrogen-containing carbon alloy comprising a step of firing a precursor comprising at least one selected from a covalently bonded organic skeleton material and a metal organic skeleton material and at least one selected from an inorganic metal salt and an organometallic complex Method;

In the general formula (1), Q represents an atomic group composed of at least one 5- to 7-membered aromatic ring or 5- to 7-membered heteroaromatic ring, and R represents a halogen atom, a substituted or When an unsubstituted alkyl group or a substituent represented by the following general formulas (2) to (5) is represented and Q does not include a nitrogen-containing heteroaromatic ring, at least one R is represented by the following general formula (2 ) To (5). n represents an integer of 1 to 4.

In the general formula (2), * represents a bond to Q.

In general formulas (3) to (5), R ¹ to R ⁸ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ¹ and R ² , R ³ and R ⁴ , R ⁷ and R ⁸ may be bonded to each other to form a ring. * Represents a bond to Q.
[2] The method for producing a nitrogen-containing carbon alloy according to [1], wherein in the general formula (1), Q is a 5- to 7-membered aromatic ring or a 5- to 7-membered heteroaromatic ring.
[3] The method for producing a nitrogen-containing carbon alloy according to [1] or [2], wherein Q in the general formula (1) is a benzene ring, a pyridine ring or an imidazole ring.
[4] The method for producing a nitrogen-containing carbon alloy according to [1] or [2], wherein in the general formula (1), Q is a 5- to 7-membered nitrogen-containing heteroaromatic ring.
[5] In the general formula (1), Q is a 5- to 7-membered nitrogen-containing heteroaromatic ring, R is a substituted or unsubstituted alkyl group, or a substituent represented by the general formula (2) The method for producing a nitrogen-containing carbon alloy according to [4], wherein
[6] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [5], wherein the metal organic framework material is a zeolite type imidazole framework material.
[7] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [6], wherein the inorganic metal salt is an inorganic metal chloride.
[8] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [7], wherein the metal species of the inorganic metal salt is Fe.
[9] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [8], wherein the inorganic metal salt is a hydrate salt.
[10] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [9], wherein the organometallic complex is at least one selected from a metal acetate complex, a β-diketone metal complex, and a salen complex.
[11] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [10], wherein the organometallic complex is an acetylacetone iron (II) complex.
[12] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [10], wherein the organometallic complex is an iron-salen complex.
[13] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [12], wherein the firing step is a step of firing the precursor at 400 ° C. or higher.
[14] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [13], wherein the firing step is a step of firing the precursor at 700 to 1050 ° C.
[15] The method for producing a nitrogen-containing carbon alloy according to [14], wherein the firing step includes a step of holding the precursor at 700 to 1050 ° C. for 1 second to 100 hours.
[16] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [15], further comprising a step of pulverizing the precursor before the firing step.
[17] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [16], further comprising a step of pulverizing the fired nitrogen-containing carbon alloy and a step of re-firing after the firing step. .
[18] The method for producing a nitrogen-containing carbon alloy according to [17], wherein the re-baking step is a step of baking at 1000 to 1500 ° C.
[19] The method for producing a nitrogen-containing carbon alloy according to [17] or [18], further comprising a step of deaeration and nitrogen substitution before the step of refiring.
[20] A nitrogen-containing carbon alloy produced by the method according to any one of [1] to [19].
[21] A fuel cell catalyst using the nitrogen-containing carbon alloy according to [20].

According to the production method of the present invention, a nitrogen-containing carbon alloy having a sufficiently high oxygen reduction activity can be obtained. For this reason, 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.
Moreover, according to the manufacturing method of this invention, the yield of a nitrogen-containing carbon alloy can be raised and productivity can be improved.

It is a schematic block diagram of the fuel cell using the nitrogen-containing carbon alloy of this invention. It is a schematic block diagram of the electric double layer capacitor using the nitrogen-containing carbon alloy of this invention.

Hereinafter, the present invention will be described in detail. The constituent elements described below may be described based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, 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.

Further, the substituent in the present invention may be any group that can be substituted. For example, a halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), hydroxyl group, cyano group, aliphatic group (aralkyl group, cyclohexane) Alkyl group, including active methine group, etc.), aryl group (regarding the position of substitution), heterocyclic group (regardless of the position of substitution), acyl group, aliphatic oxy group (alkoxy group or alkyleneoxy group, Ethyleneoxy group or a group containing a propyleneoxy group unit repeatedly), aryloxy group, heterocyclic oxy group, aliphatic carbonyl group, arylcarbonyl group, heterocyclic carbonyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, Heterocyclic oxycarbonyl group, carbamoyl group, sulfonylcarbamoyl group, acylcal Moyl group, sulfamoylcarbamoyl group, thiocarbamoyl group, aliphatic carbonyloxy group, aryloxycarbonyloxy group, heterocyclic carbonyloxy group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, acylamino group Aliphatic oxyamino group, aryloxyamino group, sulfamoylamino group, acylsulfamoylamino group, oxamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, Carbamoylamino group, mercapto group, aliphatic thio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, sulfamoyl group, fat Sulfonylureido group, arylsulfonylureido group, heterocyclic sulfonylureido group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfamoyl group, arylsulfamoyl group, heterocyclic sulfamoyl group , Acylsulfamoyl group, sulfonylsulfamoyl group or a salt thereof, carbamoylsulfamoyl group, sulfonamide group, aliphatic ureido group, arylureido group, heterocyclic ureido group, aliphatic sulfonamido group, arylsulfonamido group , Heterocyclic sulfonamido group, aliphatic sulfinyl group, arylsulfinyl group, nitro group, nitroso group, diazo group, azo group, hydrazino group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, Silyl group (eg trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), silyloxy group (eg trimethylsilyloxy, t-butyldimethylsilyloxy), borono group, ionic hydrophilic group (eg carboxyl group, sulfo group, phosphono group) Group and quaternary ammonium group). These substituent groups may be further substituted, and examples of the further substituent include groups selected from the substituents described above.

The present invention relates to at least one selected from nitrogen-containing organic compounds having a specific structure, tautomers of nitrogen-containing organic compounds, salts of nitrogen-containing organic compounds, and hydrates of nitrogen-containing organic compounds, and covalent bonding. The present invention relates to a method for producing a nitrogen-containing carbon alloy including a step of firing a precursor containing at least one selected from an organic skeleton material and a metal organic skeleton material and at least one selected from an inorganic metal salt and an organometallic complex.

In the present invention, when a nitrogen-containing carbon alloy is obtained by calcination, a nitrogen-containing organic compound having an after-mentioned structure and an inorganic metal salt or organometallic complex are mixed with a porous material (MOF (Metal-organic framework) or COF (Covalent organic framework). ) Etc.) in the reaction space field, a nitrogen-containing organic compound is coordinated to an inorganic metal salt or an organometallic complex using a pore shape as a template to form a nitrogen-containing carbon alloy having porosity. When these compounds are further heated and heated, the central atomic group of the nitrogen-containing organic compound is thermally decomposed to form an oxygen reduction reaction (ORR) active site, and a highly active nitrogen-containing carbon alloy can be obtained. . In the present invention, Q in the general formula (1) is composed of an atomic group composed of a 5- to 7-membered aromatic ring or a 5- to 7-membered heteroaromatic ring, whereby thermal decomposition of the atomic group is performed. It can be easily advanced. Thereby, formation of an oxygen reduction reaction (ORR) active site can be promoted, and a higher activity nitrogen-containing carbon alloy can be obtained.
Hereinafter, the nitrogen-containing organic compound, the covalently bonded organic skeleton material, the metal organic skeleton material, the inorganic metal salt, and the organometallic complex will be described in detail.

(Nitrogen-containing organic compounds)
The nitrogen-containing organic compound used in the method for producing a nitrogen-containing carbon alloy of the present invention is represented by the general formula (1). In the method for producing the nitrogen-containing carbon alloy of the present invention, a tautomer of the nitrogen-containing organic compound represented by the general formula (1), a salt of the nitrogen-containing organic compound or a hydrate of the nitrogen-containing organic compound is used. May be. The nitrogen-containing organic compound represented by the general formula (1), the tautomer of the nitrogen-containing organic compound, the salt of the nitrogen-containing organic compound, and the hydrate of the nitrogen-containing organic compound may be used alone. Two or more kinds may be used.

In general formula (2), * represents a bond to Q.

In general formulas (3) to (5), R ¹ to R ⁸ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ¹ and R ² , R ³ and R ⁴ , R ⁷ and R ⁸ may be bonded to each other to form a ring. * Represents a bond to Q.

The nitrogen-containing organic compound is an organic compound represented by the general formula (1), and is an organic compound having at least a carbon atom and a nitrogen atom in the molecule. The nitrogen-containing carbon alloy obtained by firing such a nitrogen-containing organic compound and other materials is considered to generate active sites having high oxygen reduction activity consisting of carbon atoms, nitrogen atoms and metals.

In the general formula (1), Q represents an atomic group composed of at least one 5- to 7-membered aromatic ring or 5- to 7-membered heteroaromatic ring. Q is preferably an atomic group composed of only a 5- to 7-membered aromatic ring or a 5- to 7-membered heteroaromatic ring, and a 5- to 7-membered aromatic ring or 5- to 7-membered ring. A heteroaromatic ring is more preferable. Q may be a condensed ring composed of a 5- to 7-membered aromatic ring or a 5- to 7-membered heteroaromatic ring, or a 5- to 7-membered aromatic ring or 5 to 7 It may be an atomic group in which membered heteroaromatic rings are directly connected. That is, the atomic group may be composed of at least one 5- to 7-membered aromatic ring or 5- to 7-membered heteroaromatic ring, and the atomic group includes a 5- to 7-membered aromatic ring. Or a condensed ring composed of a 5- to 7-membered heteroaromatic ring, a 5- to 7-membered aromatic ring, or a 5- to 7-membered heteroaromatic ring, and a 5- to 7-membered aromatic ring Alternatively, a linking ring in which a 5- to 7-membered heteroaromatic ring is directly connected is included.

In the general formula (1), Q is preferably a 5- to 7-membered aromatic ring or a 5- to 7-membered heteroaromatic ring, preferably a 5- or 6-membered aromatic ring or a 5- or 6-membered ring. The heteroaromatic ring is more preferable. Q is more preferably a benzene ring, a pyridine ring or an imidazole ring. In addition, since Q has an unsaturated bond, it becomes easy to form a carbon alloy skeleton by various interactions described later.

In the general formula (1), the 5- or 6-membered aromatic ring or the 5- or 6-membered heteroaromatic ring represented by Q is represented by the following general formulas (A-1) to (A-20). A structure is preferred.

In formula (A-1) ~ (A -20), at least one of R 51 ^{~ R 56} represents a linking portion between the R in the general formula ^(1), the R of the R 51 ^{~ R 56} Groups other than the linking part each independently represent a hydrogen atom or a substituent, and adjacent substituents may be bonded to each other to form a 5- or 6-membered ring.

The substituent represented by R ⁵¹ to R ⁵⁶ is not limited as long as it is a substitutable group, but is preferably an aliphatic group, aryl group, heterocyclic group, hydroxyl group, acyl group, aliphatic oxycarbonyl group, substituted A carbamoyl group which may have a group, an ureido group which may have a substituent, an acylamino group, a sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group or a sulfonyl group, and more Preferably, a halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), aliphatic group, aryl group, heterocyclic group, hydroxyl group, aliphatic oxycarbonyl group, carbamoyl group which may have a substituent, Examples thereof include a ureido group and an aliphatic oxy group which may have a substituent. Among them, the substituents represented by R ⁵¹ to R ⁵⁶ are alkyl groups (methyl group, ethyl group, t-butyl group, etc.), aryl groups (phenyl group, naphthyl group, etc.), halogen atoms (chlorine atom, bromine atom). , Fluorine atoms, etc.) and heteroaryl groups (pyridyl groups, etc.) are preferred.

Of R ⁵¹ to R ⁵⁶ , groups other than the linkage with R are more preferably a hydrogen atom. The number of hydrogen atoms represented by R ⁵¹ to R ⁵⁶ is preferably 1 to 4, more preferably 2 to 4.

In the general formula (1), Q is preferably a 5- to 7-membered nitrogen-containing heteroaromatic ring, more preferably a 5- or 6-membered nitrogen-containing heteroaromatic ring. The nitrogen-containing heteroaromatic ring may contain a heteroatom in addition to a nitrogen atom, but preferably contains only a nitrogen atom as a heteroatom. Thereby, since nitrogen is regularly arranged in the edge part derived from the crystal structure of the nitrogen-containing organic compound, the liberated metal ion can be coordinated.

R in the general formula (1) represents a halogen atom, a substituted or unsubstituted alkyl group, or a substituent represented by the following general formulas (2) to (5), and Q includes a nitrogen-containing heteroaromatic ring. When not present, at least one R represents a substituent represented by the following general formulas (2) to (5).
Here, when Q does not contain a nitrogen-containing heteroaromatic ring, Q is an atomic group composed of a 5- to 7-membered aromatic ring, or Q is a 5- to 7-membered heteroaromatic ring. This is an atomic group composed of a ring and a group composed of a heteroaromatic ring in which a nitrogen atom is not a ring constituent atom.

