JP2016190233A - Carbon catalyst, method for producing the same, catalyst ink and fuel battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbon catalyst obtained by effectively treating a nitrogen source for feeding a nitrogen element reported as one catalyst activity factor of the carbon catalyst to the surface of the catalyst and a metallic source on the surface of the carbon material, heat-treating the precursor including them and performing carbonization, a method for producing the same, and a fuel battery using the catalyst.SOLUTION: Provided is a carbon catalyst obtained by heat-treating a mixture including: a carbon material; and a metal element-containing nitrogen-containing pigment derivative of one or more kinds selected from a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group. Also provided is a carbon catalyst obtained by heat-treating a mixture including: a carbon material; a metal element-free nitrogen-containing pigment derivative of one or more kinds selected from a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group; and a metallic source.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a carbon catalyst that does not carry any precious metal such as platinum or a platinum alloy, a method for producing the same, a catalyst ink, and a fuel cell.

  The fuel cell, which is currently being developed for practical use, is a clean energy system that uses electrical energy when water is generated from hydrogen and oxygen and discharges only water as waste. For fuel cells, solid polymer fuel cells used in the state of a membrane electrode assembly (MEA) in which a solid polymer formed into a membrane is used as an electrolyte and electrodes are bonded to both sides of the electrolyte, and microorganisms are donated by electrons There are various types depending on the electrolyte and fuel used, such as a microbial fuel cell, which is a fuel cell system that can be used as a product and generate power while purifying wastewater and has a very high environmental compatibility.

  However, the electrode catalysts used in the various fuel cells as described above are those in which noble metals such as platinum are conventionally supported on a carbon carrier such as carbon black, and the electrolyte membrane surface is formed by a method such as plating or sputtering. A noble metal thin film or the like is used.

  While noble metals such as platinum exhibit high catalytic activity (oxygen reduction activity, hydrogen oxidation activity) and their activity stability, they are very expensive and limited in terms of resources. For this reason, the electrode catalyst contributes to increase the cost of various electrochemical devices. In particular, since a fuel cell is used in a state in which a large number of MEAs (Membrane Electrode Assembly) are stacked in order to obtain a predetermined output, the amount of electrode catalyst used per fuel cell also increases. This hinders the spread of fuel cells.

In order to solve the above problems, various measures have been taken so far. As what does not use noble metals such as platinum, for example, a carbon catalyst obtained by carbonizing a mixture of a macrocyclic compound such as metal porphyrin or metal phthalocyanine and an organic polymer material without using a carbon material (Patent Documents 1, 2, 3, 4, 5), or carbon catalysts obtained by carbonizing organic polymer materials that do not contain macrocyclic compounds (Patent Documents 6, 7, 8), and the like have been reported. However, considering that the reaction proceeds only on the surface of the catalyst, the specific surface area is large and the electronic conductivity is important. On the other hand, carbon catalysts made from these organic polymer materials have a specific surface area. There was a problem that it was small and the electron conductivity was low.
As a carbon catalyst using an electronic conductor having a large specific surface area as a carrier, a carbon catalyst (Patent Documents 9, 10, and 11) in which a macrocyclic compound is supported on a surface of an electron conductive carbon carrier such as carbon black and carbonized is also used. It has been reported. However, none of the methods has led to a proposal of a catalyst having sufficient catalytic activity.

JP 2011-6283 A JP 2010-275116 A JP 2011-6282 A Japanese Patent No. 4452887 JP 2010-275115 A JP 2011-6280 A JP 2011-6293 A JP2013-158675A Japanese Patent No. 4461427 JP 2006-314871 A International Publication No. 2009/124905 Pamphlet

The problem to be solved by the present invention is to supply nitrogen element, which has been reported as one of the catalytic activity factors, to the catalyst surface as an alternative to the noble metal catalyst that is required to reduce the usage amount from the viewpoint of cost, resource amount, etc. Catalyst obtained by effectively treating the surface of a carbon material with a nitrogen source and a metal source, and heat-treating and carbonizing a precursor containing the same, a method for producing the same, and a fuel cell using the catalyst Is to provide.

That is, the present invention provides a carbon material and at least one nitrogen-containing pigment derivative containing a metal element selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group. And a carbon catalyst obtained by heat-treating the mixture.

Further, the present invention provides a carbon material, one or more nitrogen-containing pigment derivatives not containing a metal element selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group, And a carbon catalyst obtained by heat-treating a mixture containing a metal source.

The present invention also relates to the carbon catalyst, wherein the mixture further includes a metal source.

In the present invention, the basic functional group is an -NRR ′ group (R and R ′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted group. Represents a substituted aryl group, wherein R and R ′ may combine to form a ring.).

The present invention also relates to the carbon catalyst, wherein the acidic functional group is any one of a sulfo group, a carboxy group, and a phosphoric acid group.

The present invention also relates to the carbon catalyst, wherein the nitrogen-containing pigment derivative is one or more nitrogen-containing pigment derivatives selected from the group consisting of nitrogen-containing organic dye derivatives, nitrogen-containing anthraquinone derivatives, acridone derivatives, and triazine derivatives.

The present invention also relates to the carbon catalyst, wherein the nitrogen-containing pigment derivative containing the metal element is a metal phthalocyanine pigment derivative.

The present invention also relates to the carbon catalyst, wherein the carbon material is one or more carbon materials selected from the group consisting of carbon black, graphene-based carbon materials, and carbon nanotubes.

Further, the present invention provides a nitrogen-containing pigment derivative having a basic functional group, a nitrogen-containing pigment derivative having an acidic functional group, and / or a metal element contained in a metal source, such as cobalt, iron, nickel, manganese, copper, vanadium, and It is related with the said carbon catalyst which is 1 or more types chosen from tin.

The present invention also relates to the carbon catalyst, wherein the element ratio of the metal element to nitrogen is in the range of 0.05 to 5.

The present invention also relates to the carbon catalyst, wherein the metal element is cobalt and / or iron.

The present invention also provides a carbon material, and a nitrogen-containing pigment derivative containing one or more metal elements selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group. The method for producing a charcoal catalyst is characterized by comprising a step of mixing a mixture containing the catalyst in a solvent and a step of heat-treating the mixture after drying the solvent at 700 to 1100 ° C.

Further, the present invention provides a carbon material, one or more nitrogen-containing pigment derivatives not containing a metal element selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group, In addition, the present invention relates to a method for producing a charcoal catalyst, comprising a step of mixing a mixture containing a metal source in a solvent and a step of heat-treating the mixture obtained by drying the solvent at 700 to 1100 ° C.

The present invention also relates to the method for producing a carbon catalyst, wherein a dispersion resin is included in the step of mixing in a solvent.

The present invention also relates to a carbon catalyst produced by the production method.

The present invention also relates to a catalyst ink containing the carbon catalyst, a binder, and a solvent.

The present invention also relates to a fuel cell having an electrode catalyst in which the carbon catalyst is disposed on one or both surfaces of a solid polymer electrolyte membrane.

The present invention also relates to the catalyst ink, wherein the binder is a proton conductive polymer and / or a water repellent material.

  The present invention also relates to a microbial fuel cell having the carbon catalyst.

  According to the present invention, organic and inorganic compounds containing various elemental states of nitrogen elements reported as a catalyst activity factor of carbon catalysts and metal elements contributing to the formation of catalyst active sites and the pore structure of carbon catalysts are included. By using it as a nitrogen source / metal source, it was possible to efficiently treat the surface of a carbon material having a large carrying area, and many catalytically active sites could be introduced on the surface of the carbon catalyst. Moreover, the catalytic activity of the resulting carbon catalyst can be controlled by simultaneously using a plurality of organic compounds having different nitrogen element bonding states or by effectively selecting a metal source and a carbon material.

FIG. 1 is a diagram showing a configuration of a polymer electrolyte fuel cell in which the carbon catalyst of the present invention is applied to an electrode catalyst as an application example.

The carbon catalyst in the present invention includes a carbon material, one or more nitrogen-containing pigment derivatives selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group, and a nitrogen-containing pigment derivative containing a metal element A mixture comprising, and
One or more nitrogen-containing pigment derivatives selected from the group consisting of a carbon material, a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group, and a metal source, Consists of heat denatured mixture.
A mixture containing a carbon material and at least one nitrogen-containing pigment derivative containing a metal element selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group; and
A carbon material, one or more nitrogen-containing pigment derivatives selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group, and a metal source, and a metal source By dispersing and mixing the mixture in a solvent, the nitrogen-containing pigment derivative and the metal source can be efficiently treated on the surface of the carbon material, and the nitrogen element considered to be a factor of the catalytic activity site in the carbon catalyst activity of the present invention and It becomes possible to effectively introduce the metal element and the carbon catalyst surface.

  Furthermore, the carbon catalyst in the present invention can contain a resin component, an organic pigment, a macrocyclic compound not containing a noble metal element, or a natural material as a precursor. It can be used as a raw material for a carbon catalyst because it shows a good thermal decomposition behavior, and nitrogen elements and metal elements derived from pigment derivatives tend to remain.

<Nitrogen-containing pigment derivative having basic functional group>
The nitrogen-containing pigment derivative having a basic functional group in the present invention includes an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a basic functional group. And one or more derivatives selected from the group consisting of triazine derivatives. Among the above, when using an organic dye derivative or an anthraquinone derivative, the nitrogen-containing organic dye derivative or nitrogen-containing anthraquinone containing nitrogen in the skeleton other than the functional group or terminal is used because of the ease of remaining nitrogen after carbonization. Derivatives may be preferred.

  Specific examples are shown below.

General formula (1):

In general formula (1),
X ¹ _{is, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or ^-X 2 ^-Y 1 ^{-X 3} - is and,
X ² _{is, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
X ³ is —NH— or —O—.
Y ¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by the following general formula (2), a substituent represented by the following general formula (3), or a substituent represented by the following general formula (4),
Q is —O—R ² , —NH—R ² , a halogen group, —X ¹ —R ¹ , a substituent represented by the following general formula (2), a substituent represented by the following general formula (3), or A substituent represented by the following general formula (4),
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ¹ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the following general formula (5),
n ¹ is an integer of 1 to 4.

