JP5918156B2 - Carbon alloy material, carbon alloy catalyst, and fuel cell manufacturing method - Google Patents

Description

  The present invention relates to a carbon alloy material, a production method thereof, a carbon alloy carbon catalyst using the same, and a fuel cell.

The electrode catalyst of a solid polymer electrolyte fuel cell needs to have characteristics that combine high oxygen reduction catalytic activity and conductivity. Conventionally, a noble metal catalyst using platinum (Pt), palladium (Pd) or the like is used as a catalyst having a high oxygen reduction activity, for example, in a solid polymer electrolyte fuel cell used in an automobile, a household electric heat supply system, or the like. 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. For example, a catalyst using a carbon alloy obtained by firing a polymer obtained by mixing a metal complex such as cobalt phthalocyanine or iron phthalocyanine with a precursor such as a resin has been proposed.

Non-Patent Document 1 describes that D-glucose, D-fructose, D-xylose and starch as carbohydrate precursors and [Bmim] [FeCl ₄ ] as an ionic liquid were heated and fired. There is no description regarding the catalyst characteristics for fuel cells.
Non-Patent Documents 2 and 3 describe that one or two kinds of ionic liquids are calcined, but there is no description regarding catalyst characteristics for fuel cells.
Non-Patent Document 4 describes that an ionic liquid and a nitrogen-containing organic compound such as Nucleobases are attached to a Silica support and calcined, but there is no description regarding catalyst characteristics for fuel cells.
Non-Patent Document 5 reports that a polymerizable ionic liquid and FeCl ₂ were calcined, but there is no description regarding catalyst characteristics for fuel cells.
Patent Document 1 describes a method in which a solution containing an ionic liquid, a metal precursor, and a reducing liquid is provided on a carbon substrate, and metal nanoparticles are produced on the carbon substrate by microwave heating. Yes. Patent Document 1 describes a platinum catalyst for a fuel cell, but does not describe a non-platinum catalyst.

Special table 2009-525841

Zai-Lai Xie et al. Mater. Chem. , 21, 7434 (2011) Jens Peter Paranowitsch et al., Adv. Mater. , 22, 87 (2010) Pasquale F.M. Fulvio et al., Phys. Chem. Chem. Phys ,, 13, 13486 (2011) Wen Yang et al. Am. Chem. Soc. , 133, 206 (2011) Jiain Yuan et al., Chem. Mater. , 22, 5003 (2010)

However, as a result of studying the production methods described in these documents, the inventor has found that all of them remain unsatisfactory. Specifically, when a carbon alloy catalyst for a fuel cell is produced using the carbon alloy of Non-Patent Document 1, it does not use Fe, Co, Mn, Cr, or Ni as a metal species, and is intended. It was found that the catalyst characteristics for fuel cells could not be expressed.
When a carbon alloy catalyst for a fuel cell is manufactured using the carbon alloy of Non-Patent Document 4, it does not use Fe, Co, Mn, Cr, or Ni as a metal species, and the desired catalyst characteristics for a fuel cell It was found that it was not able to express.
When a carbon alloy catalyst for a fuel cell was produced using the carbon alloy of Non-Patent Document 5, the carrier shape characteristics were not utilized, so the target fuel cell catalyst characteristics could not be achieved, rather than a high specific surface area. It turned out to be a thing. Further, in the platinum catalyst which is a noble metal catalyst described in Patent Document 1, when a metal alloy is simply changed from platinum to another metal to produce a non-noble metal carbon alloy catalyst, it is not a high specific surface area when acid cleaning is not performed. Therefore, the oxygen reduction reaction activity is low, and the resulting metal elution causes degradation in performance over time.On the other hand, acid cleaning reduces the ability to form catalytically active sites due to the influence of the reducing liquid used in combination with platinum. Thus, it was found that only a carbon alloy catalyst having a very low redox activity can be produced.

  The object of the present invention is to solve the above problems. That is, the problem to be solved by the present invention is to provide a method for producing a carbon alloy material having sufficiently high redox activity when applied to a carbon alloy catalyst.

The present inventor has intensively studied to solve the above problems. As a result, it was found that the target carbon alloy material could not be obtained simply by firing an ionic liquid (for example, a nitrogen-containing organic compound and its salt). On the other hand, after preparing a precursor in which an ionic liquid and a metal species are fixed on a support, heat-firing is performed, and then acid cleaning is performed, so that the oxygen reduction reaction non-platinum for a desired fuel cell air electrode It has been found that a catalyst (a carbon alloy catalyst for fuel cells) can be obtained.
As a result, the present invention has been completed. That is, the above problem can be solved by the following means.

[1] A step of attaching at least one kind of ionic liquid to the carrier, a step of firing the precursor containing the carrier to which the ionic liquid is attached, and a step of washing the product after firing with an acid. And the said precursor contains the metal seed | species containing 1 or more types among Fe, Co, Mn, Cr, and Ni, The manufacturing method of the carbon alloy material characterized by the above-mentioned.
[2] In the method for producing a carbon alloy material according to [1], the carrier is preferably a carbon material or an organic precursor that generates a carbon material or a carbon alloy material by firing.
[3] In the method for producing a carbon alloy material according to [1] or [2], the anion species of the ionic liquid are [N (CN) ₂ ] ⁻ , [C (CN) ₃ ] ⁻ and [FeCl ₄ ]. ^- it is preferable to use any one or more of the.
[4] In the method for producing a carbon alloy material according to any one of [1] to [3], the metal species is preferably an iron compound or a cobalt compound.
[5] In the method for producing a carbon alloy material according to [4], the iron compound is preferably at least one of a salt of a tetrachloroferrate anion and a nitrogen-containing quaternary cation, and iron chloride.
[6] A carbon alloy material produced by the method for producing a carbon alloy material according to any one of [1] to [5].
[7] A carbon alloy catalyst comprising the carbon alloy material according to [6].
[8] A fuel cell using the carbon alloy catalyst according to [7].

  According to the present invention, it is possible to provide a method for producing a carbon alloy material having a sufficiently high redox activity when applied to a carbon alloy catalyst. In addition, the carbon alloy manufactured by this invention can be used as a carbon catalyst or its substitute, and this carbon catalyst can be applied to the use of a fuel cell, an electrical storage apparatus, and an environmental catalyst.

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

  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), hydroxy group, cyano group, aliphatic group (aralkyl group, cycloalkyl group). , Active methine group, etc.), aryl group (regarding the position of substitution), heterocyclic group (regarding the position of substitution), acyl group, aliphatic oxy group (alkoxy group, alkyleneoxy group, ethyleneoxy) Group or a group repeatedly containing propyleneoxy group units), aryloxy group, heterocyclic oxy group, aliphatic carbonyl group, arylcarbonyl group, heterocyclic carbonyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic ring Oxycarbonyl group, carbamoyl group, sulfonylcarbamoyl group, acylcarbamoyl 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, aliphatic sulfoni Ureido 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, sulfonamido group, aliphatic ureido group, arylureido group, heterocyclic ureido group, aliphatic sulfonamido group, arylsulfonamido group, Heterocyclic sulfonamide group, aliphatic sulfinyl group, arylsulfinyl group, nitro group, nitroso group, diazo group, azo group, hydrazino group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, silyl group ( For example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), silyloxy group (for example, trimethylsilyloxy, t-butyldimethylsilyloxy), borono group, ionic hydrophilic group (for example, carboxyl group, sulfo group, phosphono group and 4 Secondary ammonium group) and the like. These substituent groups may be further substituted, and examples of the further substituent include groups selected from the substituents described above.

  Hereinafter, the present invention will be described in detail.

[Production method of carbon alloy]
The carbon alloy production method of the present invention (hereinafter also referred to as the production method of the present invention) includes a step of attaching at least one ionic liquid to a carrier, and a precursor containing the carrier to which the ionic liquid is adhered. The method includes a step of firing and a step of washing the product after firing with an acid, wherein the precursor includes a metal species including one or more of Fe, Co, Mn, Cr and Ni.
Although not bound by any theory, ionic liquids have higher heat resistance than ordinary organic compounds and remain without volatilization to high temperatures, so firing precursors with ionic liquids sufficiently adhered to the support surface By doing so, it is considered that a thin catalyst layer could be formed on the surface of the carrier in accordance with the shape of the carrier. Furthermore, in the production method of the present invention, the number of catalyst sites on the surface of the support is increased by allowing the ionic liquid and the specific metal species to interact with each other by containing the specific metal species in the precursor, thereby increasing the functional group density. Can be increased. As a result, after acid washing of the zero-valent metal generated on the surface of the carrier, a catalyst layer having a large number of catalyst sites can be formed by voids from which the zero-valent metal has been removed. Therefore, it is considered that a carbon alloy material having sufficiently high redox activity can be obtained when applied to a carbon alloy catalyst.
Hereinafter, the above processes will be described in order for the method for producing the carbon alloy material of the present invention.

<Precursor preparation step>
The method for producing a carbon alloy material of the present invention includes a precursor preparation step in which at least one ionic liquid is attached to a carrier.
The method for adhering the ionic liquid to the carrier is not particularly limited, but a method of adhering the ionic liquid according to the surface shape of the carrier is preferable.
As such a method, for example, a method such as coating or dipping is preferably used. There is no restriction | limiting in particular as a method of application | coating or immersion, A well-known method can be used. When the carrier is a material having pores, it is preferable that the ionic liquid is sufficiently adhered to the surface of the carrier inside the pores, and that the ionic liquid is sufficiently and thinly adhered is a carbon alloy obtained after firing. It is preferable from the viewpoint of increasing the specific surface area.

(Ionic liquid (aka ionic liquid))
There is no restriction | limiting in particular as said ionic liquid, A well-known ionic liquid can be used.
The ionic liquid preferably contains an ionic substance represented by the following general formula (11).

Formula (11)
[Q] _m ^{n +} [Y] _n ^m-
(In general formula (11), Q ^{n +} represents an n-valent organic cation, Y ^m− represents an m-valent anion, and n and m each independently represent a natural number.)

  In the general formula (11), n and m each independently represent a natural number, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2. 1 is more preferable and 1 is more particularly preferable.

[Q] Preferred structures as _m ^{n +} in the general formula (11) is a structure represented by the following general formula (C-1) ~ (C -8).

In the general formulas (C-1) to (C-8), R ^{11 to} R ¹⁴ each independently represents an alkyl group, and two of R ^{11 to} R ¹⁴ are connected to each other to form a 5- to 7-membered ring. It may be formed. However, in the general formulas (C-1) to (C-8), a possible site may have a substituent, and the alkyl group of R ^{11 to} R ¹⁴ may have a substituent.

In the general formulas (C-1) to (C-8), the alkyl group represented by R ^{11 to} R ¹⁴ is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group. Pentyl group, hexyl group, heptyl group, octyl group, hexadecyl group, octadecyl group and allyl group are more preferable, and methyl group, ethyl group, propyl group and butyl group are particularly preferable. R ^{11 to} R ¹⁴ may be the same or different, but when the molecule has two or more R ^{11 to} R ¹⁴ , it preferably contains at least two or more alkyl groups. It is preferable that any one of ^{11 to} R ¹⁴ represents a methyl group, and the other represents one of an ethyl group, a propyl group, and a butyl group.
The alkyl group represented by R ^{11 to} R ¹⁴ may further have a substituent, and preferred examples of the substituent include an alkoxy group, a vinyl group, and a hydroxyl group.

