JP2016102037A - Method for producing nitrogen-containing carbon alloy, nitrogen-containing carbon alloy, and fuel cell catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nitrogen-containing carbon alloy having high oxygen reduction reaction activity, a method for producing the same, and a fuel cell catalyst.SOLUTION: A catalyst is obtained by burning a precursor that comprises: a nitrogen-containing organic compound represented by formula (1), its tautomer, salt and hydrate; one of a covalent bonding organic skeleton material and a metal organic skeleton material; and one of an inorganic metal salt and an organic metal complex, with the precursor having its specific volume of 4 cm/g or more.SELECTED DRAWING: None

Description

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

  Conventionally, noble metal-based catalysts using platinum (Pt), palladium (Pd), etc. have high oxygen reduction reaction activity, for example, in solid polymer electrolyte fuel cells used in automobiles, household electric heat supply systems, etc. Has been used. However, since such noble metal-based catalysts are expensive, it is difficult to further spread them. For this reason, technological development of a catalyst in which platinum is greatly reduced or a catalyst formed without using platinum is being promoted.

As a catalyst that can be formed without using platinum, a carbon catalyst is known, and a nitrogen-containing carbon alloy obtained by heat-treating a nitrogen-containing organic compound is used as a carbon catalyst. For example, Patent Document 1 discloses a modified product (nitrogen-containing carbon alloy) obtained by modifying a content of a porphyrin complex. Here, the porphyrin complex has a metal element in the center, and the metal element and the porphyrin are bonded by a strong coordinate bond.
However, metal complexes containing metal elements are difficult to purify, and it is difficult to control the decomposition rate of the nitrogen-containing ligand and the rate of vaporization of the coordination metal complex when heat is applied to the nitrogen-containing metal complex. It is difficult to produce the target nitrogen-containing carbon alloy. For this reason, for example, it has been proposed to produce a nitrogen-containing carbon alloy using an organic material containing a nitrogen-containing organic compound having no central metal as in Patent Documents 2 and 3.

  Patent Documents 4 and 5 disclose a nitrogen-containing carbon alloy in which a porous material such as a nitrogen-containing heterocyclic compound, a metal complex, and MOF (Metal-Organic frameworks) is pulverized and mixed with a ball mill, and the resulting mixture is fired. A manufacturing method is disclosed. In Patent Document 4, TPTZ (2,4,6-tri (2-pyridyl) -1,3,5-triazine) is used as the nitrogen-containing heterocyclic compound. In Patent Document 5, 6- (2-pyridyl) -1,3,5-triazine-2,4-diamine is listed as a nitrogen-containing heterocyclic compound.

JP 2012-110811 A JP 2011-225431-A JP 2014-196231 A Special table 2014-512251 gazette US Patent Publication US2011 / 0294658

As described above, the nitrogen-containing carbon alloy catalyst containing a nitrogen-containing organic compound can exhibit catalytic activity without using platinum. However, in recent applications such as fuel cells, it may be required to have higher oxygen reduction reaction activity. For this reason, it is required to produce a nitrogen-containing carbon alloy that can exhibit higher oxygen reduction reaction activity.
Accordingly, the present inventor has proceeded with studies for the purpose of producing a nitrogen-containing carbon alloy having higher oxygen reduction reaction activity.

As a result of intensive studies to solve the above problems, the present inventor has a nitrogen-containing organic compound having a specific structure, at least one selected from a covalent organic skeleton material and a metal organic skeleton material, A precursor containing at least one selected from an inorganic metal salt or an organic metal complex and calcining a precursor having a specific volume of 4 cm ³ / g or more to produce a nitrogen-containing carbon alloy, thereby producing high oxygen It has been found that a nitrogen-containing carbon alloy having a reduction reaction activity ability can be obtained.
Specifically, the present invention has the following configuration.

一般式（１）中、Ｌ¹〜Ｌ⁴は、それぞれ独立に連結基、単結合または二重結合を表し、Ｚ¹〜Ｚ⁴は、それぞれ独立に環状構造を表し、Ｌ¹〜Ｌ⁴の少なくとも１つは複素芳香族基を有する連結基であるか、Ｚ¹〜Ｚ⁴の少なくとも１つは複素芳香族環を含む。
［２］一般式（１）で表される含窒素有機化合物は、下記一般式（２）で表される［１］に記載の含窒素カーボンアロイの製造方法；

一般式（２）中、Ｚ¹〜Ｚ⁴は、それぞれ独立に環状構造を表し、Ｚ¹〜Ｚ⁴の少なくとも１つは複素芳香族環を含む。
［３］一般式（１）で表される含窒素有機化合物は、下記一般式（３）で表される［１］に記載の含窒素カーボンアロイの製造方法；

一般式（３）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に水素原子または置換基を表し、Ｚ¹〜Ｚ⁴は、それぞれ独立に環状構造を表し、Ｒ¹〜Ｒ⁴の少なくとも１つは複素芳香族基であるか、Ｚ¹〜Ｚ⁴の少なくとも１つは複素芳香族環を含む。
［４］一般式（３）において、Ｒ¹〜Ｒ⁴の少なくとも１つは複素芳香族基であり、かつ、Ｚ¹〜Ｚ⁴の少なくとも１つは複素芳香族環を含む［３］に記載の含窒素カーボンアロイの製造方法。
［５］含窒素有機化合物は、金属錯体を除くピリジルポルフィリン、および、金属錯体を除くピリジルポルフィリンの塩から選ばれる少なくとも１種である［１］に記載の含窒素カーボンアロイの製造方法。
［６］金属有機骨格材料は、ゼオライト型イミダゾール骨格材料である［１］〜［５］のいずれかに記載の含窒素カーボンアロイの製造方法。
［７］有機金属錯体は、金属アセタート錯体またはβ―ジケトン金属錯体である［１］〜［６］のいずれかに記載の含窒素カーボンアロイの製造方法。
［８］無機金属塩は、無機金属塩化物である［１］〜［７］のいずれかに記載の含窒素カーボンアロイの製造方法。
［９］無機金属塩の金属種が、Ｆｅである［１］〜［８］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１０］無機金属塩は、含水塩である［１］〜［９］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１１］焼成する工程は、前駆体を４００℃以上で焼成する工程である［１］〜［１０］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１２］焼成する工程は、前駆体を７００〜１０５０℃で焼成する工程である［１］〜［１１］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１３］焼成する工程は、前駆体を７００〜１０５０℃で１秒〜１００時間保持する工程を含む［１］〜［１２］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１４］焼成する工程の前に、前駆体を粉砕する工程をさらに含む［１］〜［１３］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１５］焼成する工程の後に、焼成された含窒素カーボンアロイを粉砕する工程と、再焼成する工程とをさらに含む［１］〜［１４］のいずれかに記載の含窒素カーボンアロイの製造方法。
［１６］再焼成する工程は、９００〜１５００℃で焼成する工程である［１５］に記載の含窒素カーボンアロイの製造方法。
［１７］再焼成する工程の前に、脱気及び窒素置換する工程をさらに含む［１５］又は［１６］に記載の含窒素カーボンアロイの製造方法。
［１８］［１］〜［１７］のいずれかに記載の方法で製造された含窒素カーボンアロイ。
［１９］［１８］に記載の含窒素カーボンアロイを用いた燃料電池触媒。 [1] At least one selected from nitrogen-containing organic compounds represented by the following general formula (1), tautomers of nitrogen-containing organic compounds, salts of nitrogen-containing organic compounds, and hydrates of nitrogen-containing organic compounds And calcining a precursor comprising at least one selected from a covalent organic skeleton material and a metal organic skeleton material and at least one selected from an inorganic metal salt and an organometallic complex, the specific volume of the precursor Is a method for producing a nitrogen-containing carbon alloy of 4 cm ³ / g or more;

In the general formula (1), L ^{1 to} L ⁴ each independently represent a linking group, a single bond or a double bond, Z ^{1 to} Z ⁴ each independently represent a cyclic structure, and L ^{1 to} L ⁴ At least one is a linking group having a heteroaromatic group, or at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring.
[2] The method for producing a nitrogen-containing carbon alloy according to [1], wherein the nitrogen-containing organic compound represented by the general formula (1) is represented by the following general formula (2);

In General Formula (2), Z ^{1 to} Z ⁴ each independently represent a cyclic structure, and at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring.
[3] The method for producing a nitrogen-containing carbon alloy according to [1], wherein the nitrogen-containing organic compound represented by the general formula (1) is represented by the following general formula (3);

In General Formula (3), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituent, Z ^{1 to} Z ⁴ each independently represent a cyclic structure, and at least one of R ^{1 to} R ⁴ is or a heteroaromatic group, at least one of Z ¹ to Z ⁴ comprises a heteroaromatic ring.
[4] In the general formula (3), at least one of R ^{1 to} R ⁴ is a heteroaromatic group, and at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. A method for producing a nitrogen-containing carbon alloy.
[5] The method for producing a nitrogen-containing carbon alloy according to [1], wherein the nitrogen-containing organic compound is at least one selected from pyridyl porphyrins excluding metal complexes and pyridyl porphyrin salts excluding metal complexes.
[6] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [5], wherein the metal organic framework material is a zeolite type imidazole framework material.
[7] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [6], wherein the organometallic complex is a metal acetate complex or a β-diketone metal complex.
[8] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [7], wherein the inorganic metal salt is an inorganic metal chloride.
[9] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [8], wherein the metal species of the inorganic metal salt is Fe.
[10] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [9], wherein the inorganic metal salt is a hydrate salt.
[11] The step of firing is a method for producing a nitrogen-containing carbon alloy according to any one of [1] to [10], which is a step of firing the precursor at 400 ° C. or higher.
[12] The step of firing is the method for producing a nitrogen-containing carbon alloy according to any one of [1] to [11], which is a step of firing the precursor at 700 to 1050 ° C.
[13] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [12], wherein the firing step includes a step of holding the precursor at 700 to 1050 ° C. for 1 second to 100 hours.
[14] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [13], further including a step of pulverizing the precursor before the step of firing.
[15] The method for producing a nitrogen-containing carbon alloy according to any one of [1] to [14], further comprising a step of pulverizing the baked nitrogen-containing carbon alloy and a step of re-baking after the step of calcination. .
[16] The method for producing a nitrogen-containing carbon alloy according to [15], wherein the re-baking step is a step of baking at 900 to 1500 ° C.
[17] The method for producing a nitrogen-containing carbon alloy according to [15] or [16], further including a step of deaeration and nitrogen substitution before the step of refiring.
[18] A nitrogen-containing carbon alloy produced by the method according to any one of [1] to [17].
[19] A fuel cell catalyst using the nitrogen-containing carbon alloy according to [18].

  According to the method for producing a nitrogen-containing carbon alloy of the present invention, a nitrogen-containing carbon alloy having a sufficiently high oxygen reduction reaction activity can be obtained. For this reason, the nitrogen-containing carbon alloy obtained by the manufacturing method of the nitrogen-containing carbon alloy of this invention can be used as a carbon catalyst, for example, is preferably used for a fuel cell catalyst or an environmental catalyst.

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

  Hereinafter, the present invention will be described in detail. The constituent elements described below may be described based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

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

<Method for producing nitrogen-containing carbon alloy>
The method for producing a nitrogen-containing carbon alloy of the present invention is selected from nitrogen-containing organic compounds having a specific structure, tautomers of nitrogen-containing organic compounds, salts of nitrogen-containing organic compounds, and hydrates of nitrogen-containing organic compounds. And baking a precursor containing at least one selected from a covalent organic skeleton material and a metal organic skeleton material and at least one selected from an inorganic metal salt and an organometallic complex. Here, the specific volume of the precursor before firing is 4 cm ³ / g or more. The covalent organic framework material (COF (Covalent organic framework)) and the metal organic framework material (MOF (Metal-organic framework)) are porous materials, and in this specification, the covalent organic framework material and Metal organic framework materials may be collectively referred to as porous materials.

  In the present invention, when a nitrogen-containing carbon alloy is produced by firing, first, an inorganic metal salt or an organometallic complex is volatilized in the reaction space field (in the pores) of the porous material, and thermal decomposition is performed. Thus, a complex of an inorganic metal salt or organometallic complex and MOF or COF is formed. Next, a coordination polymer complex is formed by volatilization of a nitrogen-containing organic compound having a structure as described later in the composite. The MOF or COF metal is selectively volatilized or desorbed, thereby forming a nitrogen-containing carbon alloy having porosity. These compounds are further heated at a temperature to develop pores due to the heterocycle of the nitrogen-containing organic compound. In the present invention, it is considered that the metal site coordinated and fixed to the hetero atom in the pore contributes to high activation of the nitrogen-containing carbon alloy.

In the present invention, a nitrogen-containing carbon alloy having higher oxygen reduction reaction activity can be obtained by setting the specific volume of the precursor to 4 cm ³ / g or more. The specific volume of the precursor is preferably 5 cm ³ / g or more, and more preferably 6 cm ³ / g or more. Thus, by setting the specific volume of the precursor to a certain value or more, formation of a nitrogen-containing carbon alloy having porosity can be easily advanced. Thereby, formation of an oxygen reduction reaction (ORR) active site can be promoted, and a nitrogen-containing carbon alloy having higher oxygen reduction reaction activity can be obtained.

The specific volume of the precursor can be measured based on the method of “apparent density or apparent specific volume” of JIS-K-5101. The measurement is preferably carried out by the tap method. Specifically, 10 g of the precursor is placed in a 50 ml graduated cylinder, tapped 500 times, allowed to stand, the volume is read, and the specific volume is determined by the following formula.
Specific volume (ml / g) = V / F
In the formula, F is the mass (g) of the treated precursor in the container, and V indicates the volume (ml) of the sample after tapping.

  In the present invention, the precursor is derived from a nitrogen-containing organic compound represented by the following general formula (1), a tautomer of the nitrogen-containing organic compound, a salt of the nitrogen-containing organic compound, and a hydrate of the nitrogen-containing organic compound. It means a mixture comprising at least one selected, at least one selected from a covalently bonded organic skeleton material and a metal organic skeleton material, and at least one selected from an inorganic metal salt and an organometallic complex. That is, the precursor in the present invention is a mixture in a stage before the above materials are mixed and fired.

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

In the general formula (1), L ^{1 to} L ⁴ each independently represent a linking group, a single bond or a double bond, Z ^{1 to} Z ⁴ each independently represent a cyclic structure, and L ^{1 to} L ⁴ At least one is a linking group having a heteroaromatic group, or at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. Note that (excluding the dashed line constituting the Z ¹ to Z ⁴⁾ the dotted line that is described along the bonds of the general formula (1) indicates that it may be a double bond.