General formula (2):

General formula (3):

General formula (4):

In general formulas (2) to (4),
X ⁴ is a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 -, or ^-X 5 ^-Y 2 ^{-X 6} - a and,
X ⁵ is —NH— or —O—.
X ⁶ is a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, or -CH ₂ -,
Y ² is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
v is an integer from 1 to 10,
R ³ And R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. Where R ³ And R ⁴ together with a substituted or unsubstituted heterocyclic residue containing additional nitrogen, oxygen or sulfur atoms,
R ⁵ , R ⁶ , R ⁷ , And R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ⁹ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

General formula (5):

In general formula (5),
T ^is a -X 8 ^{-R 10,} or ^{W 1,}
U ^is, -X 9 ^{-R 11,} or a ^{W 2,}
W ¹ and W ² are each independently —O—R ²⁰ , —NH—R ²⁰ , a halogen group, a substituent represented by the general formula (2), a substituent represented by the general formula (3), or A substituent represented by the general formula (4),
R ²⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
X ⁷ is —NH— or —O—.
X ^8, and ^{X 9} are each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a _-CH 2 NHCOCH ₂ NH-,
Y ³ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
R ¹⁰ and R ¹¹ are each independently an organic dye residue, a substituted or unsubstituted heterocyclic residue, or a substituted or unsubstituted aromatic ring residue.

Specific examples of the organic dye residue represented by R ¹ , R ¹⁰ , and R ¹¹ include diketopyrrolopyrrole dyes: azo dyes such as azo, disazo, and polyazo: phthalocyanine dyes: diaminodianthraquinone, anthra Anthraquinone dyes such as pyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, and violanthrone:: Quinacridone dyes: Dioxazine dyes: Perinone dyes: Perylene dyes: Thioindigo dyes: Isoindoline dyes: Isoindo Linone dyes: quinophthalone dyes: selenium dyes: and metal complex dyes.

Specific examples of the heterocyclic and aromatic ring residues represented by R ¹ , R ¹⁰ , and R ¹¹ include thiophene, furan, pyridine, pyrazine, triazine, pyrazole, pyrrole, imidazole, isoindoline, and isoindolinone. Benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, and acridone. These heterocyclic residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), Nitro group, hydroxy group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxy group) , May be substituted with an alkoxy group, halogen, or the like), and may be substituted with a phenylamino group (alkyl group, amino group, alkylamino group, nitro group, hydroxy group, alkoxy group, halogen, or the like) May be substituted).

R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or R ³ And R ⁴ , a heterocyclic residue which may have a substituent containing a further nitrogen, oxygen or sulfur atom.

Y ¹ , Y ² , and Y ³ each independently represent a substituted or unsubstituted alkylene group, alkenylene group, or arylene group having 20 or less carbon atoms, preferably a substituted or unsubstituted phenylene group or biphenylene group. , A naphthylene group, or an alkylene group which may have a side chain having 10 or less carbon atoms.

General formula (6)

In general formula (6),
Z is a substituent represented by the following general formula (7), a substituent represented by the following general formula (8), or a substituent represented by the following general formula (9),
n ² is an integer from 1 to 4,
R ¹² is an organic dye residue, a substituted or unsubstituted heterocyclic residue, or a substituted or unsubstituted aromatic residue.

General formula (7):

General formula (8):

General formula (9):

In general formulas (7) to (9),
X ¹⁰ represents a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 -, or ^-X 11 ^-Y 4 ^{-X 12} - a and,
X ¹¹ is —NH— or —O—.
X ¹² represents a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, or -CH ₂ -,
Y ⁴ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
v ¹ is an integer from ¹ to 10,
R ¹³ And R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted phenyl group. Here, R ³ and R ⁴ may be combined to form a substituted or unsubstituted heterocyclic residue containing a further nitrogen, oxygen, or sulfur atom.
R ¹⁵ , R ¹⁶ , R ¹⁷ , And R ¹⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ¹⁹ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

Specific examples of the organic dye residue represented by R ¹² include diketopyrrolopyrrole dyes: azo dyes such as azo, disazo, and polyazo: phthalocyanine dyes: diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone , Indanthrone, pyranthrone, violanthrone and other anthraquinone dyes: quinacridone dyes: dioxazine dyes: perinone dyes: perylene dyes: thioindigo dyes: isoindoline dyes: isoindolinone dyes: quinophthalone dyes: sulene System dyes: and metal complex dyes.

Examples of the heterocyclic residue and aromatic ring residue represented by R ¹² include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, Examples include indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, and acridone. These heterocyclic residues and aromatic ring residues are alkyl groups (such as methyl, ethyl, and butyl groups), amino groups, alkylamino groups (such as dimethylamino groups, diethylamino groups, and dibutylamino groups), Nitro group, hydroxy group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxy group) , May be substituted with an alkoxy group, halogen, etc.), and may be substituted with a phenylamino group (alkyl group, amino group, alkylamino group, nitro group, hydroxy group, alkoxy group, halogen, etc.) May be substituted).

R ¹³ And R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted phenyl group, or R ^13. And R ¹⁴ together with a substituted or unsubstituted heterocyclic residue containing an additional nitrogen, oxygen or sulfur atom.

Specific examples of the amine component used for forming the substituents represented by the general formulas (2) to (4) and the general formulas (6) to (9) include the following.
Dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N- tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, Dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, , N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutyl Aminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoe Ruamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2 , 6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N- Aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N- Butyl piperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

Among the nitrogen-containing pigment derivatives having basic functional groups exemplified above, the active site structure is effectively left even after carbonization due to the fastness of the dye skeleton in addition to the dispersibility of the raw carbon material. A metal phthalocyanine pigment derivative containing a phthalocyanine dye containing a metal at the center as the organic dye residue represented by R ¹² in the general formula (6) is preferable.

  The synthesis method of the organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group of the present invention is particularly limited. Instead, a well-known method can be applied. For example, JP 54-62227, JP 56-118462, JP 56-166266, JP 60-88185, JP 63-305173, JP 3 A method described in JP-A No. 2676 or JP-A No. 11-199796 can be applied. The disclosure by the above publication is incorporated into a part of this specification by reference.

  For example, various derivatives having a basic functional group may be prepared by introducing substituents represented by the following general formulas (10) to (13) into an organic dye, anthraquinone, or acridone, and then adding these substituents and an amine component. It can synthesize | combine by making it react.

General formula (10):
-SO ₂ Cl

General formula (11):
-COCl

Formula (12):
-CH ₂ NHCOCH ₂ Cl

General formula (13):
-CH ₂ Cl

  Examples of the amine component include N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5. -Triazin-2-ylamino] aniline and the like can be used.

  For example, when introducing the substituent represented by the general formula (10), an organic dye, anthraquinone, or acridone is dissolved in chlorosulfonic acid and reacted with a chlorinating agent such as thionyl chloride. At that time, the number of substituents represented by the general formula (10) introduced into the organic dye, anthraquinone, or acridone can be controlled by adjusting conditions such as reaction temperature and reaction time.

  In addition, when the substituent represented by the general formula (11) is introduced, an organic dye having a carboxy group, anthraquinone, or acridone is first synthesized by a known method, and then thionyl chloride in an aromatic solvent such as benzene. And the like, and the like.

  During the reaction of the substituents represented by the general formulas (10) to (13) and the amine component, a part of the substituents represented by the general formulas (10) to (13) are hydrolyzed to convert the chlorine into a hydroxy group. May be replaced. In that case, the substituent represented by the general formula (10) is a sulfo group, and the substituent represented by the general formula (11) is a carboxy group. Each acid group may remain as a free acid. Or you may form the salt with 1-3 said metal or said amine, respectively.

  When the organic dye is an azo dye, a substituent represented by the general formulas (7) to (9) or the following general formula (14) is introduced in advance into the diazo component or the coupling component, and then coupled. An azo organic dye derivative can also be produced by carrying out the reaction.

General formula (14):

In general formula (14),
X ¹³ _{is, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or ^-X 14 ^-Y 5 ^{-X 15} - a and,
X ¹⁴ _{is, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
Each X ¹⁵ is independently —NH— or —O—;
Y ⁵ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
P ¹ is a substituent represented by the general formula (2), a substituent represented by the general formula (3), or a substituent represented by the general formula (4).
Q ² represents —O—R ²⁴ , —NH—R ²⁴ , a halogen group, —X ¹ —R ²⁵ , a substituent represented by the general formula (2), a substituent represented by the general formula (3), or general A substituent represented by formula (4),
R ²⁴ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ²⁵ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the general formula (5).

  The triazine derivative having a basic functional group is, for example, a substituent represented by general formulas (7) to (9) or general formula (14) in at least one chlorine of cyanuric chloride using cyanuric chloride as a starting material. It is obtained by reacting an amine component (for example, N, N-dimethylaminopropylamine, N-methylpiperazine or the like) which forms, and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  Various derivatives having a basic functional group can also be used in combination with an acidic compound. Examples of the acidic compound include a resin having any acidic functional group such as carboxylic acid, sulfonic acid, or phosphoric acid, an inorganic acid, or an organic acid having a molecular weight of 300 or less.

  Specific examples of various derivatives having a basic functional group in the present invention are shown in Table 1.

Table 1

<Nitrogen-containing pigment derivative having acidic functional group>
Examples of the nitrogen-containing pigment derivative having an acidic functional group in the present invention include one or more derivatives selected from the group consisting of an organic dye derivative having an acidic functional group and a triazine derivative having an acidic functional group.
Among the above, when using an organic dye derivative or an anthraquinone derivative, the nitrogen-containing organic dye derivative or nitrogen-containing anthraquinone containing nitrogen in the skeleton other than the functional group or terminal is used because of the ease of remaining nitrogen after carbonization. Derivatives may be preferred.
As the acidic functional group, a sulfo group (—SO ₃ H), a carboxy group (—COOH), or a phosphoric acid group (—P (═O) (OH) ₂ ) is preferable in terms of acidity and versatility.

Formula (15):

In general formula (15),
X ¹⁰¹ _{is, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or ^-X 103 ^-Y 101 ^{-X 104} - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ _{is, -CONH -, - SO 2 NH} -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
Y ¹⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms, and Z ¹⁰¹ is —SO ₃ M ¹⁰¹ (sulfo group), -COOM ¹⁰¹ (carboxy group), or -P (O) (-OM ¹⁰¹ ) ₂ (phosphate group),
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the following general formula (16).

Formula (16):

In general formula (16),
X ²⁰¹ is —NH— or —O—;
X ^202, and ^{X 203} each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a _-CH 2 NHCOCH ₂ NH-,
R ^201, and ^{R 202} are each independently an organic pigment residue, a heterocyclic residue of substituted or unsubstituted, substituted or unsubstituted aromatic ring residue, or a ^-Y 201 ^{-Z 201,}
Y ²⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
^M201 is one equivalent of a trivalent cation.

Examples of organic dye residues represented by R ¹⁰¹ , R ²⁰¹ and R ²⁰² include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, and flavan. Anthraquinone dyes such as Throne, Antanthrone, Indanthrone, Pyrantron, and Biolantron, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes Examples thereof include dyes, selenium dyes, and metal complex dyes.