In general formula (2), * represents a bond to Q.

When Q does not contain a nitrogen-containing heteroaromatic ring, at least one R represents a substituent represented by the following general formulas (2) to (5). In this case, the nitrogen-containing organic compound includes a structure represented by the general formulas (2) to (5), so that a CN bond is generated in the decomposition product, and the CN and metal interact with each other. Nitrogen is retained until carbonization. Therefore, it is preferable because nitrogen is easily introduced into the graphene of carbon alloy and the oxygen reduction reaction activity can be enhanced.

When Q is an atomic group composed of a 5- to 7-membered heteroaromatic ring and composed of a heteroaromatic ring having a nitrogen atom as a ring-constituting atom, R is a halogen atom. It represents an atom, a substituted or unsubstituted alkyl group, or a substituent represented by the following general formulas (2) to (5). In this case, nitrogen is introduced into the heteroaromatic ring, which is more preferable because nitrogen atoms are uniformly introduced into the nitrogen-containing graphene skeleton constituting the carbon alloy and the oxygen reduction reaction activity can be enhanced.

In general formulas (3) to (5), R ¹ to R ⁸ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ¹ and R ² , R ³ and R ⁴ , R ⁷ and R ⁸ may be bonded to each other to form a ring. When R ¹ to R ⁸ are groups having a substituent, examples of the substituent include the specific examples described above.

In general formulas (3) to (5), R ¹ to R ⁴ are preferably each independently a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
R ⁵ and R ⁶ are preferably each independently a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
R ⁷ and R ⁸ are preferably each independently a hydrogen atom or an alkyl group.
R ¹ and R ² , R ³ and R ⁴ , R ⁷ and R ⁸ may be bonded to each other to form a ring. Examples of the ring formed by combining R ¹ and R ² , R ³ and R ⁴ , R ⁷ and R ⁸ with each other include, for example, a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a pyrrole ring, Examples include a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, an oxadiazole ring, a thiazole ring, a thiadiazole ring, a furan ring, a thiophene ring, a selenophene ring, a silole ring, a gelmol ring, a phosphole ring, and a pyrrolidone ring. Among them, the ring formed by bonding R ⁷ and R ⁸ to each other includes pyrrolidone ring, benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring. Are preferable, and a pyrrole ring or a pyrrolidone ring is more preferable. Moreover, the ring formed by combining R ¹ and R ² , R ³ and R ⁴ , R ⁷ and R ⁸ may further have a substituent.

In general formula (1), when Q does not include a nitrogen-containing heteroaromatic ring, at least one of R is preferably a substituent represented by general formula (2).

In the general formula (1), Q is preferably a 5- to 7-membered nitrogen-containing heteroaromatic ring. In this case, at least one R is a substituted or unsubstituted alkyl group, or the general formula (2 It is preferable that it is a substituent represented by.

When at least one of R is a substituent represented by the general formula (4), the nitrogen-containing organic compound is a compound represented by the general formula (1) in JP2011-225431A. Can be mentioned.

In the general formula (1), n represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.

In the general formula (1), Q represents an atomic group composed of at least one 5- to 7-membered aromatic ring or 5- to 7-membered heteroaromatic ring. A linking ring in which a 5-membered aromatic ring or a 5- to 7-membered heteroaromatic ring is directly connected is included. That is, the nitrogen-containing organic compound represented by the general formula (1) may be a dimer or more multimer in which the general formula (7) or (8) is connected by a single bond.

In general formulas (7) and (8), n1 represents an integer of 1 to 5, and n2 represents an integer of 1 to 6. n1 is preferably 1 to 4, more preferably 2 to 4, and even more preferably 2. n2 is preferably from 1 to 4, more preferably from 2 to 4, and even more preferably 2.

The compound represented by the general formula (7) or (8) may have a substituent other than a cyano group, but preferably has only a cyano group.

Specific examples of the nitrogen-containing organic compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

When the nitrogen-containing organic compound used in the present invention is a salt of the nitrogen-containing organic compound represented by the general formula (1), the salt of the nitrogen-containing organic compound represented by the general formula (1) 9).
[Q] _m ^{n +} [Y] _n ^m− General formula (9)
In the general formula (9), Q ^{n +} represents, for example, an organic cation represented by the following general formulas (A-21) to (A-24), Y ^m− represents an m-valent anion, and n and m Each independently represents a natural number, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, particularly preferably 1 or 2, and particularly preferably 1.

In general formulas (A-21) to (A-24), R ⁶¹ to R ⁶³ each independently represents a hydrogen atom or an alkyl group. Note that the alkyl group of R ⁶¹ to R ⁶³ may have a substituent, and examples of the substituent include the above-described substituents, and a cyano group and a vinyl group can be given as preferable examples. .

As the alkyl group of R ⁶¹ to R ⁶³ , an alkyl group having 1 to 8 carbon atoms is preferable. A methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a hexadecyl group, an octadecyl group Group and allyl group are more preferable, and methyl group, ethyl group, propyl group and butyl group are particularly preferable. R ⁶¹ to R ⁶³ may be the same or different, but when the molecule has two or more substituents represented by R ⁶¹ to R ^63, it may contain at least two kinds of alkyl groups. In this case, it is preferable that any one of R ⁶¹ to R ⁶³ represents a methyl group, and the other represents one of an ethyl group, a propyl group, and a butyl group.

[Y] _n ^m- in the general formula (9) is a halogen anion (Cl ⁻ , Br ⁻ , F ⁻ , I ⁻ ), BF ₄ ⁻ , PF ₆ ⁻ , an imide anion [N (SO ₂ CF ₃ ) ₂ ⁻ , N (COCF ₃ ) (SO ₂ CF ₃ ) ⁻ , N (CN) ₂ ^— etc.], Carbanion [C (CN) ₃ ^— etc.], R ²¹ OSO ₃ ⁻ , R ²¹ SO ₃ ⁻ , FeCl ₄ ⁻ CoCl ₄ ^{2- and the} like.
R ²¹ each independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. Further, R ²¹ is preferably fluorine as a substituent of the alkyl group, more preferably a trifluoroalkyl group, and particularly preferably a trifluoromethyl group.

Specific examples of the salt of the nitrogen-containing organic compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

The nitrogen-containing organic compound is preferably a nitrogen-containing crystalline organic compound from the viewpoint of crystallinity that the molecules are easily arranged regularly. However, the nitrogen-containing crystalline organic compound is preferably other than a nitrogen-containing metal complex. Nitrogen-containing metal complexes are difficult to purify and the composition ratio of nitrogen-containing ligands and metal complexes is constant, so when decomposed during firing, the decomposition rate of nitrogen-containing ligands and the vaporization of coordination metal complexes The speed cannot be controlled and it is difficult to obtain the target nitrogen-containing carbon alloy. Even when the nitrogen-containing metal complex and the low-molecular organic compound are mixed, the nitrogen-containing metal complex crystal is decomposed and the metal is directly reduced, so that the generated adjacent metals are easily aggregated and crystallized. Since the metal is removed by acid cleaning, the obtained nitrogen-containing carbon alloy becomes non-uniform, and there is a fear that the required function may be reduced.

The nitrogen-containing crystalline organic compound preferably forms a crystal structure by two or more bonds or interactions selected from π-π interaction, coordination bond, charge transfer interaction, and hydrogen bond. By using a low molecular weight compound having a crystal structure, the intermolecular interaction can be improved, and vaporization during firing when obtaining a nitrogen-containing carbon alloy can be suppressed.
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. That is, since the arrangement of functional groups in the crystal is uniform, each molecular interaction is the same inside or outside the unit cell. For example, in the case of a nitrogen-containing organic compound having a laminated structure, aromatic rings, heterocyclic rings, condensed polycyclic rings, condensed heterocyclic polycyclic rings, unsaturated groups (C≡N group, vinyl group, allyl group, acetylene group), etc. Action (for example, an aromatic ring is face-to-face and has a π-π interaction (π-π 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.

Further, in this stacked column structure, 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 | crystallization is achieved easily.
In addition, the nitrogen-containing organic compound is preferably a low-molecular compound, has crystallinity, and is preferably heat-resistant by being relaxed by phonons (quantized lattice vibration) against heat. Therefore, the decomposition temperature is maintained up to the carbonization temperature, the vaporization of the decomposition product is reduced and carbonized, and a carbon alloy skeleton is formed.

Further, a crystalline compound is preferable because the orientation can be controlled at the time of firing, so that it becomes a uniform carbon material.

Further, the nitrogen-containing organic compound preferably has a melting point of 25 ° C. or higher. When the melting point is 25 ° C. or higher, an air layer that contributes to heat resistance during firing exists, boiling or bumping can be suppressed, and a good carbon material can be obtained.

The nitrogen-containing organic compound preferably has a molecular weight of 60 to 2000, more preferably 100 to 1500, and still more preferably 130 to 1000. By making the molecular weight within the above range, purification before firing becomes easy.

The metal content in the nitrogen-containing organic compound is preferably 10 ppm or less. The metal content in the nitrogen-containing organic compound means a content other than the inorganic metal salt described later.

The nitrogen content of the nitrogen-containing organic compound is preferably from 0.1 to 55% by mass, more preferably from 1 to 30% by mass, and even more preferably from 4 to 20% by mass. By using a nitrogen-containing organic compound containing a nitrogen atom within the above range, it is not necessary to introduce a separate nitrogen source compound, and the nitrogen atom and the metal are regularly and uniformly positioned on the crystal edge. Are more likely to interact. Thereby, the composition ratio of nitrogen atom and metal can be a composition ratio having higher oxygen reduction activity.

The nitrogen-containing organic compound is preferably a hardly volatile compound having a ΔTG of −95% to −0.1% at 400 ° C. in a nitrogen atmosphere, and is hardly volatile having a −95% to −1%. More preferably, the compound is -90% to -5%. The nitrogen-containing organic compound is preferably a hardly volatile compound that is carbonized without being vaporized during firing. Here, ΔTG is 10 ° C./min from 30 ° C. to 1000 ° C. under a flow of 100 mL / min in a TG-DTA measurement (simultaneous measurement of differential heat-thermogravimetry) of a mixture of a nitrogen-containing organic compound and an inorganic metal salt. Refers to the mass reduction rate at 400 ° C. based on the mass at room temperature (30 ° C.).

In the present invention, at least one selected from the nitrogen-containing organic compound represented by the general formula (1), a tautomer of the nitrogen-containing organic compound, a salt of the nitrogen-containing organic compound, and a hydrate of the nitrogen-containing organic compound is The content of the precursor is preferably more than 0.5% by mass, more preferably 1 to 95% by mass, and still more preferably 5 to 70% by mass. By containing the nitrogen-containing organic compound within the above range, a carbon alloy having higher oxygen reduction activity can be generated.

The nitrogen-containing organic compound is also preferably a pigment having a structure represented by the general formula (1). The pigment has a stacked column structure due to π-π interaction between molecules. Since hydrogen bonding or van der Waals interaction occurs between the stacked columns, the stacked column structure has a uniform structure with a defined intermolecular distance. For this reason, it has the effect that the heat transfer in a crystal | crystallization is achieved easily. In addition, although the pigment is a low-molecular compound, it has crystallinity and has heat resistance because the vibration is reduced by phonons (quantized lattice vibration) against heat. For this reason, it has the effect that decomposition temperature is hold | maintained to carbonization temperature, vaporization of a decomposition product is reduced, and carbonization is achieved.
Examples of pigments include isoindoline pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, oxazine pigments, phthalocyanine pigments, quinophthalone pigments, and latent pigments or dyes made from the above pigments. Preferred are lake pigments that are pigmented with metal ions, such as diketopyrrolopyrrole pigments, quinacridone pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, and latin pigments obtained by latinizing the above pigments. preferable. When these pigments are calcined, the benzonitrile (Ph-CN) skeleton, which is decomposed and formed, becomes a reactive species, and a carbon alloy catalyst having higher oxygen reduction reaction activity is generated. Further, when the metal species (M) coexists, a complex of Ph—CN... M is formed, and a carbon alloy that is more active in high oxygen reduction reaction is generated.

(Covalent organic framework materials and metal organic framework materials)
Preparation of the precursor in the method for producing a nitrogen-containing carbon alloy of the present invention includes at least selected from a covalent organic framework material (COF) and a metal-organic framework material (MOF). One kind is used. 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. When the pore diameter is in this range, it is preferable because the number of action points increases and the generated water is easily discharged. Further, it is preferable because the internal pores of the porous material have a pore volume and easily interact with oxygen.

In the present invention, by adding a covalent organic framework material (COF) and a metal organic framework material (MOF), an inorganic metal salt or an organometallic complex and a nitrogen-containing organic compound are formed inside the pores of the added material. Can form a porous nitrogen-containing carbon alloy in a form using the shape of the pores as a template.