When at least one of L ^{1 to} L ⁴ represents a linking group, specific examples of the linking group include, for example, —NR ⁸ — (R ⁸ is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. the group represented by represents a _{group), -SO 2 -, - CO-} , a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, an alkynylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted A biphenylene group, a substituted or unsubstituted naphthylene group, -O-, -S- and -SO-, and a group obtained by combining two or more thereof. Among them, the linking group represented by L ^{1 to} L ⁴ is a group represented by —NR ⁸ — (R ⁸ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group), substituted or unsubstituted. A substituted alkylene group and a substituted or unsubstituted alkenylene group are preferred. In addition, when a coupling group has a substituent, the substituent mentioned above can be mentioned. Especially, it is preferable that the substituent which a coupling group has is an aromatic group or a heteroaromatic group. Specifically, a phenyl group, a pyridyl group, a quinazolyl group, a pyrimidyl group, a pyrrolyl group, an imidazolyl group, a furyl group, and a thienyl group can be exemplified, and a phenyl group or a pyridyl group is more preferable.

Z ^{1 to} Z ⁴ each independently represent a cyclic structure, and examples of the ring constituting the cyclic structure include an aromatic ring and a heteroaromatic ring. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. The heteroaromatic ring is preferably a 5- to 7-membered heterocycle containing 1 to 3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples of the heteroaromatic ring include a pyridine ring, a quinazoline ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, a furan ring, and a thiophene ring. The aromatic ring and the heteroaromatic ring may have a substituent, and examples of the substituent include the above-described substituents.

When at least one of Z ^{1 to} Z ⁴ contains an aromatic ring, the aromatic ring is preferably a benzene ring. When none of L ^{1 to} L ⁴ has a heteroaromatic group, at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. In such a case, when at least one of Z ^{1 to} Z ⁴ includes an aromatic ring, the benzene ring is preferably included as a ring condensed with a heteroaromatic ring.

The heteroaromatic ring that Z ^{1 to} Z ⁴ may have is preferably a 5- or 6-membered heteroaromatic ring. The hetero atom constituting the heteroaromatic ring is preferably a nitrogen atom, that is, the heteroaromatic ring is preferably a pyrrole ring, an imidazole ring, a pyridine ring or a pyrimidine ring. The cyclic structure represented by Z ^{1 to} Z ⁴ may be a monocyclic structure or a condensed ring structure. When the cyclic structure represented by Z ^{1 to} Z ⁴ is a condensed ring structure, it is preferably a condensed ring structure in which 2 to 5 rings are condensed.
When none of L ^{1 to} L ⁴ has a heteroaromatic group, Z ^{1 to} Z ⁴ are preferably a condensed ring structure. In this case, the cyclic structure represented by Z ^{1 to} Z ⁴ is preferably, for example, a structure in which two or more rings described above are condensed. For example, a ring structure in which a pyrrole ring and a pyridine ring, a pyrrole ring and a pyrimidine ring, or a pyrrole ring, a pyridine ring, and a benzene ring are condensed is preferable.

At least one of L ^{1 to} L ⁴ is a linking group having a heteroaromatic group, or at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. That is, one or more heteroaromatic rings are contained in the nitrogen-containing organic compound. Even when at least one of L ^{1 to} L ⁴ has a heteroaromatic group, it is preferable that at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring.

When at least one of L ^{1 to} L ⁴ is a linking group having a heteroaromatic group, examples of the hetero atom constituting the heteroaromatic group include a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples of the heteroaromatic group include a pyridyl group, a quinazolyl group, a pyrimidyl group, a pyrrolyl group, an imidazolyl group, a furyl group, and a thienyl group. Especially, it is preferable that the hetero atom which comprises a heteroaromatic group is a nitrogen atom. The heteroaromatic ring constituting the linking group having a heteroaromatic group is preferably a 5- or 6-membered heteroaromatic ring, and more preferably a 6-membered heteroaromatic ring. Specifically, a pyridyl group, a pyrimidyl group, a pyrrolyl group or an imidazolyl group can be exemplified, and a pyridyl group can be more preferably exemplified.
Also, if at least one of L ¹ ~L ⁴ is a linking group having a heteroaromatic group, more preferably two or more of L ¹ ~L ⁴ is a linking group having a heterocyclic aromatic group, L more preferably ¹ ~L 3 or more of the ⁴ is a linking group having a heteroaromatic group, it is particularly preferable that all of L ¹ ~L ⁴ is a linking group having a heteroaromatic group. Incidentally, two of L ¹ ~L ⁴ is a linking group having a heteroaromatic group, it is also preferred the other two of the L ¹ ~L ⁴ is a linking group having an aromatic group.

When at least one of L ^{1 to} L ⁴ is a linking group having a heteroaromatic group, a pyridyl group or a pyrimidyl group can be mentioned as a preferred heteroaromatic group. In this case, in the pyridyl group or pyrimidyl group, the nitrogen atom is preferably in the para position as viewed from the ring bonding position. By arranging a nitrogen atom at such a position, a complex with a metal species (M) of an inorganic metal salt or an organometallic complex described later is easily formed. In addition, since it is possible to control the orientation of the substituents that form the oxygen reduction reaction (ORR) active site, the oxygen reduction reaction (ORR) active site can be formed at a high density, resulting in high oxygen reduction reaction activity. Can have.

If at least one of Z ¹ to Z ⁴ is containing heteroaromatic ring, heteroaromatic ring Z ¹ to Z ⁴ comprises may be a heterocyclic ring containing a nitrogen atom constituting the porphyrin ring, Separately Further, it may have a heteroaromatic ring. Examples of the heterocyclic ring without limiting the substitution position include pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, pyrrole ring, indole ring, pyrazole ring, imidazole ring, benzo Examples include imidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, pyrrolidine ring, piperidine ring, piperazine ring, imidazole ring, thiazole ring and the like.
Further, Z ¹ to Z at least one of ⁴ if it contains heteroaromatic ring, more preferably more than two of the Z ¹ to Z ⁴ comprises a heterocyclic aromatic ring, of Z ¹ to Z ⁴ It is more preferable that three or more include a heteroaromatic ring, and it is particularly preferable that all of Z ^{1 to} Z ⁴ include a heteroaromatic ring.

The nitrogen-containing organic compound preferably contains 2 or more heteroaromatic rings, more preferably 3 or more, and still more preferably 4 or more. Thus, when a certain number or more of heteroaromatic rings are contained in the nitrogen-containing organic compound, a complex of a metal species (M) of an inorganic metal salt or an organometallic complex described later and a heteroaromatic ring is easily formed. Thereby, an oxygen reduction reaction (ORR) active site can be formed with high density, and high oxygen reduction reaction activity can be exhibited.
Furthermore, when the nitrogen-containing organic compound has two or more heteroaromatic rings, the heteroaromatic rings are arranged and oriented when the metal species (M) and the heteroaromatic rings interact with each other. (ORR) A structure in which the active sites are dense and controlled can be formed. Thereby, a nitrogen-containing carbon alloy having higher oxygen reduction reaction activity can be obtained.

  As represented by the general formula (1), the nitrogen-containing organic compound does not include a metal complex containing nitrogen. Nitrogen-containing metal complexes are difficult to purify, and nitrogen-containing metal complexes have a constant composition ratio between the nitrogen-containing ligand and the metal complex. And the vaporization rate of the coordination metal complex cannot be controlled, and it is difficult to obtain the target nitrogen-containing carbon alloy. Furthermore, the nitrogen-containing carbon alloy having a central metal reduces the catalytic activity when used as a catalyst. Even if the nitrogen-containing metal complex and the low-molecular organic compound are mixed, the nitrogen-containing metal complex crystal is decomposed and the metal is directly reduced, so that the generated adjacent metals are easily aggregated and crystallized. Further, since the metal is removed by the acid cleaning, the obtained nitrogen-containing carbon alloy becomes non-uniform so that the required function is reduced. For the above reasons, in the present invention, a nitrogen-containing organic compound not containing a nitrogen-containing metal complex is used.

  The nitrogen-containing organic compound represented by the general formula (1) is preferably represented by the following general formula (2).

Here, in the general formula (2), Z ¹ ~Z ⁴ each independently represent a cyclic structure. However, at least one of Z ^{1 to} Z ⁴ contains a heteroaromatic ring. In general formula (2) Z ¹ to Z ⁴ in is synonymous with Z ¹ to Z ⁴ in the general formula (1), and preferred ranges are also the same.

  The nitrogen-containing organic compound represented by the general formula (1) is also preferably represented by the following general formula (3).

Here, in General Formula (3), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituent, and Z ^{1 to} Z ⁴ each independently represent a cyclic structure. However, at least one of R ^{1 to} R ⁴ is a heteroaromatic group, or at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. In general formula (3) Z ¹ to Z ⁴ in is synonymous with Z ¹ to Z ⁴ in the general formula (1), and preferred ranges are also the same.

When R ^{1 to} R ⁴ each independently represents a substituent, examples of the substituent include the above-described substituents. Among them, an aromatic group or a heteroaromatic group is preferable. When at least one of R ^{1 to} R ⁴ is an aromatic group, it is preferably an aryl group, and more preferably a phenyl group. When at least one of R ^{1 to} R ⁴ is a heteroaromatic group, examples of the heteroaromatic group include a heteroaromatic group that L ^{1 to} L ⁴ in the general formula (1) may have as a preferred example. it can.

At least one of R ^{1 to} R ⁴ is a heteroaromatic group, or at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. That is, one or more heteroaromatic rings are contained in the nitrogen-containing organic compound. In the general formula (3), it is more preferable that at least one of R ^{1 to} R ⁴ is a heteroaromatic group, and at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. By using a nitrogen-containing organic compound having such a structure, a nitrogen-containing carbon alloy having higher oxygen reduction reaction activity can be obtained.

When at least one of R ^{1 to} R ⁴ is a heteroaromatic group, the heteroaromatic ring constituting the heteroaromatic group is preferably a 5- or 6-membered heteroaromatic ring, More preferably, it is a group ring. Moreover, it is preferable that the hetero atom which comprises a heteroaromatic ring is a nitrogen atom. Specifically, a pyridyl group, a pyrimidyl group, a pyrrolyl group or an imidazolyl group can be exemplified, and a pyridyl group can be more preferably exemplified.
Also, if at least one of R ¹ to R ⁴ is a heteroaromatic group, more preferably two or more of R ¹ to R ⁴ is a heteroaromatic group, three of R ¹ to R ⁴ The above is more preferably a heteroaromatic group, particularly preferably all of R ^{1 to} R ⁴ are heteroaromatic groups. Note that two of R ¹ to R ⁴ is a heteroaromatic group, it is also preferred the other two of R ¹ to R ⁴ is an aromatic group.

When at least one of R ^{1 to} R ⁴ is a heteroaromatic group, a pyridyl group or a pyrimidyl group can be mentioned as a preferred heteroaromatic group. In this case, in the pyridyl group or pyrimidyl group, the nitrogen atom is preferably in the para position as viewed from the ring bonding position. By arranging a nitrogen atom at such a position, a complex with a metal species (M) of an inorganic metal salt or an organometallic complex described later is easily formed. In addition, since it is possible to control the orientation of the substituents that form the oxygen reduction reaction (ORR) active site, the oxygen reduction reaction (ORR) active site can be formed at a high density, resulting in high oxygen reduction reaction activity. Can have.

  Further, the nitrogen-containing organic compound represented by the general formula (1) may be a compound represented by the following general formula (4).

Here, in the general formula (4), R ¹ , R ² and R ⁴ each independently represent a hydrogen atom or a substituent, and Z ^{1 to} Z ⁴ each independently represent a cyclic structure. However, at least one of R ¹ , R ² and R ⁴ is a heteroaromatic group, or at least one of Z ^{1 to} Z ⁴ contains a heteroaromatic ring. Incidentally, R ^1, R ² and R ⁴ in the general formula (4) is synonymous with R ^1, R ² and R ⁴ in the general formula (3), and preferred ranges are also the same. In general formula (4) Z ¹ to Z ⁴ in is synonymous with Z ¹ to Z ⁴ in the general formula (1), and preferred ranges are also the same.

In the general formula (4), at least one of R ¹ , R ² and R ⁴ may be a heteroaromatic group even when at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. preferably, R ^1, more preferably R ² and two or more of R ⁴ is an heteroaromatic group, it is particularly preferred that all of R ^1, R ² and R ⁴ are heteroaromatic group.

  Furthermore, the nitrogen-containing organic compound represented by the general formula (1) may be a compound represented by the following general formula (5).

Here, in General Formula (5), R ² and R ⁴ each independently represent a hydrogen atom or a substituent, and Z ^{1 to} Z ⁴ each independently represent a cyclic structure. However, at least one of R ² and R ⁴ is a heteroaromatic group, or at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. Incidentally, R ² and R ⁴ in the general formula (5) is synonymous with R ² and R ⁴ in the general formula (3), and preferred ranges are also the same. In general formula (5) Z ¹ to Z ⁴ in is synonymous with Z ¹ to Z ⁴ in the general formula (1), and preferred ranges are also the same.

In the general formula (5), even when at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring, at least one of R ² and R ⁴ is preferably a heteroaromatic group, More preferably, ² and R ⁴ are heteroaromatic groups.

  Further, the nitrogen-containing organic compound represented by the general formula (1) may be a compound represented by the following general formula (6).

Here, in General Formula (6), R ¹ and R ³ each independently represent a hydrogen atom or a substituent, and Z ^{1 to} Z ⁴ each independently represent a cyclic structure. However, at least one of R ¹ and R ³ is a heteroaromatic group, or at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. Incidentally, R ¹ and R ³ in the general formula (6) is synonymous with R ¹ and R ³ in the general formula (3), and preferred ranges are also the same. In general formula (6) Z ¹ to Z ⁴ in is synonymous with Z ¹ to Z ⁴ in the general formula (1), and preferred ranges are also the same.

In the general formula (6), even when at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring, at least one of R ¹ and R ³ is preferably a heteroaromatic group, More preferably, ¹ and R ³ are heteroaromatic groups.

  The nitrogen-containing organic compound used in the present invention is preferably at least one selected from pyridyl porphyrins excluding metal complexes and pyridyl porphyrin salts excluding metal complexes.

  Specific examples of the nitrogen-containing organic compound represented by the general formula (1) include the following compounds. However, the present invention is not limited to the following specific examples.