Examples of the heterocyclic residue and aromatic ring residue represented by R ¹⁰¹ , R ²⁰¹ and R ²⁰² include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, Examples include benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, or anthraquinone.

Y ¹⁰¹ and Y ^{201 each} represent a substituted or unsubstituted alkylene group, alkenylene group or arylene group having 20 or less carbon atoms, preferably a substituted or unsubstituted phenylene group, biphenylene group, naphthylene group, or carbon number of 10 The alkylene group which may have the following side chains is mentioned.

The substituted or unsubstituted alkyl group or alkenyl group represented by R ¹⁰² contained in Q ¹⁰¹ preferably has 20 or less carbon atoms, and more preferably has a side chain having 10 or less carbon atoms. The alkyl group which may be mentioned is mentioned. In the alkyl group or alkenyl group having a substituent, the hydrogen atom of the alkyl group or alkenyl group is substituted with a halogen group such as a fluorine atom, a chlorine atom, or a bromine atom, a hydroxy group, or a mercapto group. Is.

M ¹⁰¹ and ^{M 201} represents one equivalent of a monovalent to trivalent cation, e.g., hydrogen atom (proton) represents any metal cation, or quaternary ammonium cation. Moreover, when it has two or more M in a dispersing agent structure, M may be only any one of a proton, a metal cation, or a quaternary ammonium cation, and these may be combined.

  Examples of the metal include lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt.

  The quaternary ammonium cation is a single compound having a structure represented by the general formula (17) or a mixture.

Formula (17):

In General Formula (17), R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ are any of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group It is.

R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ may be the same or different. Moreover, when R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ have a carbon atom, the number of carbon atoms is 1 to 40, preferably 1 to 30, and more preferably 1 to 20.

  Specific examples of the quaternary ammonium include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, laurylammonium, and stearylammonium. However, it is not limited to these.

General formula (18):

In general formula (18),
X ^401, a direct _{bond, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH -, - X 402 -Y-, or ^{-X 402} - YX ^403- ,
X ⁴⁰² _{is, -CONH -, - SO 2 NH} -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
X ⁴⁰³ is —NH— or —O—;
Y ⁴⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
Z ⁴⁰¹ is —SO ₃ M ⁴⁰¹ , —COOM ⁴⁰¹ , or —P (O) (— OM ⁴⁰¹ ) ₂ ;
M ⁴⁰¹ is one equivalent of a monovalent to trivalent cation,
R ⁴⁰¹ is an organic dye residue,
n ⁴⁰¹ is an integer of 1 to 4.

Examples of the organic dye residue represented by R ⁴⁰¹ include azo dyes such as diketopyrrolopyrrole dyes, azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrone, and indanthrone. Anthraquinone dyes such as pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, or And metal complex dyes. The organic dye residue represented by R ₉ includes a light yellow anthraquinone residue that is not generally called a dye.

M ⁴⁰¹ represents one equivalent of a monovalent to trivalent cation, for example, a hydrogen atom (proton), a metal cation, or a quaternary ammonium cation. When the molecular structure has two or more M, M ⁴⁰¹ may be only one of a proton, a metal cation, and a quaternary ammonium cation, or a combination thereof.

  Examples of the metal include lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt.

  The quaternary ammonium cation is a single compound having a structure represented by the following general formula (17) or a mixture.

General formula (19):

In General Formula (19), R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ are any of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group It is.

R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ may be the same or different. Moreover, when R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ have a carbon atom, the number of carbon atoms is 1 to 40, preferably 1 to 30, and more preferably 1 to 20.

  Specific examples of the quaternary ammonium include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, laurylammonium, and stearylammonium. However, it is not limited to these.

Among the nitrogen-containing pigment derivatives having an acidic functional group exemplified above, it is easy to effectively leave an active site structure even after carbonization due to the fastness of the dye skeleton in addition to the dispersibility of the raw material carbon material. In the general formula (18), the organic dye residue represented by R ⁴⁰¹ is preferably a metal phthalocyanine pigment derivative containing a phthalocyanine dye containing a metal at the center.

  The method for synthesizing one or more derivatives selected from the group consisting of an organic dye derivative having an acidic functional group and a triazine derivative having an acidic functional group in the present invention is not particularly limited. 39-28884, Japanese Examined Patent Publication No. 45-11026, Japanese Examined Patent Publication No. 45-29755, Japanese Examined Patent Publication No. 64-5070, or Japanese Patent Application Laid-Open No. 2004-217842. it can. The disclosure by the above publication is incorporated as part of the present specification.

  Specific examples of various derivatives having an acidic functional group in the present invention are shown in Table 2.

Table 2

<Organic pigment>
Examples of the organic pigment used in the method for producing a carbon catalyst in the present invention include various pigments used in printing inks, inkjet inks, color filter resist inks, and the like. Such pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments. , Anthanthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like, and phthalocyanine pigments correspond to the macrocyclic compounds containing no noble metal element. More specific examples are shown by generic names of color indexes: Pigment Black 1, 31, 32, Pigment Brown 5, 23, 25, 41, Pigment Blue 1, 6, 15, 15: 1, 15: 2, 15 : 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 24, 24: 1, 25, 26, 56, 60, 61, 62, 63, 75, 79, 80, Pigment Green 1 4, 7, 8, 10, 36, Pigment Violet 1, 2, 3, 3: 1, 3: 3, 5: 1, 13, 19, 23, 25, 27, 29, 31, 32, 36, 37 , 38, 42, 50, Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 21, 22, 23, 31 , 32, 38, 41, 48, 49, 52, 53 54, 57: 1, 58, 60: 1, 63, 64: 1, 68, 81: 1, 83, 88, 89, 95, 112, 114, 119, 122, 123, 144, 146, 147, 149, 150,166,168,169,170,171,172,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208, 209, 210, 211, 213, 214, 216, 220, 221, 224, 226, 238, 242, 245, 247, 248, 251, 253, 254, 255, 256, 257, 258, 260, 264, 266 268, 269, 272, 279, Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 31, 34, 36, 37, 38, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 81, Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 24, 49, 55, 60, 61, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 120, 123,124,126,127,128,129,130,133,138,139,150,151,152,153,154,155,167,168,169,170,172,173,175,176, 79,180,181,182,183,185,191,193,194,199,213,214,219, and the like.
However, the organic pigment is not limited to the above examples. Among them, phthalocyanine pigments, perylene pigments, dioxazine pigments, etc., which have a large number of heterocyclic rings containing nitrogen element in one molecule, can easily introduce a metal element or nitrogen element that is a catalyst activity factor into the carbon material surface. More preferred.

<Macrocyclic compound containing no precious metal element>
As the macrocyclic compound containing no noble metal element used in the method for producing a carbon catalyst in the present invention, the central metal is selected from cobalt, iron, nickel, manganese, copper, titanium, vanadium, chromium, zinc, tin, aluminum, and magnesium. And phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, and tetraazaannulene compounds in which an organic ligand is bonded. Further, a macrocyclic compound not containing a noble metal element has no problem even if an electron-withdrawing functional group or an electron-donating functional group is introduced. Among them, cobalt phthalocyanine compounds, nickel phthalocyanine compounds, iron phthalocyanine compounds, and copper phthalocyanine compounds are known to be inexpensive and also have high oxygen reduction activity, so the carbon catalysts synthesized from them are inexpensive. It is more preferable as a raw material because it becomes a carbon catalyst having high oxygen reduction activity.

Incidentally, a macrocyclic compound is defined as a compound having 9 or more atoms (including the case where all are heteroatoms) and 3 or more bonding atoms (Coordination Chemistry of Macrocyclic Compounds, G.A. Melson, Plenum Pres, New York & London, 1979). In the present invention, the macrocyclic compound refers to a compound having an N4 structure in which four nitrogen atoms are arranged in a plane in a basic skeleton, such as a phthalocyanine compound, a naphthalocyanine compound, a porphyrin compound, a tetraazaannulene. For example, a compound based on the above.

<Carbon material>
The carbon material according to the present invention has a role as a carrier for supporting highly dispersed nitrogen sources and metal sources used in the method for producing a carbon catalyst, and suppressing excessive thermal decomposition and desorption of nitrogen elements which are active factors. Fulfill. Therefore, a carbon material having a large carrying area and being thermally stable is preferable. When the BET specific surface area of the carbon material is 10 to 2000 m ² / g, an area for supporting the nitrogen source and the metal source can be secured, and 200 to 1500 m ² / g is more preferable. Further, for the purpose of further stabilizing the nitrogen source or the metal source, a functional group or the like may be introduced on the surface of the carbon material to form a physical / chemical bond between the nitrogen source and the metal source and the carbon material surface.
Examples of the carbon material include carbon black (furnace black, acetylene black, ketjen black, medium thermal carbon black), activated carbon, graphite, carbon nanotube, carbon nanofiber, carbon nanohorn, graphene nanoplatelet, nanoporous carbon, and the like. Carbon materials have various physical properties and costs such as particle diameter, shape, BET specific surface area, pore volume, pore diameter, bulk density, DBP oil absorption, surface acidity, surface hydrophilicity, and conductivity depending on the type and manufacturer. Because it is different, select the most suitable material according to the intended use and required performance.
Examples of commercially available carbon materials include:
Ketjen Black EC-300J, EC-600JD, etc. manufactured by Akzo Ketjen Black:
Tokai Carbon furnace blacks such as Toka Black # 4300, # 4400, # 4500, and # 5500:
Furnace Black made by Degussa such as Printex L:
Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULT
Furnace black manufactured by Colombian, such as RA, Conductex SC ULTRA, 975 ULTRA, PUER BLACK100, 115, and 205:
# 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3230B, # 3350B, # 3400B, and # 5400B furnace black manufactured by Mitsubishi Chemical Corporation:
Furnace blacks from Cabot, such as MONARCH 1400, 1300, 900, Vulcan XC-72R, and Black Pearls 2000:
Furnace black manufactured by TIMCAL, such as Ensaco 250G, Ensaco 260G, Ensaco 350G, and SuperP-Li:
Acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd. such as Denka Black, Denka Black HS-100, FX-35, etc .:
Carbon nanotubes manufactured by Showa Denko KK such as VGCF, VGCF-H, and VGCF-X:
Carbon nanotubes manufactured by Meijo Nano Carbon Co., Ltd .:
xGnP-C-750, xGnP-M-5 and other graphene nanoplatelets manufactured by XGSciences:
Easy-N Nanoporous Carbon:
Examples include, but are not limited to, porous carbons manufactured by Toyo Carbon Co., such as Knobel MH grade, Knobel P (2) 010 grade, Knobel P (3) 010 grade, Knobel P (4) 050 grade, etc. However, carbon black, graphene-based materials, and carbon nanotubes are particularly preferable because they have a high specific surface area and easily serve as a carrier for a nitrogen source, a metal source, and the like, and are excellent in properties such as conductivity.