In the present invention, at least one selected from a covalent organic skeleton material and a metal organic skeleton material is preferably included in an amount exceeding 5% by mass with respect to the total mass of the precursor, and is included in an amount of 10 to 95% by mass. The content is more preferably 20 to 70% by mass. By containing at least one selected from a covalent organic framework material and a metal organic framework material within the above range, a carbon alloy having higher oxygen reduction activity can be produced.

Covalent organic skeletal material (COF) 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.

Although it is not particularly specified as a covalent organic skeleton material (COF), 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 (MOF) is a material having a porous structure utilizing a coordinate bond between a metal ion and an organic substance. In the metal organic framework material (MOF), 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. Among them, 3-pyridyltriazine, 4-pyridyltriazine, alkylimidazole, or bipyridine is more preferable, and 3-pyridyltriazine, 4-pyridyltriazine, or alkylimidazole is particularly preferable. Among them, 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. Here, 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. Here, 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. In general, 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. Further, the linking part may contain nitrogen, oxygen, sulfur, boron, phosphorus, silicon or aluminum in addition to the carbon atom.

A linking cluster refers to one or more condensable reactive species containing atoms that can form a bond between a linking moiety and a metal, or between a linking moiety and another linking moiety. . Examples of such species are preferably selected from the group consisting of boron, oxygen, carbon, nitrogen, and phosphorus atoms. The linked cluster includes, for example, —COOH, —CS ₂ H, —NO ₂ , —SO ₃ H, —Si (OH) ₃ , —Ge (OH) ₃ , —Sn (OH) ₃ , —Si (SH) _4. , -Ge (SH) ₄ , -Sn (SH) ₄ , -PO ₃ H, -AsO ₃ H, -AsO ₄ H, -P (SH) ₃ , -As (SH) ₃ , -CH (RSH) ₂ , —C (RSH) ₃ , —CH (RNH ₂ ) ₂ , —C (RNH ₂ ) ₃ , —CH (ROH) ₂ , —C (ROH) ₃ , —CH (RCN) ₂ , —C (RCN) ₃ , —CH (SH) ₂ , —C (SH) ₃ , —CH (NH ₂ ) ₂ , —C (NH ₂ ) ₃ , —CH (OH) ₂ , —C (OH) ₃ , —CH (CN) ) ₂ or -C (CN) ₃ may be included. The above R is an alkyl group having 1 to 20 carbon atoms or an aryl group.

Examples of metal organic framework materials (MOF) 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.

ZIF-8

As the metal organic framework material (MOF), a restricted framework material having a polyhedral structure in which the porous structure does not expand infinitely may be used. Such materials are formed by special selection of organic compounds. For example, A.I. C. Sudik et al. Am. Chem. Soc. 127 (2005), 7110-7118 describes such a specific skeletal material and is specifically called a metal organic polyhedron (MOP). In the present invention, such a metal organic polyhedron (MOP) is also preferably used.

(Inorganic metal salts and organometallic complexes)
<Inorganic metal salt>
For the preparation of the precursor in the method for producing a nitrogen-containing carbon alloy of the present invention, at least one selected from inorganic metal salts and organometallic complexes is used. The inorganic metal salt is not particularly limited, but hydroxide, oxide, nitride, sulfite, sulfide, sulfonate, carbonylate, nitrate, nitrite, halide and the like can be used. Preferably, the counter ion is a halogen ion or a nitrate ion. It is preferable that 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.
In the present invention, the inorganic metal salt is preferably a halide, and particularly preferably an inorganic metal chloride.

Further, 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. As the inorganic metal salt containing crystal water, for example, cobalt chloride (III) hydrate salt, iron chloride (III) hydrate salt, cobalt chloride (II) hydrate salt, iron chloride (II) hydrate salt is preferably used. it can.

The metal species of the inorganic metal salt is preferably at least one of Fe, Co, Ni, Mn and Cr, more preferably Fe or Co, and even more preferably Fe. Fe, Co, Ni, Mn, and Cr salts are excellent in forming a nano-sized shell structure that improves the catalytic activity of the carbon catalyst, and in particular, Co and Fe form a nano-sized shell structure. It is preferable because it is particularly excellent. Moreover, 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. As long as the activity of the carbon catalyst is not inhibited, 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.

In the present invention, there is an advantage that it is not necessary to uniformly disperse the nitrogen-containing organic compound and the inorganic metal salt in the organic material before firing. That is, when the nitrogen-containing organic compound is decomposed by firing, if the decomposition product is in contact with a vaporized substance such as an inorganic metal salt, it is considered that an active species having oxygen reduction reaction activity is formed. The oxygen reduction reaction activity of the carbon alloy is not affected by the mixed state of the nitrogen-containing organic compound and the inorganic metal salt.

The particle diameter of the inorganic metal salt is preferably 0.001 to 100 μm. More preferably, it is 0.01 to 10 μm. By making the particle size of the inorganic metal salt within this range, it becomes possible to uniformly mix with the nitrogen-containing organic compound, and the nitrogen-containing organic compound is likely to form a complex when decomposed.

<Organic metal complex>
In the method for producing a nitrogen-containing carbon alloy of the present invention, the precursor contains at least one selected from inorganic metal salts and organometallic complexes. By adding an organometallic complex to the precursor, in addition to obtaining high ORR activity, a carbon alloy catalyst having a high number of reaction electrons can be obtained.
Examples of organometallic complexes include compounds described in the Basic Complex Engineering Study Group, Coordination Chemistry-Fundamentals and Latest Topics, and Kodansha Scientific (1994). A compound in which a ligand is coordinated can be preferably exemplified, and at least one selected from a metal acetate complex, a β-diketone metal complex, and a salen complex can be preferably used. The organometallic complex may be a derivative of the above-described metal complex. The organometallic complex can take the coordination number of various ligands, may be a coordination geometric isomer, and may have different valences of metal ions. The organometallic complex may be an organometallic compound having a metal-carbon bond.

Preferred as metal ions are Fe, Co, Ni, Mn and Cr ions. Preferable ligands include monodentate ligands (halide ions, cyanide ions, ammonia, pyridine (py), triphenylphosphine, carboxylic acid, etc.), bidentate ligands (ethylenediamine (en), β- Diketonate (acetylacetonate (acac), pivaloylmethane (DPM), diisobutoxymethane (DIBM), isobutoxypivaloylmethane (IBPM), tetramethyloctadione (TMOD)), trifluoroacetylacetonate (TFA), bipyridine (Bpy), phenanthrene (phen), etc.), polydentate ligands (ethylenediaminetetraacetate ion (edta), N, N′-bis (salicylidene) ethylenediamine (salen), etc.).

Examples of the metal complex that can be used include the β-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 (diisobutoxyphenyl methane) iron _{(III) [Fe (DIBM)} 3], preparative Scan (diisobutoxyphenyl methane) cobalt _{(III) [Co (DIBM)} 3], bis (iso-butoxy pivaloyl methane) iron _{(II) [Fe (IBPM)} 2], tris (isobutoxy pivaloyl methane) cobalt ( III) [Co (IBPM) ₃ ], bis (tetramethyloctadione) iron (II) [Fe (TMOD) ₂ ]), tris (tetramethyloctadione) iron (III) [Fe (TMOD) ₃ ], tris (Tetramethyloctadione) cobalt (III) [Co (TMOD) ₃ ])), tris (1,10-phenanthrolinato) iron (III) chloride [Fe (phen) ₃ ] Cl ₂ , tris (1, 10-phenanthrolinato) cobalt (III) chloride [Co (phen) ₃ ] Cl ₂ , N, N′-methylenebis (salicylidenea) Minato) metal complexes and analogs (salen metal complexes) (N, N′-ethylenediaminebis (salicylideneaminato) iron (II) [Fe (salen)], N, N′-ethylenediaminebis (salicylidenea) Minato) Iron (III) chloride [Fe (salen) Cl], N, N′-bis (salicylidene) -o-phenylenediaminoiron (II) [Fe (Saloph)], N, N′-ethylenediaminebis ( Salicylideneaminato) cobalt (II) [Co (salen)], N, N′-ethylenediaminebis (salicylideneaminato) cobalt (III) chloride [Co (salen) Cl], N, N′— Bis (salicylidene) -o-phenylenediaminocobalt (II) [Co (saloph)]), tris (2,2′-bipyridine) iron (II) chloride [Fe (Bpy) ₃ ] Cl ₂ , tris (2,2′-bipyridine) cobalt (II) chloride [Co (bpy) ₃ ] Cl ₂ , iron phthalocyanine (MPc) and iron acetate [Fe (OAc) ₂ ] be able to.
Among them, β-diketone metal complexes (bis (acetylacetonato) iron (II) [Fe (acac) ₂ ], tris (acetylacetonato) iron (III) [Fe (acac) ₃ ], bis (dipivaloyl) Methane) iron (II) [Fe (DPM) ₂ ], bis (diisobutoxymethane) iron (II) [Fe (DIBM) ₂ ], bis (isobutoxypivaloylmethane) iron (II) [Fe (IBPM) ₂ ], bis (tetramethyloctadione) iron (II) [Fe (TMOD) ₂ ]), N, N′-ethylenediaminebis (salicylideneaminato) iron (II) [Fe (salen)], tris (2,2'-bipyridine) iron (II) chloride _{[Fe (bpy) 3] Cl} 2, iron phthalocyanine (MPc), iron acetate _{[Fe (OAc) 2],} N, N'- ethylenediamine Bis (salicylideneaminato) iron (II) [Fe (salen)] or N, N′-ethylenediaminebis (salicylideneaminato) cobalt (II) [Co (salen)] is preferred, and acetylacetone iron (II) ) Complex bis (acetylacetonato) iron (II) [Fe (acac) ₂ ], iron acetate [Fe (OAc) ₂ ] or N, N′-ethylenediaminebis (salicylideneaminato) iron (II) [Fe (salen)] is more preferably used.

(Β-diketone metal complex)
The organometallic complex preferably contains a β-diketone metal complex. As the organometallic complex, a β-diketone metal complex may be used alone, or a β-diketone metal complex and another organometallic complex may be mixed and used. The β-diketone metal complex represents a compound represented by the following general formula (10) and tautomers thereof.

In the general formula (10), M represents a metal, R ¹ and R ³ each independently represents a hydrocarbon group which may have a substituent, and R ² has a hydrogen atom or a substituent. The hydrocarbon group which may be carried out is shown. R ¹ , R ² and R ³ may be bonded to each other to form a ring. n represents an integer of 0 or more, and m represents an integer of 1 or more. In this compound, the β-diketone or its ion is coordinated or bonded to the atom or ion of the metal M.

Preferred metals include Fe, Co, Ni, Mn and Cr, more preferably Fe and Co, and still more preferably Fe.

In the general formula (10), examples of the “hydrocarbon group” in the hydrocarbon group which may have a substituent of R ¹ , R ² , and R ³ include an aliphatic hydrocarbon group and an alicyclic hydrocarbon. A group, an aromatic hydrocarbon group, a heterocyclic (heterocyclic) hydrocarbon group, and a group in which a plurality of these groups 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 group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, and antiridinyl group Hydrocarbon group; oxygen-containing monocyclic system, oxygen-containing polycyclic system Sulfur-containing and selenium-containing tellurium ring system hydrocarbon group.

Examples of the substituent that the hydrocarbon group may have include, for example, a halogen atom such as fluorine, chlorine, bromine atom; an alkoxy group such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy, t-butyloxy group (C _1-4 alkoxy group etc.); hydroxyl group; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups (C _1-4 alkoxy-carbonyl group etc.); acyl groups such as acetyl, propionyl and benzoyl groups (C _{1- 1 10} acyl group); cyano group; nitro group and the like.

In general formula (10), R ¹ , R ² , and R ³ are each bonded to each other to form a ring of, for example, a 5- to 15-membered cyclohexane such as a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, or a cyclohexene ring. Examples include an alkane ring and a cycloalkene ring.

R ¹ and R ³ in the general formula (10) are an alkyl group (C _1-6 alkyl group etc.), an alkenyl group (C _2-6 alkenyl group etc.), a cycloalkyl group (3 to 15 membered cycloalkyl group). Etc.), cycloalkenyl groups (3- to 15-membered cycloalkenyl groups, etc.), aryl groups (C _6-15 aryl groups, etc.), substituted aryl groups (p-methylphenyl groups, p-hydroxyphenyl groups, etc.) C _6-15 aryl group having a substituent, etc.) are preferred. R ² includes a hydrogen atom, an alkyl group (C _1-6 alkyl group, etc.), an alkenyl group (C _2-6 alkenyl group, etc.), a cycloalkyl group (3-15 membered cycloalkyl group, etc.), a cycloalkenyl group. (3- to 15-membered cycloalkenyl group etc.), aryl group (C _6-15 aryl group etc.), aryl group having a substituent (C ₆ having a substituent such as p-methylphenyl group, p-hydroxyphenyl group) _-15 aryl group, etc.) are preferred.

