Method for producing nitrogen-containing carbon material

Abstract

To provide a method for efficiently producing a nitrogen-containing carbon material having an excellent structural control rate under mild conditions.SOLUTION: A method for producing a nitrogen-containing carbon material includes a heating step for heating a nitrogen-containing aromatic compound, the nitrogen-containing aromatic compound comprising a nitrogen-containing aromatic ring selected from the group consisting of a 6-membered monocyclic nitrogen-containing aromatic ring, a fused bicyclic nitrogen-containing aromatic ring of a 6-membered ring and a 5-membered ring, and a fused bicyclic nitrogen-containing aromatic ring of a 6-membered ring and a 6-membered ring, and a carbazole ring, and a halogen atom binding to the nitrogen-containing aromatic ring.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for producing a nitrogen-containing carbon material.

Background Art

[0002] In recent years, carbon materials such as carbon nanotubes, fullerenes, graphite, graphene, graphene oxide, reduced graphene oxide, artificial graphite, and carbon black have been expected as novel functional materials in various fields due to their characteristic physical properties (for example, Non-Patent Documents 1 to 6).

[0003] Graphene is a two-dimensional sheet-like carbon material with a structure paved with six-membered rings of sp2 carbon. Graphite usually refers to a material having a structure in which a large number of two-dimensional sheet-like graphenes are bonded by van der Waals forces, and a single-layer one is called graphene. A material in which 2 to 10 layers of graphene are stacked is called multilayer graphene, and a material in which 2 to 5 layers of graphene are stacked is called few-layer graphene. In single-layer graphene, the introduction of functional groups on the basal plane greatly changes the properties and shape of graphene itself. When the number of layers is 3 or more, even if functional groups are introduced on the basal plane of graphene, the graphene in the center is hardly directly affected. Therefore, basically, except that the number of layers of graphene increases and the specific surface area decreases, significant differences in properties hardly appear.

[0004] The existence of graphene has been known for a long time, but a method for extracting a single sheet of graphene from graphite has not been established until recently. In 2004, it was found that a thin sheet of graphene can be extracted by peeling the surface of highly oriented pyrolytic graphite with adhesive tape and attaching the peeled material onto a substrate. Thereafter, aiming at mass production and low-cost production, methods for producing graphene by vapor deposition methods such as CVD (chemical vapor deposition film formation method) and methods for producing graphene (reduced graphene oxide: RGO) by reducing graphene oxide (GO) have been studied.

[0005] However, the method for manufacturing graphene by a vapor deposition method such as CVD (chemical vapor deposition film formation method) has problems that it cannot be obtained as a shape other than a film (typically, a bulk shape), that a flammable gas must be used, and that it can only be manufactured on the surface of a metal and cannot be mass-produced.

[0006] In addition, a method for producing a carbon material by heating a compound in which a condensation reaction occurs between the same molecules and / or between different molecules has been disclosed (Patent Document 1). This technique has shown that a carbon material can be synthesized under mild conditions.

[0007] Commercially produced carbon materials have various functional groups. For this reason, it is difficult to precisely control the structure of the carbon material, and there is a problem that variations occur in physical properties. In recent years, there has been a demand for carbon materials that can surely exhibit targeted physical properties, and for this reason, the development of carbon materials with precisely controlled structures has been demanded.

[0008] Among such carbon materials with precisely controlled structures, if a carbon material in which atoms other than carbon are introduced and the structure is precisely controlled can be obtained, applications to various uses are expected. In particular, nitrogen-containing carbon materials in which nitrogen atoms are introduced and the structure is precisely controlled may have a wide range of applications.

[0009]

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Non-Patent Documents

[0011]

Non-Patent Document 1

Non-Patent Document 2

Non - Patent Document 3

Non - Patent Document 4

Non - Patent Document 5

Non - Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0012] The problem of the present invention is to provide a method for efficiently producing a nitrogen - containing carbon material having an excellent structure control rate under mild conditions.