The nitrogen-containing organic compound described above preferably forms a crystal structure by two or more bonds or interactions selected from π-π interaction, coordination bond, charge transfer interaction and hydrogen bond. By using a nitrogen-containing organic compound having a crystal structure, the intermolecular interaction can be improved, and vaporization during firing when obtaining a nitrogen-containing carbon alloy can be suppressed.
The crystal structure here refers to the arrangement and arrangement of molecules in the crystal. In other words, the crystal structure consists of a repeating structure of unit cell, and the molecules are arranged at any position in the unit cell and oriented. In the crystal, the molecules have a uniform appearance. That is, since the arrangement of functional groups in the crystal is uniform, each molecular interaction is the same inside or outside the unit cell. For example, in the case of a nitrogen-containing organic compound having a laminated structure, interaction with an aromatic ring, heterocyclic ring, condensed polycyclic ring, condensed heterocyclic polycyclic ring, unsaturated group (nitrile group, vinyl group, allyl group, acetylene group) ( For example, in an aromatic ring, a π-π interaction (π-π stack) occurs in a face-to-face. Stacking is performed by SP ² orbits of carbons derived from unsaturated bonds in these rings and groups and regularly overlapping at equal intervals between molecules to form a stacked column structure.

  Further, in this stacked column structure, adjacent stacked columns have a uniform structure in which the intermolecular distance is defined by hydrogen bonding or van der Waals interaction. For this reason, it has the effect that the heat transfer in a crystal | crystallization is achieved easily.

  The nitrogen-containing organic compound used in the present invention preferably has crystallinity. Since the nitrogen-containing organic compound has crystallinity, the orientation of the compound can be controlled at the time of firing, which is preferable because it becomes a uniform carbon material.

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

  The nitrogen-containing organic compound preferably has a molecular weight of 60 to 2000, more preferably 100 to 1500, and particularly preferably 130 to 1000. By making molecular weight into the said range, refinement | purification of a nitrogen-containing organic compound becomes easy.

  In addition, a nitrogen-containing organic compound may be used independently and may be used in mixture of 2 or more types. Moreover, it is preferable that the metal content in a nitrogen-containing organic compound is 10 mass ppm or less.

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

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

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

The nitrogen-containing organic compound is also preferably a pigment having a structure represented by the general formula (1). The pigment forms a stacked column structure by π-π interaction between molecules. Since hydrogen bonding or van der Waals interaction exists between the stacked columns, it can have a uniform structure with a defined intermolecular distance, and heat transfer within the crystal is easily achieved. In addition, it has crystallinity, and is vibration-reduced and heat-resistant by phonon (quantized lattice vibration) against heat. For this reason, the decomposition temperature is maintained up to the carbonization temperature, and there is an effect that the vaporization of the decomposition product is reduced and the carbonization is achieved.
Among them, isoindoline pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, oxazine pigments, phthalocyanine pigments, quinophthalone pigments, and latent pigments obtained from the above pigments, and dyes made of metal Preferred are pigments such as lake pigments pigmented with ions, such as diketopyrrolopyrrole pigments, quinacridone pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, and latent pigments (later described) ) Is more preferable. When these pigments are calcined, the decomposition-generated benzonitrile (Ph-CN) skeleton becomes a reactive species, and a nitrogen-containing carbon alloy catalyst having higher oxygen reduction reaction activity is generated. In addition, when the metal species (M) coexists, a complex of Ph—CN... M is formed, and a nitrogen-containing carbon alloy that is highly active in oxygen reduction reaction is generated.

<Covalent organic framework material and metal organic framework material>
The preparation of the precursor in the method for producing a nitrogen-containing carbon alloy of the present invention includes at least selected from a covalent organic framework material (COF) and a metal-organic framework material (MOF). One kind is used. The covalent organic skeleton material (COF) and the metal organic skeleton material (MOF) are porous materials, and an infinite number of pores of several nm exist inside the structure. The porous material may be a structure having pores therein, and an organic skeleton material or a metal organic skeleton material can be preferably used.

  The pore diameter of the porous material used in the present invention is preferably 0.1 to 100 nm, and more preferably 0.2 to 10 nm. The porous material preferably has one or more of micropores having a pore diameter of 2 nm or less, mesopores of 2 to 50 nm, and macropores of 50 nm or more, and more preferably have mesopores. When the pore diameter is in this range, it is preferable because the number of action points increases and the generated water is easily discharged. Further, it is preferable because the internal pores of the porous material have a pore volume and easily interact with oxygen.

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

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

  A covalent organic skeleton material (COF) is a material having a crystalline porous structure using only an organic skeleton. The porous structure is formed from a two-dimensional or three-dimensional network of organic compounds linked by covalent bonds. The covalent organic framework material (COF) preferably contains at least one atom of an element other than carbon, such as hydrogen, oxygen, nitrogen, silicon, phosphorus, selenium, fluorine, boron or sulfur.

  Although it does not specify in particular as a covalent bond organic frame | skeleton material (COF), For example, Science, 2005,310,1166. J. et al. Am. Chem. Soc. 2007, 129, 12914. , Science, 2007, 316, 268. J. et al. Am. Chem. Soc. , 2009, 131, 4570. Chem. Matter, 2006, 18, 5296. , Angew. Chem. , Int. Ed. 2008, 47, 8826. Covalent organic skeletal materials (COF) described in US Patent Publication No. US2006 / 0154807 A1 and JP-T 2010-516869 are preferably used.

A metal organic framework material (MOF) is a material having a porous structure utilizing a coordinate bond between a metal ion and an organic substance. In the metal organic framework material (MOF), an organic compound coordinated to at least one metal ion forms a porous structure. The metal ions constituting the metal organic framework material (MOF) can be almost any metal in the periodic table, among which Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ or Zn ² It is preferably ⁺ , and more preferably Zn ²⁺ . Examples of organic substances that form coordinate bonds with metal ions include 3-pyridyltriazine, 4-pyridyltriazine, alkylimidazole, bipyridine, terephthalic acid, 2,6-naphthalenedicarboxylic acid, or 1,3,5-benzenetricarboxylic acid. Among them, 3-pyridyltriazine, 4-pyridyltriazine, alkylimidazole, or bipyridine is more preferable, and 3-pyridyltriazine, 4-pyridyltriazine, or alkylimidazole is particularly preferable. Among them, the metal organic framework material (MOF) is particularly preferably an equi-reticular metal organic framework material (IRMOF) or a zeolite type imidazole framework material (ZIF).

  The metal ion becomes the core of the metal organic framework material (MOF), and the cores are linked using a linking ligand or linking moiety. Here, the core refers to a repeating unit (single or plural) found in the skeleton. Such a skeleton may include a uniform repeating core structure or a non-uniform repeating core structure. The core includes a metal or metal cluster and a connecting portion, and a skeleton is defined by a plurality of cores connected to each other. Here, the metal cluster is a combination of two or more metal atoms.

  A linking moiety refers to a monodentate or multidentate compound that binds a metal or metals, respectively, via a linking cluster. Generally, the linking moiety includes a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aryl group. Further, the linking part may contain nitrogen, oxygen, sulfur, boron, phosphorus, silicon or aluminum in addition to the carbon atom.

A linking cluster refers to one or more condensable reactive species containing atoms that can form a bond between a linking moiety and a metal, or between a linking moiety and another linking moiety. . Examples of such species are preferably selected from the group consisting of boron, oxygen, carbon, nitrogen, and phosphorus atoms. The linked cluster is, for example, —COOH, —CS ₂ H, —NO ₂ , —SO ₃ H, —Si (OH) ₃ , —Ge (OH) ₃ , —Sn (OH) ₃ , —Si (SH) _{4. , -Ge (SH) 4, -Sn} (SH) 4, -PO 3 H, -AsO 3 H, -AsO 4 H, -P (SH) 3, -As (SH) 3, -CH (RSH) 2 _{, -C (RSH) 3, -CH} (RNH 2) 2, -C (RNH 2) 3, -CH (ROH) 2, -C (ROH) 3, -CH (RCN) 2, -C (RCN) ₃ , —CH (SH) ₂ , —C (SH) ₃ , —CH (NH ₂ ) ₂ , —C (NH ₂ ) ₃ , —CH (OH) ₂ , —C (OH) ₃ , —CH (CN ) ₂ or -C (CN) ₃ may be included. In addition, said R is a C1-C20 alkyl group or an aryl group.

  Examples of the metal organic framework material (MOF) include US Pat. No. 5,648,508, US Pat. No. 7,196,210, European Patent Publication No. EP 0790253 A2, M.S. O'Keeff et al. Sol. State Chem. , 152 (2000), pages 3 to 20, H.C. Li et al., Nature 402, (1999), p. Edaudidi et al., Topics, in, Catalysis 9, (1999), pages 105-111, B.R. Chen et al., Science 291, (2001), pages 1021-1023, German Patent Publication DE 10111230 A1, European Patent Publication EP 1785428 A1, International Publication WO 2007/045481, International Publication WO 2005/049892 and International Publication WO 2007. The materials described in Japanese Patent No. 023134 can be used. Among these, ZIF-8 (Zn (2-Methylimidazole)) is preferable.

ＺＩＦ−８

ZIF-8

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

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

  The inorganic metal salt can contain water of crystallization, and the inorganic metal salt is preferably a hydrated salt. Since the inorganic metal salt contains crystal water, the thermal conductivity is improved, which is preferable in that it can be uniformly fired. As the inorganic metal salt containing crystal water, for example, cobalt chloride (III) hydrate salt, iron chloride (III) hydrate salt, cobalt chloride (II) hydrate salt, iron chloride (II) hydrate salt is preferably used. it can.

  The metal species of the inorganic metal salt is preferably at least one of Fe, Co, Ni, Mn and Cr, more preferably Fe or Co, and even more preferably Fe. Fe, Co, Ni, Mn, and Cr salts are excellent in forming a nano-sized shell structure that improves the catalytic activity of the carbon catalyst, and in particular, Co and Fe form a nano-sized shell structure. It is preferable because it is particularly excellent. Further, Co and Fe contained in the carbon catalyst can improve the oxygen reduction reaction activity of the catalyst in the carbon catalyst. Most preferably, it is Fe as a transition metal. The Fe-containing nitrogen-containing carbon alloy has a high rising potential, has a higher number of reaction electrons than Co, and can relatively improve the durability of the fuel cell. As long as the activity of the carbon catalyst is not inhibited, elements other than transition metals (for example, B, alkali metals (Na, K, Cs), alkaline earths (Mg, Ca, Ba), lead, tin, indium, thallium, etc. ) May be included in one or more types.

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

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

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

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

Examples of organometallic complexes that can be used include β-diketone metal complexes (bis (acetylacetonato) iron (II) [Fe (acac) ₂ ], tris (acetylacetonato) iron (III) [Fe (acac ₃ ], bis (acetylacetonato) cobalt (II) [Co (acac) ₂ ], tris (acetylacetonato) cobalt (III) [Co (acac) ₃ ]), bis (dipivaloylmethane) iron (II) [Fe (DPM) ₂ ], tris (dipivaloylmethane) iron (III) [Fe (DPM) ₃ ], tris (dipivaloylmethane) cobalt (III) [Co (DPM) ₃ ] , bis (diisobutoxyphenyl methane) iron (II) [Fe (DIBM) 2], tris (diisobutoxyphenyl methane) iron (III) [Fe (DIBM) 3], tris (diisobutyronitrile Kishimetan) cobalt (III) [Co (DIBM) 3], bis (iso-butoxy pivaloyl methane) iron (II) [Fe (IBPM) 2], tris (isobutoxy pivaloyl methane) cobalt (III) [Co (IBPM) ₃ ], bis (tetramethyloctadione) iron (II) [Fe (TMOD) ₂ ]), tris (tetramethyloctadione) iron (III) [Fe (TMOD) ₃ ], tris (tetramethylocta Dione) cobalt (III) [Co (TMOD) ₃ ]), tris (1,10-phenanthrolinato) iron (III) chloride [Fe (phen) ₃ ] Cl ₂ , tris (1,10-phenant) Rorinato) cobalt (III) chloride _{[Co (phen) 3] Cl} 2, N, N'- methylenebis (salicylidene A Minato) metal complexes and analogues (Salen metal complex) (N, N′-ethylenediaminebis (salicylideneaminato) iron (II) [Fe (salen)], N, N′-ethylenediaminebis (salicylideneaminato) iron (III) chloride [Fe (salen) Cl], N, N′-bis (salicylidene) -o-phenylenediaminoiron (II) [Fe (Saloph)], N, N′-ethylenediaminebis (salicylideneaminato) cobalt (II) [Co (salen)], N, N′-ethylenediaminebis (salicylideneaminato) cobalt (III) chloride [Co (salen) Cl], N, N′-bis (salicylidene) -o— phenylene diethylene amino cobalt (II) [Co (saloph) ]), tris (2,2'-bipyridine) iron (II) chloride _{[Fe (bpy) 3] Cl} 2, tri (2,2'-bipyridine) may be mentioned cobalt (II) chloride _{[Co (bpy) 3] Cl} 2, iron phthalocyanine (MPc) and iron acetate [Fe (OAc) _2].
Among them, β-diketone metal complexes (bis (acetylacetonato) iron (II) [Fe (acac) ₂ ], tris (acetylacetonato) iron (III) [Fe (acac) ₃ ]), bis (dipivalo Ylmethane) iron (II) [Fe (DPM) ₂ ], bis (diisobutoxymethane) iron (II) [Fe (DIBM) ₂ ], bis (isobutoxypivaloylmethane) iron (II) [Fe (IBPM) ₂ ), bis (tetramethyloctadione) iron (II) [Fe (TMOD) ₂ ]), N, N′-ethylenediaminebis (salicylideneaminato) iron (II) [Fe (salen)], tris (2,2'-bipyridine) iron (II) chloride _{[Fe (bpy) 3] Cl} 2, iron phthalocyanine (MPc), iron acetate _{[Fe (OAc) 2],} N, N'- ethylenediamine bis (Sa Chiledenaminato) iron (II) [Fe (salen)] or N, N′-ethylenediaminebis (salicylideneaminato) cobalt (II) [Co (salen)] is preferred, and bis ( Acetylacetonato) iron (II) [Fe (acac) ₂ ] or iron acetate [Fe (OAc) ₂ ] which is a metal acetate complex is more preferably used.