  Among the general formulas (C-1) to (C-8), those containing a nitrogen atom are preferable from the viewpoint that an ionic liquid serves as a nitrogen-containing organic compound described later, and a more preferable structure is the general formula (C-1). ) To (C-3), and a particularly preferred structure is the general formula (C-1).

[Y] _n ^m− in the general formula (1) includes halogen anions (Cl ⁻ , Br ⁻ , F ⁻ , I ⁻ ), BF ₄ ⁻ , PF ₆ ⁻ , and imide anions [N (SO ₂ CF ₃ ). ₂ ⁻ , N (COCF ₃ ) (SO ₂ CF ₃ ) ⁻ , N (CN) ₂ ^{− and the} like], carbanion [C (CN) ₃ ^{− and the} like], R ²¹ OSO ₃ ⁻ , R ²¹ SO ₃ ⁻ and FeCl ₄ ^- , CoCl ₄ ^{2- and the} like.
Each R ²¹ 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.

[Y] _n ^m− in the general formula (1) is preferably an anion containing a nitrogen atom from the viewpoint of increasing the N / C ratio of the obtained carbon alloy material. On the other hand, [Y] _n ^m− in the general formula (1) is a metal species including one or more of Fe, Co, Mn, Cr and Ni from the viewpoint of including a specific metal species in the ionic liquid. It is preferable that it is an anion containing. From these viewpoints, in the production method of the present invention, [Y] _n ^m− , that is, any one of N (CN) ₂ ⁻ , C (CN) ₃ ⁻ and FeCl ₄ ⁻ as the anionic species of the ionic liquid. It is preferable to use one or more types.

  Preferable specific examples of the ionic liquid represented by the general formula (1) include, for example, those represented by the following combinations.

R ¹¹ = methyl group, allyl group;
R ¹² = ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, octadecane group, allyl group;

As said ionic liquid, only 1 type of ionic liquid may be used, 2 or more types of ionic liquids may be used together, and it is preferable to use 2 types of ionic liquids together.
Here, the ionic liquid preferably contains at least one nitrogen-containing organic compound. Moreover, it is preferable that the said ionic liquid contains the metal seed | species which contains 1 or more types among at least 1 sort (s) of Fe, Co, Mn, Cr, and Ni. Furthermore, it is more preferable that the ionic liquid contains at least one nitrogen-containing organic compound and at least one metal species including at least one of Fe, Co, Mn, Cr and Ni. The ionic liquid contains the nitrogen-containing organic compound and the metal species including one or more of the Fe, Co, Mn, Cr, and Ni, thereby making it difficult to volatilize when each component is heated. it can.

When two or more ionic liquids are used in combination, a first ionic liquid containing an organic cation containing a nitrogen atom and an anion containing a nitrogen atom, an organic cation containing a nitrogen atom, and Fe, Co, Mn, Cr It is preferable to use a combination of a second ionic liquid containing a metal species including at least one of Ni and Ni.
As the second ionic liquid containing an organic cation containing a nitrogen atom and a metal species containing one or more of Fe, Co, Mn, Cr and Ni, a salt of a tetrachloroferrate anion and a nitrogen-containing quaternary cation It is more preferable to use an ionic liquid containing

In addition, in this invention, the said ionic liquid is not limited to the aspect which uses these nitrogen-containing organic compounds and the metal seed | species containing one or more types among Fe, Co, Mn, Cr, and Ni as an essential component.
When the nitrogen-containing organic compound is not contained in the ionic liquid, it is preferable that the precursor contains a nitrogen-containing organic compound described later as the other component.
Further, when the ionic liquid does not contain a metal species including one or more of Fe, Co, Mn, Cr and Ni, the precursor includes other components such as Fe, Co, Mn, Cr and the like described later. It is preferable that the metal seed | species which contains 1 or more types among Ni is contained.

(Nitrogen-containing organic compounds)
The precursor preferably contains a nitrogen-containing organic compound as the ionic liquid, or contains a nitrogen-containing organic compound in addition to the ionic liquid.
The nitrogen-containing organic compound is preferably a compound containing a nitrogen atom in the compound represented by the general formula (11) used as the ionic liquid.
In addition, the nitrogen-containing machine compound is preferably a compound represented by the following general formula (1), a tautomer thereof, a salt thereof, or a hydrate thereof.

In the general formula (1), Q ¹ represents a 5- to 7-membered aromatic ring or heterocycle, R ⁰ represents a substituent represented by the following general formulas (2) to (5), and n0 is 1 Represents an integer from 4 to 4.

General formula (2)
* -CN

In the general formulas (3) to (5), R ^{1 to} R ⁸ are each independently formed by a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, or two adjacent substituents. Represents a heterocycle, and * represents a bond to Q ¹ .

The nitrogen-containing organic compound is represented by the general formula (1), and is an organic compound having at least one structure represented by the general formulas (2) to (5) and an unsaturated bond in the molecule.
By having at least one of the structures represented by the general formulas (2) to (5) in the molecule, the nitrogen-containing carbon alloy obtained by firing has high oxygen reduction activity consisting of C, N, and metal. It is thought that the active point which has is produced | generated.

In the general formula (1), Q ¹ represents a 5- to 7-membered aromatic ring or heterocyclic ring. However, Q ¹ may be a condensed ring partially including a 5- to 7-membered aromatic ring or a hetero ring.
In the present invention, in the general formula (1), Q ¹ is preferably a 5- or 6-membered aromatic ring or heterocycle, or a condensed ring containing them.
Further, in the general formula (1), Q ¹ is preferably an aromatic ring or an aromatic heterocycle. The presence of the unsaturated bond makes it easier to form a carbon alloy skeleton due to various interactions described later.

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

In formula (A-1) ~ (A -20), at least one of R ⁵¹ to R ⁵⁶ represents a linking portion between the R in the general formula (1), the R of the R ⁵¹ to 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. Further, it may be a condensed heteropolycyclic compound.

The substituents represented by R ^{51 to} R ⁵⁶ are selected without any particular limitation as long as they are groups described in the above-mentioned substituent group and can be substituted. As a substituent for R ^{51 to} R ⁵⁶ , an alkyl group, a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), an aliphatic group, an aryl group, a heterocyclic group, a hydroxyl group, an acyl group, and an aliphatic group are preferable. An oxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted ureido group, an acylamino group, a sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group or a sulfonyl group More preferably, it has a halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), aliphatic group, aryl group, heterocyclic group, hydroxyl group, aliphatic oxycarbonyl group, and substituent. And a carbamoyl group which may be substituted, an ureido group which may have a substituent, an aliphatic oxy group and the like.
Preferable 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, A fluorine atom) and a heteroaryl group (such as a pyridyl group). Among these, as a substituent represented by R ^{51 to} R ⁵⁶ , a halogen atom and a heteroaryl group are preferable, and a chlorine atom and a pyridyl group are more preferable. In the heterocycle, it is preferable that nitrogen is contained in the heterocycle, and as a result, nitrogen is regularly arranged at the edge portion derived from the crystal structure of the nitrogen-containing organic compound, so that the free metal ion is coordinated. It becomes easy.

The number of hydrogen atoms contained in R ^{51 to} R ⁵⁶ is preferably 1 to 4, and more preferably 2 to 4.

In the general formulas (A-1) to (A-20), preferred structures of Q ¹ of the compound represented by the general formula (1) are represented by the general formulas (A-1) to (A-6). Is the structure.

Q ¹ is more preferably a benzene ring, a pyridine ring, or a condensed ring containing them.

R ¹ in the general formula (1) represents a substituent represented by the following general formulas (2) to (5).

General formula (2)
* -CN

In the general formulas (3) to (5), R ^{1 to} R ⁸ are each independently formed by a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, or two adjacent substituents. Represents a heterocycle, and * represents a bond to Q ¹ .

  By including the structures represented by the general formulas (2) to (5), a CN bond is generated in the decomposition product, and this CN and metal interact to hold nitrogen until carbonization. Is done. Therefore, it is preferable because nitrogen is easily introduced into the graphene of carbon alloy and is excellent in oxygen reduction reaction activity.

Preferable embodiments of each group represented by R ^{1 to} R ⁸ include a hydrogen atom or a group described in the above-mentioned substituent group.
Among them, 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, and may be bonded to each other to form a ring. Examples of the ring formed by combining 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, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, Examples thereof include 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. Preferred are pyrrolidone ring, benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, more preferably pyrrole ring or pyrrolidone ring. Can do.

Among the compounds represented by the general formula (1), preferable R is a structure represented by the general formula (2) or (3).
In addition, as a compound represented by the said General formula (1) including the structure represented by the said General formula (4), the compound represented by General formula (1) in Unexamined-Japanese-Patent No. 2011-225431 is mentioned. Can be mentioned.

  N0 in the general formula (1) represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.

  In the present invention, the nitrogen-containing organic compound is preferably a compound represented by the general formula (6) or (7) or a multimer of dimers or more thereof.

In general formula (6) and (7), n1 represents the integer of 1-5, n2 represents the integer of 1-6. n1 is preferably 1 to 4, preferably 2 to 4, and more preferably 2. n2 is preferably 1 to 4, preferably 2 to 4, and more preferably 2.
However, the compound represented by the general formula (6) or (7) may have a substituent other than a cyano group, but preferably has only a cyano group.

  The compound represented by the general formula (1) is specifically exemplified, but the present invention is not limited thereto.

In addition, the nitrogen-containing organic compound is preferably a nitrogen-containing crystalline organic compound from the viewpoint of having crystallinity that molecules are easily arranged regularly. However, the nitrogen-containing crystalline organic compound preferably contains at least one kind other than the 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 It is difficult to obtain a nitrogen-containing carbon alloy having a sufficiently high target oxygen reduction reaction activity because the speed cannot be controlled.
Even if the decomposition rate of the nitrogen-containing ligand of the coordination metal complex can be adjusted, the nitrogen-containing metal complex is decomposed and the metal undergoes direct reduction, so that the adjacent zero-valent metals are easily aggregated and crystallized. As a result, the number of interactions between the nitrogen-containing ligand formed by decomposition of the nitrogen-containing metal complex and the specific metal species decreases, and the functional group density decreases, so that the target oxygen reduction reaction activity is sufficiently high. It is difficult to obtain a nitrogen carbon alloy.
However, it is preferable to mix a nitrogen-containing metal complex and a nitrogen-containing organic compound. This is because the nitrogen-containing organic compound complements the decrease in the number of interactions between the nitrogen-containing ligand formed by decomposition of the nitrogen-containing metal complex and the specific metal species, so that an extremely high functional group density can be achieved. This is because a target nitrogen-containing carbon alloy having sufficiently high oxygen reduction reaction activity can be obtained.

  The nitrogen-containing crystalline organic compound has a crystal structure formed by two or more bonds or interactions selected from π-π interaction, coordination bond, charge transfer interaction, and hydrogen bond. preferable. This is because the use of a low-molecular compound having a crystal structure can improve the intermolecular interaction and suppress vaporization during firing when obtaining a nitrogen-containing carbon alloy.