In the compound represented by the general formula (10), the valence n of the metal may be any of 0, 1, 2, 3 and the like, but is usually divalent or trivalent. When the metal is divalent or trivalent, the β-diketone coordinates as the corresponding anion, β-diketonate. When the metal valence is n, the coordination number m is usually the same. However, a solvent or the like may be axially coordinated with the metal. In that case, the valence n and the coordination number m of the metal may be different. Examples of the solvent that may be axially coordinated include pyridine, acetonitrile, alcohol, and the like, but are not particularly limited as long as they are axially coordinated.

As the β-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 β-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.

In the present invention, at least one selected from an inorganic metal salt and an organometallic complex is preferably contained in an amount exceeding 0.1% by mass, and 0.5 to 85% by mass with respect to the total mass of the precursor. More preferably, the content is 0.5 to 70% by mass. By containing at least one selected from an inorganic metal salt and an organometallic complex within the above range, a carbon alloy having higher oxygen reduction activity can be generated by interaction with a nitrogen atom. In the present invention, at least one selected from inorganic metal salts and organometallic complexes may be 0.1 to 10% by mass relative to the total mass of the precursor. Thus, in the present invention, by using a nitrogen-containing organic compound having a specific structure in combination with a covalent organic skeleton material and a metal organic skeleton material, at least one selected from inorganic metal salts and organometallic complexes is used. Even when the content is kept low, a carbon alloy having high oxygen reduction activity can be generated.

The oxygen reduction activity (ORR activity) can be measured as an ORR activity value by obtaining a potential by the method described in detail in Examples. To obtain high output, 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. According to Ohm's law, the coating amount and the potential are similarly deviated from the straight line in the relationship between the coating amount and the potential. The value of the potential at 0.5 mg / cm ² is a value that takes into account the potential of the catalyst activity at 0.05 mg / cm ² and the conductivity of the carbon alloy. By making this potential range, the conductivity is excellent. This is particularly preferable.

By firing an organic material containing a nitrogen-containing organic compound, the nitrogen-containing organic compound is decomposed, and the generated decomposition product forms a nitrogen-containing carbon alloy catalyst in the gas phase. At that time, if a metal is present in the vicinity of the gas phase, the decomposition product interacts with the metal (forms a complex), and the performance of the nitrogen-containing carbon alloy catalyst is further improved. In addition, the nitrogen atom (N) is immobilized on the surface of the carbon catalyst at a high concentration due to the catalytic action of a specific transition metal compound added to the nitrogen-containing organic compound containing the nitrogen atom (N) as a constituent element. It is preferable that carbon fine particles containing a transition metal compound that forms a nitrogen carbon alloy and interacts with the nitrogen atom (N) are formed. In addition, the transition metal compound which interacted with some nitrogen atoms (N) by the acid treatment mentioned later may drop off.

(Conductive aid)
In the present invention, a conductive additive may be added to the precursor and fired, or may be added to the carbon alloy. Since a conductive support agent is disperse | distributed uniformly, it is more preferable to add a conductive support agent and to bake.

Although it does not specifically limit as 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. By setting the addition amount of the conductive assistant within the above range, the aggregation and growth of the metal generated from the inorganic metal salt in the system becomes uniform, and the target porous nitrogen-containing carbon can be obtained.

<Method for producing nitrogen-containing carbon alloy>
The method for producing the nitrogen-containing carbon alloy of the present invention comprises:
(1) A precursor is prepared by mixing a nitrogen-containing organic compound, at least one selected from a covalent organic skeleton material and a metal organic skeleton material, and at least one selected from an inorganic metal salt and an organometallic complex. Process,
(2) a temperature raising step of raising the temperature of the precursor from 1 to 2000 ° C. per minute from room temperature to the carbonization temperature under an inert atmosphere;
(3) a carbonization step of holding at 400 to 2000 ° C. for 1 second to 100 hours;
(4) It is preferable to include a cooling step of cooling from the carbonization temperature to room temperature.
Further, after the step of firing the precursors (2) to (4) (after carbonization treatment, after cooling the carbon alloy to room temperature),
(5) A pulverization process may be performed.
Furthermore, 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.
Hereinafter, 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.

(1) Precursor preparation step In the precursor preparation step, the above-mentioned nitrogen-containing organic compound, at least one selected from a covalent organic skeleton material and a metal organic skeleton material, an inorganic metal salt and an organometallic complex are used. A precursor is prepared by mixing at least one selected.

The precursor prepared in the production process of the nitrogen-containing carbon alloy is then fired, but preferably further includes a step of pulverizing the precursor before the firing step.

In the case of including a step of pulverizing the precursor before the firing step, the pulverization method can be any method known to those skilled in the art, for example, using ball mill, agate pulverization, mechanical pulverization, etc. And can be crushed. Among these, the mechanical pulverization method is preferably used. By using the mechanical pulverization method, the specific surface area of the produced nitrogen-containing carbon alloy is increased, and high oxygen reduction activity (ORR activity) is obtained. For machine pulverization, for example, X-TREME MX1200XTM manufactured by Waring Co., Ltd. can be used. Although there are no particular limitations on the pulverization conditions, mixing is preferably performed at a rotating blade rotation speed of 80 to 30000 rpm, more preferably 300 to 25000 rpm, and even more preferably 1300 to 20000 rpm. The rotation method can be performed by continuous rotation, intermittent rotation, or a combination of continuous and intermittent rotation. The pulverization time is preferably from 0.1 seconds to 15 minutes, and the pulverization frequency is preferably at least once.
In the intermittent pulverization, the stop time of the rotary blade is preferably 0.1 to 100 times, more preferably 1 to 50 times, and further preferably 2 to 30 times the pulverization time. For example, when the rotational speed is 10000 rpm or more, the pulverization time is 10 seconds or less, the rotary blade stop time is 0.1 times or more, and the number of pulverizations is 2 times or more, decomposition of the precursor mixture by heat is reduced, and the precursor mixture Since the mixing can be made uniform, the oxygen reduction reaction activity can be increased more effectively.
When the pulverization time by continuous pulverization is 30 seconds or more, the precursor mixture generates heat, and at least one kind of pores selected from a covalently bonded organic skeleton material and a metal organic skeleton material has a nitrogen-containing organic compound and a nitrogen-containing organic compound. More effective because at least one selected from tautomers of compounds, salts of nitrogen-containing organic compounds and hydrates of nitrogen-containing organic compounds and at least one selected from inorganic metal salts and organometallic complexes are volatilized. In particular, the oxygen reduction reaction activity can be increased.

(2) Temperature raising step, (3) Carbonization step and (4) Cooling step In the production method of the present invention, the nitrogen-containing organic compound having a specific structure, its tautomer, its salt and its hydrate The precursor containing at least one selected from the group consisting of at least one selected from the group consisting of a covalent organic skeleton material and a metal organic skeleton material and at least one selected from inorganic metal salts and organometallic complexes is heated to a carbonization temperature. After the heat treatment, it is preferable to cool to room temperature.

Further, 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.
Of the multi-stage temperature raising processes, 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. Alternatively, after cooling to room temperature, the temperature may be raised and a subsequent temperature increase process may be performed.
Moreover, when it cools to room temperature after the temperature rising process of a front | former stage, the sample after a process may be grind | pulverized uniformly by the below-mentioned (5) grinding | pulverization process, and you may shape | mold further. Alternatively, the metal may be removed by acid cleaning of the sample after the treatment in (6) acid cleaning step described later.

In the temperature raising process, the sample before treatment may be inserted from the normal temperature to a predetermined temperature after being inserted into the carbonization apparatus, or the temperature may be increased by inserting the sample before treatment into the carbonization apparatus at the predetermined temperature. May be warm.
Preferably, the temperature of the sample before processing is raised from room temperature to a predetermined temperature. When raising the temperature to a predetermined temperature, it is preferable to keep the temperature raising rate constant. More specifically, 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 pre-carbide having pores, the pre-treatment of the organic material containing the nitrogen-containing organic compound, the covalently bonded organic skeleton material or the metal organic skeleton material, the inorganic metal salt, etc. is performed at a relatively low temperature. Preferably it is done. In such a low temperature treatment, a constant temperature may be maintained. As a result, only the heat-stable structure can be maintained, and unstable impurity components, solvents, and the like can be removed.

In the temperature raising treatment performed at a relatively low temperature, the temperature of the organic material containing the nitrogen-containing organic compound and the inorganic metal salt is preferably raised to 100 to 1500 ° C., more preferably raised to 150 to 1050 ° C., More preferably, the temperature is raised to 200 to 1000 ° C. Thereby, a uniform preliminary carbide is obtained.

It is preferable to perform the above temperature raising process in an inert atmosphere. The inert atmosphere refers to a gas atmosphere such as a nitrogen gas or a rare gas atmosphere. Note that even if oxygen is contained, the atmosphere may be any atmosphere in which the amount of oxygen is limited to such an extent that the workpiece is not combusted. The inert atmosphere may be either a closed system or a distribution system for circulating a new gas, and is preferably a distribution system. In the case of a circulation system, it is preferable to circulate a gas of 0.01 to 2.0 liter / min per 36 mmφ inner diameter, and a gas of 0.05 to 1.0 liter / min per 36 mmφ inner diameter. More preferably, it is particularly preferable to circulate a gas of 0.1 to 0.5 liter / min per 36 mmφ inside diameter.

After the temperature raising treatment, the temperature holding time is 1 second to 100 hours, preferably 1 minute to 50 hours, and more preferably 5 minutes to 10 hours. Even if the carbonization treatment is performed for more than 100 hours, an effect corresponding to the treatment time may not be obtained.

The heating device used in the above temperature raising treatment is not particularly limited, but is a tubular furnace (Kantar wire furnace, imaging furnace), muffle furnace, vacuum gas replacement furnace, rotary furnace (rotary kiln), roller hearth kiln, pusher kiln, multistage It is preferable to use a furnace, a tunnel furnace, a fluidized firing furnace or the like, and it is more preferable to use a tubular furnace (a cantal wire furnace, an imaging furnace), a muffle furnace, a rotary furnace (rotary kiln), a fluidized firing furnace, a tubular furnace (a cantal wire) Furnaces, imaging furnaces) and muffle furnaces are particularly preferred.

(Infusible)
In the heat treatment up to the carbonization temperature, the portions of the temperature rise treatment are collectively referred to as an infusible treatment. In order to obtain an infusible material, a nitrogen-containing organic compound having a specific structure in the previous stage, at least one selected from a covalent organic skeleton material and a metal organic skeleton material, and an inorganic metal salt and an organometallic complex are selected. It is preferable that the subsequent temperature raising treatment is continuously performed following the temperature raising treatment of the precursor containing at least one kind. As a result, 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. In addition, it is preferable to use what contains an iron ion in a bivalent state as a metal. As a result, a carbon alloy having high oxygen reduction performance can be produced.

The subsequent temperature increase treatment is preferably performed in an inert atmosphere, and the inert atmosphere may be either a closed system or a distribution system for circulating a new gas, and is preferably a distribution system. In the case of a circulation system, it is preferable to circulate a gas of 0.01 ml to 2.0 liter / min per 36 mmφ inner diameter, and a gas of 0.02 ml to 1.0 liter / min per 36 mmφ inner diameter. More preferably, a gas of 0.05 milliliter to 0.5 liter / min is circulated per 36 mmφ inside diameter. The downstream gas flow rate may be different from the upstream gas flow rate.

(carbide)
In order to obtain a carbide, it is preferable to cool to room temperature after the temperature rising treatment in the previous stage, uniformly pulverize, perform acid cleaning, and then perform the temperature rising process in the subsequent stage. As a result, the treatment temperature in the carbonization treatment can be increased, and it becomes possible to obtain a carbon alloy in which the regularity of the carbon structure is further improved. As a result, the conductivity of the carbon alloy is improved, high oxygen reduction performance is obtained, and durability as a catalyst is also improved.
It is also preferable to perform carbonization treatment at a high temperature directly from the previous stage. Thereby, 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. As a result, it becomes possible to produce a carbon alloy having excellent oxygen reduction performance. In addition, it is preferable that such process temperature does not exceed carbonization temperature, and an appropriate carbon alloy can be obtained by performing carbonization process in such a temperature range.

The firing temperature of the carbonization treatment of the precursor containing a nitrogen-containing organic compound having a specific structure and an inorganic metal salt is not particularly limited as long as the nitrogen-containing organic compound is thermally decomposed and carbonized. The upper limit of is required to be 2000 ° C.
In the case of a precursor containing at least one selected from inorganic metal salts and organometallic complexes, 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. By setting the reaction temperature within the above range, carbon alloy having high catalytic performance due to progress of 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. When carbonization treatment is performed within this range, the yield of carbon alloy may be reduced, but the crystallite size of the obtained carbon alloy is uniform, so that the metal is uniformly distributed and the state of high activity is maintained. The As a result, it becomes possible to produce a carbon alloy having excellent oxygen reduction performance. Further, by performing the carbonization treatment within the above range, nitrogen easily remains in the carbon skeleton due to the action of the generated inorganic metal, and the oxygen reduction reaction activity can be enhanced.