  In this invention, it is preferable that at least 1 type selected from an inorganic metal salt and an organometallic complex is contained exceeding 0.1 mass% with respect to the total mass of a precursor, and 0.1-50 mass% is contained. It is more preferable that 0.1 to 20% by mass is further included. By containing at least one selected from inorganic metal salts and organometallic complexes within the above range, inorganic metal salts or organometallic complexes are volatilized in the reaction space (in the pores) of the porous material (MOF, COF, etc.). However, even if pyrolysis and reduction, the metal nanoclusters form a catalytically active site without agglomeration, so that it becomes easy to produce a nitrogen-containing carbon alloy having high oxygen reduction reaction activity. In the present invention, by using a covalent organic skeleton material and a metal organic skeleton material in combination, it is also possible to suppress the addition amount of at least one selected from inorganic metal salts and organometallic complexes. Specifically, even if it is a case where it is 0.1-50 mass% with respect to the total mass of a precursor, the nitrogen-containing carbon alloy which has high oxygen reduction reaction activity can be produced | generated with a high yield. . By suppressing the addition amount of at least one selected from an inorganic metal salt and an organometallic complex, it is possible to perform a reduction reaction efficiently and obtain a nitrogen-containing carbon alloy having high oxygen reduction reaction activity.

The oxygen reduction reaction activity (ORR activity) can be measured as an ORR activity value by obtaining a potential by the method described in detail in Examples. To obtain high output, it is preferred high value of the potential at the time of oxygen reduction, specifically, the potential at a current density value -2 mA / cm ² in the electrode coating amount of 0.5 mg / cm ^2, 0 .70 V or more is preferable, 0.73 V or more is more preferable, and 0.80 V or more is more preferable. The coating amount and the current density increase linearly, but as the coating amount increases, the current density decreases from the assumed straight line due to an increase in resistance between the nitrogen-containing carbon alloy particles, an increase in diffusion resistance of oxygen and water, and the like. According to Ohm's law, the coating amount and the potential are similarly deviated from the straight line in the relationship between the coating amount and the potential. The value of the potential at 0.5 mg / cm ² is a value that takes into account the potential of the catalyst activity at 0.05 mg / cm ² and the conductivity of the nitrogen-containing carbon alloy. It is particularly preferable because it can obtain the properties.

(Conductive aid)
In the present invention, a conductive additive may be added to the precursor and baked, or may be added to the nitrogen-containing carbon alloy. Although it does not specifically limit as a conductive support agent, For example, Norrit (made by NORIT), Ketjen black (made by Lion), Vulcan (made by Cabot), black pearl (made by Cabot), acetylene black (Chevron) Carbon black such as (manufactured) (all are trade names), graphite, and carbon materials such as fullerenes such as C60 and C70, carbon nanotubes, carbon nanohorns, and carbon fibers.

  The addition rate of the conductive assistant is preferably 0.01 to 50% by mass, more preferably 0.1 to 20% by mass, and more preferably 1 to 10% by mass with respect to the total mass of the precursor. More preferably it is. By setting the addition amount of the conductive additive within the above range, the aggregation and growth of the metal generated from the inorganic metal salt or organometallic complex in the system becomes uniform, and the desired porous nitrogen-containing carbon alloy is obtained. I can do it.

<Each process in the manufacturing method of nitrogen-containing carbon alloy>
The method for producing the nitrogen-containing carbon alloy of the present invention comprises:
(1) A nitrogen-containing organic compound having the structure described above, at least one selected from a covalent organic skeleton material and a metal organic skeleton material, and at least one selected from an inorganic metal salt and an organometallic complex are mixed. Preparing a precursor; and
(2) a temperature raising step for raising the temperature of the precursor from 1 to 2000 ° C. per minute from room temperature to the carbonization temperature under an inert atmosphere;
(3) a carbonization step of holding at 400 to 2000 ° C. for 1 second to 100 hours;
(4) It is preferable to include a cooling step of cooling from the carbonization temperature to room temperature.

After the step of preparing the precursor of (1), it is preferable to further include a step of pulverizing the precursor (1-2). Further, after the step of firing the precursors (2) to (4) (after the carbonization treatment, the nitrogen-containing carbon alloy is cooled to room temperature), (5) pulverization treatment may be performed.
Furthermore, the manufacturing method of the nitrogen-containing carbon alloy of the present invention is the firing step,
(6) It preferably includes a step of washing the baked nitrogen-containing carbon alloy with an acid,
(7) More preferably, after the acid cleaning step, a step of refiring the acid-cleaned nitrogen-containing carbon alloy is included.
Hereinafter, the above-described steps (1) to (7) will be described in order for the method for producing a nitrogen-containing carbon alloy of the present invention.

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

(1-2) Step of grinding the precursor The precursor prepared in the production process of the nitrogen-containing carbon alloy is then fired, but it is preferable to further include a step of grinding the precursor before the firing step.

  When the step of pulverizing the precursor is included before the firing step, the pulverization method can be performed by any method known to those skilled in the art, and for example, pulverization can be performed using agate pulverization, mechanical pulverization, or the like. . Of these, the mechanical grinding method is preferably used. In the mechanical grinding method, grinding is performed by rotating a cutting mill. That is, in the mechanical pulverization method, pulverization is performed by applying a shearing force to the precursor. By using such a mechanical pulverization method, the specific volume of the precursor can be set to a certain value or more, thereby obtaining a nitrogen-containing carbon alloy having high oxygen reduction reaction activity (ORR activity).

For machine pulverization, for example, X-TREME MX1200XTM manufactured by Waring Co., Ltd. can be used. Although it does not specifically limit regarding grinding | pulverization conditions, It is preferable that the rotation speed of a rotary blade is 80 to 30000 rpm, it is more preferable to mix at 300 to 25000 rpm, and it is further more preferable to mix at 1300 to 20000 rpm. The rotation method can be performed by continuous rotation, intermittent rotation, or a combination of continuous and intermittent rotation. The pulverization time is preferably 0.1 seconds to 15 minutes, and the number of pulverizations is preferably at least once.
In the intermittent pulverization, the stop time of the rotary blade is preferably 0.1 to 100 times the pulverization time, more preferably 1 to 50 times, and even more preferably 2 to 30 times. For example, when the rotational speed is 10000 rpm or more, the pulverization time is 10 seconds or less, the rotary blade stop time is 0.1 times or more, and the number of pulverizations is 2 times or more, decomposition of the precursor mixture by heat is reduced, and the precursor mixture Since the mixing can be made uniform, the oxygen reduction reaction activity can be increased more effectively.
When the pulverization time by continuous pulverization is 30 seconds or more, the precursor mixture generates heat, and at least one kind of pores selected from a covalently bonded organic skeleton material and a metal organic skeleton material has a nitrogen-containing organic compound and a nitrogen-containing organic compound. More effective because at least one selected from tautomers of compounds, salts of nitrogen-containing organic compounds and hydrates of nitrogen-containing organic compounds and at least one selected from inorganic metal salts and organometallic complexes are volatilized. In particular, the oxygen reduction reaction activity can be increased.

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

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

In the temperature raising process, the sample before treatment may be inserted from the normal temperature to a predetermined temperature after being inserted into the carbonization apparatus, or the temperature may be increased by inserting the sample before treatment into the carbonization apparatus at the predetermined temperature. May be warm.
Preferably, the temperature of the sample before processing is raised from room temperature to a predetermined temperature. When raising the temperature to a predetermined temperature, it is preferable to keep the temperature raising rate constant. More specifically, the rate of temperature increase is preferably 1 to 2000 ° C./min, more preferably 1 to 1000 ° C./min, and 1 to 500 ° C./min. Is more preferable.

(Preliminary carbide)
In order to obtain a pre-carbide with pores formed, the previous treatment of the organic material containing a nitrogen-containing organic compound, a covalently bonded organic skeleton material or metal organic skeleton material, and an inorganic metal salt or organometallic complex is compared. It is preferable to carry out at a low temperature. In such a low temperature treatment, a constant temperature may be maintained. As a result, only the heat-stable structure can be maintained, and unstable impurity components, solvents, and the like can be removed.

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

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

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

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

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

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

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

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

(carbide)
In order to obtain a carbide, it is preferable to cool to room temperature after the temperature rising treatment in the previous stage, uniformly pulverize, perform acid cleaning, and then perform the temperature rising process in the subsequent stage. As a result, the treatment temperature in the carbonization treatment can be increased, and a nitrogen-containing carbon alloy having a more regular carbon structure can be obtained. As a result, the conductivity of the nitrogen-containing carbon alloy is improved, high oxygen reduction performance is obtained, and durability as a catalyst is also improved.
It is also preferable to perform carbonization treatment at a high temperature directly from the previous stage. Thereby, the yield of the nitrogen-containing carbon alloy may be reduced, but the crystallite size of the obtained nitrogen-containing carbon alloy is uniform, so that the metal is uniformly distributed and the state of high activity is maintained. As a result, it becomes possible to produce a nitrogen-containing carbon alloy having excellent oxygen reduction performance. In addition, it is preferable that such process temperature does not exceed carbonization temperature, and a suitable nitrogen-containing carbon alloy can be obtained by performing carbonization process in such a temperature range.

The firing temperature of the carbonization treatment of the precursor containing a nitrogen-containing organic compound having a specific structure and an inorganic metal salt is not particularly limited as long as the nitrogen-containing organic compound is thermally decomposed and carbonized. The upper limit of is required to be 2000 ° C.
In the case of a precursor containing at least one selected from inorganic metal salts and organometallic complexes, the lower limit of the reaction temperature is preferably 400 ° C, more preferably 500 ° C, and even more preferably 600 ° C. 700 ° C. is even more preferable. By setting the reaction temperature within the above range, a carbon-containing carbon alloy having advanced catalytic performance and high catalytic performance can be obtained. Moreover, if reaction temperature is 2000 degrees C or less, nitrogen will remain in carbon skeleton and it can be set as desired N / C atomic ratio, and sufficient oxygen reduction reaction activity will be obtained.
The firing temperature is preferably 600 to 1500 ° C, more preferably 700 to 1200 ° C, and particularly preferably 700 to 1050 ° C. When the carbonization treatment is performed within this range, the yield of the nitrogen-containing carbon alloy may be reduced, but the crystallite size of the obtained nitrogen-containing carbon alloy is uniform, so that the metal is uniformly distributed and the activity is high. State is maintained. As a result, it becomes possible to produce a nitrogen-containing carbon alloy having excellent oxygen reduction performance. Further, by performing the carbonization treatment within the above range, nitrogen easily remains in the carbon skeleton due to the action of the generated inorganic metal, and the oxygen reduction reaction activity can be enhanced.

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

  In the carbonization treatment step, it is also preferable to perform continuous firing. Here, continuous firing refers to firing at a higher temperature without cooling to room temperature after the temperature rise. For example, the temperature can be raised to 300 to 950 ° C., held for 1 to 50 hours, then heated, and held at 900 to 1050 ° C. for 0.1 to 10 hours. In the continuous firing, the covalent organic skeleton material or the metal organic skeleton material is decomposed by firing at a relatively low temperature of 300 to 950 ° C. for a long time, and the decomposed covalent organic skeleton material or metal organic skeleton material Other insoluble materials can be volatilized. Furthermore, by firing at a relatively high temperature of 900 to 1050 ° C., the oxygen reduction reaction activity of the nitrogen-containing carbon alloy having high conductivity can be enhanced.

(5) Crushing treatment After the carbonization treatment, the nitrogen-containing carbon alloy may be cooled to room temperature and then crushed. The pulverization treatment can be performed by any method known to those skilled in the art, and for example, pulverization can be performed using a ball mill, agate pulverization, mechanical pulverization, or the like.

(6) Acid Washing Process The method for producing a nitrogen-containing carbon alloy of the present invention may include an acid washing process for washing the fired nitrogen-containing carbon alloy with an acid after the firing process. The ORR activity can be improved by acid-washing the metal on the surface of the produced nitrogen-containing carbon alloy catalyst. By this acid cleaning treatment, it is expected that a porous nitrogen-containing carbon alloy having optimum porosity can be obtained.
In the acid cleaning treatment, any aqueous Bronsted (proton) acid including a strong acid or a weak acid having a pH of 7 or less can be used in the acid cleaning step. Furthermore, an inorganic acid (mineral acid) or an organic acid can be used. Examples of suitable acids include HCI, HBr, HI, H ₂ SO ₄ , H ₂ SO ₃ , HNO ₃ , HClO ₄ , [HSO ₄ ] ⁻ , [HSO ₃ ] ⁻ , [H ₃ O] ⁺ , H ₂ [C ₂ O ₄ ], HCO ₂ H, HCIO ₃ , HBrO ₃ , HBrO ₄ , HIO ₃ , HIO ₄ , FSO ₃ H, CF ₃ SO ₃ H, CF ₃ CO ₂ H, CH ₃ CO ₂ H, B (OH) ₃ , etc. (including any combination thereof), but are not limited to these. In addition, the method described in JP-T-2010-524195 can also be used in the present invention.

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

  Since the refiring process needs to be performed at a temperature higher than the calcining process for the purpose of promoting graphitization of carbon, the calcining temperature in the refiring process is preferably 500 to 2000 ° C, and preferably 600 to 1500 ° C. Is more preferable, and it is more preferable that it is 900-1500 degreeC. Moreover, it is preferable that the calcination temperature of a rebaking process is a temperature higher than the calcination temperature in the first baking process.

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

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

It is preferable to further include a step of deaeration and nitrogen substitution before the step of refiring. By providing such a process, the oxygen concentration can be reduced. In the step of deaeration and nitrogen replacement, it is preferable to perform nitrogen gas replacement after deaeration with a vacuum pump. In particular, it is preferable to repeat the operation of replacing nitrogen gas multiple times after deaeration with a vacuum pump. At this time, the apparatus used for deaeration is not particularly limited as long as it can be deaerated, but it is preferable to use a vacuum gas replacement furnace or a vacuum gas replacement rotary furnace (rotary kiln). The pressure during vacuum degassing is not particularly limited, but is preferably 4 × 10 ⁴ Pa or less, more preferably 4 × 10 ³ Pa or less, and particularly preferably 2 × 10 ² Pa or less.

When re-firing the nitrogen-containing carbon alloy, it is preferable to flow the nitrogen-containing carbon alloy for the purpose of uniformizing the performance of the nitrogen-containing carbon alloy. The apparatus used at this time is not particularly limited as long as it can flow the nitrogen-containing carbon alloy, but it is preferable to use a rotary furnace (rotary kiln), a vacuum gas replacement rotary furnace (rotary kiln), or a fluidized firing furnace.
When using a rotary furnace (rotary kiln) or a vacuum gas replacement rotary furnace (rotary kiln), the sample tube is rotated during firing, but the rotational speed, speed change, etc. are not particularly limited. The rotation speed is preferably 10 rpm or less, more preferably 5 rpm or less. By setting the rotation speed within this range, rubbing occurs between the tube wall and the preliminary carbon, so that the nitrogen-containing carbon alloy is refined and made porous, so that the oxygen reduction reaction activity can be enhanced more effectively.