Means for Solving the Problems

[0013] The method for producing a nitrogen - containing carbon material according to an embodiment of the present invention includes a heating step of heating a nitrogen - containing aromatic compound, wherein the nitrogen - containing aromatic compound has a nitrogen - containing aromatic ring selected from the group consisting of a 6 - membered monocyclic nitrogen - containing aromatic ring, a condensed bicyclic nitrogen - containing aromatic ring of a 6 - membered ring and a 5 - membered ring, a condensed bicyclic nitrogen - containing aromatic ring of a 6 - membered ring and a 6 - membered ring, and a carbazole ring, and a halogen atom bonded to the nitrogen - containing aromatic ring.

[0014] In one embodiment, the nitrogen - containing aromatic ring is one selected from the group consisting of a triazine ring, an indolizine ring, a quinoline ring, an isoquinoline ring, a naphthyridine ring, and a carbazole ring.

[0015] In one embodiment, in the heating step, the nitrogen-containing aromatic compound is heated in the presence of a copper catalyst.

Advantages of the Invention

[0016] According to the present invention, it is possible to provide a method for efficiently producing a nitrogen-containing carbon material having an excellent structure control rate under mild conditions.

Brief Description of the Drawings

[0017]

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Mode for Carrying Out the Invention

[0018] ≪≪1. Method for Producing Nitrogen-Containing Carbon Material≫≫ The method for producing a nitrogen-containing carbon material according to an embodiment of the present invention includes a heating step of heating a nitrogen-containing aromatic compound. The nitrogen-containing aromatic compound has a nitrogen-containing aromatic ring and a halogen atom bonded to the nitrogen-containing aromatic ring. By heating a nitrogen-containing aromatic compound containing a halogen atom to produce a nitrogen-containing carbon material, it is possible to reduce the carbonization temperature of the nitrogen-containing aromatic compound and precisely control the structure of the nitrogen-containing carbon material. Therefore, a nitrogen-containing carbon material having an excellent structure control rate can be efficiently produced under mild conditions.

[0019] ≪1-1. Nitrogen-Containing Aromatic Compound≫ A nitrogen-containing aromatic compound is a compound having a nitrogen-containing aromatic ring (aromatic heterocycle) in which at least one nitrogen atom is introduced into an aromatic ring. The number of nitrogen atoms introduced into the aromatic ring is, for example, 1 or more and 3 or less. One or more halogen atoms are bonded to the nitrogen-containing aromatic ring of the nitrogen-containing aromatic compound. The nitrogen-containing aromatic ring contained in the above nitrogen-containing aromatic compound is any one selected from the group consisting of a 6-membered monocyclic nitrogen-containing aromatic ring, a condensed bicyclic nitrogen-containing aromatic ring of a 6-membered ring and a 5-membered ring (hereinafter referred to as a 6-5 member nitrogen-containing condensed ring), a condensed bicyclic nitrogen-containing aromatic ring of a 6-membered ring and a 6-membered ring (hereinafter referred to as a 6-6 member nitrogen-containing condensed ring), and a carbazole ring.

[0020] The 6-membered monocyclic nitrogen-containing aromatic ring contains at least one nitrogen atom introduced into the benzene ring. Representative examples of the 6-membered monocyclic nitrogen-containing aromatic ring include a triazine ring (e.g., 1,2,3-triazine ring, 1,3,5-triazine ring), a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and the like.

[0021] The 6-5 member nitrogen-containing condensed ring is a condensed ring in which a 6-membered ring and a 5-membered ring are condensed by sharing two or more atoms, and contains at least one nitrogen atom introduced into the condensed ring. Representative examples of the 6-5 member nitrogen-containing condensed ring include an indolizine ring, an indole ring, a benzimidazole ring, a pyrrolopyridine ring, an imidazopyridine ring, and the like.

[0022] The 6-6 member nitrogen-containing condensed ring is a condensed ring in which a 6-membered ring and a 6-membered ring are condensed by sharing two or more atoms, and contains at least one nitrogen atom introduced into the condensed ring. Representative examples of the 6-6 member nitrogen-containing condensed ring include azanaphthalene rings such as a quinoline ring, an isoquinoline ring, a naphthyridine ring (e.g., 1,5-naphthyridine ring, 1,6-naphthyridine ring).