The temperature raising treatment is preferably performed under a flow of an inert gas or a non-oxidizing gas, and these atmospheres may be either a closed system or a flow system through which a new gas is circulated. is there. In the case of a circulation system, the gas flow rate is preferably 0.01 to 2.0 liters / min per 36 mmφ inner diameter, and 0.02 to 1.0 liter / min per 36 mmφ inner diameter. Is more preferable, and it is particularly preferably 0.05 to 0.5 liter / min per 36 mmφ inside diameter. It is preferable for the flow rate to be within this range because the desired nitrogen-containing carbon alloy can be suitably obtained.

The treatment time for the carbonization treatment is 1 second to 100 hours, preferably 1 minute to 50 hours, and more preferably 1 hour to 10 hours. By setting the treatment time of the carbonization treatment within the above range, the oxygen reduction reaction activity can be enhanced. In particular, by holding at 700 ° C. or higher for 1 to 10 hours, a nitrogen-containing organic compound present outside the pores of the covalently bonded organic skeleton material or the metal organic skeleton material, a tautomer of the nitrogen-containing organic compound, Of the salt of the nitrogen-containing organic compound, the hydrate of the nitrogen-containing organic compound, the inorganic metal salt, and the organometallic complex, unnecessary substances that have not been used in the carbonization reaction can be volatilized. Furthermore, by setting the holding time to 1 to 10 hours, the decomposition product of the precursor mixture can be removed, and the oxygen reduction reaction activity can be enhanced more effectively.

(5) Crushing treatment After the carbonization treatment, 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. For example, the pulverization can be performed using a ball mill, agate pulverization, mechanical pulverization, or the like.

(6) Acid Washing Process 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. By this acid cleaning treatment, it is expected that a porous nitrogen-containing carbon alloy having optimum porosity can be obtained.
In the 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. Furthermore, an inorganic acid (mineral acid) or an organic acid can be used. Examples of 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.

(7) Re-baking process It is preferable that the manufacturing method of the nitrogen-containing carbon alloy of this invention further includes the process of grind | pulverizing the baked nitrogen-containing carbon alloy, and the process of re-baking after a baking process. More preferably, after the acid cleaning step, a step of refiring the acid-cleaned nitrogen-containing carbon alloy is included. By such a refiring step, the potential can be improved with an increase in the coating amount when the nitrogen-containing carbon alloy is applied to the electrode, and the ORR activity can be improved. In addition, by providing a refiring step, MOF decomposes and the metal is volatilized and desorbed from the carbon material, so that it can be made porous and the specific surface area can be increased. Can be increased.

Since the refiring process needs to be performed at a higher temperature than the calcining process for the purpose of promoting carbon graphitization, 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.

From the viewpoint of promoting graphitization of carbon while maintaining a high nitrogen atom content ratio in the carbon alloy during firing, firing may be performed in a pressurized state during the reaction. The gas discharge port may be trapped with water and fired in a state where back pressure is applied. The pressure in the carbonization step is 0.01 to 5 MPa, preferably 0.05 to 1 MPa, more preferably 0.08 to 0.3 MPa, and particularly preferably 0.09 to 0.15 MPa.

The method of the refiring step is not particularly limited, but preferably a tubular furnace, a rotary furnace (rotary kiln), a roller hearth kiln, a pusher kiln, a multi-stage furnace, a vacuum gas replacement furnace, a tunnel furnace, a fluidized firing furnace, and the like are more preferable. Uses 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, and particularly preferably a vacuum gas replacement rotary furnace (vacuum gas replacement rotary kiln).

It is preferable to further include a step of deaeration and nitrogen substitution before the step of refiring. By providing such a process, the oxygen concentration can be reduced. In the step of deaeration and nitrogen replacement, it is preferable to perform nitrogen gas replacement after deaeration with a vacuum pump. In particular, it is preferable to repeat the operation of replacing nitrogen gas multiple times after deaeration with a vacuum pump. At this time, 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.

When re-firing the carbon alloy, it is preferable to flow the carbon alloy in order to make the performance of the carbon alloy uniform. 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.
When using a rotary furnace (rotary kiln) or a vacuum gas replacement rotary furnace (rotary kiln), the sample tube is rotated during firing, but the rotational speed, speed change, etc. are not particularly limited. The rotation speed is preferably 10 rpm or less, more preferably 5 rpm or less. By setting the rotation speed within this range, rubbing occurs between the tube wall and the preparatory carbon, and the carbon alloy is further refined and made porous. Therefore, the oxygen reduction reaction activity can be enhanced more effectively.

In 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). By carbonizing at high temperature in the presence of an activator, 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. To do. Note that 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. For example, 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. Examples of the inert gas to be diluted include nitrogen gas and rare gases (for example, argon gas, helium gas, and neon gas).
The gas activator may be contained in the atmosphere of carbonization treatment in an amount of 2 to 80 mol%, preferably 10 to 60 mol%. By including the gas activator so as to be within the above range, a sufficient activation effect can be obtained. In addition, 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.
During the heat treatment, 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. At this time, as a method of introducing nitrogen atoms, a liquid phase doping method, a gas phase doping method, or a gas phase-liquid phase doping method can be used. For example, 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.

(Nitrogen-containing carbon alloy)
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.

Furthermore, in the nitrogen-containing carbon alloy of the present invention, 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. By setting the atomic ratio (N / C) of nitrogen atoms to carbon atoms within the above range, the number of effective nitrogen atoms bonded to the metal can be ensured, and sufficient oxygen reduction catalyst characteristics can be obtained. Moreover, the intensity | strength of the carbon skeleton of a carbon alloy can be raised by making atomic ratio (N / C) of a nitrogen atom and a carbon atom into the said range, and the fall of electrical conductivity can be suppressed.

Further, 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. In that case, the atomic ratio ((other atoms) / (C + N)) of other atoms to carbon atoms and nitrogen atoms is preferably 0.3 or less.

In specific surface area analysis, 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. And the BET (Brunauer-Emmett-Teller) method for calculating the specific surface area of the sample from the molecular occupation cross section (0.162 cm ² ) of nitrogen.

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. When pores are also formed inside, for example, it 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. However, when the catalytically active site (metal coordination product or configuration space (field) having at least C, N, and metal ions as constituents) is generated and formed at a high density, it may be outside the above range.
From the viewpoint of sufficient oxygen reaching the depth of the pores and obtaining sufficient oxygen reduction catalyst characteristics, 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. For example, 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. From the viewpoint of easy dispersion, it is preferably a block shape or a particle shape. However, when 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.

Furthermore, the slurry containing a carbon alloy can be produced by dispersing the nitrogen-containing carbon alloy of the present invention in a solvent. Thus, for example, when preparing an electrode catalyst for a fuel cell or an electrode material for a power storage device, 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.
In the carbon alloy catalyst for fuel cells of the present invention, 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 .
As 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. For example, as 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), γ-butyrolactone (GBL), etc., can be used alone or in combination. In addition, examples of the solvent used in preparing the fuel cell electrode catalyst include water, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, methyl ethyl ketone, and acetone.

(Use of nitrogen-containing carbon alloy)
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. In the electrode membrane assembly including the solid polymer electrolyte membrane and the catalyst layer provided in contact with the solid polymer electrolyte membrane, the catalyst can be included in the catalyst layer. Furthermore, the electrode membrane assembly can be provided in a fuel cell.

(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. As the solid polymer electrolyte 14, a fluorine-based cation exchange resin membrane represented by a perfluorosulfonic acid resin membrane is used. Moreover, the fuel cell 10 provided with the carbon catalyst in the anode electrode catalyst 13 and the cathode electrode catalyst 15 is configured by bringing the carbon catalyst into contact with both the solid polymer electrolyte 14 as the anode electrode catalyst 13 and the cathode electrode catalyst 15. The By forming the carbon catalyst described above on both sides of the solid polymer electrolyte, and adhering the anode electrode catalyst 13 and the cathode electrode catalyst 15 to both main surfaces of the solid polymer electrolyte 14 on the electrode reaction layer side by hot pressing, It integrates as MEA (Membrane Electrode Assembly).

In conventional fuel cells, 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. In contrast, in the fuel cell 10 of FIG. 1, a carbon catalyst having a large specific surface area and high gas diffusibility can be used as the anode and cathode electrode catalyst. By using the above-mentioned carbon catalyst as an electrode, even when there is no gas diffusion layer, the carbon catalyst has a gas diffusion layer function, and the anode and

cathode electrode catalysts

13, 15 and the gas diffusion layer are integrated. Since the battery can be configured, the fuel cell can be reduced in size and the cost can be reduced by omitting the gas diffusion layer.

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 . When 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 | occur | produces by producing an electrochemical reaction.
In the electrochemical reaction, the following reaction occurs.
Cathode side: O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O
Anode side: H ₂ → 2H ⁺ + 2e ⁻
H ⁺ ions generated on the anode side move in the solid polymer electrolyte 14 toward the cathode side, and e ⁻ (electrons) move to the cathode side through an external load. On the other hand, on the cathode side, oxygen contained in the oxidant gas reacts with H ⁺ ions and e ⁻ that have moved from the anode side to generate water. As a result, the above-described fuel cell generates direct-current power from hydrogen and oxygen to generate water.

(Power storage device)
Next, a power storage device in which the carbon catalyst made of the nitrogen-containing carbon alloy of the present invention is applied to an electrode material will be described. 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.
In the electric double layer capacitor 20 shown in FIG. 2, 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.

In the electric double layer capacitor 20 of FIG. 2, 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. And 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. Furthermore, 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.

Also, like the above-described 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.

(Environmental catalyst)
Next, an example in which 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 will be described.
As 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. For this reason, since it is not necessary to use expensive noble metals, such as platinum, by comprising an environmental catalyst using the above-mentioned carbon catalyst, a low-cost environmental catalyst can be provided. Further, since 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.
By using the above-mentioned carbon catalyst as a carrier, 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. Can be configured. In addition, 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.

Further, 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”.

Hereinafter, the features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the specific examples shown below.

(Example 1)
<Synthesis of non-acid-washed carbon material (1E) of ZIF8, Fe (OAc) ₂ added (2-mim) mixture>
(Preparation of ZIF8, Fe (OAc) ₂ addition (2-mim) mixture)
2-methylimidazole (2-mim) (manufactured by Aldrich) 0.10 g, ZIF8 (manufactured by BASF, Basolite Z1200) 0.90 g, Fe (OAc) ₂ (manufactured by Aldrich, iron (II) acetate, purity 99. 99% or more (residual metal amount standard) 32 mg, SUS (Stainless Used Steel) 304 steel balls were placed in a 45 ml container (made by Fritsch) made of zirconia, vacuum degassed, purged with nitrogen, and sealed with an overpot. Using a planetary ball mill Classic Line P-7 (manufactured by Fritsch), the mixture was pulverized at 400 rpm for 3 hours, and SUS304 steel balls were removed with a metal mesh to obtain ZIF8, Fe (OAc) ₂ added 2-mim mixture (1A). .

ZIF-8

Molecular _{_{_{formula: C 8 H 10 N 4 Zn}}} 1, molecular weight: 227.57
Elemental analysis (calculated values): C, 42.22; H, 4.43; N, 24.62; Zn, 28.73

Fe (OAc) ₂

Molecular _{_{_{_{formula: C 4 H 6 Fe 1 O}}}} 4, molecular weight: 173.93
Elemental analysis (calculated values): C, 27.62; H, 3.48; Fe, 32.11; O, 36.79

Molecular formula: C ₄ H ₆ N ₂ , molecular weight: 82.10
Elemental analysis (calculated values): C, 58.51; H, 7.37; N, 34.12

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
0.9591 g of ZIF8, Fe (OAc) ₂ added 2-mim mixture (1A) was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace, The nitrogen flow rate was set at 200 mL / min and was allowed to flow at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (1B). The obtained carbon precursor (1B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.3463 g of acid-washed carbon precursor (1C).

(Firing, grinding, water washing treatment, second firing, vacuum gas replacement / rotary furnace)
We measure 0.1882 g of carbon precursor (1C) in a quartz boat and place it in the center of a 4.0 cmφ (inside diameter 3.6 cmφ) quartz tube inserted in a vacuum gas displacement rotary furnace, with a nitrogen flow rate of 200 mL per minute. And allowed to circulate at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. At that time, the quartz tube was rotated at 2.0 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (1D) of non-acid washing | cleaning. The carbon material (1D) was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.1381 g of non-acid washed carbon material (1E). The obtained non-acid cleaned carbon material (1E) was used as the nitrogen-containing carbon alloy of Example 1.