In the method for producing a nitrogen-containing carbon alloy of the present invention, it is preferable to perform a carbonization treatment in the presence of an activator (activation step). By performing carbonization treatment at a high temperature in the presence of an activator, the pores of the nitrogen-containing carbon alloy develop and the surface area increases, and the degree of exposure of the metal on the surface of the nitrogen-containing carbon alloy improves, so that as a catalyst Improved performance. The surface area of the carbide can be measured by the N ₂ adsorption amount.

The activator that can be used is not particularly limited. For example, carbon dioxide, ammonia gas, water vapor, air, oxygen gas, hydrogen gas, carbon monoxide gas, methane gas, alkali metal hydroxide, zinc chloride, and phosphoric acid. At least one selected from the group consisting of carbon dioxide, ammonia gas, water vapor, air, and oxygen gas can be used, more preferably at least one selected from the group consisting of:
The gas activator is preferably diluted with an inert gas. Examples of the inert gas to be diluted include nitrogen gas and rare gases (for example, argon gas, helium gas, and neon gas).
The gas activator may be contained in an atmosphere of carbonization treatment in an amount of 2 to 80 mol%, preferably 10 to 60 mol%. By including the gas activator so as to be within the above range, a sufficient activation effect can be obtained. In addition, the solid activator such as alkali metal hydroxide may be mixed with the carbonized substance in a solid state, or after being dissolved or diluted with a solvent such as water, impregnated with the carbonized substance or in a slurry state. And may be kneaded into the article to be carbonized. The liquid activator may be diluted with water or the like and then impregnated with the carbonized material or kneaded into the carbonized material.
During the heat treatment, the pressure in the gas phase may be any of normal pressure, pressurization, and reduced pressure, but is preferably pressurized at a high temperature.
The gas may be stationary or distributed, but is preferably distributed from the viewpoint of discharging generated impurities.

  Nitrogen atoms can also be introduced after carbonization. At this time, as a method for introducing nitrogen atoms, a liquid phase doping method, a gas phase doping method, or a gas phase-liquid phase doping method can be used. For example, nitrogen atoms can be introduced into the surface of the carbon catalyst by heat treatment by holding the nitrogen-containing carbon alloy at 200 to 1200 ° C. for 5 to 180 minutes in an ammonia atmosphere as a nitrogen source.

(Nitrogen-containing carbon alloy)
The present invention relates to a nitrogen-containing carbon alloy produced by the above-described method for producing a nitrogen-containing carbon alloy.

The nitrogen-containing carbon alloy of the present invention obtained by firing the precursor is a nitrogen-containing carbon alloy into which nitrogen has been introduced. The nitrogen-containing carbon alloy of the present invention preferably contains graphene, which is an aggregate of carbon atoms having a hexagonal network structure in which carbon is chemically bonded by sp ² hybrid orbitals and spreads in two dimensions.

  Furthermore, in the nitrogen-containing carbon alloy of the present invention, the content of surface nitrogen atoms in the carbon catalyst is more preferably 0.02 to 0.3 in terms of atomic ratio (N / C) to the surface carbon. By setting the atomic ratio (N / C) of nitrogen atoms to carbon atoms within the above range, the number of effective nitrogen atoms bonded to the metal can be ensured, and sufficient oxygen reduction catalyst characteristics can be obtained. In addition, by setting the atomic ratio (N / C) of the nitrogen atom to the carbon atom within the above range, the strength of the carbon skeleton of the nitrogen-containing carbon alloy can be increased, and the decrease in electrical conductivity can be suppressed. it can.

  Further, the skeleton of the nitrogen-containing carbon alloy only needs to be formed of at least carbon atoms and nitrogen atoms, and may contain hydrogen atoms, oxygen atoms, and the like as other atoms. In that case, the atomic ratio ((other atoms) / (C + N)) of other atoms to carbon atoms and nitrogen atoms is preferably 0.3 or less.

In specific surface area analysis, nitrogen-containing carbon alloy is put in a predetermined container, cooled to liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced into the container and adsorbed, and from the adsorption isotherm, The adsorption parameter can be calculated, and the BET (Brunauer-Emmett-Teller) method can be used to calculate the specific surface area of the sample from the molecular occupation cross section (0.162 cm ² ) of nitrogen.

  The pore shape of the nitrogen-containing carbon alloy is not particularly limited, and for example, pores may be formed only on the surface, or pores may be formed not only on the surface but also inside. When pores are also formed inside, for example, it may be tunnel-shaped, and it has a shape in which polygonal cavities such as spherical or hexagonal columns are connected to each other. It may be.

The specific surface area of nitrogen-containing carbon alloy is preferably at 90m ² / g or more, more preferably 350 meters ² / g or more, and particularly preferably 560 m ² / g or more. However, when the catalytically active site (metal coordination product or configuration space (field) having at least C, N, and metal ions as constituents) is generated and formed at a high density, it may be outside the above range.
From the viewpoint of sufficient oxygen reaching the depths of the pores and obtaining sufficient oxygen reduction catalytic properties, the specific surface area of the nitrogen-containing carbon alloy is preferably 3000 m ² / g or less, and 2000 m ² / g or less. It is more preferable that it is 1500 m ² / g or less.

  The shape of the nitrogen-containing carbon alloy of the present invention is not particularly limited as long as it has oxygen reduction reaction activity. For example, a large distorted structure such as a sheet shape, a fiber shape, a plate shape, a column shape, a block shape, a particle shape, many ellipses other than a spherical shape, a flat shape, a square shape, and the like can be given. From the viewpoint of easy dispersion, it is preferably a block shape or a particle shape. However, when a slurry described later is applied and dried, it is preferably a fiber shape, a plate shape, or a column shape from the viewpoint of imparting thixotropy.

Furthermore, the slurry containing a nitrogen-containing carbon alloy can be produced by dispersing the nitrogen-containing carbon alloy of the present invention in a solvent. Thereby, for example, when making an electrode catalyst (fuel cell catalyst) of a fuel cell or an electrode material of a power storage device easy, a slurry in which a nitrogen-containing carbon alloy is dispersed in a solvent is applied to a support material and fired. The carbon catalyst processed into arbitrary shapes can be formed by making it dry. Thus, by making a nitrogen-containing carbon alloy into a slurry, the workability of a carbon catalyst improves and it can be easily used as an electrode catalyst or an electrode material.
Fuel cell carbon alloy catalyst of the present invention preferably has a coating amount after drying of the nitrogen-containing carbon alloy is 0.01 mg / cm ² or more, more preferably 0.02~100mg / cm ^2, Particularly preferred is 0.05 to 10 mg / cm ² .
As the solvent, a solvent used when producing an electrode catalyst for a fuel cell or an electrode material for a power storage device can be appropriately selected and used. For example, as a solvent used when producing an electrode material for a power storage device, diethyl carbonate (DEC), dimethyl carbonate (DMC), 1,2-dimethoxyethane (DME), ethylene carbonate (EC), ethyl methyl carbonate (EMC) ), N-methyl-2-pyrrolidone (NMP), propylene carbonate (PC), γ-butyrolactone (GBL), etc., can be used alone or in combination. In addition, examples of the solvent used in preparing the fuel cell electrode catalyst include water, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, methyl ethyl ketone, and acetone.

<Application of nitrogen-containing carbon alloy>
The use of the nitrogen-containing carbon alloy of the present invention is not particularly limited to structural materials, electrode materials, filtration materials, catalyst materials, etc., but is preferably used as electrode materials for power storage devices such as capacitors and lithium secondary batteries. More preferably, it is used as a carbon catalyst for a fuel cell, zinc-air battery, lithium-air battery or the like having reactive activity. In the electrode membrane assembly including the solid polymer electrolyte membrane and the catalyst layer provided in contact with the solid polymer electrolyte membrane, the catalyst may be included in the catalyst layer. Furthermore, the electrode membrane assembly can be provided in a fuel cell.

<Fuel cell>
FIG. 1 shows a schematic configuration diagram of a fuel cell 10 using a carbon catalyst made of a nitrogen-containing carbon alloy of the present invention. The carbon catalyst is applied to the anode electrode and the cathode electrode.
The fuel cell 10 includes a separator 12, an anode electrode catalyst (fuel electrode) 13, a cathode electrode catalyst (oxidant electrode) 15, and a separator 16 that are disposed so as to sandwich the solid polymer electrolyte 14. As the solid polymer electrolyte 14, a fluorine-based cation exchange resin membrane represented by a perfluorosulfonic acid resin membrane is used. Moreover, the fuel cell 10 provided with the carbon catalyst in the anode electrode catalyst 13 and the cathode electrode catalyst 15 is configured by bringing the carbon catalyst into contact with both of the solid polymer electrolyte 14 as the anode electrode catalyst 13 and the cathode electrode catalyst 15. The By forming the carbon catalyst described above on both sides of the solid polymer electrolyte, and adhering the anode electrode catalyst 13 and the cathode electrode catalyst 15 to both main surfaces of the solid polymer electrolyte 14 on the electrode reaction layer side by hot pressing, It integrates as MEA (Membrane Electrode Assembly).

  In a conventional fuel cell, a gas diffusion layer made of a porous sheet (for example, carbon paper) that also functions as a current collector is interposed between the separator and the anode and cathode electrode catalyst. In contrast, in the fuel cell 10 of FIG. 1, a carbon catalyst having a large specific surface area and high gas diffusibility can be used as the anode and cathode electrode catalyst. By using the above-mentioned carbon catalyst as an electrode, even when there is no gas diffusion layer, the carbon catalyst has a gas diffusion layer function, and the anode and cathode electrode catalysts 13, 15 and the gas diffusion layer are integrated. Since the battery can be configured, the fuel cell can be reduced in size and the cost can be reduced by omitting the gas diffusion layer.

The separators 12 and 16 support the anode and cathode electrode catalyst layers 13 and 15 and supply and discharge reaction gases such as fuel gas H ₂ and oxidant gas O ₂ . When a reaction gas is supplied to each of the anode and cathode electrode catalysts 13 and 15, a gas phase (reaction gas) and a liquid phase (solid) are formed at the boundary between the carbon catalyst provided on both electrodes and the solid polymer electrolyte 14. A three-phase interface of a polymer electrolyte membrane) and a solid phase (a catalyst possessed by both electrodes) is formed. And direct-current power generate | occur | produces by producing an electrochemical reaction.
In the electrochemical reaction, the following reaction occurs.
Cathode side: O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O
Anode side: H ₂ → 2H ⁺ + 2e ⁻
H ⁺ ions generated on the anode side move in the solid polymer electrolyte 14 toward the cathode side, and e ⁻ (electrons) move to the cathode side through an external load. On the other hand, on the cathode side, oxygen contained in the oxidant gas reacts with H ⁺ ions and e ⁻ that have moved from the anode side to generate water. As a result, the above-described fuel cell generates direct-current power from hydrogen and oxygen to generate water.

(Power storage device)
Next, a power storage device in which the carbon catalyst made of the nitrogen-containing carbon alloy of the present invention is applied to an electrode material will be described. FIG. 2 shows a schematic configuration diagram of an electric double layer capacitor 20 using a carbon catalyst made of nitrogen-containing carbon alloy and having an excellent storage capacity.
In the electric double layer capacitor 20 shown in FIG. 2, the first electrode 21 and the second electrode 22 which are polarizable electrodes are opposed to each other through the separator 23, and are accommodated in the outer lid 24a and the outer case 24b. ing. The first electrode 21 and the second electrode 22 are connected to the exterior lid 24a and the exterior case 24b via current collectors 25, respectively. The separator 23 is impregnated with an electrolytic solution. The electric double layer capacitor 20 is configured by caulking and sealing the outer lid 24a and the outer case 24b while being electrically insulated via the gasket 26.

  In the electric double layer capacitor 20 of FIG. 2, the carbon catalyst made of the above-described nitrogen-containing carbon alloy can be applied to the first electrode 21 and the second electrode 22. And the electric double layer capacitor by which the carbon catalyst was applied to the electrode material can be comprised. The above-described carbon catalyst has a fibrous structure in which nanoshell carbon is aggregated, and furthermore, since the fiber diameter is in a nanometer unit, the specific surface area is large, and the electrode interface where charges are accumulated in the capacitor is large. Furthermore, the above-mentioned carbon catalyst is electrochemically inactive with respect to the electrolytic solution, and has appropriate electrical conductivity. For this reason, the electrostatic capacitance per unit volume of an electrode can be improved by applying as an electrode of a capacitor.

  Similarly to the above-described capacitor, for example, the above-described carbon catalyst can be applied as an electrode material composed of a carbon material, such as a negative electrode material of a lithium ion secondary battery. And since the specific surface area of a carbon catalyst is large, a secondary battery with a large electrical storage capacity can be comprised.

<Environmental catalyst>
Next, an example in which the nitrogen-containing carbon alloy of the present invention is used as a substitute for an environmental catalyst containing a noble metal such as platinum will be described.
As a catalyst for exhaust gas purification for removing pollutants contained in polluted air (mainly gaseous substances) etc. by decomposition treatment, a catalyst material composed of noble metal materials such as platinum alone or in combination Environmental catalysts are used. The above-mentioned carbon catalyst can be used as an alternative to these exhaust gas purifying catalysts containing noble metals such as platinum. Since the above-described carbon catalyst is provided with an oxygen reduction reaction catalytic action, it has a function of decomposing substances to be treated such as pollutants. For this reason, since it is not necessary to use expensive noble metals, such as platinum, by comprising an environmental catalyst using the above-mentioned carbon catalyst, a low-cost environmental catalyst can be provided. Further, since the specific surface area is large, the treatment area for decomposing the material to be treated per unit volume can be increased, and an environmental catalyst having an excellent decomposition function per unit volume can be constituted.
By using the above-mentioned carbon catalyst as a carrier, a noble metal-based material such as platinum used in conventional environmental catalysts is carried alone or in a composite, so that an environmental catalyst with more excellent catalytic action such as a decomposition function can be obtained. Can be configured. In addition, the environmental catalyst provided with the above-mentioned carbon catalyst can also be used as a purification catalyst for water treatment as well as the above-described exhaust gas purification catalyst.