  The crystal structure here refers to the arrangement and arrangement of molecules in the crystal. In other words, the crystal structure consists of a repeating structure of unit cell, and the molecules are arranged at any position in the unit cell and oriented. In the crystal, the molecules have a uniform appearance. 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 organic compound having a laminated structure, an aromatic ring, a heterocyclic ring, a condensed polycyclic ring, a condensed heterocyclic polycyclic ring, an unsaturated group (C≡N group, vinyl group, allyl group, acetylene group) and the like interact with each other ( For example, in an aromatic ring, a π-π interaction (π-π stack) occurs in a face-to-face. Stacking is performed by SP2 orbitals of carbons derived from unsaturated bonds in these rings and groups being regularly stacked 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 and has crystallinity, and is preferably relaxed by phonons (quantized lattice vibration) against heat and has heat resistance. Therefore, the decomposition temperature is maintained up to the carbonization temperature, the vaporization of the decomposition product is reduced and carbonized, and a carbon alloy skeleton is formed.

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

  The nitrogen-containing organic compound preferably further has a melting point of 25 ° C. or higher. When the melting point is less than 25 ° C., there is no air layer contributing to heat resistance during firing, and boiling or bumping occurs due to the relationship between temperature and vapor pressure, and a carbon material cannot be obtained.

  The nitrogen-containing organic compound preferably has a molecular weight of 60 to 2000, more preferably 100 to 1500, and particularly preferably 130 to 1000.

  The nitrogen-containing organic compounds may be used alone or in combination of two or more. Moreover, it is preferable that the metal content in nitrogen-containing organic compounds other than the inorganic metal salt mentioned later is 10 ppm or less. In addition, the refinement | purification before baking becomes easy by making molecular weight into the said range.

  The nitrogen content of the nitrogen-containing organic compound is preferably 0.1% by mass to 55% by mass, more preferably 1% by mass to 30% by mass, and further 4% by mass to 20% by mass. It is particularly preferred. By using a compound containing a nitrogen atom (N) within the above range, there is no need to introduce a separate nitrogen source compound, the nitrogen atom and metal are regularly positioned uniformly on the crystal edge, and the nitrogen and metal are It becomes easy to interact. Thereby, the composition ratio of nitrogen atom and metal can be a composition ratio having higher oxygen reduction activity.

Further, 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 that is −95% to −1%. More preferably, it is a compound, and it is especially preferable that it is a hardly volatile compound which 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 the room temperature when the temperature is increased from 30 ° C. to 1000 ° C. at 10 ° C./min in a TG-DTA measurement of the mixture of the nitrogen-containing organic compound and the inorganic metal salt at a flow rate of 100 mL / min. The mass reduction rate at 400 ° C. based on the mass at (30 ° C.).

The nitrogen-containing organic compound is also preferably a pigment having a structure represented by the general formula (1).
The pigment forms a stacked column structure by π-π interaction between molecules, and has a uniform structure in which the intermolecular distance is defined by hydrogen bonding or van der Waals interaction between the stacked columns. It has the effect that heat transfer is easily achieved. Moreover, although it is a low molecular weight compound, it has crystallinity, and is vibration-reduced by phonons (quantized lattice vibration) against heat, and has heat resistance. Therefore, the decomposition temperature is maintained up to the carbonization temperature, and there is an effect that the vaporization of the decomposition product is reduced and the carbonization is achieved.
Among them, isoindoline pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, oxazine pigments, phthalocyanine pigments, quinophthalone pigments, and latent pigments or dyes obtained by converting the above pigments into A pigment such as a lake pigment pigmented with a metal ion is preferred, and a diketopyrrolopyrrole pigment, a quinacridone pigment, an isoindoline pigment, an isoindolinone pigment, a quinophthalone pigment, and a latent pigment obtained by laminating the above pigment ( (Described later) is more preferable. This is because, when these pigments are fired, 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. In addition, when the metal species (M) coexists, a complex of Ph—CN... M is formed, and a carbon alloy having a high oxygen reduction reaction activity is generated.

(Metal species)
The carbon alloy production method of the present invention uses a metal species including one or more of Fe, Co, Ni, Mn and Cr in the precursor preparation step. In the present specification, the “metal species” means a metal element contained in an inorganic metal salt, an organic metal complex, or an organic metal salt (ionic liquid, magnetic fluid).

  The total ratio of Fe, Co, Ni, Mn and Cr to the total amount of metal atoms contained in the metal species is preferably 90% by mass or more, more preferably 95% by mass or more, and 100% by mass. % Is particularly preferred.

In the production method of the present invention, the metal species is preferably an iron compound or a cobalt compound.
The total ratio of Fe and Co to the total amount of metal atoms contained in the metal species is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 100% by mass. preferable.

More preferably, the metal species is an iron compound.
The total proportion of Fe with respect to the total amount of metal atoms contained in the metal species is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 100% by mass.
More preferably, the iron compound is at least one of a salt of a tetrachloroferrate anion and a nitrogen-containing quaternary cation, and iron chloride.

・ Organic metal salt:
As the metal species as the organic metal salt, the metal species mentioned as the ionic liquid can be used. The preferred range of the metal species as the organic metal salt is the same as the preferred range of the metal contained as an anion in the ionic liquid, for example, a salt of a tetrachloroferrate anion and a nitrogen-containing quaternary cation. Is particularly preferred.

・ Inorganic metal salts:
For the preparation of the precursor, an inorganic metal salt containing one or more of Fe, Co, Ni, Mn and Cr is preferably used.
Thereby, the carbon alloy which has higher oxygen reduction activity can be produced | generated by interaction with a nitrogen atom. 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 a carbon fine particle containing a transition metal compound that has formed a nitrogen carbon alloy and interacted with the nitrogen atom (N) is formed. In addition, the transition metal compound which interacted with a part of nitrogen atoms (N) may be removed by the acid treatment described later.

  The salts of cobalt, iron, manganese, nickel, and chromium are excellent in forming a nano-sized shell structure that improves the catalytic activity of the carbon catalyst, and in particular, cobalt and iron form a nano-sized shell structure. It is preferable because it is particularly excellent. Further, cobalt and iron contained in the carbon catalyst can improve the oxygen reduction activity of the catalyst in the carbon catalyst. Most preferably, the transition metal is iron. This is because the iron-containing nitrogen-containing carbon alloy has a high rise potential, a higher number of reaction electrons (described later) than cobalt, and relatively improves 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, boron, alkali metals (Na, K, Cs), alkaline earths (Mg, Ca, Ba), lead, tin, indium, thallium, etc. ) May be included in one or more types.

The inorganic metal salt is not particularly limited, but hydroxide, oxide, nitride, sulfate, sulfite, sulfide, sulfonate, carbonylate, nitrate, nitrite, halide, etc. Can do. Preferably, the counter ion is a halogen ion, a nitrate ion or a sulfate ion. Halides, nitrates or sulfates whose counter ions are halogen ions, nitrate ions or sulfate ions are preferred because they bind to carbon on the carbon surface produced during thermal decomposition and increase the specific surface area.
In the present invention, the inorganic metal salt is preferably a halide. Among these, iron chloride is more preferable.

  The inorganic metal salt can contain crystal water. 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.

  Sum of inorganic metal salts containing one or more of the ionic liquid, the nitrogen-containing organic compound, the Fe, Co, Ni, Mn and Cr contained in the precursor (however, the sum is the mass of hydrated water) The amount of the inorganic metal salt (including the mass of hydrated water in the inorganic metal salt herein) is preferably 0.1% by mass or more and 85% by mass or less, and 0.5% by mass It is more preferably 80% by mass or less and most preferably 1% by mass or more and 75% by mass or less.

  By setting it within this range, a carbon alloy having high oxygen reduction reaction activity (ORR activity) can be generated.

The ORR activity can be measured as the ORR activity value by obtaining the current density by the method described in detail in the Examples. To obtain high output, it is preferable current density value is low at the time of oxygen reduction, specifically, preferably -400μA / cm ² or less, more preferably -500μA / cm ² or less, -600μA / cm ² The following is more preferable, and most preferable is −700 μA / cm ² or less.

  In the organic material before firing, there is an advantage that the nitrogen-containing organic compound and the inorganic metal salt do not need to be uniformly dispersed. 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 size of the inorganic metal salt is preferably 0.001 μm or more and 100 μm or less. More preferably, it is 0.01 μm or more and 10 μm or less. 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 complexes:
In the method for producing a carbon alloy material of the present invention, it is preferable that the precursor further contains at least one organometallic complex. By adding an organometallic complex to the precursor, a carbon alloy catalyst exhibiting a high number of reaction electrons can be obtained in addition to high ORR activity.
Examples of the organometallic complex include compounds described in Basic Complex Engineering Study Group, Complex Chemistry-Fundamentals and Latest Topics-, Kodansha Scientific (1994), specifically, metal ions. A compound in which a ligand is coordinated to can be preferably exemplified. In addition, 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 the metal ions are cobalt, iron, manganese, nickel, and chromium ions.
Preferred as the ligand are monodentate ligands (halide ion, cyanide ion, ammonia, pyridine (py), triphenylphosphine, carboxylic acid, etc.), bidentate ligands (ethylenediamine (en), β -Diketonates (acetylacetonate (acac), pivaloylmethane (DPM), diisobutoxymethane (DIBM), isobutoxypivaloylmethane (IBPM), tetramethyloctadione (TMOD)), trifluoroacetylacetonate (TFA), Bipyridine (bpy), phenanthrene (phen), etc.), multidentate ligands (ethylenediaminetetraacetate ion (edta), etc.).

Preferred metal complexes are β-diketonate metal complexes (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 ], tris (dipivaloylmethane) iron (III) [Fe (DPM ₃ ], tris (dipivaloylmethane) cobalt (III) [Co (DPM) ₃ ], tris (diisobutoxymethane) iron (III) [Fe (DIBM) ₃ ], tris (diisobutoxymethane) cobalt ( III) [Co (DIBM) ₃ ], tris (isobutoxypivaloylmethane) cobalt (III) [Co (IBPM) ₃ ], tris (tetramethyloctadione) iron (III) [Fe (TMOD) ₃ ], tris (tetramethyloctadione) cobalt (III) [Co (TMOD) ₃ ], tris (1,10-phenanthroli Nate) iron (III) chloride [Fe (phen) ₃ ] Cl ₂ , tris (1,10-phenanthrolinato) cobalt (III) chloride [Co (phen) ₃ ] Cl ₂ , N, N′— Ethylenediaminebis (salicylideneaminato) acid iron (II) [Fe (salen)], N, N′-ethylenediaminebis (salicylideneaminato) cobalt (II) [Co (salen)], tris (2 , 2′-bipyridine) iron (II) chloride [Fe (bpy) ₃ ] Cl ₂ , tris (2,2′-bipyridine) cobalt (II) chloride [Co (bpy) ₃ ] Cl ₂ Metal phthalocyanine (MPc) and iron acetate [Fe (OAc) ₂ ] iron acetate [Fe (OAc) ₂ ].
Among them, β-diketonate iron complex (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 ] bis (acetylacetonate) iron (II) [Fe (acac) ₂ ] is preferred.

(Β-diketonate metal complex)
In the method for producing a carbon alloy material of the present invention, the organometallic complex is a β-diketonate iron (II) complex, which is acetylacetone iron (II), bis (dipivaloylmethane) 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 ] is particularly preferred.

  A β-diketonate metal complex will be described in detail as the metal complex. The β-diketonate metal complex represents a compound represented by the following general formula (8) and a tautomer thereof.

In the formula (8), 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, β-diketone or its ion is coordinated or bonded to the atom or ion of metal M.