<Evaluation method of nitrogen-containing carbon alloy>
1. Specific surface area measurement by BET method Nitrogen-containing carbon alloy (carbon material (1E)) was dried under vacuum at 200 ° C. for 3 hours using a sample pretreatment apparatus (BELPREP-flow, manufactured by Nippon Bell Co., Ltd.). Thereafter, the specific surface area of the nitrogen-containing carbon alloy was measured under simple measurement conditions using an automatic specific surface area / pore distribution measuring device (BELSORP-mini II (trade name) manufactured by Nippon Bell Co., Ltd.).
The specific surface area was determined by the BET (Brunauer-Emmett-Teller) method using an analysis program installed in the apparatus. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

2. Oxygen reduction reaction (ORR) activity of carbon alloy coated electrode (preparation of carbon alloy coated electrode)
To 25 mg of the nitrogen-containing carbon alloy of Example 1, 220 mg of Nafion solution (5% alcohol aqueous solution) as a binder, 2.4 mL of water as a solvent and 1.6 mL of 1-propanol (IPA) were added, and a 7 mmφ attachment was connected. The mixture was dispersed with an ultrasonic homogenizer (Nissei Corp., US-150T) for 30 minutes. Using a rotating ring disk electrode (HR2-RD1-Pt8 / GC5 manufactured by Hokuto Denko), a nitrogen-containing carbon alloy dispersion was applied on the carbon electrode so that the nitrogen-containing carbon alloy was 0.50 mg / cm ^2, and And dried to obtain a carbon alloy coated electrode.

(Measurement of oxygen reduction reaction (ORR) activity of carbon alloy coated electrode)
A rotating electrode device (Hokuto Denko Co., Ltd., HR-201) is connected to an Automatic Polarization System (Hokuto Denko Co., Ltd., HZ-3000), and the obtained carbon alloy coated electrode is connected to the working electrode. The platinum electrode and saturated calomel electrode (SCE) were used for the counter electrode and the reference electrode, respectively, and the measurement was performed according to the following procedure.
A. For cleaning the carbon alloy-coated electrode, a sweep potential of 0.946 to -0.204 V (vs. SCE) and a sweep speed of 50 mV / s in a 0.1 M sulfuric acid aqueous solution bubbled with argon for 30 minutes or more at 20 ° C. Ten cycles of cyclic voltammetry were measured.
B. For a blank measurement, in a 0.1 M sulfuric acid aqueous solution bubbled with argon for 30 minutes or more at 20 ° C., a sweep potential of 0.746 to −0.204 V (vs. SCE), a sweep speed of 5 mV / s, and an electrode rotation speed of 1500 rpm. Linear sweep voltammetry was measured.
C. To measure oxygen reduction activity, sweep linearly with a sweep potential of 0.746 to -0.204 V (vs. SCE), a sweep speed of 5 mV / s, and an electrode rotational speed of 1500 rpm in a 0.5 M sulfuric acid aqueous solution bubbled with oxygen for 30 minutes or more. Voltammetry was measured.
D. The measurement data of B was subtracted from the measurement data of C and adopted as the true oxygen reduction activity. From the obtained voltammogram (voltage-current density curve), a voltage (V vs. RHE) at a current density of −2.00 mA / cm ² was obtained and used as an ORR activity value.
The obtained results are shown in Table 1 below.

(Example 2)
<Synthesis of ZIF8, Fe (OAc) ₂ Addition (2-Mim) Mixture of Acid-washed Carbon Material (2E)>
The above-mentioned carbon material (1D) (0.1055 g) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.0921 g of acid-cleaned carbon material (2E). The obtained acid cleaned carbon material (2E) was used as the nitrogen-containing carbon alloy of Example 2.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the acid cleaned carbon material (2E) was used. The results are shown in the column of nitrogen-containing carbon alloy isolated after acid washing in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the acid cleaned carbon material (2E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 3)
<Synthesis of carbon material of ZIF8, Fe (OAc) ₂ addition (2-mim) mixture (3E)>
(Preparation of ZIF8, Fe (OAc) ₂ addition (2-mim) mixture)
2-methylimidazole (2-mim) (Aldrich) 1.00 g, ZIF8 9.00 g (BASF, Basolite Z1200), Fe (OAc) ₂ 0.32 g (Aldrich, iron (II) acetate, Purified 99.99% or more (residual metal amount standard)) was added to an X-TREME MX1200XTM container manufactured by Waring Co., purged with nitrogen, mixed at 10,000 rpm for 40 seconds, and added with ZIF8, Fe (OAc) ₂ 2 A -mim mixture (3A) was obtained.

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
0.9604 g of ZIF8, Fe (OAc) ₂ added 2-mim mixture (3A) was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace, The nitrogen flow rate was set at 200 mL / min and was allowed to flow at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (3B). The obtained carbon precursor (3B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.3225 g of acid-washed carbon precursor (3C).

(Baking, grinding, acid cleaning treatment, second firing, vacuum gas replacement / rotary furnace)
We measure 0.1326 g of carbon precursor (3C) in a quartz boat and install it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted in a vacuum gas displacement rotary furnace, with a nitrogen flow rate of 200 mL per minute. And allowed to circulate at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. At that time, the quartz tube was rotated at 2.0 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (3D) of non-acid washing | cleaning. The carbon material (3D) was pulverized in an agate mortar to obtain 0.1175 g of a non-acid-washed carbon material (3E). The obtained non-acid cleaned carbon material (3E) was used as the nitrogen-containing carbon alloy of Example 3.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the non-acid cleaned carbon material (3E) was used. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (3E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

Example 4
<Synthesis of ZIF8, Fe (OAc) ₂ addition (2-mim) mixture of acid washed carbon material (4E)>
0.0786 g of the above carbon material (3D) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight to obtain 0.0674 g of acid-washed carbon material (4E). The obtained acid-washed carbon material (4E) was used as the nitrogen-containing carbon alloy of Example 4.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the acid cleaned carbon material (4E) was used. The results are shown in the column of nitrogen-containing carbon alloy isolated after acid washing in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the acid cleaned carbon material (4E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 5)
<Synthesis of carbon material of ZIF8, Fe (acac) ₂ addition (2-mim) mixture (5E)>
(Preparation of ZIF8, Fe (acac) ₂ addition (2-mim) mixture)
2-methylimidazole (2-mim) (Aldrich) 1.00 g, ZIF8 9.00 g (BASF, Basolite Z1200), Fe (acac) ₂ 0.47 g (Aldrich, purity 99.95% or more) (Based on the amount of residual metal)) was added to an X-TREME MX1200XTM container manufactured by Waring Co., purged with nitrogen, mixed at 10000 rpm for 40 seconds, and ZIF8, Fe (acac) ₂ added 2-mim mixture (5A) Got.

Molecular _{_{_{_{formula: C 10 H 14 Fe 1 O}}}} 4, molecular weight: 254.061
Elemental analysis (calculated values): C, 47.27; H, 5.55; Fe, 21.98; O, 25.19

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
ZIF8, Fe (acac) _2- added 2-mim mixture (5A) 2.0361 g was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace, The nitrogen flow rate was set at 200 mL / min and was allowed to flow at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 1000 ° C. by 5 ° C. per minute, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (5B). The obtained carbon precursor (5B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.6244 g of acid-washed carbon precursor (5C).

(Firing / Crushing process, Second firing, Vacuum gas replacement / Rotating furnace)
Weigh 0.4100 g of carbon precursor (5C) in a quartz boat and place it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace, with a nitrogen flow rate of 200 mL per minute. And allowed to circulate at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. At that time, the quartz tube was rotated at 2.0 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (5D) of non-acid washing | cleaning. The carbon material (5D) was pulverized in an agate mortar to obtain 0.3587 g of a non-acid-cleaned carbon material (5E). The obtained non-acid cleaned carbon material (5E) was used as the nitrogen-containing carbon alloy of Example 5.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the non-acid cleaned carbon material (5E) was used. The results are shown in the column of nitrogen-containing carbon alloy isolated after acid washing in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (5E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 6)
<Synthesis of carbon material of ZIF8, Fe (acac) ₂ addition (2-mim) mixture (6E)>
(Continuous firing distribution furnace, pulverization)
The above-mentioned ZIF8, Fe (acac) ₂ added 2-mim mixture (5A) (2.0666 g) was weighed into a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. Then, the nitrogen flow rate was set to 200 mL per minute, and the mixture was circulated at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 700 ° C. at 5 ° C. per minute, held at 700 ° C. for 5 hours, further raised from 700 ° C. to 1000 ° C. at 5 ° C. per minute, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (6B). The obtained carbon precursor (6B) was pulverized in an agate mortar to obtain 0.6206 g of an unacid-washed carbon precursor (6C). The obtained non-acid cleaned carbon material (6E) was used as the nitrogen-containing carbon alloy of Example 6.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the non-acid cleaned carbon material (6E) was used. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (6E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 7)
<Synthesis of carbon material of ZIF8, Fe (acac) ₂ addition (2-mim) mixture (7E)>
(Continuous firing, pulverization, acid cleaning treatment, first firing, distribution furnace)
We measure 2.2351 g of ZIF8, Fe (acac) ₂ added 2-mim mixture (5A) in a quartz boat and place it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. Then, the nitrogen flow rate was set to 200 mL / min and the mixture was allowed to flow at room temperature for 30 minutes. Thereafter, the flow rate of nitrogen is lowered to 20 mL per minute, the temperature is raised from 30 ° C. to 700 ° C. at 5 ° C. per minute, held at 700 ° C. for 10 hours, and further raised from 700 ° C. to 1000 ° C. at 5 ° C. per minute. And held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (7B). The obtained carbon precursor (7B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.6257 g of acid-washed carbon precursor (7C).

(Firing / Crushing process 2nd firing Vacuum gas replacement furnace)
We measure 0.4424 g of carbon precursor (7C) in a quartz boat and place it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement furnace, and set the nitrogen flow rate to 200 mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (7D). Carbon material (7D) was pulverized in an agate mortar to obtain 0.3806 g of carbon material (7E) that was not acid-washed. The obtained non-acid cleaned carbon material (7E) was used as the nitrogen-containing carbon alloy of Example 7.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the non-acid cleaned carbon material (7E) was used. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (7E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 8)
<Synthesis of carbon material of ZIF8, FeCl ₂ .4H ₂ O added (2-mim) mixture (8E)>
(Preparation of ZIF8, FeCl ₂ .4H ₂ O addition (2-mim) mixture)
2-methylimidazole (2-mim) (Aldrich) 1.00 g, ZIF8 9.00 g (BASF, Basolite Z1200), FeCl ₂ .4H ₂ O 0.37 g (Wako Pure Chemical Industries, purity 99) 9%) was added to an X-TREME MX1200XTM container manufactured by Waring Co., purged with nitrogen, and mixed at 10,000 rpm for 40 seconds to obtain a 2-mim mixture (8A) containing ZIF8 and FeCl ₂ .4H ₂ O. It was.

(Continuous firing, pulverization, acid cleaning treatment, first firing, distribution furnace)
Measure 2.0584 g of ZIF8 and FeCl ₂ · 4H ₂ O added 2-mim mixture (8A) in a quartz boat and place it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. The nitrogen flow rate was 200 mL per minute and the mixture was allowed to flow at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 700 ° C. at 5 ° C. per minute, held at 700 ° C. for 10 hours, further raised from 700 ° C. to 1000 ° C. at 5 ° C. per minute, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (8B). The obtained carbon precursor (8B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.5412 g of an acid cleaned carbon precursor (8C).

(Baking / Crushing process, Second baking, Vacuum gas replacement furnace)
We measure 0.1409g of carbon precursor (8C) in a quartz boat and install it in the center of a 4.0cmφ (inside diameter 3.6cmφ) quartz tube inserted in a vacuum gas replacement furnace, and set the nitrogen flow rate to 200mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (8D) of non-acid washing | cleaning. The carbon material (8D) was pulverized in an agate mortar to obtain 0.1141 g of non-acid cleaned carbon material (8E). The obtained non-acid cleaned carbon material (8E) was used as the nitrogen-containing carbon alloy of Example 8.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the non-acid cleaned carbon material (8E) was used. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (8E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

Example 9
<Carbon Material Synthesis of ZIF8, Fe (salen) Addition (2-Mim) Mixture (9E)>
(Preparation of ZIF8, Fe (salen) addition (2-mim) mixture)
2-methylimidazole (2-mim) (manufactured by Aldrich) 1.00 g, ZIF8 (manufactured by BASF, Basolite Z1200) 9.00 g, N, N′-ethylenebis (salicylideneaminato) iron (II) ( Fe (salen)) (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.596 g was added to a Waring Co., Ltd. X-TREME MX1200XTM container, purged with nitrogen, mixed at 10,000 rpm for 40 seconds, and ZIF8 and Fe (salen) added. A 2-mim mixture (9A) was obtained.

Molecular formula: C ₁₆ H ₁₄ Fe ₁ N ₂ O ₂ , molecular weight: 322.14
Elemental analysis (calculated value): C, 59.65; H, 4.38; Fe, 17.34; N, 8.70; O, 9.93

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
ZIF8, Fe (salen) added 2-mim mixture (9A) 2.1658g was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tube furnace, The flow rate was 200 mL per minute, and the mixture was circulated at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 700 ° C. at 5 ° C. per minute, held at 700 ° C. for 10 hours, further raised from 700 ° C. to 1000 ° C. at 5 ° C. per minute, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (9B). The obtained carbon precursor (9B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.6795 g of acid-washed carbon precursor (9C).