<Metal source>
The metal source contained in the nitrogen source and the metal source used in the method for producing a carbon catalyst in the present invention has a “metal N-4 structure” which is itself coordinated with the nitrogen source and reported as one of the active sites. It plays the role of forming, assisting the formation of active sites, and developing the pore structure of the carbon catalyst. For this reason, when the nitrogen-containing pigment derivative serving as the nitrogen source does not contain a metal element, it is preferable to add the metal source separately. The metal source is not particularly limited as long as it is a material containing a base metal element and does not depart from the spirit of the present invention. Examples thereof include organic compounds such as pigments and polymers, and inorganic compounds such as simple metals, metal oxides, and metal salts. Base metal elements are metal elements excluding noble metal elements (ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold) among transition metal elements. Base metal elements include cobalt, iron, nickel, manganese, and copper. It is preferable to contain at least one selected from titanium, vanadium, chromium, zinc, tin, aluminum, zirconium, niobium, tantalum, and magnesium, and cobalt, iron, nickel, and copper are more preferable.

<Resin component>
Resin components used in the carbon catalyst production method of the present invention include acrylic resin, polyurethane resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, formaldehyde resin, silicone resin, fluorine Examples thereof include resin, cellulose resin such as carboxymethyl cellulose, synthetic rubber such as styrene-butadiene rubber and fluorine rubber, and conductive resin such as polyaniline and polyacetylene. Moreover, the modified body of these resin, a mixture, or a copolymer may be sufficient.

  Specifically, ethylene, propylene, vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylonitrile, styrene, vinyl butyral, vinyl acetal, vinyl pyrrolidone, etc. Examples thereof include a copolymer contained as a structural unit.

<Natural materials>
Examples of natural materials used in the method for producing a carbon catalyst in the present invention include natural materials selected from the group consisting of unmodified or modified polysaccharides, natural waxes, natural resins, and vegetable oils.

<Carbon catalyst>
The carbon catalyst in the present invention is preferably as the specific surface area is large and the electron conductivity is high. Since the reduction reaction of oxygen occurs on the surface of the carbon catalyst, the larger the specific surface area, the more the reaction field between oxygen and protons, which leads to improvement in catalyst activity, which is preferable. Also, the higher the electron conductivity, the more the electrons necessary for the oxygen reduction reaction in the electrode can be supplied to the reaction field. Further, it is preferable that the amount of nitrogen on the catalyst surface is large because the number of active sites on the surface tends to increase, and it is more preferable that the nitrogen is terminal nitrogen mainly composed of pyridine type nitrogen.

  The carbon catalyst in the present invention preferably has an element ratio of metal to nitrogen contained in the range of 0.05 to 5.

  When the elemental ratio of the metal to nitrogen is in the above range, the active point acts by effectively acting as a carbonization catalyst for promoting crystallization of carbon, development of pores, generation of edges, etc. in the active site formation stage. Can be expected to improve the number and quality of Furthermore, even in the oxygen reduction catalytic reaction stage, metal species act as a reduction catalyst for hydrogen peroxide generated mainly at the active sites derived from nitrogen, effectively promoting reduction to water (four-electron reduction). It is preferable because it can be expected.

  Furthermore, since the function with respect to the above-mentioned catalytic action is strong, as a metal to contain, cobalt and / or iron are preferable.

<Method for producing carbon catalyst>
The method for producing a carbon catalyst in the present invention includes a carbon material, one or more metal elements selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group. A precursor mixed with a nitrogen-containing pigment derivative; and
A carbon material, one or more nitrogen-containing pigment derivatives selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group, and a metal source, and a metal source Examples include a method including a step of producing a precursor and a step of heat-treating the precursor.

  The method for producing the precursor includes a carbon material, one or more nitrogen-containing pigment derivatives selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group, and a metal source May be used independently, but two or more of them may be used. When the nitrogen-containing pigment derivative contains a base metal element, it may not be necessary to add a metal source separately. In addition to the above materials, organic pigments, macrocyclic compounds containing no noble metal elements, resin components, or natural materials may be used in combination. When two or more kinds of components are mixed or combined, it is carried out by wet processing in a solvent, and the following wet processing machine can be used as a mixing apparatus.

As a wet processing machine, for example,
Mixers such as dispersers, homomixers, or planetary mixers:
Homogenizers such as “Clairemix” manufactured by M Technique or “Fillmix” manufactured by PRIMIX:
Paint shaker (manufactured by Red Devil, Mitsuwa Tech “Scandex”, etc.), ball mill, sand mill (Shinmaru Enterprises “Dynomill”, etc.), attritor, pearl mill (Eirrich “DCP mill”, etc.), Or media-type dispersers such as coball mills:
Wet jet mill (“Genus PY” manufactured by Genus, “Starburst” manufactured by Sugino Machine, “Nanomizer” manufactured by Nanomizer, etc.) “Claire SS-5” manufactured by M Technique, or “Micro” manufactured by Nara Machinery Co., Ltd. Medialess dispersers such as
Other examples include, but are not limited to, roll mills and kneaders. Moreover, it is preferable to use what performed the metal mixing prevention process from an apparatus as a wet processing machine.

  For example, when using a media-type disperser, a disperser in which the agitator and vessel are made of a ceramic or resin disperser, or the surface of the metal agitator and vessel is treated with tungsten carbide spraying or resin coating. Is preferably used. And as a medium, it is preferable to use ceramic beads, such as glass beads, zirconia beads, or alumina beads. Moreover, also when using a roll mill, it is preferable to use a ceramic roll. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.

Moreover, in order to improve the wettability and dispersibility of each raw material to a solvent, a general dispersant can be added together and dispersed and mixed.
The dispersant is not particularly limited, such as a pigment derivative, a surfactant, or a dispersion resin, but the dispersion resin not only improves the dispersibility of each raw material, but also the effective selection of the material, the surface of the carbon catalyst after calcination Since the role which controls a structure can also be fulfilled, it is preferable.

  Further, in the case of wet mixing, a step of drying the dispersion produced using a wet processing machine is required. In this case, examples of the drying device to be used include a shelf dryer, a rotary dryer, a flash dryer, a spray dryer, a stirring dryer, and a freeze dryer.

  In the production method of the present invention, at least one nitrogen-containing pigment selected from the group consisting of a carbon material that is a raw material for the carbon catalyst, a nitrogen-containing pigment derivative having a basic functional group, and a nitrogen-containing pigment derivative having an acidic functional group Excellent catalytic activity for derivatives, metal sources, other organic pigments, macrocycles that do not contain precious metal elements, resin components, natural materials, etc. A carbon catalyst can be obtained.

  Furthermore, as a precursor, one or more nitrogen-containing pigment derivatives selected from the group consisting of a carbon material, a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group, and a metal source, When the resin component is used in combination, the monomer can be polymerized in an organic compound dispersion or solution, and the resin component and the carbon material or organic compound can be taken out and used.

Next, the mixture containing the carbon material, the nitrogen source, and the metal source differs depending on the type and ratio of the raw materials used, but in order to serve as a support, the mass ratio of the carbon material is It is preferable that it is 0.1-0.5. Moreover, as for mass ratio of a metal source, 0.01-1.0 are preferable with respect to a nitrogen source.

Next, in the step of heat-treating the precursor obtained as described above, the heating temperature varies depending on the type and mixing ratio of the raw material to be treated, but is 500 to 1200 ° C, preferably 700 to 1100 ° C. It is preferable that
The heating time is not particularly limited, but it is usually preferably 1 to 5 hours.

  In this case, heat treatment at a certain high temperature often stabilizes the structure of the active sites, resulting in a catalyst surface that can withstand practical battery operating conditions. The temperature at this time is preferably 600 ° C. or higher.

  Furthermore, regarding the atmosphere in the heat treatment process, it is necessary to carbonize the raw material by incomplete combustion as much as possible, and to leave the nitrogen element or metal element on the surface of the carbon material. Therefore, an inert gas atmosphere such as nitrogen or argon, nitrogen A reducing gas atmosphere in which hydrogen is mixed with argon is preferable. In addition, in order to suppress reduction of the amount of nitrogen element in the carbon catalyst during heat treatment, heat treatment is performed in an ammonia gas atmosphere containing a large amount of nitrogen element, and in order to control the surface structure of the carbon catalyst, water vapor, carbon dioxide Alternatively, heat treatment may be performed in a low oxygen atmosphere. In this case, depending on the atmosphere, as the oxidation proceeds, the metal becomes an oxide and the particle components tend to aggregate, so it is necessary to select the temperature and time appropriately.

  In addition, regarding the heat treatment process, not only a method of performing the treatment in a single stage under a constant atmosphere and temperature, but also heat treatment at a relatively low temperature of about 500 ° C. once in an inert gas atmosphere, and then an inert gas It is also possible to perform heat treatment at a temperature exceeding the first stage in an atmosphere, a reducing gas atmosphere, or an activation gas atmosphere. By doing so, the active site part which consists of a nitrogen element and a metal element considered as a catalyst active site may be left more efficiently and in large quantities.

  Furthermore, in the method for producing a carbon catalyst in the present invention, there is a method including a step of washing the heat-treated product with an acid and drying to obtain an acid-washed product. As for the acid used here, any acid can be used as long as it can elute at least the metal present on the surface of the heat-treated product. Dilute sulfuric acid is preferred. As a specific cleaning method, an acid is added to a glass container, a heat-treated product is added, the mixture is stirred for several hours while being dispersed, and then allowed to stand to remove the supernatant. And the said method is repeatedly performed until coloring of a supernatant liquid is no longer confirmed, Finally, the method of removing an acid by filtration and washing with water, and drying is mentioned. These acid treatments may be performed any number of times in the firing step, and can be suitably selected for the raw material, temperature, time, gas atmosphere, and the like.

<Catalyst ink>
Next, the catalyst ink using the carbon catalyst in the present invention will be described.
The catalyst ink of the present invention contains a carbon catalyst, a binder, and a solvent. The binder component is preferably a material having proton conductivity and resistance to oxidation. The proportions of the carbon catalyst, binder and solvent are not particularly limited, and are appropriately selected within a wide range.