  Preferred metals are cobalt, iron, manganese, nickel, chromium, more preferably cobalt, iron, and still more preferably iron.

Examples of the “hydrocarbon group” in the hydrocarbon group optionally having a substituent for R ¹ , R ² , and R ³ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. , Heterocyclic (heterocyclic) hydrocarbon groups, and groups in which a plurality of these are bonded. Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, and hexyl groups (C _1-6 alkyl groups and the like); An alkenyl group ( _C2-6 alkenyl group etc.) etc. are mentioned. Examples of alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl and cyclohexyl groups (3 to 15 membered cycloalkyl groups); 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 group such as carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, antiridinyl group, etc. Hydrocarbon group; oxygen-containing monocyclic system, oxygen-containing polycyclic system Sulfur-containing and selenium-containing tellurium ring system hydrocarbon group.

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

Examples of the ring formed by combining R ¹ , R ² , and R ³ with each other include, for example, a 5- to 15-membered cycloalkane ring or cycloalkene ring such as a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, and a cyclohexene ring. Is mentioned.

R ¹ and R ³ include an alkyl group (C _1-6 alkyl group etc.), an alkenyl group (C _2-6 alkenyl group etc.), a cycloalkyl group (3-15 membered cycloalkyl group etc.), a cycloalkenyl group. (3- to 15-membered cycloalkenyl group etc.), aryl group (C _6-15 aryl group etc.), aryl group having a substituent (C ₆ having a substituent such as p-methylphenyl group, p-hydroxyphenyl group) _-15 aryl group). 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).

In the compound represented by the formula (8), 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 is coordinated 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 any solvent that can be axially coordinated may be used.

  As the β-diketonate 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.

  The amount of β-diketonate iron complex added is usually 0.001 to 50 mol%, preferably 0.01 to 10 mol%, particularly preferably about 0.1 to 1 mol%.

(Conductive aid)
The precursor in the present invention may be fired by adding a conductive additive, or may be added to a carbon alloy. Since the conductive auxiliary agent is uniformly dispersed, it is preferable to add a conductive auxiliary agent and fire.

  Although it does not limit as said conductive support agent, For example, Norit (made by NORIT), Ketjen black (made by Lion), Vulcan (made by Cabot), black pearl (made by Cabot), acetylene black (made by Chevron) ) (All are trade names), carbon materials such as carbon black, graphite, fullerenes such as C60 and C70, carbon nanotubes, carbon nanohorns, and carbon fibers.

As addition amount of a conductive support agent, Preferably it is 0.01 mass%-50 mass%, More preferably, it is 0.1 mass%-20 mass%, More preferably, it is 1 mass%-10 mass%.
If too much conductive additive is added, the aggregation / growth of the metal produced from the inorganic metal salt in the system becomes non-uniform and the desired porous nitrogen-containing carbon cannot be obtained, which is not suitable.

(Carrier)
The carrier that can be used in the method for producing the carbon alloy material of the present invention is not particularly limited as long as it is not contrary to the gist of the present invention.
In the method for producing a carbon alloy material according to the present invention, the carrier is preferably a carbon material or an organic precursor that generates a carbon material or a carbon alloy material by firing.
Specifically, the carrier is more preferably a carbon material having pores or an organic precursor that generates a carbon material or a carbon alloy material by firing.

Examples of the carbon material include, but are not limited to, Ketjen Black (manufactured by Lion), Vulcan Black (manufactured by Cabot), Black Pearl (manufactured by Cabot), Norrit (manufactured by NORIT), and acetylene black (manufactured by Chevron). (All are trade names) such as carbon black, fullerenes such as C60 and C70, carbon nanotubes, graphene, carbon nanohorns, carbon fibers, graphite, activated carbon and the like. Two or more of these may be used in combination or may be obtained by firing.
As the organic precursor for producing the carbon alloy material, the nitrogen-containing organic compound having a molecular weight of 2000 or less can be used. Among these, as a carbon material, the porous carbon material which has electroconductivity is preferable, and electroconductive porous carbon black is more preferable.
In addition, a carbon substrate described in JP-A-2009-525841 can also be preferably used as a carrier in the present invention.

There is no restriction | limiting in particular as an acquisition method of such a support | carrier, It can obtain commercially.
Specific examples of the carrier preferably used in the present invention include the Ketjen Black series (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name), etc.).

There is no restriction | limiting in particular as a ratio of each component in the said precursor.
In the precursor, the ratio of the ionic liquid, the nitrogen-containing organic compound, the metal species including one or more of Fe, Co, Mn, Cr, and Ni and the organometallic complex, and the carrier is a mass ratio. It is preferably 0.1: 9.9 to 9.9: 0.1, more preferably 0.5: 9.5 to 9.5: 0.5, and 1: 9 to 9: 1. It is particularly preferred that
In the precursor, the content of metal atoms with respect to the total of the ionic liquid, the nitrogen-containing organic compound, the ionic liquid containing one or more of the Fe, Co, Mn, Cr and Ni and the organometallic complex is: It is preferably 0.1 to 85% by mass, more preferably 0.5 to 50% by mass, and particularly preferably 1 to 20% by mass.

<Step of firing the precursor>
In the method for producing the carbon alloy material, the step of firing the precursor includes:
1) preparing the precursor,
2) A temperature raising step in which the temperature is raised from room temperature to the carbonization temperature at 1 ° C. or more and 1000 ° C. or less under an inert atmosphere;
3) A carbonization step for holding from 500 ° C to 1000 ° C for 0.1 to 100 hours,
4) It is preferable to include a cooling step of cooling from the carbonization temperature to room temperature.
5) After the carbonization treatment, the carbon alloy may be cooled to room temperature and then pulverized.
The method for producing the carbon alloy material of the present invention includes the firing step,
6) It is preferable to include 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.

<Temperature raising process / carbonization process>
In the production method of the present invention, it is preferable to heat-treat the precursor containing the carrier to which the ionic liquid is adhered to the carbonization temperature.

In the heat treatment up to this carbonization temperature, the portions of the temperature rise treatment are collectively referred to as an infusible treatment.
The firing temperature of the carbonization treatment is not particularly limited as long as the nitrogen-containing organic compound is thermally decomposed and carbonized, but the upper limit of the carbonization temperature needs to be 1000 ° C. When the carbonization temperature exceeds 1000 ° C., it is difficult for nitrogen to remain in the carbon skeleton, so the N / C atomic ratio tends to decrease and the oxygen reduction reaction activity tends to decrease. Furthermore, the yield of carbide may be significantly reduced, and the carbide may not be produced with good yield.
The lower limit of the reaction temperature is preferably 400 ° C, more preferably 500 ° C, and still more preferably 600 ° C. By setting the reaction temperature to 400 ° C. or higher, a carbon alloy having sufficiently high carbon performance due to sufficiently advanced carbonization can be obtained. Moreover, if reaction temperature is 1000 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.
When the production method of the present invention includes a re-baking step described later, the firing temperature of the carbonization treatment is 400 to 900 ° C. from the viewpoint of performing the re-baking step at a temperature higher than the temperature at which the carbonization treatment is started. Is preferable, it is more preferable that it is 500-850 degreeC, and it is still more preferable that it is the range of 600-800 degreeC.

  In the carbonization treatment, the workpiece is held at 400 ° C. to 1000 ° C. for 0.1 hour to 100 hours, more preferably 1 hour to 10 hours. Even if the carbonization treatment is performed for more than 10 hours, the effect corresponding to the treatment time may not be obtained.

  The carbonization treatment is preferably performed under an inert atmosphere, and is preferably performed under a flow of an inert gas or a non-oxidizing gas. The gas flow rate is preferably 0.01 to 2.0 liters / min per 36 mmφ inner diameter, more preferably 0.05 to 1.0 liters / min per 36 mmφ inner diameter, and 0.1 per liter 36 mmφ inner diameter. It is particularly preferred to flow a gas of ~ 0.5 liter / min. When firing at 0.01 liters or less per minute, the amorphous carbon produced as a by-product during firing cannot be distilled off, causing a decrease in the processing temperature of the nitrogen-containing carbon alloy to be produced, and 2.0 liters per minute The above baking is not preferable because the substrate is vaporized before carbonization and a nitrogen-containing carbon alloy is not generated. It is preferable for the flow rate to be within this range because the desired nitrogen-containing carbon alloy can be suitably obtained.

  When carbonizing at a high temperature in the first stage, the yield of carbon alloy is reduced, but the crystallite size of the obtained carbon alloy is uniform, so that the metal is uniformly distributed and maintains a high activity state. . As a result, it became possible to produce a carbon alloy having excellent oxygen reduction performance.

Further, the temperature increase process may be performed in two stages. More specifically, by performing the first stage treatment at a relatively low temperature, it is possible to remove thermally unstable impurity components, solvents, and the like.
Subsequently, by performing the second stage treatment, not only the decomposition reaction and carbonization reaction of the organic material can be performed continuously, but also the decomposition product and the metal interact, It can be stabilized with high activity. For example, iron ions can be included in a divalent state. As a result, a carbon alloy having high oxygen reduction performance can be produced.

  Furthermore, by performing the second stage treatment, the treatment temperature in the subsequent 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.

  The reason for raising the temperature to the temperature of the first stage is to keep only the heat-stable structure and perform the preheating operation for the second stage processing. The reason for raising the temperature to the carbonization temperature in the second stage is to obtain an appropriate carbon alloy. On the other hand, when the carbonization temperature is exceeded, carbonization proceeds excessively, and an appropriate carbon alloy may not be obtained, and the yield may decrease.

  It is preferable to perform the temperature rising process in the first stage 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 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, the gas flow rate is preferably 0.01 to 2.0 liters / minute per 36 mmφ inner diameter, and the gas flow rate is 0.05 to 1.0 per 36 mmφ inner diameter. It is more preferable to circulate a gas of 1 liter / min, and it is particularly preferable that the gas flow rate is 0.1 to 0.5 liter / min of gas per an inner diameter of 36 mmφ.

  In the first stage temperature increase treatment, the organic material containing the nitrogen-containing organic compound and the inorganic metal salt is preferably heated to 100 ° C. to 500 ° C., more preferably 150 ° C. to 400 ° C. . By doing so, a uniform preliminary carbide is obtained.

  In the first stage temperature increase treatment, an organic material containing a nitrogen-containing organic compound and an inorganic metal salt may be inserted into a carbonization apparatus and then heated from room temperature to a predetermined temperature, or carbonization at a predetermined temperature may be performed. An organic material may be inserted into the device or the like. Preferably, the temperature is raised from room temperature to a predetermined temperature. In the case where the temperature is raised from room temperature to a predetermined temperature, it is preferable to keep the temperature raising rate constant. More specifically, the temperature rising rate is preferably 1 to 1000 ° C./min, more preferably 1 to 500 ° C./min.

In the second-stage temperature increase process, the temperature may be increased as it is after the first-stage temperature increase process, and the second-stage temperature increase process may be performed. Moreover, after cooling to room temperature once, you may raise temperature and perform the temperature rising process of a 2nd step. Further, when the preliminary carbide is cooled to room temperature after the temperature raising process in the first stage, it may be uniformly pulverized, further molded, or acid washed to remove the metal. . It is preferable to pulverize uniformly and perform acid cleaning.
More specifically, the temperature increase rate is preferably 10 ° C. or more and 1000 ° C. or less per minute, and more preferably 10 ° C. or more and 500 ° C. or less per minute.
The second temperature increase treatment is preferably performed in an inert atmosphere, and in the case of a flow system, the gas flow rate is 0.01 to 2.0 liters / minute of gas per 36 mmφ inner diameter. More preferably, the gas flow rate is more preferably 0.05 to 1.0 liter / min for an inner diameter of 36 mmφ, and the gas flow rate is 0.1 to 0.5 liter / min for an inner diameter of 36 mmφ. It is particularly preferable to circulate the gas.
It may be different from the gas flow rate in the first stage.