(Firing / Crushing process 2nd firing Vacuum gas replacement furnace)
We measure 0.1618 g of carbon precursor (9C) in a quartz boat and install it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted in a vacuum gas replacement furnace, and set the nitrogen flow rate to 200 mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (9D) of non-acid washing | cleaning. The carbon material (9D) was pulverized in an agate mortar to obtain 0.1366 g of non-acid cleaned carbon material (9E). The obtained non-acid cleaned carbon material (9E) was used as the nitrogen-containing carbon alloy of Example 9.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the non-acid cleaned carbon material (9E) was used. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (9E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 10)
<Synthesis of carbon material of ZIF8, FeCl ₂ · 4H ₂ O added DCPy mixture (10E)>
(Preparation of DCPy mixture containing ZIF8 and FeCl ₂ .4H ₂ O)
3,4-dicyanopyridine (DCPy, Aldrich) 1.00 g, ZIF8 (BASF, Basolite Z1200) 9.00 g, FeCl ₂ .4H ₂ O (Wako Pure Chemical Industries, purity 99.9%) 0.37 g was added to an X-TREME MX1200XTM container manufactured by Waring Co., purged with nitrogen, and mixed at 10,000 rpm for 40 seconds to obtain a DCPy mixture (10A) containing ZIF8 and FeCl ₂ .4H ₂ O.

Molecular formula: C ₇ H ₃ N ₃ , molecular weight: 129.119
Elemental analysis (calculated values): C, 65.11; H, 2.34; N, 32.54

(Continuous firing distribution furnace, pulverization)
ZIF8, FeCl ₂ .4H ₂ O added DCPy mixture (10A) 3.2329 g was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. The flow rate was 200 mL per minute, and the mixture was circulated at room temperature for 30 minutes.
The temperature was raised from 30 ° C. to 700 ° C. at 5 ° C. per minute, held at 700 ° C. for 10 hours, further raised from 700 ° C. to 1000 ° C. at 5 ° C. per minute, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained 0.9369g of carbon precursors (10B). The obtained carbon precursor (10B) was pulverized in an agate mortar to obtain a non-acid cleaned carbon material (10E). The obtained non-acid cleaned carbon material (10E) was used as the nitrogen-containing carbon alloy of Example 10.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the non-acid cleaned carbon material (10E) was used. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (10E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Example 11)
<Synthesis of carbon material of ZIF8 and FeCl ₂ .4H ₂ O added DCPy mixture (11E)>
(Acid cleaning treatment)
0.8496 g of the above-mentioned non-acid cleaned carbon material (10B) was pulverized in an agate mortar, and concentrated hydrochloric acid cleaning, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.7923 g of acid-washed carbon material (11C).

(Firing / Crushing process, Second firing, Vacuum gas replacement / Rotating furnace)
0.6589 g of the carbon precursor (11C) described above was measured in a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement furnace, and the nitrogen flow rate was adjusted every minute. It was made 200 mL and it was distribute | circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. At that time, the quartz tube was rotated at 2.0 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained 0.6017g of carbon materials (11D). The carbon material (11D) was pulverized in an agate mortar, and the non-acid cleaned carbon material (11E) was used as the nitrogen-containing carbon alloy of Example 11.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the non-acid cleaned carbon material (11E) was used. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (11E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

Example 12
<Synthesis of carbon material of ZIF8 and FeCl ₂ .4H ₂ O added DCPN mixture (12E)>
(Preparation of DCPN mixture containing ZIF8 and FeCl ₂ .4H ₂ O)
3,4-dichlorophthalonitrile (DCPN, manufactured by Aldrich) 1.00 g, ZIF8 (BASF, Basolite Z1200) 9.00 g, FeCl ₂ .4H ₂ O (Wako Pure Chemical Industries, purity 99.9%) ) 0.37 g was added to an X-TREME MX1200XTM container manufactured by Waring Co., and purged with nitrogen, followed by mixing at 10,000 rpm for 40 seconds to obtain a DCPN mixture (12A) containing ZIF8 and FeCl ₂ .4H ₂ O.

Molecular formula: C ₈ H ₂ Cl ₂ N ₂ , molecular weight: 197.02
Elemental analysis (calculated): C, 48.77; H, 1.02; Cl, 35.99; N, 14.22

(Firing / Crushing treatment, First firing, Distribution furnace)
Weighing 2.1185 g of DCIF mixture (12A) containing ZIF8 and FeCl ₂ .4H ₂ O (12A) in a quartz boat and installing it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted in a tubular furnace, The flow rate was 300 mL per minute and the mixture was circulated at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 1000 ° C. by 5 ° C. per minute, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained 0.7043g of carbon precursors (12B). The obtained carbon precursor (12B) was pulverized in an agate mortar to obtain an unacid-washed carbon precursor (12C).

(Baking / Crushing process, Second baking, Vacuum gas replacement furnace)
Weigh 0.2096 g of carbon precursor (12C) in a quartz boat and place it in the center of a 4.0 cmφ (inside diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement furnace, and the nitrogen flow rate is 200 mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (12D) 0.1910g. The carbon material (12D) was pulverized in an agate mortar, and the non-acid cleaned carbon material (12E) was used as the nitrogen-containing carbon alloy of Example 12.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the non-acid cleaned carbon material (12E) was used. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (12E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 1)
<ZIF8, Fe (OAc) ₂ Addition (2-Py) ₃ -TAz Mixture of Non-Acid Washed Carbon Material Synthesis (C1-E)>
(Preparation of ZIF8, Fe (OAc) ₂ added (2-Py) ₃ -TAz mixture)
(2-Py) ₃ -TAz (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.10 g, ZIF8 (manufactured by BASF, Basolite Z1200) 0.90 g, Fe (OAc) ₂ (manufactured by Aldrich, iron (II) acetate, purity 99 .99% or more (residual metal amount standard) 32 mg and 20 SUS304 steel balls were put into a 45 ml container (made by Fritsch) made of zirconia, vacuum deaerated, purged with nitrogen, and sealed with an overpot. Using a planetary ball mill Classic Line P-7 (manufactured by Fritsch), pulverization was performed at 400 rpm for 3 hours, SUS304 steel balls were removed with a metal mesh, and ZIF8, Fe (OAc) ₂ added (2-Py) ₃ -TAz mixture ( C1-A) was obtained.

Molecular formula: C ₁₈ H ₁₂ N ₆ , molecular weight: 312.33
Elemental analysis (calculated value): C, 69.22, H, 3.87, N, 26.91

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
0.5823 g of ZIF8, Fe (OAc) ₂ added (2-Py) ₃ -TAz mixture (C1-A) was weighed into a quartz boat and inserted into a tubular furnace with 4.0 cmφ (inner diameter 3.6 cmφ) quartz It installed in the center of a pipe | tube, the nitrogen flow rate was 200 mL / min, and it was distribute | circulated at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (C1-B). The obtained carbon precursor (C1-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.1870 g of an acid cleaned carbon precursor (C1-C).

(Firing, grinding, water washing treatment, second firing, vacuum gas replacement / rotary furnace)
We measure 0.0909 g of carbon precursor (C1-C) in a quartz boat and install it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted in a vacuum gas-replacement rotary furnace. The minute volume was 200 mL, and the mixture was allowed to flow at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. At that time, the quartz tube was rotated at 2.0 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon material (C1-D). The carbon material (C1-D) was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.0540 g of non-acid washed carbon material (C1-E). The obtained non-acid cleaned carbon material (C1-E) was used as the nitrogen-containing carbon alloy of Comparative Example 1.

(Specific surface area measurement by BET method)
The specific surface area of the non-acid cleaned carbon material (C1-E) was measured by the BET method. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (C1-E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 2)
<Synthesis of ZIF8, Fe (OAc) ₂ added (2-Py) ₃ -TAz mixture with acid washed carbon material (C2-E)>
0.0547 g of the above carbon material (C1-D) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight to obtain 0.0441 g of acid-cleaned carbon material (C2-E). The obtained acid-washed carbon material (C2-E) was used as the nitrogen-containing carbon alloy of Comparative Example 2.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the acid-cleaned carbon material (C2-E) was used. The results are shown in the column of nitrogen-containing carbon alloy isolated after acid washing in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the acid-cleaned carbon material (C2-E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 3)
<Preparation of heat-dried ZIF8 (C3-E)>
ZIF8 (BASF Corp., Basolite Z1200) 2.0 g was measured without pulverizing into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. After substituting with nitrogen for 3 times, the nitrogen flow rate was set to 200 mL per minute and the mixture was allowed to flow at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 100 ° C. at 5 ° C. per minute, dried at 100 ° C. for 24 hours, and then cooled to room temperature over 12 hours to obtain 1.98 g of heat-dried ZIF8. The obtained heat-dried ZIF8 was used as heat-dried ZIF8 (C3-E) of Comparative Example 3. In the yield column of Table 1, the yield of heat-dried ZIF8 is described.

(Specific surface area measurement by BET method)
The specific surface area of heat-dried ZIF8 (C3-E) was measured by the BET method. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that heat-dried ZIF8 (C3-E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 4)
<Synthesis of ZIF8 non-acid washed carbon material (C4-E)>
(Preparation of ZIF8 ground product)
1.00 g of ZIF8 (manufactured by BASF, Basolite Z1200) and 20 SUS304 steel balls were placed in a 45 ml container (manufactured by Fritsch) made of zirconia, vacuum degassed, purged with nitrogen, and sealed with an overpot. Using a planetary ball mill Classic Line P-7 (manufactured by Fritsch), grinding was performed at 400 rpm for 3 hours, and SUS304 steel balls were removed with a metal mesh to obtain a ZIF8 ground product (C4-A).

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
Weigh 0.5126 g of ZIF8 pulverized product (C4-A) into a quartz boat and place it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted in a tubular furnace, and set the nitrogen flow rate to 200 mL per minute. For 30 minutes at room temperature. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the preliminary carbide (C4-B) of ZIF8. The obtained preliminary carbide (C4-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained preliminary carbide material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.2026 g of acid-cleaned preliminary carbide (C4-C).

(Firing / Crushing process, Second firing, Vacuum gas replacement / Rotating furnace)
0.1836 g of the above-mentioned acid-cleaned pre-carbide precursor (C4-C) was weighed into a quartz boat and installed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace. Then, the nitrogen flow rate was set at 200 mL per minute and the mixture was allowed to flow at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. At that time, the quartz tube was rotated at 2.0 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained carbon material (C4-D). The carbon material (C4-D) was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.1159 g of non-acid washed carbon material (C4-E). The obtained non-acid cleaned carbon material (C4-E) was used as the nitrogen-containing carbon alloy of Comparative Example 4.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the non-acid cleaned carbon material (C4-E) was used. The results are shown in the column of non-acid-washed nitrogen-containing carbon alloy in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the non-acid cleaned carbon material (C4-E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 5)
<Synthesis of ZIF8 acid-washed carbon material (C5-E)>
0.0570 g of the above 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. 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 0.0513 g of acid-washed carbon material (C5-E). The obtained acid-washed carbon material (C5-E) was used as the nitrogen-containing carbon alloy of Comparative Example 5.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the acid-cleaned carbon material (C5-E) was used. The results are shown in the column of nitrogen-containing carbon alloy isolated after acid washing in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the acid-washed ZIF8 material (C5-E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 6)
<ZIF8, Fe (OAc) _2- added 2-PyTAz (NH ₂ ) ₂ mixture carbon material synthesis (C6-E)>
(Preparation of 2-PyTAz (NH ₂ ) ₂ )
J. et al. Org. Chem. , 2003, 68, 1158. From the above, 2-PyTAz (NH ₂ ) ₂ was prepared. 2-Pyridylcarboxaldehyde (Tokyo Chemical Industry Co., Ltd.) 107.1 mg and iodine 500 mg were added to a mixed solvent of 28% aqueous ammonia 9 mL and THF 1 mL, and the mixture was stirred at room temperature for 1 hour. To this was added a mixture of 100 mg of dicyanodiamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 120 mg of KOH, and the mixture was heated to reflux for 18 hours. The produced precipitate was filtered, washed with Et2O (20% ethanol) and dried to obtain 80 mg of 2-PyTAz (NH ₂ ) ₂ .

2-PyTAz (NH ₂ )

Molecular formula: C ₈ H ₈ N ₆ , molecular weight: 188.19
Elemental analysis (calculated values): C, 51.06, H, 4.28, N, 44.66

(Preparation of ZIF8, Fe (OAc) ₂ added 2-PyTAz (NH ₂ ) ₂ mixture)
2-PyTAz (NH ₂ ) ₂ 0.10 g, ZIF8 (manufactured by BASF, Basolite Z1200) 0.90 g, Fe (OAc) ₂ (manufactured by Aldrich, iron (II) acetate, purity 99.99% or more (residual metal) Amount standard)) 32 mg, 20 SUS304 steel balls were put into a 45 ml container (manufactured by Fritsch) made of zirconia, vacuum degassed, purged with nitrogen, and sealed with an overpot. Using a planetary ball mill Classic Line P-7 (manufactured by Fritsch), pulverization was performed at 400 rpm for 3 hours, SUS304 steel balls were removed with a metal mesh, and ZIF8, Fe (OAc) ₂ added 2-PyTAz (NH ₂ ) ₂ mixture ( C6-A) was obtained.