Furthermore, in the catalyst ink in the present invention, a dispersant may be used in order to improve the wettability and dispersibility of the carbon catalyst in the solvent.
Content of a dispersing agent is 0.01-5 mass% with respect to the carbon catalyst in catalyst ink, Preferably it is 0.02-3 mass%. By setting the content in this range, the dispersion stability of the carbon catalyst can be sufficiently achieved, and at the same time, aggregation of the carbon catalyst can be effectively prevented, and precipitation of the dispersant on the surface of the catalyst layer can be prevented.

In the catalyst ink of the present invention, a conductive carbon material may be added in order to increase the conductive path in the catalyst layer and reduce the contact resistance at the catalyst layer interface.
Content of electroconductive carbon material is 1-300 mass% with respect to the carbon catalyst in catalyst ink, Preferably it is 50-150 mass%.

  The method for preparing the catalyst ink is not particularly limited. In the preparation, each component may be dispersed at the same time, or a carbon catalyst may be dispersed only with a dispersant and then a binder may be added, and can be optimized depending on the carbon catalyst, binder and solvent type to be used.

  The apparatus for dispersing and mixing the carbon catalyst and the binder in the solvent is not particularly limited.

<Binder>
The binder in the present invention is used for binding particles such as a carbon catalyst, and the effect of dispersing these particles in a solvent is small.
As the binder, conventionally known binders can be used. For example, acrylic resin, polyurethane resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, formaldehyde resin, silicon resin, Fluorine resin, cellulose resin such as carboxymethyl cellulose, synthetic rubber such as styrene-butadiene rubber and fluorine rubber, conductive resin such as polyaniline and polyacetylene, etc., containing fluorine atoms such as polyvinylidene fluoride, polyvinyl fluoride, and tetrafluoroethylene A high molecular compound is mentioned. Further, a modified product, a mixture, or a copolymer of these resins may be used, which may be a water-soluble resin or a water-dispersed resin. These binders can be used alone or in combination.
As a binder for an ordinary fuel cell catalyst layer, a polymer having proton conductivity is more preferable from the viewpoint of conducting protons in the membrane, but this is not the case when a liquid electrolyte is used in a microbial fuel cell. .
In addition, a water-repellent material may be more preferable from the viewpoint of water generated by reaction of oxygen and hydrogen ions in the catalyst layer on the positive electrode side, and drainage of this excess water.

<Proton conducting polymer>
The proton conductive polymer is preferably a binder having a hydrophilic functional group, and preferably exhibits a proton conductivity of 100% RH and 10 ⁻³ Scm ⁻¹ or more at 25 ° C.
Here, examples of the hydrophilic functional group include acidic functional groups such as a sulfo group, a carboxy group, and a phosphoric acid group, and basic functional groups such as a hydroxyl group and an amino group. From the viewpoint of proton dissociation, a sulfo group, A carboxy group, a phosphate group, and a hydroxyl group are more preferable.
Polymers exhibiting proton conductivity include sulfo group-introduced olefin resins (polystyrene sulfonic acid, polyvinyl sulfonic acid, etc.), polyimide resins, phenol resins, polyether ketone resins, polybenzimidazole resins, and polystyrene. -Based resins, sulfonic acid doped products of styrene / ethylene / butylene / styrene copolymers, resins having sulfonic acids such as perfluorosulfonic acid resins:
Resin having carboxylic acid such as polyacrylic acid and carboxymethylcellulose:
Resin having a hydroxyl group such as polyvinyl alcohol:
Resins having an amino group, such as polyallylamine, polydiallylamine, polydiallyldimethylammonium salt, and polybenzimidazole-based resin salted with an acid at the imidazole moiety:
Examples thereof include resins having other hydrophilic functional groups such as polyacrylamide, polyvinyl pyrrolidone, and polyvinyl imidazole. In particular, a perfluorosulfonic acid resin is chemically very stable by introducing a fluorine atom having a high electronegativity, has a high degree of dissociation of a sulfo group, and can realize high proton conductivity. Specific examples of such proton conductive polymers include “Nafion” (registered trademark) manufactured by DuPont. Usually, the proton conductive polymer is used as an alcohol aqueous solution containing about 5 to 30% by mass of the polymer. As the alcohol, for example, methanol, propanol, ethanol diethyl ether and the like are used.

<Water repellent material>
As the water repellent material, it refers to a binder having no hydrophilic functional group, and preferably has a surface tension lower than the surface tension of water (about 72 dyn / cm). For example, fluorine resins, olefin resins such as polypropylene and polyethylene, and silicon resins such as polydimethylsiloxane can be used. Of these, fluorine resins are preferable. Examples of the fluororesin include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).

<Solvent>
The solvent is not particularly limited. As the main solvent, water or a solvent having high affinity with water is preferable, and alcohol can be particularly preferably used. As such an alcohol, for example, a monohydric alcohol or a polyhydric alcohol having a boiling point of about 80 to 200 ° C. can be used, and an alcohol solvent having 4 or less carbon atoms is preferable. Specific examples include 1-propanol, 2-propanol, 1-butanol, 2-butanol, and t-butanol. Alcohol is used individually by 1 type or in mixture of 2 or more types. Among these monohydric alcohols, 2-propanol, 1-butanol and t-butanol are preferable. Specifically, the polyhydric alcohol is preferably, for example, propylene glycol, ethylene glycol or the like, particularly propylene glycol, from the viewpoint of compatibility with proton conductive resin and drying efficiency when used as a catalyst ink. preferable.

<Conductive carbon material>
The conductive carbon material is not particularly limited as long as it is a conductive carbon material, but carbon black, graphite, conductive carbon fiber (carbon nanotube, carbon nanofiber, carbon fiber, carbon nanohorn), graphene , Graphene nanoplatelets, fullerenes and the like can be used alone or in combination of two or more. From the viewpoint of conductivity, availability, and cost, it is preferable to use carbon black.

  Carbon black is a furnace black produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially ketjen black using ethylene heavy oil as a raw material. Channel black that has been rapidly cooled and precipitated, thermal black obtained by periodically repeating combustion and thermal decomposition using gas as a raw material, and particularly various types such as acetylene black using acetylene gas as a raw material, or 2 More than one type can be used in combination. Ordinarily oxidized carbon black, hollow carbon and the like can also be used.

  Examples of commercially available carbon black include Toka Black # 4300, # 4400, # 4500, # 5500 (Tokai Carbon Co., Furnace Black), Printex L and the like (Degussa Co., Furnace Black), Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULTRA, etc., Conductex SC ULTRA, Conductex 975 ULTRA, etc., PUER BLACK100, 115, 205, etc. (manufactured by Colombian, furnace black), # 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3030B, # 3030B # 3350B, # 3400B, # 5400B etc. (Mitsubishi Chemical Co., Furnace Black), MONARCH1400, 1300, 900, VulcanXC- 2R, BlackPearls2000, etc. (Cabot, Furnace Black), Ensaco 250G, Ensaco 260G, Ensaco 350G, SuperP-Li (manufactured by TIMCAL), Ketjen Black EC-300J, EC-600JD (manufactured by Akzo), Denka Black, Denka Black HS Examples of graphite such as -100, FX-35 (manufactured by Denki Kagaku Kogyo Co., Ltd., acetylene black) include natural graphite such as artificial graphite, flake graphite, massive graphite, and earth graphite, but are not limited thereto. They may be used in combination of two or more.

As the specific surface area of the carbon black to be used increases, the contact point between the carbon black particles increases, which is advantageous in reducing the resistance in the catalyst layer. Specifically, the specific surface area (BET) determined from the amount of nitrogen adsorbed is preferably 20 m ² / g or more and 1500 m ² / g or less.

  Further, the particle size of the carbon black to be used is preferably 0.005 to 1 μm, particularly preferably 0.01 to 0.2 μm in terms of primary particle size. However, the primary particle diameter here is an average of the particle diameters measured with an electron microscope.

  As the conductive carbon fibers, those obtained by firing from petroleum-derived raw materials are preferable, but those obtained by firing from plant-derived raw materials can also be used. For example, VGCF manufactured by Showa Denko Co., Ltd. manufactured with petroleum-derived raw materials can be mentioned.

<Fuel cell>
Fuel cells can be classified into several types according to the electrolyte used, and the carbon catalyst of the present invention can be applied to various fuel cells. In the following, two types of fuel cells are given as examples.

<Solid polymer fuel cell>
FIG. 1 shows a schematic configuration diagram of a polymer electrolyte fuel cell. In the polymer electrolyte fuel cell, a separator 1, a gas diffusion layer 2, an anode electrode catalyst (fuel electrode) 3, a cathode electrode catalyst (air electrode) 5, and gas diffusion are arranged so as to sandwich the polymer electrolyte 4. It is composed of a layer 6 and a separator 7.
As the solid polymer electrolyte 4, a fluorine-based cation exchange resin membrane represented by a perfluorosulfonic acid resin membrane is used.

  Further, the carbon catalyst produced by the production method of the present invention is brought into contact with both the solid polymer electrolyte 4 as the anode electrode catalyst 3 and the cathode electrode catalyst 5, whereby the anode catalyst 3 and the cathode electrode catalyst 5 are brought into contact with the carbon catalyst. Is provided.

  By forming the above-described carbon catalyst on both sides of the solid polymer electrolyte, and adhering the anode electrode catalyst 3 and the cathode electrode catalyst 5 to both main surfaces of the solid polymer electrolyte 4 on the electrode reaction layer side by hot pressing, It integrates as MEA (Membrane Electrode Assembly).

  Recently, since the carbon catalyst has a high specific surface area, a function of a gas diffusion layer is imparted to the carbon catalyst, and a simple and inexpensive fuel cell configuration without a gas diffusion layer has been proposed. The carbon catalyst of the present invention can be sufficiently used as a gas diffusion layer.

  The separators 1 and 7 supply and discharge reaction gases such as fuel gas (hydrogen) and oxidant gas (oxygen). Then, when the reaction gas is uniformly supplied to the anode and cathode electrode catalysts 3 and 5 through the gas diffusion layers 2 and 6, the gas at the boundary between the carbon catalyst provided in both electrodes and the solid polymer electrolyte 4 is obtained. A three-phase interface is formed: a phase (reactive gas), a liquid phase (solid polymer electrolyte membrane), and a solid phase (catalyst possessed by both electrodes). A direct current is generated by causing an electrochemical reaction.

In the above electrochemical reaction,
Cathode side: O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O
Anode side: H ₂ → 2H ⁺ + 2e ⁻
Thus, H ⁺ ions generated on the anode side move in the solid polymer electrolyte 4 toward the cathode side, and e ⁻ (electrons) move to the cathode side through an external load.