Further, the nitrogen-containing carbon alloy of the present invention can be widely used as a catalyst for chemical reaction, and in particular, can be used as a substitute for a platinum catalyst. That is, the above-mentioned carbon catalyst can be used as a substitute for a general process catalyst for the chemical industry containing a noble metal such as platinum. For this reason, according to the above-mentioned carbon catalyst, a low-cost chemical reaction process catalyst can be provided without using expensive noble metals such as platinum. Furthermore, since the above-mentioned carbon catalyst has a large specific surface area, it can constitute a chemical reaction process catalyst excellent in chemical reaction efficiency per unit volume.
Such a carbon catalyst for chemical reaction is applied to, for example, a hydrogenation reaction catalyst, a dehydrogenation reaction catalyst, an oxidation reaction catalyst, a polymerization reaction catalyst, a reforming reaction catalyst, and a steam reforming catalyst. be able to. More specifically, it is possible to apply a carbon catalyst to each chemical reaction with reference to a catalyst related literature such as “Catalyst Preparation (Kodansha) by Takaho Shirasaki and Naoyuki Todo, 1975”.

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

Example 1
<Carbon Material Synthesis of ZIF-8, Fe (OAc) ₂ Addition (Ph ₄ -Por) Mixture (1E)>
(Preparation of ZIF-8, Fe (OAc) ₂ added (Ph ₄ -Por) mixture)
Ph ₄ -Por 1.00 g (manufactured by Aldrich), ZIF-8 9.00 g (manufactured by BASF, Basolite Z1200), 0.32 g of Fe (OAc) ₂ (manufactured by Aldrich, iron (II) acetate, purity 99.99). 995% or more (residual metal amount standard)) is added to a standard container made by Waring, 75 mL SUS, and after nitrogen substitution, rotation of a cutting mill (X-TREME MX1200XTM, standard container made by 75 SUS) made by Waring is started. Then, in 5 seconds, it is rotated at 1300 rpm to 10000 rpm with a stepless speed change, and then rotated at 10000 rpm for 40 seconds to obtain a ZIF-8, Fe (OAc) ₂ added Ph ₄ -Por mixture (precursor) (1A). It was. The specific volume of the precursor (1A) was measured by the following method. The results are shown in Table 1 below.
In addition, in this specification, a precursor means the mixture which mixed each material as mentioned above, and points out the mixture before baking. In the examples, a precursor and a carbon precursor described later are distinguished.

<Measurement of specific volume>
The specific volume was measured based on the method of “apparent density or apparent specific volume” of JIS-K-5101. The measurement was performed by the tap method. Specifically, 10 g of the precursor was placed in a 50 ml graduated cylinder, tapped 500 times, allowed to stand, the volume was read, and the specific volume was determined by the following formula.
Specific volume (ml / g) = V / F
In the formula, F is the mass (g) of the treated precursor in the container, and V indicates the volume (ml) of the sample after tapping.

ＺＩＦ−８

ZIF-8

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

Ｆｅ（ＯＡｃ）₂

Fe (OAc) ₂

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

Molecular formula: C ₄₄ H ₃₀ N ₄ , molecular weight: 614.74
Elemental analysis (calculated values): C, 85.97; H, 4.92; N, 9.11

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
2.2548 g of ZIF-8, Fe (OAc) ₂ -added Ph ₄ -Por mixture (1A) was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. It was installed and the nitrogen flow rate was 200 mL / min, and it was circulated at room temperature for 30 min. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained 0.8373g of carbon precursors (1B). The obtained carbon precursor (1B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.7639 g of acid-washed carbon precursor (1C).

(Firing, grinding, water washing treatment, second firing, vacuum gas replacement furnace)
We measure 0.5333g of carbon precursor (1C) in a quartz boat and install it in the center of a 4.0cmφ (inside diameter 3.6cmφ) quartz tube inserted in a vacuum gas replacement furnace, and set the nitrogen flow rate to 200mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (1D) of non-acid washing | cleaning. Carbon material (1D) 0.2849 g was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.2763 g of non-acid washed carbon material (1E). The obtained non-acid cleaned carbon material (1E) was used as the nitrogen-containing carbon alloy of Example 1.

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

2. Oxygen reduction reaction (ORR) activity of carbon alloy coated electrode (preparation of carbon alloy coated electrode)
To 25 mg of the nitrogen-containing carbon alloy of Example 1, 220 mg of Nafion solution (5% alcohol aqueous solution) as a binder, 2.4 mL of water and 1.6 mL of 1-propanol (IPA) as a solvent were added, and a 7 mmφ attachment was connected. It was dispersed for 30 minutes with an ultrasonic homogenizer (Nissei's US-150T). Using a rotating ring disk electrode (HR2-RD1-Pt8 / GC5 manufactured by Hokuto Denko), a nitrogen-containing carbon alloy dispersion was applied onto the carbon electrode so that the nitrogen-containing carbon alloy was 0.50 mg / cm ^2, and And dried to obtain a carbon alloy coated electrode.

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

(Example 2)
<Synthesis of ZIF-8, Fe (OAc) ₂ Addition (Ph ₄ -Por) Mixture with Acid-washed Carbon Material (2E)>
The above-mentioned carbon material (1D) 0.1821 g was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.1589 g of acid-cleaned carbon material (2E). The obtained acid cleaned carbon material (2E) was used as the nitrogen-containing carbon alloy of Example 2.

(Example 3)
<Carbon Material Synthesis of ZIF-8, Fe (OAc) ₂ Addition (Ph ₄ -Por) Mixture (3E)>
(Continuous firing distribution furnace, pulverization)
The above-mentioned ZIF-8, Fe (OAc) ₂ -added Ph ₄ -Por mixture (1A) 1.2169 g was weighed into a quartz boat and inserted into a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. It was installed in the center, the nitrogen flow rate was 200 mL per minute, and it was circulated at room temperature for 30 minutes. Thereafter, the flow rate of nitrogen is lowered to 20 mL per minute, the temperature is raised from 30 ° C. to 700 ° C. at 5 ° C. per minute, held at 700 ° C. for 10 hours, and further raised from 700 ° C. to 1000 ° C. at 5 ° C. per minute. And held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (3B). The obtained carbon precursor (3B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.2925 g of acid-washed carbon precursor (3C).

(Firing, grinding, water washing treatment, second firing, vacuum gas replacement furnace)
We measure 0.1482g of carbon precursor (3C) in a quartz boat and install it in the center of a 4.0cmφ (inside diameter 3.6cmφ) quartz tube inserted in a vacuum gas replacement furnace, and set the nitrogen flow rate to 200mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (3D) of non-acid washing | cleaning. The carbon material (3D) was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.1275 g of non-acid-washed carbon material (3E). The obtained non-acid cleaned carbon material (3E) was used as the nitrogen-containing carbon alloy of Example 3.

Example 4
<Synthesis of carbon material of ZIF-8, Fe (OAc) ₂ added (H ₂ Pc) mixture (3E)>
(Preparation of ZIF-8, Fe (OAc) ₂ added (H ₂ Pc) mixture)
H ₂ Pc 1.00 g (manufactured by Tokyo Chemical Industry Co., Ltd.), ZIF-8 9.00 g (manufactured by BASF, Basolite Z1200), Fe (OAc) ₂ 0.32 g (manufactured by Aldrich, iron (II) acetate, purity 99) .995% or more (remaining metal amount standard)) was added to a standard container made by Waring, 75 mL SUS, and after nitrogen substitution, rotation of a cutting mill made by Waring (X-TREME MX1200XTM, 75 mL SUS standard container) was started. Then, in 5 seconds, it was rotated at 1300 rpm to 10,000 rpm with a stepless speed change, and then rotated at 10,000 rpm for 40 seconds to obtain a ZIF-8, Fe (OAc) ₂ added H ₂ Pc mixture (precursor) (4A). . The specific volume of the precursor (4A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

Molecular formula: C ₃₂ H ₁₈ N ₈ , molecular weight: 514.17
Elemental analysis (calculated values): C, 70.70; H, 3.53; N, 21.20

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
ZIF-8, Fe (OAc) ₂ -added H ₂ Pc mixture (4A) 1.2365 g was measured in a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. Then, the nitrogen flow rate was set to 200 mL per minute, and the mixture was circulated at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 800 ° C. by 5 ° C. per minute and held at 800 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (4B). The obtained carbon precursor (4B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.4690 g of acid-washed carbon precursor (4C).

(Firing, grinding, water washing treatment, second firing, vacuum gas replacement / rotary furnace)
We measure 0.2769 g of carbon precursor (4C) in a quartz boat and place it in the center of a 4.0 cmφ (inside diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace, with a nitrogen flow rate of 200 mL per minute. And allowed to circulate at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. At that time, the quartz tube was rotated at 2.0 rpm. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (4D) of non-acid washing | cleaning. The carbon material (4D) was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.1946 g of non-acid-washed carbon material (4E). The obtained non-acid cleaned carbon material (4E) was used as the nitrogen-containing carbon alloy of Example 4.

(Example 5)
<Synthesis of carbon material of ZIF-8, Fe (OAc) ₂ added ((4-Py) ₄ -Por) mixture (5E)>
(Preparation of (4-Py) ₄ -Por)
Chemistry Letters, 2007, 36, 848-849. Was prepared to prepare (4-Py) ₄ -Por.
6.4 g of 4-pyridyl aldehyde (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.0 g of 2-hydroxybenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added to 0.4 liter of xylene (xylene A). Under heating under reflux, 4.0 g of pyrrole (manufactured by Kanto Chemical Co., Inc.) was dissolved in 0.1 liter of xylene (xylene B), and the resulting solution (xylene B) was added dropwise to xylene A over 1 hour. The resulting solution was heated to reflux for 3 hours under a nitrogen stream, and then xylene was distilled off under reduced pressure. Thereafter, to wash with heat, the solid residue was heated to reflux with 0.3 liter of ethyl acetate and filtered, and then heated to reflux with 0.03 liter of methanol for filtration. Furthermore, this heat washing operation was repeated once more and dried to obtain 3.95 g of (4-Py) ₄ -Por (ultramarine color powder).

Molecular formula: C ₄₀ H ₂₆ N ₈ , molecular weight: 618.69
Elemental analysis (calculated values): C, 77.65; H, 4.24; N, 18.11

(ZIF-8, Fe (OAc) ₂ addition (Preparation of (4-Py) ₄ -Por) mixture)
(4-Py) ₄ -Por 1.00 g, ZIF-8 9.00 g (BASF, Basolite Z1200), Fe (OAc) ₂ 0.32 g (Aldrich, iron (II) acetate, purity 99 .995% or more (residual metal amount standard)) is added to a standard container made of Warling, 75 mL SUS, and after nitrogen substitution, a cutting mill (X-TREME MX1200XTM, standard container made of 75 mL SUS) manufactured by Waring is rotated. After starting, it is rotated in a stepless manner from 1300 rpm to 10000 rpm in 5 seconds, and then rotated at 10000 rpm for 40 seconds to add ZIF-8, Fe (OAc) ₂ (4-Py) ₄ -Por mixture (precursor) (5A) was obtained. The specific volume of the precursor (5A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

(Continuous firing, pulverization, acid cleaning treatment, first firing, distribution furnace)
ZIF-8, Fe (OAc) ₂ added (4-Py) ₄ -Por mixture (5A) 1.2590 g was measured in a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) quartz It installed in the center of a pipe | tube, the nitrogen flow rate was 200 mL / min, and it was distribute | circulated at room temperature for 30 minutes. Thereafter, the flow rate of nitrogen is lowered to 20 mL / min, the temperature is raised from 30 ° C. to 800 ° C. at 5 ° C./min, held at 800 ° C. for 10 hours, and further raised from 800 ° C. to 1000 ° C. at 5 ° C./min. And held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (5B). The obtained carbon precursor (5B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and left overnight to obtain 0.3019 g of an acid cleaned carbon precursor (5C).

(Firing / Crushing process, Second firing, Vacuum gas replacement / Rotating furnace)
We measure 0.1794 g of carbon precursor (5C) in a quartz boat and install it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted in a vacuum gas replacement furnace, and set the nitrogen flow rate to 200 mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. At that time, the quartz tube was rotated at 2.0 rpm. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (5D) of non-acid washing | cleaning. The carbon material (5D) was pulverized in an agate mortar to obtain 0.1650 g of a non-acid-washed carbon material (5E). The obtained non-acid cleaned carbon material (5E) was used as the nitrogen-containing carbon alloy of Example 5.

(Example 6)
<Carbon Material Synthesis of ZIF-8, Fe (OAc) ₂ Addition ((4-Py) ₂ Ph ₂ -Por) Mixture (6E)>
(Preparation of (Pyrrole) ₂ (4-Py) CH)
J. et al. Org. Chem. 2000, 65, 2249-2252. (Pyrrole) ₂ (4-Py) CH was prepared by the method described in 1).
2.14 g of 4-pyridylaldehyde was added to 20 mL of pyrrole and heated at 85 ° C. for 15 hours. Thereafter, pyrrole was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 2.23 g of (Pyrrole) ₂ (4-Py) CH.

(Preparation of (4-Py) ₂ Ph ₂ -Por)
J. et al. Org. Chem. 2001, 66, 4973-4988. (4-Py) ₂ Ph ₂ -Por was prepared with reference to the method described in 1.
1.1 g of (Pyrrol) ₂ (4-Py) CH and 0.53 g of benzaldehyde were dissolved in 500 mL of a methylene chloride / ethanol mixed solution (95: 5). To the obtained solution, 1.4 g of TFA was added over 2 hours under a nitrogen atmosphere and allowed to react at room temperature for 24 hours. Thereafter, 1.7 g of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) was added, and the mixture was further stirred for 3 hours. The mixture was filtered, washed with chloroform and dried. Purification by column chromatography prepared (4-Py) ₂ Ph ₂ -Por.