The carbonization treatment is preferably performed in the presence of an activator. By carbonizing at a high temperature in the presence of an activator, the pores of the carbon alloy develop and the surface area increases, and the degree of exposure of the metal on the surface of the carbon alloy improves, thereby improving the performance as a catalyst. . The surface area of the carbide can be measured by the N ₂ adsorption amount.

  The activator that can be used is not particularly limited, and for example, at least one selected from the group consisting of carbon dioxide, water vapor, air, oxygen, alkali metal hydroxide, zinc chloride, and phosphoric acid can be used. More preferably, at least one selected from the group consisting of carbon dioxide, water vapor, air, and oxygen can be used. A gas activator such as carbon dioxide or water vapor may be contained in the atmosphere of the second carbonization treatment in an amount of 2 to 80 mol%, preferably 10 to 60 mol%. If it is 2 mol% or more, a sufficient activation effect can be obtained, while if it exceeds 80 mol%, the activation effect becomes remarkable and the yield of carbide is remarkably reduced, making it impossible to produce carbide efficiently. There is a fear. 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.

  Nitrogen atoms can also be introduced after carbonization. At this time, as a method for 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, by holding the carbon alloy at 200 ° C. or more and 800 ° C. or less for 5 minutes or more and 180 minutes or less in an ammonia atmosphere as a nitrogen source, nitrogen atoms can be introduced on the surface of the carbon catalyst by heat treatment.

<Cooling process and grinding process>
Further, after the carbonization treatment, the carbon alloy may be cooled to room temperature and then pulverized. The pulverization can be performed by any method known to those skilled in the art. For example, the pulverization can be performed using a ball mill, a mechanical pulverizer, or the like.

<Acid cleaning process>
The method for producing a carbon alloy material of the present invention includes a step of washing the fired nitrogen-containing carbon alloy with an acid after the firing step.
By washing the metal on the surface of the produced carbon alloy catalyst with acid, the ORR activity can be dramatically improved. Without being bound by any theory, it is expected that this acid cleaning treatment can obtain an optimal porosity (porous nitrogen-containing carbon).
As the acid cleaning treatment, any aqueous Bronsted (proton) acid including a strong acid or a weak acid 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.
In addition, the method described in JP-T-2010-524195 can also be used in the present invention.

<Refiring process>
The method for producing a carbon alloy material of the present invention preferably includes a step of re-baking the acid-cleaned nitrogen-containing carbon alloy after the acid cleaning step. By such a refiring step, the current density can be improved with the 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, even if the conventional carbon alloy which has not passed through the acid treatment process (for example, the 700 degreeC baking product of the carbon alloy described in Unexamined-Japanese-Patent No. 2011-225431) increases application amount, current density is improved so much. Absent.
From the viewpoint of performing the re-baking step at a temperature higher than the temperature at which the carbonization treatment is first performed, the upper limit of the firing temperature in the re-baking step is preferably 1000 ° C. or less, and the lower limit of the firing temperature is preferably 500 ° C. or more. The temperature is more preferably 600 ° C. or higher, and further preferably 700 ° C. or higher.

[Carbon alloy materials]
The carbon alloy material of the present invention is produced by the method for producing a carbon alloy material of the present invention.

The carbon alloy material of the present invention obtained by firing the precursor is preferably a nitrogen-containing carbon alloy into which nitrogen has been introduced. The 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 carbon alloy of the present invention, the content of surface nitrogen atoms in the carbon catalyst is more preferably 0.05 or more and 0.3 or less in terms of atomic ratio (N / C) to the surface carbon. When the atomic ratio (N / C) of nitrogen atoms to carbon atoms is less than 0.05, the number of effective nitrogen atoms bonded to the metal decreases, and sufficient oxygen reduction catalyst characteristics cannot be obtained. Moreover, when the atomic ratio (N / C) of a nitrogen atom and a carbon atom exceeds 0.4, the strength of the carbon skeleton of the carbon alloy is lowered, and the electrical conductivity is lowered.

  Further, the skeleton of the carbon alloy only needs to 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 and 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 670m 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 preferred is 1300 m ² / g or less.

The shape of the carbon alloy of the present invention is not particularly limited as long as it has redox reaction activity.
When the shape of the carbon alloy of the present invention is described in detail, as a macro viewpoint (outer shape), for example, a sheet shape, a scale shape, a fiber shape, a block shape, a column shape, a particle shape, many ellipses other than a spherical shape, a flat shape, a curved shape And a large distorted structure such as a square shape. From the viewpoint of easy dispersion, it is preferably a block or particle.
Furthermore, as a microscopic viewpoint (local structure), it may have an inner hole, an outer hole, a communication hole (monolith shape), a high surface roughness, a surface microstructure, and the like.
For example, it is preferable that the particles have communication holes because the specific surface area is higher than that of the particles without communication holes, so that the number of catalytically active sites increases dramatically and the oxygen reduction reaction activity becomes extremely high.

Furthermore, the slurry containing a carbon alloy can be produced by dispersing the 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.
Fuel cell carbon alloy catalyst of the present invention preferably has a coating amount after drying of the carbon alloy material is 0.01 mg / cm ² or more, more preferably 0.02~100mg / 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 when 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.

<Uses of carbon alloy materials>
The use of the carbon alloy material of the present invention is not particularly limited, such as a structural material, an electrode material, a filtration material, and a catalyst material, but it is preferably used as an electrode material of a power storage device such as a capacitor or a lithium secondary battery, and has a high oxygen reduction reaction. More preferably, it is used as a carbon catalyst for a fuel cell, a zinc-air cell, a lithium-air cell, etc. characterized by having activity. Further, 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 comprising a 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 of the solid polymer electrolyte 14 as the anode electrode catalyst 13 and the cathode electrode catalyst 15. The By forming the carbon catalyst described above on both sides of the solid polymer electrolyte, and adhering the anode electrode catalyst 13 and the cathode electrode catalyst 15 to both main surfaces of the solid polymer electrolyte 14 on the electrode reaction layer side by hot pressing, It integrates as MEA (Membrane Electrode Assembly).

  In a conventional fuel cell, 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. On the other hand, 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 above electrochemical reaction,
Cathode side: O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O
Anode side: H ₂ → 2H ⁺ + 2e ⁻
The H ⁺ ions generated on the anode side move toward the cathode side in the solid polymer electrolyte 14, 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 a carbon catalyst made of the 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 the carbon catalyst 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 above-described carbon catalyst 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-described 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.

  Similarly to the above-described capacitor, for example, 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 carbon alloy of the present invention is used as an alternative to 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.

Moreover, the carbon alloy of the present invention can be widely used as a catalyst for chemical reaction, and can be used as an alternative to 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 by referring to a catalyst related document such as “Catalyst Preparation (Kodansha) by Takaho Shirasaki and Naoyuki Todo, 1975”.

  The present invention will be described more specifically with reference to the following 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 limited to the examples shown below. Unless otherwise specified, “part” is based on mass.

Example 1
<Synthesis of carbon material of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] impregnated KB600 (1C)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd.) [Emim] [FeCl ₄ ]) 0.66 g was dissolved in 350 g of acetone, and Ketjen Plaque (KB600, Lion Corporation, carbon ECP600JD (trade name)) 6.99 g was added, and the suspension was 30 ° C. For 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum heating drying was performed and pulverized to obtain a precursor (1A).

[Infusibilization and carbonization treatment]
1.0178 g of the precursor (1A) was measured on 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, and nitrogen was added at 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (1B) 0.7952g.

[Crushing and acid cleaning treatment]
The carbon material (1B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and left as it was overnight to obtain an acid cleaned carbon material (1C).

Molecular formula: C ₁₂ H ₁₅ N ₅ , molecular weight: 229.28
Elemental analysis (calculated value): C, 62.86; H, 6.59; N, 30.54

Molecular formula: C ₆ H ₁₁ Cl ₄ Fe ₁ N ₂ , molecular weight: 308.82
Elemental analysis (calculated values): C, 23.34; H, 3.59; Fe, 18.08; N, 9.07

(Example 2)
<Synthesis of carbon material of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] impregnated KB600 (2C)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd.) [Emim] [FeCl ₄ ]) 0.66 g was dissolved in 350 g of acetone, and 4.66 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) was added, and the suspension was 30 ° C. For 1 hour, and the solvent was distilled off under heating. Then, vacuum heating drying was performed and pulverized to obtain a precursor (2A).

[Infusibilization and carbonization treatment]
1.0200 g of the precursor (2A) 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, and nitrogen was added at 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (2B) 0.6597g.

[Crushing and acid cleaning treatment]
The carbon material (2B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant liquid were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (2C).

(Example 3)
<Synthesis of Carbon Material of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] Impregnated KB600 (3C)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd.) [Emim] [FeCl ₄ ]) 0.66 g was dissolved in 350 g of acetone, and Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) 3.11 g was added thereto as a suspension solution at 30 ° C. For 1 hour, and the solvent was distilled off under heating. Then, vacuum heating drying was performed and pulverized to obtain a precursor (3A).

[Infusibilization and carbonization treatment]
1.0191 g of the precursor (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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (3B) 0.5711g.

[Crushing and acid cleaning treatment]
The carbon material (3B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and left as it was overnight to obtain an acid cleaned carbon material (3C).

Example 4
<Synthesis of Carbon Material of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] Impregnated KB600 (4C)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd.) [Emim] [FeCl ₄ ]) 0.66 g was dissolved in 350 g of acetone, and 2.00 g of Ketjen Plaque (KB600, Lion Corporation, carbon ECP600JD (trade name)) was added, and the suspension was 30 ° C. For 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (4A).

[Infusibilization and carbonization treatment]
1.0317 g of the precursor (4A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (4B) 0.4721g.

[Crushing and acid cleaning treatment]
The carbon material (4B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (4C).

(Example 5)
<Synthesis of Carbon Material of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] Impregnated KB600 (5C)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd.) [Emim] [FeCl ₄ ]) 0.66 g was dissolved in 350 g of acetone, and 1.17 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) was added, and the suspension was 30 ° C. For 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (5A).

[Infusibilization and carbonization treatment]
1.0243 g of the precursor (5A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (5B) 0.4565g.

[Crushing and acid cleaning treatment]
The carbon material (5B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain an acid cleaned carbon material (5C).

(Example 6)
<Synthesis of carbon material of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] impregnated KB600 (6C)>
[Infusibilization and carbonization treatment]
1.0497 g of the precursor (5A) described in Example 5 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, and nitrogen was removed every minute. 300 mL was distributed for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 700 ° C. at 5 ° C. per minute and held at 700 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (6B) 0.5145g.

[Crushing and acid cleaning treatment]
The carbon material (6B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (6C).