On the other hand, on the cathode side, oxidant gas (oxygen) reacts with H ⁺ ions and e ⁻ that have migrated from the anode side to produce water. As a result, the above-described fuel cell generates direct-current power from hydrogen and oxygen to generate water.

<Microbial fuel cell>
A microbial fuel cell is a battery that promotes the decomposition of organic matter while collecting electrons generated from metabolic activities in which microorganisms anaerobically decompose organic matter. Electron-donating microorganisms are held in the negative electrode, and metabolize using organic substances contained in organic wastewater to generate e ⁻ (electrons) and H ⁺ ions (protons). On the positive electrode side, power can be generated by an oxygen reduction reaction using generated e ⁻ (electrons) and H ⁺ ions (protons).
The structure of the microbial fuel cell is that a conductive support serving as a negative electrode holding electron-donating microorganisms and a conductive support serving as a positive electrode coated with a fuel cell catalyst material are inserted into a liquid tank containing organic waste water or the like. Alternatively, a single tank type configuration or a two tank type configuration in which a negative electrode tank and a positive electrode tank are separated by using a solid polymer membrane as in a solid polymer fuel cell may be used.
As a positive electrode, the catalyst electrode for microbial fuel cells which apply | coated the catalyst ink for microbial fuel cells in this invention to the electroconductive support body, and the electrode membrane assembly for fuel cells can also be used conveniently.

<Electron donating microorganisms for microbial fuel cells>
As the electron-donating microorganism for the microbial fuel cell, Shewanella genus, Pseudomonas genus, Rhodoferax genus, Geobacter genus and the like can be used.

<Nutrient substrate>
Nutrient substrates (organic substances) that can be used as fuel for power generation are not particularly limited as long as the electron-donating microorganisms that can be used as a catalyst can be decomposed. Alcohols such as methanol and ethanol, acetic acid, etc. contained in organic wastewater and sludge Carboxylic acids, monosaccharides such as glucose, polysaccharides such as starch and cellulose, and the like can be suitably used.

<Electrolyte solution>
The electrolyte solution is not limited as long as it has no electron conductivity and can transport protons. In particular, a neutral buffer solution such as a phosphate buffer solution can be suitably used.

  The use of the carbon catalyst produced by the production method of the present invention is not limited to the above-mentioned fuel cell electrode catalyst, but a metal-air battery electrode catalyst, exhaust gas purification catalyst, water treatment purification catalyst, organic It can be used as a catalyst for synthesis.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to an Example. In the examples, parts represent parts by mass, and% represents mass%.

The following measuring equipment was used for the physical property analysis of the used material.
-Measurement of BET specific surface area: Measurement of nitrogen adsorption amount (BELSORP-mini manufactured by Nippon Bell Co., Ltd.)
・ Measurement of element ratio of metal element to nitrogen (Fe, Co, Ni / N molar ratio)
-Measurement of metal content: ICP emission spectroscopic analyzer (Spectro AROCOS manufactured by Spectro)
-Measurement of nitrogen content: Fully automatic elemental analyzer (Perkin Elmer 2400II)

The properties of the carbon material, metal phthalocyanine pigment derivative, resin-type dispersant, and metal phthalocyanine used are shown below.
Graphene nanoplatelet xGnP-C-750 (manufactured by XGscience: specific surface area 670 m ² / g) (GNP)
・ Ketjen Black EC-600JD (manufactured by Lion Corporation: specific surface area 1200 m ² / g) (KB)
Carbon nanotube VGCF-H (manufactured by Showa Denko KK: specific surface area 13 m ² / g) (CNT)
・ Nitrogen-containing pigment derivatives having basic functional groups (F, G)
-Nitrogen-containing pigment derivatives having acidic functional groups (Db, Df, Dh, Dj, Dt, Dw)
: Iron phthalocyanine derivative FePc- (SO ₃ NH ₄ ) ₄ (manufactured by Nippon Steel & Mining Co., Ltd .: 10% solid content aqueous solution) (Du)
: Copper phthalocyanine derivative SOLPERSE 12000 (manufactured by Nippon Lubrizol Co., Ltd.) (Dv)
Iron (II) chloride tetrahydrate (Kishida Chemical Co., Ltd.) (FeCl ₂ )
Nickel (II) chloride hexahydrate (manufactured by Kishida Chemical) (NiCl ₂ )
Iron (III) acetylacetonate (manufactured by Kanto Chemical Co.) (Fe (acac) ₃ )
Resin-type dispersant Jonkrill JDX-6500 (manufactured by BASF Japan Ltd .: 30% solid content aqueous solution) (JDX-6500)
・ Resin type dispersant PVP K-90 (manufactured by ISP Japan) (PVP)
・ Iron phthalocyanine P-26 (manufactured by Sanyo Dye) (FePc)

The conductive carbon material used for the oxygen reduction activity evaluation is shown below.
HS-100 (manufactured by Denki Kagaku Kogyo Co., Ltd .: specific surface area 39 m ² / g)
[Preparation Example 1: Nitrogen-containing pigment derivative having basic functional group ((basic pigment derivative (I))]
In 300 parts of methanol, 20 parts of p-aminoacetanilide and 25 parts of cyanuric chloride were charged and reacted at 20 ° C. or lower for 2 hours, and then 46 parts of N, N-dibutylaminoethylamine was added and heated to reflux for 2 hours. Next, 100 parts of hydrochloric acid was added for hydrolysis, methanol was distilled off, 40 parts of sodium hydroxide and 1000 parts of water were added, filtration, washing with water and drying were performed to obtain a basic pigment derivative (I).

[Example 1: Carbon catalyst (1)]
A glass bottle is weighed with 60 parts of ion-exchanged water and 33.7 parts of iron phthalocyanine derivative (Du) (10% solid content aqueous solution) to prepare a uniform aqueous solution. Then, 6.7 parts of graphene nanoplatelet is added and further used as a medium. After adding zirconia beads, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (1).

[Example 2: Carbon catalyst (2)]
In a glass bottle, 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate and 3.2 parts of copper phthalocyanine derivative (Dv) were weighed to prepare a uniform aqueous solution, and then graphene nanoplatelet 6.6. After adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (2).

[Example 3: Carbon catalyst (3)]
In a glass bottle, 86.4 parts of ion-exchanged water, 0.17 part of iron (II) chloride tetrahydrate, 2.7 parts of copper phthalocyanine derivative (Dv), resin type dispersant Joncryl (solid content: 30% aqueous solution) After weighing 5.4 parts to prepare a uniform aqueous solution, 5.5 parts of graphene nanoplatelets are added, and zirconia beads are further added as a medium, and then dispersed with a paint shaker (manufactured by Mitsuwa Tech: Scandex SK450). A precursor mixed paste was obtained. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (3).

[Example 4: Carbon catalyst (4)]
In a glass bottle, weigh 90 parts of methanol, 0.2 part of iron (II) chloride tetrahydrate, and 3.2 parts of a nitrogen-containing pigment derivative (basic pigment derivative (I)) having a basic functional group. After preparing the solution, 6.6 parts of graphene nanoplatelets were added, and zirconia beads were further added as media, and then dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure using a rotary evaporator, and the obtained solid content was finely pulverized in a mortar to obtain a uniform precursor powder.The obtained precursor powder was filled in an alumina crucible. Then, carbonization treatment was performed at 800 ° C. for 2 hours in a nitrogen atmosphere in an electric furnace to obtain a carbon catalyst (4).

[Example 5: Carbon catalyst (5)]
In a glass bottle, 86.4 parts of ion-exchanged water, 0.17 part of iron (II) chloride tetrahydrate, 2.7 parts of a nitrogen-containing pigment derivative having a basic functional group ((basic pigment derivative (I)), After weighing 1.6 parts of the resin-type dispersant PVP to prepare a uniform aqueous solution, 5.5 parts of graphene nanoplatelets are added, zirconia beads are further added as a medium, and then a paint shaker (manufactured by Mitsuwa Tech: Scandex SK450) is added. The precursor mixed paste was distilled off under reduced pressure using a rotary evaporator, and the resulting solid content was finely pulverized in a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled into an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (5).

[Example 6: Carbon catalyst (6)]
In a glass bottle, 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate and 3.2 parts of copper phthalocyanine derivative (Dv) were weighed to prepare a uniform aqueous solution, and then graphene nanoplatelet 6.6. After adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 1000 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (6).

[Example 7: Carbon catalyst (7)]
A glass bottle is weighed with 60 parts of ion-exchanged water and 33.7 parts of an iron phthalocyanine derivative (Du) (10% solid content aqueous solution) to prepare a uniform aqueous solution. Then, 6.7 parts of Ketjen Black is added, and zirconia is used as a medium. After adding the beads, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled into an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (7).

[Example 8: Carbon catalyst (8)]
Weigh 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate and 3.2 parts of copper phthalocyanine derivative (Dv) in a glass bottle to prepare a uniform aqueous solution, and then 6.6 parts of Ketjen Black After adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (8).

[Example 9: Carbon catalyst (9)]
Weigh 60 parts of ion-exchanged water and 33.7 parts of iron phthalocyanine derivative (Du) (10% solids aqueous solution) into a glass bottle to prepare a uniform aqueous solution, add 6.7 parts of carbon nanotubes, and add zirconia beads as media. After being added, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (9).

[Example 10: Carbon catalyst (10)]
In a glass bottle, weigh 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate and 3.2 parts of copper phthalocyanine derivative (Dv) to prepare a uniform aqueous solution, and then add 6.6 parts of carbon nanotubes. In addition, zirconia beads were further added as a medium, and then dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (10).

[Example 11: Carbon catalyst (14)]
A glass bottle is weighed with 90 parts of ion-exchanged water and 3.3 parts of a nitrogen-containing pigment derivative (Dt) having an acidic functional group to prepare a uniform aqueous solution. Then, 6.7 parts of graphene nanoplatelets are added, and zirconia is used as a medium. After adding the beads, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (14).

[Example 12: Carbon catalyst (15)]
In a glass bottle, 90 parts of ion-exchanged water, 0.2 part of nickel chloride (II) hexahydrate and 3.2 parts of copper phthalocyanine derivative (Dv) were weighed to prepare a uniform aqueous solution, and then graphene nanoplatelet 6.6. After adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (15).

[Example 13: Carbon catalyst (16)]
Weigh 90 parts of ion-exchanged water, 0.2 part of iron (III) acetylacetonate and 3.2 parts of copper phthalocyanine derivative (Dv) in a glass bottle to prepare a uniform aqueous solution, and then add 6.6 parts of graphene nanoplatelets. In addition, zirconia beads were further added as a medium, and then dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (16).