Molecular formula: C ₄₂ H ₂₈ N _6, molecular weight: 616.71
Elemental analysis (calculated values): C, 81.80; H, 4.58; N, 13.63

(ZIF-8, Fe (OAc) ₂ addition (Preparation of (4-Py) ₂ Ph ₂ -Por) mixture)
(4-Py) ₂ Ph ₂ -Por 1.00 g, ZIF-8 9.00 g (manufactured by BASF, Basolite Z1200), Fe (OAc) ₂ 0.32 g (manufactured by Aldrich, iron (II) acetate), Purity 99.995% (residual metal amount standard)) is added to a standard container made of Warling, 75 mL SUS, purged with nitrogen, and then a cutting mill manufactured by Waring (X-TREME MX1200XTM, standard container made of 75 mL SUS). Rotate at 1300 rpm to 10,000 rpm in 5 seconds after starting rotation, and then rotate at 10000 rpm for 40 seconds to add ZIF-8, Fe (OAc) ₂ (4-Py) ₂ Ph ₂ -Por mixture (Precursor) (6A) was obtained. The specific volume of the precursor (6A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

(Continuous firing, pulverization, acid cleaning treatment, first firing, distribution furnace)
ZIF-8, Fe (OAc) ₂ added (4-Py) ₂ Ph ₂ -Por mixture (6A) 2.2113 g was measured in a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) Was installed at the center of the quartz tube, the nitrogen flow rate was 200 mL per minute, and the mixture was allowed to flow at room temperature for 30 minutes. Thereafter, the flow rate of nitrogen is lowered to 20 mL / min, the temperature is raised from 30 ° C. to 800 ° C. at 5 ° C./min, held at 800 ° C. for 10 hours, and further raised from 800 ° C. to 1000 ° C. at 5 ° C./min. And held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (6B). The obtained carbon precursor (6B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.7476 g of acid-washed carbon precursor (6C).

(Firing / Crushing process, Second firing, Vacuum gas replacement / Rotating furnace)
We measure 0.5847g of carbon precursor (6C) in a quartz boat and place it in the center of a 4.0cmφ (inside diameter 3.6cmφ) quartz tube inserted in a vacuum gas replacement furnace, and set the nitrogen flow rate to 200mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. At that time, the quartz tube was rotated at 2.0 rpm. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (6D) of non-acid washing | cleaning. The carbon material (6D) was pulverized in an agate mortar to obtain 0.5284 g of non-acid cleaned carbon material (6E). The obtained non-acid cleaned carbon material (6E) was used as the nitrogen-containing carbon alloy of Example 6.

(Example 7)
<Carbon Material Synthesis of ZIF-8, FeCl ₂ .4H ₂ O Addition (H ₂ AzPc) Mixture (7E)>
(Preparation of H ₂ AzPc)
Synthetic Communication. 2004, 34, 3373-3380. 3,4-dicyanopyridine and 1,8-diazabicyclo [5.4.0] unday7-ene (DBU) were dissolved in octanol and reacted at 185 ° C. for 2 hours. H ₂ AzPc was prepared.

Molecular formula: C ₂₈ H ₁₄ N ₁₂ , molecular weight: 518.49
Elemental analysis (calculated values): C, 64.86; H, 2.72; N, 32.42

(Preparation of ZIF-8, FeCl ₂ .4H ₂ O added (H ₂ AzPc) mixture)
Waring the above-mentioned H ₂ AzPc 1.00 g, ZIF-8 9.00 g (BASF, Basolite Z1200), FeCl ₂ .4H ₂ O 0.37 g (Wako Pure Chemical Industries, purity 99.9%) After adding nitrogen to a 75 mL SUS standard container and substituting with nitrogen, a rotating mill (X-TREME MX1200XTM, 75 mL SUS standard container) was continuously rotated from 1300 rpm to 10000 rpm in 5 seconds after starting rotation. After rotating at 10000 rpm for 40 seconds, a ZIF-8, FeCl ₂ .4H ₂ O-added H ₂ AzPc mixture (precursor) (7A) was obtained. The specific volume of the precursor (7A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

(Continuous firing, pulverization, acid cleaning treatment, first firing, distribution furnace)
Weighed 1.8074 g of ZIF-8, FeCl ₂ .4H ₂ O added H ₂ AzPc mixture (7A) into a quartz boat and placed it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tube furnace. It was installed and the nitrogen flow rate was 200 mL / min, and it was circulated at room temperature for 30 min. Thereafter, the flow rate of nitrogen is lowered to 20 mL / min, the temperature is raised from 30 ° C. to 800 ° C. at 5 ° C./min, held at 800 ° C. for 10 hours, and further raised from 800 ° C. to 1000 ° C. at 5 ° C./min. And held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (7B). The obtained carbon precursor (7B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.84702 g of acid-washed carbon precursor (7C).

(Firing / Crushing process, Second firing, Vacuum gas replacement / Rotating furnace)
We measure 0.2835g of carbon precursor (7C) in a quartz boat and install it in the center of a 4.0cmφ (inside diameter 3.6cmφ) quartz tube inserted in a vacuum gas replacement furnace, and set the nitrogen flow rate to 200mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. At that time, the quartz tube was rotated at 2.0 rpm. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (7D) of non-acid washing. The carbon material (7D) was pulverized in an agate mortar to obtain 0.1710 g of a non-acid cleaned carbon material (7E). The obtained non-acid cleaned carbon material (7E) was used as the nitrogen-containing carbon alloy of Example 7.

(Example 8)
<Carbon Material Synthesis of ZIF-8, Fe (acac) ₂ Addition (Ph ₄ -Por) Mixture (8E)>
(Preparation of ZIF-8, Fe (acac) ₂ added (Ph ₄ -Por) mixture)
Ph ₄ -Por 1.00 g (Aldrich), ZIF-8 9.00 g (BASF, Basolite Z1200), Fe (acac) ₂ 0.47 g (Aldrich, purity 99.95% or more (residual metal) Is added to a standard container made of Warling Co., Ltd., 75 mL SUS and purged with nitrogen. Then, a cutting mill manufactured by Waring Co., Ltd. (X-TREME MX1200XTM, standard container made of 75 mL SUS) is started for 5 seconds. After rotating at a stepless speed from 1300 rpm to 10000 rpm, it was rotated at 10,000 rpm for 40 seconds to obtain a ZIF-8, Fe (acac) ₂ -added Ph ₄ -Por mixture (precursor) (8A). The specific volume of the precursor (8A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

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

(Continuous firing distribution furnace, pulverization)
1.7982 g of the ZIF-8, Fe (acac) ₂ -added Ph ₄ -Por mixture (8A) described above was measured in a quartz boat and inserted into a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. It was installed in the center, the nitrogen flow rate was 200 mL per minute, and it was circulated at room temperature for 30 minutes. Thereafter, the flow rate of nitrogen is lowered to 20 mL per minute, the temperature is raised from 30 ° C. to 700 ° C. at 5 ° C. per minute, held at 700 ° C. for 10 hours, and further raised from 700 ° C. to 1000 ° C. at 5 ° C. per minute. And held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (8B). The obtained carbon precursor (8B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.9823 g of acid-washed carbon precursor (8C).

(Firing, grinding, water washing treatment, second firing, vacuum gas replacement / rotary furnace)
We measure 0.3019 g of carbon precursor (8C) in a quartz boat and place it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted in a vacuum gas replacement furnace, and the nitrogen flow rate is 200 mL per minute. It was circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. At that time, the quartz tube was rotated at 2.0 rpm. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (8D) of non-acid washing | cleaning. The carbon material (8D) was pulverized with an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.1714 g of an unacid-washed carbon material (8E). The obtained non-acid cleaned carbon material (8E) was used as the nitrogen-containing carbon alloy of Example 8.

(Comparative Example 1)
<ZIF-8, Fe (OAc) ₂ Addition (2-Py) ₃ -TAz Mixture of Non-Acid Washed Carbon Material Synthesis (C1-E)>
(Preparation of ZIF-8, Fe (OAc) ₂ added (2-Py) ₃ -TAz mixture)
(2-Py) ₃ -TAz (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.10 g, ZIF-8 (manufactured by BASF, Basolite Z1200) 0.90 g, Fe (OAc) ₂ (manufactured by Aldrich, iron (II) acetate), Purity 99.99% or more (residual metal amount standard) 32 mg, 20 SUS304 steel balls were put into a 45 ml container (manufactured by Fritsch) made of zirconia, vacuum deaerated, purged with nitrogen, and sealed with an overpot. Using planetary ball mill Classic Line P-7 (manufactured by Fritsch), pulverize at 400 rpm for 3 hours, remove SUS304 steel balls with metal mesh, and add ZIF-8, Fe (OAc) ₂ (2-Py) ₃ -TAz A mixture (precursor) (C1-A) was obtained. The specific volume of the precursor (C1-A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

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

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
ZIF-8, Fe (OAc) ₂ added (2-Py) ₃ -TAz mixture (C1-A) 0.5823 g was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3.6 cmφ) Was installed at the center of the quartz tube, the nitrogen flow rate was 200 mL per minute, and the mixture was allowed to flow at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (C1-B). The obtained carbon precursor (C1-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.1870 g of an acid cleaned carbon precursor (C1-C).

(Firing, grinding, water washing treatment, second firing, vacuum gas replacement furnace)
We measure 0.0990 g of carbon precursor (C1-C) in a quartz boat and install it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace. The minute volume was 200 mL, and the mixture was allowed to flow at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon material (C1-D). The carbon material (C1-D) was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and then left overnight to obtain 0.0568 g of a non-acid cleaned carbon material (C1-E). The obtained non-acid cleaned carbon material (C1-E) was used as the nitrogen-containing carbon alloy of Comparative Example 1.

(Comparative Example 2)
<Synthesis of ZIF-8, Fe (OAc) ₂ -added (2-Py) ₃ -TAz Mixture with Acid-washed Carbon Material (C2-E)>
0.0540 g of the carbon material (C1-D) described above was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.0435 g of an acid cleaned carbon material (C2-E). The obtained acid-washed carbon material (C2-E) was used as the nitrogen-containing carbon alloy of Comparative Example 2.

(Comparative Example 3)
<Preparation of heat-dried ZIF-8 (C3-E)>
ZIF-8 (BASF Corp., Basolite Z1200) 2.0 g was measured in a quartz boat without crushing, and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. After degassing nitrogen substitution three times, the nitrogen flow rate was 200 mL / min and the mixture was allowed to flow at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 100 ° C. at 5 ° C. per minute, dried at 100 ° C. for 24 hours, and then cooled to room temperature over 12 hours to obtain 1.98 g of heat-dried ZIF-8. The obtained heat-dried ZIF-8 was used as heat-dried ZIF-8 (C3-E) of Comparative Example 3. The specific volume of heat-dried ZIF-8 (C3-E) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

(Comparative Example 4)
<Synthesis of ZIF-8 non-acid-cleaned carbon material (C4-E)>
(Preparation of ZIF-8 ground product)
1.00 g of ZIF-8 (Basolite Z1200, manufactured by BASF) and 20 SUS304 steel balls were placed in a 45 ml container (manufactured by Fritsch) made of zirconia, vacuum degassed, purged with nitrogen, and sealed with an overpot. Using a planetary ball mill Classic Line P-7 (manufactured by Fritsch), the mixture was pulverized at 400 rpm for 3 hours, and SUS304 steel balls were removed with a metal mesh to obtain a ZIF-8 pulverized product (C4-A). The specific volume of the ZIF-8 ground product (C4-A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
Weigh 0.5126 g of ZIF-8 pulverized product (C4-A) into a quartz boat and place it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. It was made 200 mL and it was made to distribute | circulate at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the preliminary carbide (C4-B) of ZIF-8. The obtained preliminary carbide (C4-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained preliminary carbide material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.2026 g of acid-cleaned preliminary carbide (C4-C).

(Firing, grinding, water washing, second firing, vacuum gas replacement furnace)
Weigh 0.1863 g of the above-mentioned acid-cleaned preliminary carbide (C4-C) in a quartz boat and place it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas replacement furnace. The flow rate was 200 mL per minute and the mixture was allowed to flow at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained carbon material (C4-D). The carbon material (C4-D) was pulverized in an agate mortar, washed with water, filtered and air-dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.1195 g of non-acid cleaned carbon material (C4-E). The obtained non-acid cleaned carbon material (C4-E) was used as the nitrogen-containing carbon alloy of Comparative Example 4.

(Comparative Example 5)
<Carbon material synthesis of ZIF-8, Fe (OAc) ₂ added (2-Py) TAz (NH ₂ ) ₂ mixture>(C5-E)>
(Preparation of (2-Py) TAz (NH ₂ ) ₂ )
J. et al. Org. Chem. , 2003, 68, 1158. (2-Py) TAz (NH ₂ ) ₂ was prepared with reference to FIG. 107.1 mg of 2-pyridylcarboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 mg of iodine were added to a mixed solvent of 9 mL of 28% aqueous ammonia and 1 mL of THF, and the mixture was stirred at room temperature for 1 hour. To this was added a mixture of 100 mg of dicyanodiamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 120 mg of KOH, and the mixture was heated to reflux for 18 hours. The produced precipitate was filtered, washed with Et ₂ O (20% ethanol) and dried to obtain 80 mg of (2-Py) TAz (NH ₂ ) ₂ .

（２−Ｐｙ）ＴＡｚ（ＮＨ₂）

(2-Py) TAz (NH ₂ )

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

(Preparation of ZIF-8, Fe (OAc) ₂ added (2-Py) TAz (NH ₂ ) ₂ mixture)
(2-Py) TAz (NH ₂ ) ₂ 0.10 g, ZIF-8 (manufactured by BASF, Basolite Z1200) 0.90 g, Fe (OAc) ₂ (manufactured by Aldrich, iron (II) acetate, purity 99.99) % Or more (residual metal amount standard) 32 mg, 20 SUS304 steel balls were put into a 45 ml container (made by Fritsch) made of zirconia, vacuum degassed, purged with nitrogen, and sealed with an overpot. Using a planetary ball mill Classic Line P-7 (manufactured by Fritsch), pulverization was performed at 400 rpm for 3 hours, SUS304 steel balls were removed with a metal mesh, and ZIF-8, Fe (OAc) ₂ added (2-Py) TAz (NH ₂ ) ₂ mixture (precursor) (C5-A) was obtained. The specific volume of the precursor (C5-A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
2.5315 g of ZIF-8, Fe (OAc) ₂ added (2-Py) TAz (NH ₂ ) ₂ mixture (C5-A) was weighed into a quartz boat and inserted into a tubular furnace, 4.0 cmφ (inner diameter 3 .6 cmφ) at the center of the quartz tube, the nitrogen flow rate was 200 mL per minute, and the mixture was allowed to flow at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (C6-B). The obtained carbon precursor (C5-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and allowed to stand overnight to obtain 0.4994 g of acid-washed carbon precursor (C5-C).

(Firing, grinding, acid cleaning treatment, second firing, vacuum gas replacement furnace)
We measure 0.3096g of carbon precursor (C5-C) in a quartz boat and place it in the center of a 4.0cmφ (inside diameter 3.6cmφ) quartz tube inserted into a vacuum gas-replacement rotary furnace. The minute volume was 200 mL, and the mixture was allowed to flow at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (C5-D). The carbon material (C5-D) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then allowed to stand overnight to obtain 0.2084 g of an acid cleaned carbon material (C5-E). The obtained acid cleaned carbon material (C5-E) was used as the carbon material of Comparative Example 5.