(Example 7)
<[Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] impregnated KB600 carbon material refired and acid treated (7C)>

[Carbonization treatment]
1.0263 g of the acid-cleaned carbon material (6C) described in Example 6 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, and nitrogen was added. Was circulated at 300 mL / min for 30 minutes at room temperature.
The temperature was raised from 30 ° 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 carbon-material (7B) 0.3842g.

[Crushing and acid cleaning treatment]
The carbon material (7B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and left overnight to obtain an acid cleaned carbon material (7C).

(Example 8)
<Synthesis of carbon material of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] impregnated KB600 (8C)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd.) Manufactured by [Emim] [FeCl ₄ ]) in 350 g of acetone, 3.55 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added, and the suspension is 30 ° C. For 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (8A).

[Infusibilization and carbonization treatment]
1.0220 g of the precursor (8A) was measured on 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, and nitrogen was added at 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (8B) 0.6090g.

[Crushing and acid cleaning treatment]
The carbon material (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. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain an acid cleaned carbon material (8C).

Example 9
<Synthesis of Carbon Material of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] Impregnated KB600 (9C)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd.) Manufactured by [Emim] [FeCl ₄ ]) in 350 g of acetone, 2.28 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added, and the suspension is 30 ° C. For 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (9A).

[Infusibilization and carbonization treatment]
1.0188 g of the precursor (9A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (9B) 0.5070g.

[Crushing and acid cleaning treatment]
The carbon material (9B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (9C).

(Example 10)
<Synthesis of carbon material of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] impregnated KB600 (10C)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd.) [Emim] [FeCl ₄ ]) 1.32 g dissolved in acetone 350 g, Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) 1.33 g was added, and the suspension was 30 ° C. For 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (10A).

[Infusibilization and carbonization treatment]
1.0228 g of the precursor (10A) was measured on 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, and nitrogen was added at 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (10B) 0.4257g.

[Crushing and acid cleaning treatment]
The carbon material (10B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (10C).

(Example 11)
<[Bmim] [C (CN) ₃ ] and [Emim] ⁺ ₂ [CoCl ₄ ] ^2- Carbon Material Synthesis of Impregnated KB600 (11C)>
[Preparation of 1-ethyl-3-methylimidazolium cobalt (II) chloride ([Emim] ⁺ ₂ [CoCl ₄ ] ²⁻ )]
1-ethyl-3-methylimidazolium cobalt (II) chloride ([Emim] ⁺ ₂ [CoCl ₄ ] ²⁻ ) is B. Hitchcock et al. Chem. Soc. , Dalton Trans. , 2639 (1993).

[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium cobalt (II) chloride described above ( [Emim] ⁺ ₂ [CoCl ₄ ] ²⁻ ) 0.96 g is dissolved in 350 g of acetone, and 2.13 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added as a suspension solution. The mixture was stirred at 30 ° C. for 1 hour, and the solvent was distilled off under heating. Then, vacuum heating drying was performed and pulverized to obtain a precursor (11A).

[Infusibilization and carbonization treatment]
1.0458 g of the precursor (11A) was measured on 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, and nitrogen was added at 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (11A) 0.4921g.
[Crushing and acid cleaning treatment]
The carbon material (11B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain an acid cleaned carbon material (11C).

Molecular formula: C ₁₂ H ₂₂ Cl ₄ Co ₁ N ₄ , molecular weight: 423.075
Elemental analysis (calculated values): C, 34.07; H, 5.24; Cl, 33.52; Co, 13.93; N, 13.24

(Comparative Example 1)
<Carbon Material Synthesis of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] (C1C)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd.) Manufactured, [Emim] [FeCl ₄ ]) 0.66 g was mixed to obtain a precursor (C1A).

[Infusibilization and carbonization treatment]
2.4107 g of the precursor (C1A) was measured on 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, and nitrogen was added at 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C1B) 0.7968g.

[Crushing and acid cleaning treatment]
The carbon material (C1B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (C1C).

(Comparative Example 2)
<Carbon Material Synthesis of [Bmim] [C (CN) ₃ ] (C2C)>
[Infusibilization and carbonization treatment]
2.0222 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]) was weighed into a quartz boat and inserted into a tubular furnace at 4.0 cmφ ( It was installed in the center of a quartz tube having an inner diameter of 3.6 cmφ, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C2B) 0.6112g.

[Crushing and acid cleaning treatment]
The carbon material (C2B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (C2C).

(Comparative Example 3)
<Carbon Material Synthesis of [Emim] [FeCl ₄ ] (C3C)>
[Infusibilization and carbonization treatment]
1.0117 g of 1-ethyl-3-methylimidazolium tetrachloroferrate (manufactured by Tokyo Chemical Industry Co., Ltd., [Emim] [FeCl ₄ ]) was measured into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3 .6 cmφ) at the center of the quartz tube, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C3B) 0.1715g.

[Crushing and acid cleaning treatment]
The carbon material (C3B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain an acid cleaned carbon material (C3C).

(Comparative Example 4)
<[Bmim] [C (CN) ₃ ] Carbon Material Synthesis of Impregnated KB600 (C4C)>
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]) was dissolved in 350 g of acetone, and Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name) 1.33 g was added, and the suspension was stirred as a suspension at 30 ° C. for 1 hour, and the solvent was distilled off under heating. Then, vacuum heating drying was performed and pulverized to obtain a precursor (C4A).

[Infusibilization and carbonization treatment]
1.0228 g of the precursor (C4A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C4B) 0.449g.

[Crushing and acid cleaning treatment]
The carbon material (C4B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain an acid cleaned carbon material (C4C).

(Comparative Example 5)
<Synthesis of Carbon Material of Iron (II) Tetrahydrate Impregnated KB600 (C5C)>
[Precursor adjustment]
Iron chloride (II) tetrahydrate 99.9% (manufactured by Wako Pure Chemical Industries, Ltd.) 4.00 g was dissolved in acetone 350 g, and Ketjen Plaque (KB600, Lion Corporation, carbon ECP600JD (trade name)) 1.71 g. Was added and stirred as a suspension solution at 30 ° C. for 1 hour, and the solvent was distilled off under heating. Then, vacuum heating drying was performed and pulverized to obtain a precursor (C5A).

[Infusibilization and carbonization treatment]
1.0578 g of the precursor (C5A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C5B) 0.3755g.

[Crushing and acid cleaning treatment]
The carbon material (C5B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain an acid cleaned carbon material (C5C).

(Example 12)
<Synthesis of carbon material of [Bmim] [C (CN) ₃ ] and [Bmim] [FeCl ₄ ] impregnated KB600 (12C)>
[Precursor adjustment]
1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., [Bmim] [C (CN) ₃ ]) 4.00 g, 1-butyl-3-methylimidazolium tetrachloroferrate (III) ( Wako Pure Chemical Industries, Ltd. [Bmim] [FeCl ₄ ]) 1.31 g was dissolved in acetone 350 g, and Ketjen Plaque (KB600, Lion Corporation, Carbon ECP600JD (trade name)) 2.88 g was added and suspended. The solution was stirred at 30 ° C. for 1 hour, and the solvent was distilled off under heating. Then, vacuum heating drying was performed and pulverized to obtain a precursor (12A).

[Infusibilization and carbonization treatment]
1.0266 g of the precursor (12A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (12B) 0.4854g.

[Crushing and acid cleaning treatment]
The carbon material (12B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant liquid were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (12C).

Molecular formula: C ₈ H ₁₅ Cl ₄ Fe ₁ N, molecular weight: 336.87
Elemental analysis (calculated values): C, 28.52; H, 4.49; Cl, 42.10; Fe, 16.58; N, 8.32.

(Comparative Example 6)
<Carbon Material Synthesis of [Bmim] [C (CN) ₃ ] and [Bmim] [FeCl ₄ ] (C6C)>
[Precursor adjustment]
1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., [Bmim] [C (CN) ₃ ]) 4.00 g, 1-butyl-3-methylimidazolium tetrachloroferrate (III) ( 1.31 g of [Bmim] [FeCl ₄ ] manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to obtain a precursor (C6A).

[Infusibilization and carbonization treatment]
Precursor (C6A) (1.2444 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C6B) 0.3494g.

[Crushing and acid cleaning treatment]
The carbon material (C6B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain an acid cleaned carbon material (C6C).

(Comparative Example 7)
<Synthesis of [Bmim] [FeCl ₄ ] Carbon Material (C7C)>
[Infusibilization and carbonization treatment]
1.9995 g of 1-butyl-3-methylimidazolium tetrachloroferrate (III) (manufactured by Wako Pure Chemical Industries, Ltd., [Bmim] [FeCl ₄ ]) was weighed into a quartz boat and inserted into a tubular furnace. It was installed in the center of a quartz tube with 0 cmφ (inner diameter 3.6 cmφ), and nitrogen was circulated at room temperature for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C7B) 0.0815g.

[Crushing and acid cleaning treatment]
The carbon material (C7B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and left as it was overnight to obtain an acid cleaned carbon material (C7C).

(Example 13)
<Synthesis of Carbon Material of [Bmim] [C (CN) ₃ ] and [Et ₄ N] [FeCl ₄ ] Impregnated KB600 (13C)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), tetraethylammonium tetrachloroferrate (III) (manufactured by Santa Cruz Biotechnology, Inc.) , [Et ₄ N] [FeCl ₄ ]) is dissolved in 350 g of acetone, and 2.02 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added as a suspension solution. The mixture was stirred at 0 ° C. for 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (13A).

[Infusibilization and carbonization treatment]
1.0289 g of the precursor (13A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (13B) 0.5159g.

[Crushing and acid cleaning treatment]
The carbon material (13B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (13C).
Using a precursor obtained by removing at least one kind of raw material from the precursor (13A), a carbon material (13X) obtained through an infusibilization and carbonization treatment step, a pulverization / acid washing treatment step in the same manner as in Example 13. ) Confirmed that the current density at 0.7 V, which is an index of the oxygen reduction reaction (ORR) activity, was 100 μA / cm ² or less as compared with the carbon material (13C) of the present invention.

Molecular formula: C ₈ H ₂₀ Cl ₄ Fe ₁ N, molecular weight: 327.91
Elemental analysis (calculated values): C, 29.30; H, 6.15; Cl, 43.25; Fe, 17.03; N, 4.27

(Example 14)
<Synthesis of Carbon Material (14C) of [Emim] [N (CN) ₂ ] and [Bmim] [FeCl ₄ ] -impregnated KB600>
[Precursor adjustment]
4.00 g of 1-ethyl-3-methylimidazolium dicyanamide (manufactured by Tokyo Chemical Industry, [Emim] [N (CN) ₂ ]), 1-butyl-3-methylimidazolium tetrachloroferrate (manufactured by Tokyo Chemical Industry Co., Ltd.) , [Bmim] [FeCl ₄ ]) is dissolved in 350 g of acetone, and 2.00 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added thereto as a suspension solution at 30 ° C. The mixture was stirred for 1 hour, and the solvent was distilled off under heating. Then, vacuum heating drying was performed and pulverized to obtain a precursor (14A).

[Infusibilization and carbonization treatment]
1.0412 g of the precursor (14A) was measured on 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, and nitrogen was added at 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (14B) 0.4276g.

[Crushing and acid cleaning treatment]
The carbon material (14B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (14C).