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
2.51.5 g of ZIF8, Fe (OAc) ₂ added 2-PyTAz (NH ₂ ) ₂ mixture (C6-A) was weighed into a quartz boat and inserted into a tubular furnace with 4.0 cmφ (inner diameter 3.6 cmφ) quartz It installed in the center of a pipe | tube, the nitrogen flow rate was 200 mL / min, and it distribute | circulated at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (C6-B). The obtained carbon precursor (C6-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.4994 g of acid-washed carbon precursor (C6-C).

(Baking, grinding, acid cleaning treatment, second firing, vacuum gas replacement / rotary furnace)
We measure 0.3069 g of carbon precursor (C6-C) in a quartz boat and place it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace. The minute volume was 200 mL, and the mixture was allowed to flow at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. At that time, the quartz tube was rotated at 2.0 rpm per minute. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (C6-D). The carbon material (C6-D) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.2048 g of acid-washed carbon material (C6-E). The obtained acid cleaned carbon material (C6-E) was used as the carbon material of Comparative Example 6.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the acid-cleaned carbon material (C6-E) was used. The results are shown in the column of nitrogen-containing carbon alloy isolated after acid washing in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the acid-cleaned carbon material (C6-E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 7)
<Synthesis of carbon material of Fe (acac) ₂ , FeCl ₂ .4H ₂ O added 2-mim mixture (C7-E)>
(Preparation of 2- (mim) mixture containing Fe (acac) ₂ and FeCl ₂ .4H ₂ O)
FeCl ₂ · _4H ₂ O (Wako Pure Chemical Industries, Ltd., purity 99.9%) 6.30 g, 2-methylimidazole (2-mim) (Aldrich _{Co.) 6.30g, Fe (acac) 2} (Aldrich Co. 0.40 g (manufactured, purity 99.95%) was added to a Waring Co. X-TREME MX1200XTM container, purged with nitrogen, mixed at 10000 rpm for 40 seconds, Fe (acac) ₂ , FeCl ₂ .4H ₂ O An added 2-mim mixture (C7-A) was obtained.

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
2.99987 g of Fe (acac) ₂ , FeCl ₂ .4H ₂ O added 2-mim mixture (C7-A) was weighed into a quartz boat and inserted into a tubular furnace with 4.0 cmφ (inner diameter 3.6 cmφ) quartz It installed in the center of a pipe | tube, the nitrogen flow rate was 200 mL / min, and it distribute | circulated at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 800 ° C. by 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (C7-B). The obtained carbon precursor (C7-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and left overnight to obtain 0.2561 g of an acid cleaned carbon precursor (C7-C).

(Baking / Crushing / Acid cleaning treatment 2nd baking Vacuum gas replacement furnace)
The carbon precursor (C7-B) was pulverized in an agate mortar, 0.1607 g was weighed into a quartz boat, and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace. It was installed and the nitrogen flow rate was 200 mL per minute and allowed to flow at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of 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. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (C7-D). The carbon material (C7-D) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.1119 g of acid-cleaned carbon material (C7-E). The obtained acid cleaned carbon material (C7-E) was used as the carbon material of Comparative Example 7.

(Specific surface area measurement by BET method)
The specific surface area was measured by the BET method in the same manner as in Example 1 except that the acid-cleaned carbon material (C7-E) was used. The results are shown in the column of nitrogen-containing carbon alloy isolated after acid washing in Table 1 below.

(Production of carbon alloy coated electrode / Oxygen reduction reaction (ORR) activity measurement)
A carbon alloy-coated electrode was produced in the same manner as in Example 1 except that the acid-cleaned carbon material (C7-E) was used, and the ORR activity value was measured. The results are shown in Table 1 below.

(Comparative Example 8)
To 1.00 g of 2-methylimidazole (2-mim) (manufactured by Aldrich) so that the ratio of inorganic metal salt or organometallic complex is 1% by mass (vs. substrate + catalyst), FeCl ₂ .4H ₂ O ( Wako Pure Chemical Industries, Ltd., purity 99.9%) 16 mg, Fe (acac) ₂ (Aldrich, purity 99.95%) 23 mg were added to Waring Co., X-TREME MX1200XTM container and purged with nitrogen. The mixture was mixed at 10,000 rpm for 40 seconds to obtain a 2-mim mixture (C8-A) containing Fe (acac) ₂ and FeCl ₂ .4H ₂ O.
A 2-mim mixture (C8-A) containing Fe (acac) ₂ and FeCl ₂ .4H ₂ O was calcined in the same manner as in Comparative Example 7, but only a very small amount of carbon material was obtained, and the specific surface area was measured by the BET method. In addition, the production of carbon alloy-coated electrodes and the measurement of oxygen reduction reaction (ORR) activity could not be performed.

From Table 1, it was found that the nitrogen-containing carbon alloy of the example had a sufficiently high ORR voltage indicating catalyst performance. Furthermore, the yield of nitrogen-containing carbon alloy was also good.
On the other hand, the nitrogen-containing carbon alloy of the comparative example had a low ORR voltage and poor performance as a catalyst. Comparative Examples 1, 2, 6, 7, and 8 were inferior in yield. Further, in Comparative Example 8 in which the ratio of the inorganic metal salt or the organometallic complex was 1% by mass without adding the covalent organic skeleton material and the metal organic skeleton material, only a very small amount of nitrogen-containing carbon alloy was obtained. .

(Fuel cell power generation performance evaluation)
(1) Preparation of catalyst ink (1) -1 Preparation of catalyst ink for cathode 0.1 g of nitrogen-containing carbon alloy material of each example and 1.0 g of 5 mass% Nafion (registered trademark) solution (solvent: water and A mixture of lower alcohols, WAKO number 321-86703), 0.25 mL of water (ion-exchanged water), and 0.5 mL of 1-propanol were dispersed with an ultrasonic disperser for 2.5 hours, and the non-platinum catalyst for cathode Ink was obtained.

(1) -2 Preparation of anode catalyst ink 0.5 g of platinum-supported carbon (TEC 10V50E, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) carrying 50% by mass of platinum was weighed in a glass container, and 0.8 mL of water was added. After the addition, the glass container was sealed with a septum seal, and the inside of the container was purged with nitrogen. The catalyst ink for anode was obtained by injecting 4.3 mL of 5% by mass Nafion and 1 mL of 1-propanol into a glass container and irradiating with ultrasonic waves for 2.5 hours.

(2) Preparation of transfer catalyst coating film (2) -1 Preparation of cathode catalyst film (1) Cathode catalyst ink prepared in (1) -1 was applied onto a Teflon (registered trademark) sheet base with a 200 μm clearance applicator. It was applied and slowly dried over 24 hours. After drying, it was cut into a 5 cm × 5 cm size square. The coating weight obtained by subtracting the base weight from the weight of the coating film was 47.6 mg (1.9 mg / cm ² ).

(2) -2 Preparation of anode catalyst membrane The anode catalyst ink prepared in (1) -2 was applied onto a Teflon (registered trademark) sheet base with a 300 μm clearance applicator and slowly dried over 24 hours. It was. After drying, it was cut into a 5 cm × 5 cm size square. The coating weight obtained by subtracting the base weight from the weight of the coating film was 21.5 mg (0.86 mg / cm ² ).

(3) Preparation of transfer proton conducting membrane A Nafion membrane (NR211, manufactured by DuPont) cut into a square of 8 cm x 8 cm size was immersed in a 1 mol / L CsCl aqueous solution for 10 hours and washed with ion-exchanged water. Thereafter, it was dried to obtain a proton conductive membrane for transfer.

(4) Preparation of electrode composite membrane Between two polyimide membranes (UPILEX 75: manufactured by Ube Industries Co., Ltd.) cut into 10 cm × 10 cm squares, a catalyst membrane prepared in (2) -1; The proton conducting membrane prepared and the catalyst membrane prepared in (2) -2 were superposed in this order. At this time, the catalyst membrane was at the center of the proton conducting membrane, and the coating surface was in contact with the ptrone conducting membrane. The laminated sheet was pressed at 210 ° C. and 15 MPa for 10 minutes. The 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. 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.

(5) Assembly of fuel cell for evaluation The electrode composite membrane obtained in (4) is sandwiched between two carbon cloths (made by gas diffusion layer ELAT BASF) cut into a square of 5 cm × 5 cm size, and a gasket having a thickness of 200 μm (Made by Tepron) was incorporated into a JARI standard cell (manufactured by FC Development Co., Ltd.) to obtain a fuel cell having a catalyst effective area of 25 cm ² .

(6) Power generation performance evaluation While keeping the fuel cell at 80 ° C., humidified hydrogen was supplied to the anode and humidified air was supplied to the cathode. Hydrogen and air were humidified by passing each gas through a bubbler containing water. The water temperature of the hydrogen bubbler was 80 ° C, and the water temperature of the air bubbler was 80 ° C. Here, the hydrogen gas flow rate was 1000 ml / min, the air gas flow rate was 2500 ml / min, and measurement was performed under normal pressure. A current-voltage curve was obtained by changing the current value of the fuel cell from 0 A to 7.5 A every 30 seconds and measuring a stable voltage at each current.

10 Fuel cell,
12 separator,
13 Anode electrocatalyst,
14 solid polymer electrolyte,
15 cathode catalyst,
16 separator,
20 electric double layer capacitor,
21 first electrode;
22 second electrode,
23 separator,
24a exterior lid,
24b exterior case,
25 Current collector,
26 Gasket

Claims

At least one selected from a nitrogen-containing organic compound represented by the following general formula (1), a tautomer of the nitrogen-containing organic compound, a salt of the nitrogen-containing organic compound, and a hydrate of the nitrogen-containing organic compound ,
At least one selected from a covalent organic framework material and a metal organic framework material;
A method for producing a nitrogen-containing carbon alloy comprising a step of firing a precursor containing at least one selected from an inorganic metal salt and an organometallic complex;

In the general formula (1), Q represents an atomic group composed of at least one 5- to 7-membered aromatic ring or 5- to 7-membered heteroaromatic ring, and R represents a halogen atom, a substituted or When an unsubstituted alkyl group or a substituent represented by the following general formulas (2) to (5) is represented and Q does not include a nitrogen-containing heteroaromatic ring, at least one R is represented by the following general formula (2 ) To (5). n represents an integer of 1 to 4.

In the general formula (2), * represents a bond to Q.

In general formulas (3) to (5), R 1 to R 8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R 1 and R 2 , R 3 and R 4 , R 7 and R 8 may be bonded to each other to form a ring. * Represents a bond to Q.
The method for producing a nitrogen-containing carbon alloy according to claim 1, wherein in the general formula (1), Q is a 5- to 7-membered aromatic ring or a 5- to 7-membered heteroaromatic ring.
In the said General formula (1), Q is a benzene ring, a pyridine ring, or an imidazole ring, The manufacturing method of the nitrogen-containing carbon alloy of Claim 1 or 2.
The method for producing a nitrogen-containing carbon alloy according to claim 1 or 2, wherein in the general formula (1), Q is a 5- to 7-membered nitrogen-containing heteroaromatic ring.
In the general formula (1), Q is a 5- to 7-membered nitrogen-containing heteroaromatic ring, and R is a substituted or unsubstituted alkyl group, or a substituent represented by the general formula (2). The manufacturing method of the nitrogen-containing carbon alloy of Claim 4 represented.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 5, wherein the metal organic framework material is a zeolite type imidazole framework material.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 6, wherein the inorganic metal salt is an inorganic metal chloride.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 7, wherein the metal species of the inorganic metal salt is Fe.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 8, wherein the inorganic metal salt is a hydrate salt.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 9, wherein the organometallic complex is at least one selected from a metal acetate complex, a β-diketone metal complex, and a salen complex.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 10, wherein the organometallic complex is an acetylacetone iron (II) complex.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 10, wherein the organometallic complex is an iron-salen complex.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 12, wherein the firing step is a step of firing the precursor at 400 ° C or higher.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 13, wherein the firing step is a step of firing the precursor at 700 to 1050 ° C.
The method for producing a nitrogen-containing carbon alloy according to claim 14, wherein the firing step includes a step of holding the precursor at 700 to 1050 ° C for 1 second to 100 hours.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 15, further comprising a step of pulverizing the precursor before the firing step.
The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 16, further comprising a step of pulverizing the calcined nitrogen-containing carbon alloy and a step of re-firing after the calcining step.
The method for producing a nitrogen-containing carbon alloy according to claim 17, wherein the re-baking step is a step of baking at 1000 to 1500 ° C.
The method for producing a nitrogen-containing carbon alloy according to claim 17 or 18, further comprising a step of deaeration and nitrogen substitution before the re-baking step.
A nitrogen-containing carbon alloy produced by the method according to any one of claims 1 to 19.
A fuel cell catalyst using the nitrogen-containing carbon alloy according to claim 20.