[Example 14: Carbon catalyst (17)]
After weighing 90.17 parts of ion-exchanged water, 0.03 part of iron (II) chloride tetrahydrate, and 3.2 parts of copper phthalocyanine derivative (Dv) in a glass bottle to prepare a uniform aqueous solution, graphene nanoplatelet 6 After adding 6 parts and further adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (17).

[Example 15: Carbon catalyst (18)]
After weighing 87.6 parts of ion-exchanged water, 2.6 parts of iron (II) chloride tetrahydrate, and 3.2 parts of copper phthalocyanine derivative (Dv) in a glass bottle to prepare a uniform aqueous solution, graphene nanoplatelet 6 After adding 6 parts and further adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (18).

[Example 16: Carbon catalyst (19)]
In a glass bottle, 79.64 parts of ion-exchanged water, 10.56 parts of iron (II) chloride tetrahydrate and 3.2 parts of copper phthalocyanine derivative (Dv) were weighed to prepare a uniform aqueous solution, and then graphene nanoplatelet 6 After adding 6 parts and further adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (19).

[Example 17: Carbon catalyst (20)]
In a glass bottle, 58.52 parts of ion exchange water, 31.68 parts of iron (II) chloride tetrahydrate and 3.2 parts of copper phthalocyanine derivative (Dv) were weighed to prepare a uniform aqueous solution, and then graphene nanoplatelet 6 After adding 6 parts and further adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (20).

[Example 18: Carbon catalyst (21)]
After weighing 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate, and 3.2 parts of a nitrogen-containing pigment derivative (F) having a basic functional group into a glass bottle, a uniform aqueous solution was prepared. After adding 6.6 parts of graphene nanoplatelets and further adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled into an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (21).

[Example 19: Carbon catalyst (22)]
After weighing 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate, and 3.2 parts of a nitrogen-containing pigment derivative (G) having a basic functional group into a glass bottle to prepare a uniform aqueous solution, After adding 6.6 parts of graphene nanoplatelets and further adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (22).

[Example 20: Carbon catalyst (23)]
After weighing 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate, and 3.2 parts of nitrogen-containing pigment derivative (Db) having an acidic functional group into a glass bottle to prepare a uniform aqueous solution, graphene nano After adding 6.6 parts of platelets and further adding zirconia beads as media, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (23).

[Example 20: Carbon catalyst (24)]
After weighing 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate, and 3.2 parts of a nitrogen-containing pigment derivative (Dh) having an acidic functional group into a glass bottle to prepare a uniform aqueous solution, graphene nano After adding 6.6 parts of platelets and further adding zirconia beads as media, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (24).

[Example 22: Carbon catalyst (25)]
After weighing 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate, and 3.2 parts of nitrogen-containing pigment derivative (Dw) having an acidic functional group into a glass bottle to prepare a uniform aqueous solution, graphene nano After adding 6.6 parts of platelets and further adding zirconia beads as media, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (25).

[Example 23: Carbon catalyst (26)]
After weighing 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate, and 3.2 parts of a nitrogen-containing pigment derivative (Df) having an acidic functional group into a glass bottle to prepare a uniform aqueous solution, graphene nano After adding 6.6 parts of platelets and further adding zirconia beads as media, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled into an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (26).

[Example 24: Carbon catalyst (27)]
After weighing 90 parts of ion-exchanged water, 0.2 part of iron (II) chloride tetrahydrate, and 3.2 parts of a nitrogen-containing pigment derivative (Dj) having an acidic functional group into a glass bottle to prepare a uniform aqueous solution, After adding 6.6 parts of platelets and further adding zirconia beads as media, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste. This precursor mixed paste was distilled off under reduced pressure with a rotary evaporator, and the obtained solid content was finely pulverized with a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (27).

[Comparative Example 1: Carbon catalyst (11)]
The iron phthalocyanine derivative (Du) (10% solid content aqueous solution) was distilled off under reduced pressure using a rotary evaporator, and the obtained solid content was finely pulverized in a mortar to obtain a uniform precursor powder. The obtained precursor powder was filled in an alumina crucible, and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (11).

[Comparative Example 2: Carbon catalyst (12)]
In a glass bottle, 90 parts of methanol and 3.3 parts of a nitrogen-containing pigment derivative having a basic functional group ((basic pigment derivative (I)) were weighed to prepare a uniform aqueous solution, and then 6.7 parts of graphene nanoplatelets were added. In addition, after adding zirconia beads as a medium, the mixture was dispersed with a paint shaker (manufactured by Mitsuwa Tech Co., Ltd .: Scandex SK450) to obtain a precursor mixed paste, which was distilled off under reduced pressure using a rotary evaporator. The obtained solid content was finely pulverized in a mortar to obtain a uniform precursor powder, which was filled in an alumina crucible, and heated in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere. Carbonization was performed to obtain a carbon catalyst (12).

[Comparative Example 3: Carbon catalyst (13)]
Iron phthalocyanine and ketjen black were weighed at a mass ratio of 1: 1 and dry-mixed in a mortar to obtain a precursor powder. The obtained precursor powder was filled in an alumina crucible and carbonized in an electric furnace at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a carbon catalyst (13).

Table 4 shows the raw material types used for the precursors and the metal / N ratio of the carbon catalyst obtained from each precursor.

<Evaluation of oxygen reduction activity of carbon catalyst>
Oxygen reduction activity evaluation was performed using the electrodes in which the carbon catalysts (1) to (27) obtained in Examples 1 to 24 and Comparative Examples 1 to 3 were dispersed on glassy carbon, respectively. The evaluation method is as follows.

<Evaluation in acid electrolyte>
(1) Inking method 0.01 part of carbon catalyst and 0.01 part of conductive carbon material are weighed, Nafion (manufactured by DuPont) as a binder, and a mixed solution 0 consisting of water, 1-propanol and ethanol as a solvent. After adding to 98 parts (water / 1-propanol / ethanol / Nafion = 45% / 48% / 2% / 5%), the mixture was subjected to dispersion treatment with ultrasonic waves (45 kHz) for 60 minutes to obtain a carbon catalyst ink.

(2) Working electrode preparation method After the surface of the rotating electrode (glassy carbon electrode radius 0.2 cm) is polished to a mirror surface, 1.5 μL of the carbon catalyst ink is dropped onto the electrode surface and dried at 25 ° C. under saturated water vapor pressure for 15 hours. To produce a working electrode.

(3) LSV (Linear Sweep Voltammetry) Measurement Electrolytic solution (0.1 M perchloric acid aqueous solution) in an electrolytic cell to which the working electrode prepared above, a counter electrode (platinum), and a reference electrode (reversible hydrogen electrode RHE) were attached. ) And an oxygen reduction activity test was conducted.

  The oxygen reduction starting potential as an index of the degree of oxygen reduction activity was measured by LSV measurement at 25 ° C. after bubbling with oxygen in the electrolytic solution and then rotating the working electrode at 2000 rpm in an oxygen atmosphere. By the way, after performing bubbling with argon in the electrolyte, the numerical value obtained by performing LSV measurement in an argon atmosphere was used as the background.

The oxygen reduction starting potential was read as the potential when the current density reached −50 μA / cm ² . The oxygen reduction start potential indicates that the higher the potential, the higher the oxygen reduction activity. The evaluation results are shown in Table 4.

As a standard sample, the oxygen reduction activity level of platinum-supported carbon (platinum support ratio 30% by mass) was measured by the above-described evaluation method. As a result, the oxygen reduction start potential was 0.90 V (vs RHE).
<Evaluation in alkaline electrolyte>
(1) Inking method 0.01 part of catalyst and 0.01 part of conductive carbon material are weighed, and a mixed solution composed of water, propanol and ethanol as a solvent (water / 1-propanol / ethanol = 50% / 48). % / 2%) was added to 0.98 parts, and then subjected to dispersion treatment with ultrasonic waves (45 kHz) for 60 minutes to obtain a carbon catalyst ink.

(2) Working electrode preparation method After the surface of the rotating electrode (glassy carbon electrode radius 0.2 cm) is polished to a mirror surface, 1.5 μL of the carbon catalyst ink is dropped onto the electrode surface and dried at 25 ° C. under saturated water vapor pressure for 15 hours. To produce a working electrode.

(3) LSV (Linear Sweep Voltammetry) Measurement Electrolytic solution (0.1M potassium hydroxide aqueous solution) in an electrolytic cell in which the working electrode prepared above, a counter electrode (platinum), and a reference electrode (Ag / AgCl) are attached The oxygen reduction activity test was conducted.

  The oxygen reduction starting potential as an index of the degree of oxygen reduction activity was measured by LSV measurement at 25 ° C. after bubbling with oxygen in the electrolytic solution and then rotating the working electrode at 2000 rpm in an oxygen atmosphere. By the way, after performing bubbling with argon in the electrolyte, the numerical value obtained by performing LSV measurement in an argon atmosphere was used as the background.

The oxygen reduction starting potential was calculated by reading the potential when the current density reached −50 μA / cm ² and converting it to a potential based on the reversible hydrogen electrode (RHE). The oxygen reduction start potential indicates that the higher the potential, the higher the oxygen reduction activity. The evaluation results are shown in Table 3.

  As can be seen from Table 3, the carbon catalysts (1) to (10) and (14) to (27) synthesized by the production method of the examples are the carbon catalysts (11) to (13) synthesized by the production method of the comparative example. ), The acid-based and alkaline-based systems have higher oxygen reduction activity.

  Next, using the carbon catalysts (1) to (10), (14) to (27) obtained in Examples 1 to 24 and the carbon catalysts (11) to (13) of Comparative Examples 1 to 3, respectively. Catalyst ink and catalyst electrode were prepared, and performance evaluation of solid polymer fuel cell and microbial fuel cell was performed.

<Preparation of catalyst ink for polymer electrolyte fuel cell>
Carbon catalysts (1) to (10), (14) to (27) of Examples 1 to 24 and 12 parts of carbon catalysts (11) to (13) of Comparative Examples 1 to 3 were respectively weighed, and 1-butanol 48 parts and a Nafion solution (manufactured by DuPont: 20% solid content water-alcohol mixed solution) in a mixed solution of 40 parts by mass, and then stirred and mixed with a disper (Primix, TK homodisper) As a result, catalyst inks (1) to (27) for solid polymer fuel cells (solid content concentration of 20% by mass, ratio of carbon catalyst and binder when the catalyst ink was 100% by mass) were prepared.