Molecular formula: C ₈ H ₁₁ N ₅ , molecular weight: 177.21
Elemental analysis (calculated values): C, 54.22; H, 6.26; N, 39.52

(Comparative Example 8)
<Carbon Material Synthesis of [Emim] [N (CN) ₂ ] and [Bmim] [FeCl ₄ ] (C8C)>
[Precursor adjustment]
4.00 g of 1-ethyl-3-methylimidazolium dicyanamide (manufactured by Tokyo Chemical Industry, [Emim] [N (CN) ₂ ]), 1-butyl-3-methylimidazolium tetrachloroferrate (manufactured by Tokyo Chemical Industry Co., Ltd.) , [Bmim] [FeCl ₄ ]) were mixed to obtain a precursor (C8A).

[Infusibilization and carbonization treatment]
1.0439 g of the precursor (C8A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C8B) 0.6918g.

[Crushing and acid cleaning treatment]
The carbon material (C8B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain an acid cleaned carbon material (C8C).

(Comparative Example 9)
<Carbon Material Synthesis of [Emim] [N (CN) ₂ ] (C9C)>
[Infusibilization and carbonization treatment]
1.1798 g of 1-ethyl-3-methylimidazolium dicyanamide (manufactured by Tokyo Chemical Industry Co., Ltd., [Emim] [N (CN) ₂ ]) was measured into a quartz boat and inserted into a tubular furnace at 4.0 cmφ (inner diameter It was installed at the center of a quartz tube of 3.6 cmφ, and nitrogen was circulated at 300 mL per minute for 30 minutes at room temperature.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (C9B) 0.0834g.

[Crushing and acid cleaning treatment]
The carbon material (C9B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain an acid cleaned carbon material (C9C).

(Example 15)
<Synthesis of Carbon Material of [1-Allyl-mim] [N (CN) ₂ ] and [Bmim] [FeCl ₄ ] Impregnated KB600 (15C)>
[Precursor adjustment]
1-allyl-3-methylimidazolium dicyanamide (Aldrich, [1-Allyl-mim] [N (CN) ₂ ]) 4.00 g, 1-butyl-3-methylimidazolium tetrachloroferrate (Tokyo) 0.66 g of [Bmim] [FeCl ₄ ] manufactured by Kasei Co., Ltd.) is dissolved in 350 g of acetone, and 2.00 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, Carbon ECP600JD (trade name)) is added as a suspension solution. The mixture was stirred at 30 ° C. for 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (15A).

[Infusibilization and carbonization treatment]
1.0377 g of the precursor (15A) 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, and nitrogen was added at 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (15B) 0.4474g.

[Crushing and acid cleaning treatment]
The carbon material (15B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain an acid cleaned carbon material (15C).
Using a precursor obtained by removing at least one kind of raw material from the precursor (15A), a carbon material (15X) obtained through an infusibilization and carbonization treatment step, a pulverization / acid washing treatment step in the same manner as in Example 15. ) Confirmed that the current density at 0.7 V, which is an index of oxygen reduction reaction (ORR) activity, was 100 μA / cm ² or less as compared with the carbon material (15C) of the present invention.

Molecular formula: C ₉ H ₁₁ N ₅ , molecular weight: 189.22
Elemental analysis (calculated values): C, 57.13; H, 5.86; N, 37.01

(Example 16)
<Synthesis of carbon material of [3-CN-Propyl-mim] [N (CN) ₂ ] and [Bmim] [FeCl ₄ ] impregnated KB600 (16C)>
[Precursor adjustment]
3-cyanopropyl-3-methylimidazolium dicyanamide (manufactured by Aldrich, [3-CN-Propyl-imi] [N (CN) ₂ ]) 4.00 g, 1-butyl-3-methylimidazolium tetrachloroferrferer (Bmim [FeCl ₄ ], manufactured by Tokyo Chemical Industry Co., Ltd.) is dissolved in 350 g of acetone, and 2.00 g of Ketjen Plaque (KB600, manufactured by Lion, Carbon ECP600JD (trade name)) is added. The mixture was stirred as a turbid solution at 30 ° C. for 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (16A).

[Infusibilization and carbonization treatment]
1.0367 g of the precursor (16A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
The temperature was raised from 30 ° C. to 800 ° C. at 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon-material (16B) 0.3934g.

[Crushing and acid cleaning treatment]
The carbon material (16B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain an acid cleaned carbon material (16C).
Using a precursor obtained by removing at least one kind of raw material from the precursor (16A), a carbon material (16X) obtained through an infusibilization and carbonization treatment step and a pulverization / acid washing treatment step in the same manner as in Example 16. ) Confirmed that the current density at 0.7 V, which is an index of oxygen reduction reaction (ORR) activity, was 100 μA / cm ² or less as compared with the carbon material (16C) of the present invention.

Molecular formula: C ₁₀ H ₁₂ N ₆ , molecular weight: 216.24
Elemental analysis (calculated values): C, 55.54; H, 5.59; N, 38.86

(Example 17)
<Synthesis of Carbon Material of [Emim] [N (CN) ₂ ] and Fe (acac) ₂ Impregnated KB600 (17C)>
[Precursor adjustment]
1-ethyl-3-methylimidazolium dicyanamide (Tokyo Chemical Co., Ltd. [Emim] [N (CN) ₂ ]) 4.00 g, iron (II) acetylacetonate (Fe (acac) ₂ , Aldrich) 0.53 g is dissolved in 350 g of acetone, 1.94 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added, and the suspension is stirred at 30 ° C. for 1 hour. Distilled off. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (17A).

[Infusibilization and carbonization treatment]
1.0814 g of the precursor (17A) was measured on 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (17B) 0.5445g.

[Crushing and acid cleaning treatment]
The carbon material (17B) was pulverized with an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain an acid cleaned carbon material (17C).

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

(Example 18)
<Synthesis of carbon material of [Emim] [N (CN) ₂ ] and Fe (acac) ₃ impregnated KB600 (18C)>
[Precursor adjustment]
1-ethyl-3-methylimidazolium dicyanamide (Tokyo Chemical Co., Ltd., [Emim] [N (CN) ₂ ]) 4.00 g, iron (III) acetylacetonate (Fe (acac) ₃ , Aldrich) 0.77 g is dissolved in 350 g of acetone, 2.05 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added, and the suspension is stirred at 30 ° C. for 1 hour, and the solvent is heated under heating. Distilled off. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (18A).

[Infusibilization and carbonization treatment]
0.9294g of the precursor (18A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (18B) 0.5907g.

[Crushing and acid cleaning treatment]
The carbon material (18B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant liquid were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (18C).

Molecular formula: C ₁₅ H ₂₁ Fe ₁ O ₆ , molecular weight: 353.17
Elemental analysis (calculated values): C, 51.01; H, 5.99; Fe, 15.81; O, 27.18

(Example 19)
<Synthesis of Carbon Material of [Emim] [N (CN) ₂ ] and Fe (DPM) ₂ Impregnated KB600 (19C)>
[Preparation of Fe (DPM) 2]
Inorg. Chem. 1965, 4, 920-921. The Fe (DPM) 2 was adjusted according to the following procedure by improving the method described in 1).
Under a nitrogen atmosphere, 9.0 g FeSO ₄ .7H ₂ O, 1.4 g Na ₂ S ₂ O ₄ , 135 ml nitrogen degassed water was added to a 500 ml three-necked flask, and then 14.9 g DPM was added. It melt | dissolved in 270 ml of methanol, the nitrogen deaeration solution was added, and it stirred at room temperature for 1 hour. To this solution was added 97 ml of 1N NaOH aqueous solution. The obtained crystal was filtered, washed with water and hexane, and then dried to obtain 11.7 g of Fe (DPM) 2 in a yield of 85%.

[Precursor adjustment]
4.00 g of 1-ethyl-3-methylimidazolium dicyanamide (Tokyo Chemical Co., Ltd., [Emim] [N (CN) ₂ ]) and 0.96 g of Fe (DPM) ₂ described above were dissolved in 350 g of acetone, 2.13 g of CHEMPLAC (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) was added, and the suspension was stirred at 30 ° C. for 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (19A).

[Infusibilization and carbonization treatment]
1.0381 g of the precursor (19A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (19B) 0.6495g.

[Crushing and acid cleaning treatment]
The carbon material (19B) 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 allowed to stand overnight to obtain an acid cleaned carbon material (19C).

Molecular formula: C ₂₂ H ₃₈ Fe ₁ O ₄ , molecular weight: 422.38
Elemental analysis (calculated values): C, 62.56; H, 9.07; Fe, 13.22; O, 15.15

(Example 20)
<Synthesis of carbon material (20C) of [Emim] [N (CN) ₂ ] and Fe (TMOD) ₂ impregnated KB600>
(Preparation of Fe (TMOD) 2)
Inorg. Chem. 1965, 4, 920-921. According to the following procedure, Fe (TMOD) 2 was adjusted by improving the method described in 1).
Under a nitrogen atmosphere, add 3.0 g FeSO ₄ .7H ₂ O, 0.47 g Na ₂ S ₂ O ₄ , 45 ml nitrogen degassed water to a 500 ml 3 neck flask, then add 5.4 g TMOD to 90 ml Was dissolved in methanol, a nitrogen degassed solution was added, and the mixture was stirred at room temperature for 1 hour. To this solution was added 32 ml of 1N NaOH aqueous solution. The obtained crystals were filtered, washed with water and hexane, and then dried to obtain 40 g of Fe (TMOD) 2 in 89% yield.

[Precursor adjustment]
4.00 g of 1-ethyl-3-methylimidazolium dicyanamide (manufactured by Tokyo Chemical Industry Co., Ltd., [Emim] [N (CN) ₂ ]) and 1.04 g of Fe (TMOD) ₂ described above were dissolved in 350 g of acetone, 2.13 g of CHEMPLAC (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) was added, and the suspension was stirred at 30 ° C. for 1 hour, and the solvent was distilled off under heating. Then, vacuum heating drying was performed and pulverized to obtain a precursor (20A).

[Infusibilization and carbonization treatment]
1.0168 g of the precursor (20A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (20B) 0.6383g.

[Crushing and acid cleaning treatment]
The carbon material (20B) 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 allowed to stand overnight to obtain an acid cleaned carbon material (20C).

Molecular formula: C ₂₄ H ₄₂ Fe ₁ O ₄ , molecular weight: 450.43
Elemental analysis (calculated values): C, 64.00; H, 9.40; Fe, 12.40; O, 14.21

(Example 21)
<Synthesis of DCPy and [Emim] [FeCl ₄ ] impregnated KB600 carbon material (21C)>
[Precursor adjustment]
4.00 g of 3,4-dicyanopyridine (DCPy, manufactured by Aldrich), 0.66 g of 1-ethyl-3-methylimidazolium tetrachloroferrate (manufactured by Tokyo Chemical Industry Co., Ltd., [Emim] [FeCl ₄ ]), 350 g of acetone Then, 6.99 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) was added, and the mixture was stirred as a suspension at 30 ° C. for 1 hour, and the solvent was distilled off under heating. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (21A).

[Infusibilization and carbonization treatment]
1.0326 g of the precursor (21A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (21B) 0.6529g.

[Crushing and acid cleaning treatment]
The carbon material (21B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain an acid cleaned carbon material (21C).

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

(Example 22)
<Synthesis of Carbon Material of DCPN and [Emim] [FeCl ₄ ] Impregnated KB600 (22C)>
[Precursor adjustment]
DCPN (manufactured by Aldrich, the compound (B-3)) 4.00 g, 1-ethyl-3-methylimidazolium tetrachloroferrate (manufactured by Tokyo Kasei Co., Ltd., [Emim] [FeCl ₄ ]) 66 g is dissolved in 350 g of acetone, 6.99 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added, and the suspension is stirred at 30 ° C. for 1 hour, and the solvent is distilled off under heating. did. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (22A).