(Comparative Example 6)
<Carbon Material Synthesis of ZIF-8-added (ClFe- (MeOPh) ₄ -Por) Mixture (C6-E)>
(Addition of ZIF-8 (Preparation of ClFe- (MeOPh) ₄ -Por) mixture)
ZIF-8 1.00 g (BASF, Basolite Z1200), ClFe- (MeOPh) ₄ -Por 0.15 g (Aldrich) and 20 SUS304 steel balls are put into a 45 ml container (made by Fritsch) made of zirconia. After vacuum degassing and replacement with nitrogen, it was sealed with an overpot. Using a planetary ball mill Classic Line P-7 (manufactured by Fritsch), pulverization was performed at 400 rpm for 3 hours, SUS304 steel balls were removed with a metal mesh, and ZIF-8-added ClFe- (MeOPh) ₄ -Por mixture (precursor) ( C6-A) was obtained. The specific volume of the precursor (C1-A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

Molecular formula: C ₄₈ H ₃₆ Cl ₁ Fe ₁ N ₄ O ₄ , molecular weight: 824.12
Elemental analysis (calculated values): C, 69.95; H, 4.40; N, 4.30; Fe, 6.78; N, 6.80; O, 7.77

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
Measure 0.7152 g of the ZIF-8-added ClFe- (MeOPh) ₄ -Por mixture (C6-A) in a quartz boat and place it in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted in a tubular furnace. It was installed and the nitrogen flow rate was 200 mL / min, and it was circulated at room temperature for 30 min. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (C6-B). The obtained carbon precursor (C6-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until no coloration occurred. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and left overnight to obtain 0.2611 g of an acid cleaned carbon precursor (C6-C).

(Baking / Crushing / Acid cleaning treatment 2nd baking Vacuum gas replacement furnace)
The carbon precursor (C6-B) was pulverized in an agate mortar, and 0.1013 g was weighed into a quartz boat and placed in the center of a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a vacuum gas displacement rotary furnace. It was installed and the nitrogen flow rate was 200 mL per minute and allowed to flow at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (C6-D). The carbon material (C6-D) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand to room temperature, and left overnight to obtain 0.0821 g of acid-cleaned carbon material (C6-E). The obtained acid cleaned carbon material (C6-E) was used as the carbon material of Comparative Example 6.

(Comparative Example 7)
<Carbon Material Synthesis of Fe (OAc) ₂ Addition (Ph ₄ -Por) Mixture (C7-E)>
(Preparation of Ball Mill ground Fe (OAc) ₂ addition (Ph ₄ -Por) mixture)
Ph ₄ -Por 1.00 g (manufactured by Aldrich), 32 mg of Fe (OAc) ₂ (manufactured by Aldrich, iron (II) acetate, purity 99.995% or more (based on the amount of residual metal)), SUS304 steel ball 20 The pieces were placed in a zirconia 45 ml container (manufactured by Fritsch), vacuum degassed, purged with nitrogen, and sealed with an overpot. Using a planetary ball mill Classic Line P-7 (manufactured by Fritsch), pulverized at 400 rpm for 3 hours, SUS304 steel balls were removed with a metal mesh, Ball Mill pulverized Fe (OAc) ₂ added Ph ₄ -Por mixture (precursor) ) (C7-A) was obtained. The specific volume of the precursor (C7-A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.
Ball Mill crushed Fe (OAc) ₂ added Ph ₄ -Por mixture (C7-A) was calcined in the same manner as in Comparative Example 6, but only a very small amount of carbon material was obtained. Specific surface area measurement and carbon by BET method were obtained. Preparation of alloy-coated electrodes and measurement of oxygen reduction reaction (ORR) activity could not be performed.

(Comparative Example 8)
<Synthesis of carbon material (C8-E) of ZIF-8, Fe (OAc) ₂ added (Ph ₄ -Por) mixture>
(Preparation of ZIF-8, Fe (OAc) ₂ added (Ph ₄ -Por) mixture)
Ph ₄ -Por 0.10 g (manufactured by Aldrich), ZIF-8 0.90 g (manufactured by BASF, Basolite Z1200), and 32 mg of Fe (OAc) ₂ (manufactured by Aldrich, iron (II) acetate, purity 99. 995% or more (residual metal amount standard)) and 20 SUS304 steel balls were put into a 45 ml container (made by Fritsch) made of zirconia, vacuum degassed, purged with nitrogen, and sealed with an overpot. Using a planetary ball mill Classic Line P-7 (manufactured by Fritsch), pulverization was carried out at 400 rpm for 3 hours, SUS304 steel balls were removed with a metal mesh, and Fe (OAc) ₂ added Ph ₄ -Por mixture (precursor) (C8- A) was obtained. The specific volume of the precursor (C8-A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.

(Baking / Crushing / Acid cleaning treatment, 1st baking, Distribution furnace)
2.2548 g of ZIF-8, Fe (OAc) ₂ added Ph ₄ -Por mixture (C8-A) was weighed into a quartz boat and inserted into a 4.0 cmφ (inner diameter 3.6 cmφ) quartz tube inserted into a tubular furnace. It was installed in the center, the nitrogen flow rate was 200 mL per minute, and it was circulated at room temperature for 30 minutes. The temperature was raised from 30 ° C. to 900 ° C. at 5 ° C. per minute, and held at 900 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon precursor (C8-B). The obtained carbon precursor (C8-B) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.8373 g of acid-washed carbon precursor (C8-C).

(Firing, grinding, acid cleaning treatment, second firing, vacuum gas replacement furnace)
We measure 0.1882g of carbon precursor (C8-C) in a quartz boat and install it in the center of a 4.0cmφ (inside diameter 3.6cmφ) quartz tube inserted in a vacuum gas replacement furnace, and the nitrogen flow rate is changed every minute. It was made 200 mL and it was distribute | circulated at room temperature for 1 minute. Next, the inside of a pipe | tube was exhausted with the vacuum pump until it became 1.9 * 10 < ¹ > Pa, and nitrogen substitution was repeated 3 times. Thereafter, the flow rate of nitrogen was lowered to 20 mL / min, the temperature was raised from 30 ° C. to 1000 ° C. at 5 ° C./min, and held at 1000 ° C. for 1 hour. Then, it cooled to room temperature over 3 hours, and obtained the carbon material (C8-D) of non-acid washing | cleaning. The carbon material (C8-D) was pulverized in an agate mortar, and concentrated hydrochloric acid washing, centrifugal filtration, and removal of the supernatant were repeated until there was no coloration. After washing with water, it was filtered and air dried. The obtained carbon material was vacuum-dried at 110 ° C. for 3 hours, allowed to stand at room temperature, and then left overnight to obtain 0.1381 g of non-acid washed carbon material (C8-E). The obtained acid-washed carbon material (C8-E) was used as the nitrogen-containing carbon alloy of Comparative Example 8.

(Comparative Example 9)
<Carbon Material Synthesis of Fe (OAc) ₂ Addition (Ph ₄ -Por) Mixture (C7-E)>
(Preparation of Cutting Mill ground Fe (OAc) ₂ addition (Ph ₄ -Por) mixture)
Ph ₄ -Por 10.0 g (manufactured by Aldrich), 0.32 g of Fe (OAc) ₂ (manufactured by Aldrich, iron (II) acetate, purity 99.995% or more (based on the amount of residual metal)), Waring After adding nitrogen to a 75 mL SUS standard container and substituting with nitrogen, a rotating mill (X-TREME MX1200XTM, 75 mL SUS standard container) manufactured by Waring Co., Ltd. started to rotate continuously from 1300 rpm to 10,000 rpm in 5 seconds. Then, it was rotated at 10,000 rpm for 40 seconds to obtain a Cutting Mill-pulverized Fe (OAc) ₂ added Ph ₄ -Por mixture (precursor) (C9-A). The specific volume of the precursor (C9-A) was measured in the same manner as in Example 1. The results are shown in Table 1 below.
Cutting Mill pulverized Fe (OAc) ₂ added Ph ₄ -Por mixture (C9-A) was calcined in the same manner as in Comparative Example 6, but only a very small amount of carbon material was obtained. Specific surface area measurement and carbon alloy by BET method were obtained. Preparation of a coated electrode and measurement of oxygen reduction reaction (ORR) activity could not be performed.

  In Table 1 below, “acid cleaning” indicates the presence or absence of a step of acid cleaning the carbon material after the firing step. In addition, calculation of specific surface area by BET method in Examples 2 to 8 and Comparative Examples 1 to 6 and 8, and preparation of carbon alloy-coated electrode / oxygen reduction reaction (ORR) activity measurement were performed in Examples 2 to 8 and Comparative Examples. The measurement was performed in the same manner as in Example 1 except that the carbon materials of Examples 1 to 6 and 8 were used instead of the carbon material of Example 1.

From Table 1, it was found that the nitrogen-containing carbon alloy of the example had a sufficiently high ORR voltage indicating catalyst performance.
On the other hand, the nitrogen-containing carbon alloy of the comparative example had a low ORR voltage and poor performance as a catalyst. Further, Comparative Examples 7 and 9 were inferior in yield.

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

(1) -2 Preparation of anode catalyst ink 0.5 g of platinum-supported carbon (Tanaka Kikinzoku Kogyo Co., Ltd., TEC10V50E) carrying 50% by mass of platinum was weighed in a glass container, and 0.8 mL of water was added. After the addition, the glass container was sealed with a septum seal, and the inside of the container was purged with nitrogen. The catalyst ink for anode was obtained by inject | pouring 4.3 mL of 5 mass% Nafion mentioned above and 1 mL of 1-propanol in a glass container, and irradiating an ultrasonic wave for 2.5 hours.

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

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

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

(4) Preparation of electrode composite membrane Between two polyimide membranes (UPILEX 75: manufactured by Ube Industries Co., Ltd.) cut into 10 cm x 10 cm squares, the catalyst membrane prepared in (2) -1; (3) The prepared proton conducting membrane and the catalyst membrane prepared in (2) -2 were superposed in this order. At this time, the catalyst membrane was at the center of the proton conducting membrane, and the coating surface was in contact with the ptrone conducting membrane. The laminated sheet was pressed at 210 ° C. and 15 MPa for 10 minutes. The thermocompression-bonded film was taken out from the two polyimide films, and the catalyst layer was transferred to both sides of the proton conducting film by peeling off the Teflon (registered trademark) sheet which is the base of the cathode coating film and the anode coating film. An electrode composite membrane was obtained. This electrode composite membrane was immersed in a 0.5 mol / L sulfuric acid aqueous solution for 10 hours, washed with ion-exchanged water, and dried to obtain the desired electrode composite membrane.

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

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

DESCRIPTION OF SYMBOLS 10 Fuel cell 12 Separator 13 Anode electrode catalyst 14 Solid polymer electrolyte 15 Cathode electrode catalyst 16 Separator 20 Electric double layer capacitor 21 1st electrode 22 2nd electrode 23 Separator 24a Exterior cover,
24b Outer case 25 Current collector 26 Gasket

Claims (19)

At least one selected from a nitrogen-containing organic compound represented by the following general formula (1), a tautomer of the nitrogen-containing organic compound, a salt of the nitrogen-containing organic compound, and a hydrate of the nitrogen-containing organic compound ,
At least one selected from a covalent organic framework material and a metal organic framework material;
Calcining a precursor containing at least one selected from inorganic metal salts and organometallic complexes,
A method for producing a nitrogen-containing carbon alloy, wherein the specific volume of the precursor is 4 cm ³ / g or more;

In the general formula (1), L ^{1 to} L ⁴ each independently represent a linking group, a single bond or a double bond, Z ^{1 to} Z ⁴ each independently represent a cyclic structure, and L ^{1 to} L ⁴ At least one is a linking group having a heteroaromatic group, or at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. The method for producing a nitrogen-containing carbon alloy according to claim 1, wherein the nitrogen-containing organic compound represented by the general formula (1) is represented by the following general formula (2);

In General Formula (2), Z ^{1 to} Z ⁴ each independently represent a cyclic structure, and at least one of Z ^{1 to} Z ⁴ includes a heteroaromatic ring. The method for producing a nitrogen-containing carbon alloy according to claim 1, wherein the nitrogen-containing organic compound represented by the general formula (1) is represented by the following general formula (3);

In General Formula (3), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituent, Z ^{1 to} Z ⁴ each independently represent a cyclic structure, and at least one of R ^{1 to} R ⁴ is or a heteroaromatic group, at least one of Z ¹ to Z ⁴ comprises a heteroaromatic ring. In the said General formula (3), at least ^{1 of} R < ¹ > -R < ⁴ > is a heteroaromatic group, and at least 1 of Z < ¹ > -Z < ⁴ > contains a hetero aromatic ring. A method for producing a nitrogen carbon alloy.   The method for producing a nitrogen-containing carbon alloy according to claim 1, wherein the nitrogen-containing organic compound is at least one selected from pyridyl porphyrins excluding metal complexes and pyridyl porphyrin salts excluding metal complexes.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 5, wherein the metal organic framework material is a zeolite type imidazole framework material.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 6, wherein the organometallic complex is a metal acetate complex or a β-diketone metal complex.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 7, wherein the inorganic metal salt is an inorganic metal chloride.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 8, wherein a metal species of the inorganic metal salt is Fe.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 9, wherein the inorganic metal salt is a hydrate salt.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 10, wherein the firing step is a step of firing the precursor at 400 ° C or higher.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 11, wherein the firing step is a step of firing the precursor at 700 to 1050 ° C.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 12, wherein the firing step includes a step of holding the precursor at 700 to 1050 ° C for 1 second to 100 hours.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 13, further comprising a step of pulverizing the precursor before the step of firing.   The method for producing a nitrogen-containing carbon alloy according to any one of claims 1 to 14, further comprising a step of pulverizing the fired nitrogen-containing carbon alloy and a step of re-firing after the step of firing.   The method for producing a nitrogen-containing carbon alloy according to claim 15, wherein the re-baking step is a step of baking at 900 to 1500 ° C.   The method for producing a nitrogen-containing carbon alloy according to claim 15 or 16, further comprising a step of deaeration and nitrogen substitution before the re-baking step.   The nitrogen-containing carbon alloy manufactured by the method of any one of Claims 1-17.   A fuel cell catalyst using the nitrogen-containing carbon alloy according to claim 18.

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