<Preparation of catalyst layer for cathode of polymer electrolyte fuel cell>
Catalyst inks (1) to (10), (14) to (27) for polymer electrolyte fuel cells of Examples 1 to 24 and catalyst inks for polymer electrolyte fuel cells (11) of Comparative Examples 1 to 3 To (13) are each applied onto a Teflon (registered trademark) film with a doctor blade so that the weight of the carbon catalyst after drying is 2 mg / cm ² and dried at 95 ° C. for 15 minutes in an air atmosphere. Thus, uniform solid polymer electrolyte fuel cell cathode catalyst layers (1) to (27) having no unevenness were produced.

<Preparation of catalyst layer for anode of polymer electrolyte fuel cell>
Here, a method for producing a catalyst layer for a polymer electrolyte fuel cell anode used for producing an electrode membrane assembly for a fuel cell will be described below.
Instead of the carbon catalyst, 4 parts of platinum catalyst-supporting carbon (manufactured by Tanaka Kikinzoku Co., Ltd., 46% platinum), 56 parts of 1-propanol as a solvent, and 20 parts of water are stirred and mixed in a disper (Primics, TK homodisper). Thus, a catalyst paste composition (solid content concentration 4%) was prepared. Next, 20 parts of a Nafion solution (manufactured by DuPont: 20% solids water-alcohol mixed solution) is added, and the mixture is stirred and mixed with a disper (manufactured by Primics, TK homodisper) to obtain catalyst ink (solid A partial concentration of 8%). By applying the obtained catalyst ink on a Teflon (registered trademark) film so that the weight per unit area of the platinum catalyst-supported carbon is 0.46 mg / cm ² and drying it in an air atmosphere at 70 ° C. for 15 minutes, A catalyst layer for a polymer electrolyte fuel cell anode was prepared.

<Preparation of electrode membrane assembly for polymer electrolyte fuel cell>
The solid polymer fuel cell cathode catalyst layers (1) to (27) prepared in Examples 1 to 24 and Comparative Examples 1 to 3 and the solid polymer fuel cell anode catalyst layer were respectively separated from the solid polymer fuel cell anode catalyst layer. After closely adhering to both surfaces of a molecular electrolyte membrane (Nafion 211, manufactured by DuPont, film thickness 25.4 μm) at 150 ° C. and 5 MPa, the Teflon (registered trademark) film was peeled off. Next, electrode substrates (gas diffusion layer GDL, carbon paper made of carbon fiber, TGP-H-090, manufactured by Toray Industries, Inc.) are further adhered from both sides, and electrode membrane bonding for the polymer electrolyte fuel cell of the present invention is performed. The bodies (GDL / catalyst layer / solid polymer electrolyte membrane / catalyst layer / GDL) (1) to (27) were produced.

<Production of polymer electrolyte fuel cell (single cell)>
The fuel cell electrode membrane assemblies (1) to (27) obtained in Examples 1 to 24 and Comparative Examples 1 to 3 were used as 2 cm square samples, two gaskets from both sides, and then a separator 2 as a graphite plate. The sheet was sandwiched between two sheets, and two current collector plates were mounted from both sides to produce a polymer electrolyte fuel cell (single cell). The measurement was carried out by AutoPEM series “PEFC evaluation system” manufactured by Toyo Technica. As a polymer electrolyte fuel cell operating condition, a power generation test was conducted under conditions of a temperature of 80 ° C. and a relative humidity of 100% by flowing hydrogen at 300 ml / min on the anode side and oxygen at 300 ml / min on the cathode side. .

<Evaluation of polymer electrolyte fuel cell (single cell)>
The battery performance was evaluated by measuring the current-voltage characteristics of the single cells prepared in Examples 1-24 and Comparative Examples 1-3.
As a result, in the single cells produced in Examples 1 to 10 from Table 3, the open-circuit voltage was 0.80 V to 0.88 V, the short-circuit current density was 1820 to 2320 mA / cm ² , and the single cells produced in Examples 11 to 24 were used. In the cell, the open-circuit voltage is 0.73 to 0.90 V and the short-circuit current density is 1710 to 2510 mA / cm ² , whereas the single cells fabricated in Comparative Examples 1 to 3 have an open-circuit voltage of 0.32 to 0. It was a result lower than 70V and short circuit current density 520-1500mA / cm < ² > compared with an Example.

<Preparation of carbon catalyst ink for microbial fuel cell>
Carbon catalysts (1) to (10), (14) to (27) of Examples 1 to 24 and 12 parts of carbon catalysts (11) to (13) of Comparative Examples 1 to 3 were respectively weighed, and 1-butanol 48 parts and a Nafion solution (manufactured by DuPont: solid content 20% water-alcohol mixed solution (water / 1-propanol / ethanol = 34% / 44% / 2%) in a mixed solution of 40 parts, Carbon catalyst inks for microbial fuel cells (1) to (27) (solid content concentration 20% by mass, carbon catalyst ink 100% by mass) by stirring and mixing with a disper (Primix Co., Ltd., TK homodisper) Of carbon catalyst and binder).

<Production of catalyst electrode for microbial fuel cell>
The carbon catalyst inks (1) to (10) and (14) to (27) of Examples 1 to 24 and the carbon catalyst inks (11) to (13) for microbial fuel cells of Comparative Examples 1 to 3 Is applied on a carbon paper substrate (TGP-H-090, manufactured by Toray Industries, Inc.) made of carbon fiber as a conductive support so that the basis weight of the carbon catalyst after drying is 4 mg / cm ² , and the atmosphere The catalyst electrode (1)-(27) for microbial fuel cells was produced by drying at 95 ° C. for 60 minutes.

<Microbial fuel cell>
Below, the method of producing a microbial fuel cell using the catalyst electrode for microbial fuel cells produced from the carbon catalyst ink of this invention is illustrated.

After anaerobically culturing a mixed solution of Shewanella oneidenis MR-1 (single culture, 10 ⁵ cells / mL) and paddy soil in an electrolytic cell having a capacity of 30 mL at 30 ° C. for 3 days, A buffer solution of K ₂ HPO ₄ / KH ₂ PO ₄ (pH 7.0) is used as an electrolyte solution, and 2.0 g COD / L / day (COD: chemical oxygen demand) of domestic wastewater containing glucose as a nutrient substrate is used. It was allowed to flow continuously. Carbon cloth was inserted into the electrolytic cell as the negative electrode conductive support, and catalyst electrodes (1) to (27) for the microbial fuel cell as the positive electrode.

(Power generation test of microbial fuel cell)
When the current-voltage measurement was performed using a potentio galvanostat (VersaSTAT3, manufactured by Princeton Applied Research) and evaluated, the catalyst electrodes for microbial fuel cells produced in Examples 1 to 10 were 0.13 to 0.16 W. / ^m is ^2, the catalyst electrode for a microbial fuel cell fabricated in example 11 to 24, whereas a 0.12～0.18W / ^{m 2,} for microbial fuel cell manufactured in Comparative examples 1 to 3 In the case of the catalyst electrode, the result was 0.06 to 0.09 W / m ² , which is lower than that of the example.

  From the above, it was found that the catalyst of the present invention has high catalytic activity in both acid and alkaline systems, and the polymer electrolyte fuel cell and microbial fuel cell produced from the catalyst have excellent cell performance. .

Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the present invention.

1 Separator 2 Gas diffusion layer 3 Anode electrode catalyst (fuel electrode)
4 Solid polymer electrolyte 5 Cathode electrode catalyst (Air electrode)
6 Gas diffusion layer 7 Separator

Claims (19)

Heat-treating a mixture comprising a carbon material and at least one nitrogen-containing pigment derivative containing a metal element selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group A carbon catalyst characterized by being obtained. One or more nitrogen-containing pigment derivatives selected from the group consisting of a carbon material, a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group, and a metal source, A carbon catalyst obtained by heat-treating a mixture containing the carbon catalyst.   The carbon catalyst according to claim 1, wherein the mixture further comprises a metal source. The basic functional group is a —NRR ′ group (R and R ′ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. The carbon catalyst according to any one of claims 1 to 3, wherein R and R 'may combine to form a ring. The carbon catalyst according to any one of claims 1 to 4, wherein the acidic functional group is any one of a sulfo group, a carboxy group, and a phosphoric acid group. The carbon catalyst according to any one of claims 1 to 5, wherein the nitrogen-containing pigment derivative is one or more nitrogen-containing pigment derivatives selected from the group consisting of nitrogen-containing organic dye derivatives, nitrogen-containing anthraquinone derivatives, acridone derivatives, and triazine derivatives. The carbon catalyst according to claim 1, wherein the nitrogen-containing pigment derivative containing a metal element is a metal phthalocyanine pigment derivative. The carbon catalyst according to any one of claims 1 to 7, wherein the carbon material is one or more carbon materials selected from the group consisting of carbon black, graphene-based carbon materials, and carbon nanotubes. The nitrogen-containing pigment derivative having a basic functional group, the nitrogen-containing pigment derivative having an acidic functional group and / or the metal element contained in the metal source is at least one selected from cobalt, iron, nickel, manganese, copper, vanadium and tin The carbon catalyst according to any one of claims 1 to 8. The carbon catalyst according to any one of claims 1 to 9, wherein an element ratio of the metal to nitrogen is in the range of 0.05 to 5. The carbon catalyst according to any one of claims 1 to 10, wherein the metal element is cobalt and / or iron. A solvent comprising a carbon material and at least one nitrogen-containing pigment derivative containing a metal element selected from the group consisting of a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group A method for producing a carbon catalyst, comprising: a step of mixing in a heat treatment, and a step of heat-treating the mixture obtained by drying the solvent thereafter at 700 to 1100 ° C. One or more nitrogen-containing pigment derivatives selected from the group consisting of a carbon material, a nitrogen-containing pigment derivative having a basic functional group and a nitrogen-containing pigment derivative having an acidic functional group, and a metal source, A method for producing a carbon catalyst, comprising: a step of mixing a mixture containing a solvent in a solvent; and a step of heat-treating the mixture obtained by drying the solvent at 700 to 1100 ° C. The method for producing a carbon catalyst according to claim 12 or 13, wherein a dispersion resin is included in the step of mixing in a solvent. The carbon catalyst manufactured by the manufacturing method in any one of Claims 12-14. A catalyst ink comprising the carbon catalyst according to any one of claims 1 to 11 or 15, a binder, and a solvent.   A fuel cell comprising an electrode catalyst in which the carbon catalyst according to any one of claims 1 to 11 or 15 is disposed on one or both surfaces of a solid polymer electrolyte membrane.   The catalyst ink according to claim 16, wherein the binder is a proton conductive polymer and / or a water repellent material.   A microbial fuel cell comprising the carbon catalyst according to claim 1.