[Infusibilization and carbonization treatment]
1.0326 g of the precursor (22A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (22B) 0.6529g.

[Crushing and acid cleaning treatment]
The carbon material (22B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain an acid cleaned carbon material (22C).

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

(Example 23)
<Synthesis of Carbon Material of TCB and [Emim] [FeCl ₄ ] Impregnated KB600 (23C)>
[Precursor adjustment]
TCB of the following structure (Tokyo Chemical Industry Co., Ltd., Compound (B-4)) 4.00 g, 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd. [Emim] [FeCl ₄ ]) 0.66 g is dissolved in 350 g of acetone, 6.99 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added, the suspension is stirred at 30 ° C. for 1 hour, and the solvent is heated under heating. Distilled off. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (23A).

[Infusibilization and carbonization treatment]
1.0326 g of the precursor (23A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (23B) 0.6529g.

[Crushing and acid cleaning treatment]
The carbon material (23B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain an acid cleaned carbon material (23C).

Molecular formula: C ₁₀ H ₂ N ₄ , molecular weight: 178.15
Elemental analysis (calculated values): C, 67.42; H, 1.13; N, 31.45

(Example 24)
<Synthesis of carbon material of PyDA and [Emim] [FeCl ₄ ] impregnated KB600 (24C)>
[Precursor adjustment]
PyDA (Tokyo Chemical Industry Co., Ltd., Compound (B-10)) 4.00 g, 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Chemistry, [Emim] [FeCl ₄ ]) 0.66 g is dissolved in 350 g of acetone, 6.99 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added, the suspension is stirred at 30 ° C. for 1 hour, and the solvent is heated under heating. Distilled off. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (24A).

[Infusibilization and carbonization treatment]
1.0326 g of the precursor (24A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (24B) 0.6529g.

[Crushing and acid cleaning treatment]
The carbon material (24B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and left as it was overnight to obtain an acid cleaned carbon material (24C).

Molecular formula: C ₇ H ₇ N ₃ O ₂ , molecular weight: 165.15
Elemental analysis (calculated values): C, 50.91; H, 4.27; N, 25.44; O, 19.38

(Example 25)
<Synthesis of Carbon Material of [Emim] [N (CN) ₂ ] and Iron (II) Chloride Tetrahydrate-Added Impregnated KB600 (25C)>
[Precursor adjustment]
4.00 g of 1-ethyl-3-methylimidazolium dicyanamide (manufactured by Tokyo Chemical Industry Co., Ltd., [Emim] [N (CN) ₂ ]), 99.9% iron chloride (II) tetrahydrate (Wako Pure Chemical Industries, Ltd.) 0.40 g) is dissolved in 350 g of acetone, 1.89 g of Ketjen Plaque (KB600, manufactured by Lion Corporation, carbon ECP600JD (trade name)) is added, and the suspension is stirred at 30 ° C. for 1 hour and heated. The solvent was distilled off. Thereafter, vacuum drying was performed and pulverized to obtain a precursor (25A).

[Infusibilization and carbonization treatment]
1.0349 g of the precursor (25A) 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, and nitrogen was 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (25B) 0.1376g.

[Crushing and acid cleaning treatment]
The carbon material (25B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain an acid cleaned carbon material (25C).

(Comparative Example 10)
<Synthesis of carbon material of [Bmim] [C (CN) ₃ ] and [Emim] [FeCl ₄ ] impregnated KB600 (C10B)>
[Precursor adjustment]
4.00 g of 1-butyl-3-methylimidazolium tricyanomethane (manufactured by Kanto Chemical Co., Inc., [Bmim] [C (CN) ₃ ]), 1-ethyl-3-methylimidazolium tetrachloroferrate (Tokyo Kasei Co., Ltd.) [Emim] [FeCl ₄ ]) 0.66 g was dissolved in 350 g of acetone, and 2.00 g of Ketjen Plaque (KB600, Lion Corporation, carbon ECP600JD (trade name)) was added, and the suspension was 30 ° C. For 1 hour, and the solvent was distilled off under heating. Then, vacuum heating drying was performed and pulverized to obtain a precursor (C10A).

[Infusibilization and carbonization treatment]
1.0317 g of the precursor (C10A) was measured on 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, and nitrogen was added at 300 mL per minute for 30 minutes at room temperature. Circulated.
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 carbon-material (C10B) 0.4721g.

[Crushing process]
The carbon material (C10B) was pulverized in an agate mortar, washed with water, filtered and air-dried. Further, the obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, left to room temperature, and left overnight as it was to obtain a carbon material (C10B) not subjected to acid cleaning.

<Physical property evaluation>
[BET measurement]
The carbon alloy material was dried under vacuum at 200 ° C. for 3 hours using a sample pretreatment apparatus (BELPREP-flow (trade name) manufactured by Nippon Bell Co., Ltd.).
The specific surface area of the carbon alloy material was measured under simple measurement conditions using an automatic specific surface area / pore distribution measuring device (BELSORP-mini II (trade name) manufactured by Bell Japan Co., Ltd.).
The specific surface area was determined by the BET (Brunauer-Emmett-Teller) method using an analysis program installed in the apparatus.

[Production of carbon alloy coated electrode]
10 mg of the carbon alloy material obtained in Examples 1 to 25 and Comparative Examples 1 to 10, 110 mg of Nafion solution (5% alcohol aqueous solution) as a binder, 2.4 mL of water as a solvent, 1.6 mL of 1-propanol (IPA) And dispersed with an ultrasonic homogenizer (Nissei's US-150T (trade name)) connected with an attachment of 7 mmφ for 30 minutes. 4 μL of the obtained dispersion was sampled and using a rotating disk electrode (HR2-RD1-Pt8 / GC5 (trade name) manufactured by Hokuto Denko), the carbon alloy dispersion was carbonized so that the carbon alloy material was 0.05 mg. It apply | coated on the electrode and it was made to dry at room temperature, and the carbon alloy coating electrode was obtained.
Each characteristic evaluation was performed about the produced sample of each Example and a comparative example. The results are shown in Table 1 below.

[Measurement of oxygen reduction reaction (ORR) activity of carbon alloy coated electrode]
A rotating electrode device (Hokuto Denko Co., Ltd., HR-201 (Brand name)) is connected to an Automatic Polarization System (Hokuto Denko Co., Ltd., HZ-3000 (Brand name)). The obtained carbon alloy coated electrode, counter electrode and reference electrode were measured by the following procedure using a platinum electrode and a saturated calomel electrode (SCE), respectively.
A. For cleaning the carbon alloy material-coated electrode, a sweep potential of 0.946 to −0.204 V (vs. SCE), a sweep rate of 50 mV / s in a 0.1 M sulfuric acid aqueous solution bubbled with argon at 30 ° C. for 30 minutes or more, Ten cycles of cyclic voltammetry were measured.
B. For blank measurement, linear at 20 ° C. in 0.1 M sulfuric acid aqueous solution bubbled with argon for 30 minutes or more, sweep potential 0.746 to −0.204 V (vs. SCE), sweep speed 5 mV / s, electrode rotation speed 1500 rpm Sweep voltammetry was measured.
C. In order to measure the oxygen reduction activity, a linear sweep was performed at 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 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 of 0.7 V vs. The current density at the time of NHE was determined and used as the ORR activity value.

From Table 1 above, it was found that the carbon alloy catalyst using the carbon alloy material produced by the production method of the present invention has a large specific surface area and sufficiently high redox activity.
On the other hand, it was found from Comparative Examples 1 to 3 and 6 to 9 that when the carrier was not used, the obtained carbon alloy material had a small specific surface area and low redox activity. From Comparative Examples 2 and 9, it was found that when the support was not used and the precursor did not contain a specific metal species, the obtained carbon alloy material had a smaller specific surface area and lower redox activity. From Comparative Example 4, it was found that when the precursor did not contain a specific metal species, the obtained carbon alloy material had low redox activity. From Comparative Example 5, it was found that redox activity was low when no ionic liquid was used. From Comparative Example 10, it was found that when the obtained carbon alloy material was not subjected to acid cleaning, the obtained carbon alloy material had a small specific surface area and low redox activity.
In addition, "-" of the specific surface area of the comparative example 3 means that the carbide could not be obtained.
In addition, the carbon alloy material of each example manufactured by the manufacturing method of the present invention has a shape having a local structure of a communication hole (monolith) having a large specific surface area on a thin sheet-like outer shape. Was confirmed using a scanning electron microscope (SEM).

10 ... Fuel cell,
12 ... separator,
13 ... anode catalyst,
14 ... solid polymer electrolyte,
15 ... Cathode electrode catalyst,
16 ... separator,
20: Electric double layer capacitor,
21 ... 1st electrode,
22 ... second electrode,
23 ... separator,
24a ... exterior lid,
24b ... exterior case,
25 ... current collector,
26 ... Gasket

Claims (8)

Attaching at least one or more ionic liquids to the carrier;
Firing the precursor containing the carrier to which the ionic liquid is attached;
Having a step of washing the product after firing with an acid;
The precursor includes a metal species including one or more of Fe, Co, Mn, Cr and Ni;
The method for producing a carbon alloy material, wherein the anion species of the ionic liquid is an anion containing a nitrogen atom or an anion containing one or more metal species among Fe, Co, Mn, Cr and Ni .   The method for producing a carbon alloy material according to claim 1, wherein the carrier is a carbon material or an organic precursor that generates a carbon material or a carbon alloy material by firing.   The method for producing a carbon alloy material according to claim 1 or 2, wherein the carrier is an organic precursor that generates a carbon alloy material by firing. The anionic species of the ionic liquid is any one or more selected from [N (CN) ₂ ] ⁻ , [C (CN) ₃ ] ⁻ and [FeCl ₄ ] ⁻ . 4. The method for producing a carbon alloy material according to any one of 3 above. The said metal seed | species is an iron compound or a cobalt compound, The manufacturing method of the carbon alloy material of any one of Claims 1-4 characterized by the above-mentioned.   6. The method for producing a carbon alloy material according to claim 5, wherein the iron compound is at least one of a salt of a tetrachloroferrate anion and a nitrogen-containing quaternary cation and iron chloride. Attaching at least one or more ionic liquids to the carrier;
Firing the precursor containing the carrier to which the ionic liquid is attached;
Having a step of washing the product after firing with an acid;
The precursor includes a metal species including one or more of Fe, Co, Mn, Cr and Ni;
The method for producing a carbon alloy catalyst, wherein the anion species of the ionic liquid is an anion containing a nitrogen atom or an anion containing one or more metal species among Fe, Co, Mn, Cr and Ni . Attaching at least one or more ionic liquids to the carrier;
Firing the precursor containing the carrier to which the ionic liquid is attached;
Washing the product after calcination with an acid to obtain a carbon alloy catalyst;
Producing a fuel cell using the carbon alloy catalyst,
The precursor includes a metal species including one or more of Fe, Co, Mn, Cr and Ni;
The method for producing a fuel cell, wherein the anionic species of the ionic liquid is an anion containing a nitrogen atom, or an anion containing one or more metal species among Fe, Co, Mn, Cr and Ni.

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