[0023] Among such nitrogen-containing aromatic rings, preferably, a triazine ring, an indolizine ring, a quinoline ring, an isoquinoline ring, a naphthyridine ring, and a carbazole ring are mentioned, and more preferably, a 1,3,5-triazine ring, an indolizine ring, a quinoline ring, an isoquinoline ring, a 1,6-naphthyridine ring, and a carbazole ring are mentioned. When the nitrogen-containing aromatic compound has the above specific nitrogen-containing aromatic ring, the structure of the nitrogen-containing carbon material can be controlled more precisely.

[0024] The halogen atom is typically directly bonded to the carbon atom contained in the above-described nitrogen-containing aromatic ring. The number of substituted halogen atoms is, for example, 1 or more and 6 or less, preferably 1 or more and 4 or less. The number of substituted halogen atoms is preferably equal to or more than the number of nitrogen atoms contained in the nitrogen-containing aromatic ring. Typical examples of the halogen atom include fluorine, chlorine, bromine, and iodine, preferably chlorine and bromine, and more preferably bromine.

[0025] The molecular weight of such a nitrogen-containing aromatic compound is, for example, 100 or more, preferably 110 or more, and, for example, 700 or less, preferably 530 or less. In addition, the nitrogen-containing aromatic compound may have any appropriate substituent other than the halogen atom at any appropriate position as long as the effects of the present invention are not impaired. Examples of such substituents include an alkyl group; an aryl group; a substituent having an eliminability such as a tosylate group or a triflate group; and the like. Since the presence of a substituent that can become an impurity in the carbon material after heating has no adverse effect on physical properties and the like, a hydrogen group (having no substituent) or a substituent having an eliminability is preferable. Such a nitrogen-containing aromatic compound can be used alone or in combination of two or more.

[0026] Specific examples of the above-described nitrogen-containing aromatic compounds include 2,4,6-trichloro-1,3,5-triazole, 8-bromo-indolizine, 3,7-dibromo-1,5-naphthyridine, 2,4-dibromoquinoline, 3,6-dibromoquinoline, 4,8-dibromoquinoline, 5,8-dibromoquinoline, 1-bromoisoquinoline, 4-bromoisoquinoline, 5-bromoisoquinoline, 8-bromoisoquinoline, and 1,4,8-tribromoisoquinoline.

[0027] ≪1-2. Heating step≫ In the heating step, the above-described nitrogen-containing aromatic compound is carbonized by heating to produce a nitrogen-containing carbon material. The "heating" in the heating step may be referred to as "firing".

[0028] In the heating step, the nitrogen-containing aromatic compound may be heated, and its mode is not particularly limited. For example, the nitrogen-containing aromatic compound in a bulk state may be heated, or a composition containing the nitrogen-containing aromatic compound may be heated. In the heating step, preferably, the nitrogen-containing aromatic compound in a bulk state is heated.

[0029] In the present specification, the "bulk state" means a solid state at normal temperature (23 °C), and includes a particulate state (for example, a powder state), a pellet state, a film state, and the like. The nitrogen-containing aromatic compound in a pellet state or a film state can be obtained by molding particles (for example, powder) composed of the nitrogen-containing aromatic compound by compression molding or the like.

[0030] When heating the nitrogen-containing aromatic compound in the heating step, for example, it may be heated in a container. As the container, any appropriate container can be adopted. As such a container, for example, those made of a material that does not substantially deteriorate at the heating temperature in the heating step are preferable. Further, it is preferable that the surface in contact with the nitrogen-containing aromatic compound is a material that does not chemically react with the nitrogen-containing aromatic compound during heating. By the heating step of heating the nitrogen-containing aromatic compound under preferable conditions, it becomes possible to obtain a nitrogen-containing carbon material, and in the heating step, the nitrogen-containing aromatic compound may melt and become liquid near the melting point of the nitrogen-containing aromatic compound. Even when such a process occurs, it is included in "firing the nitrogen-containing aromatic compound in a bulk state". On the other hand, examples that are not "firing in a bulk state" as meant by the present invention include, for example, a method of forming a thin film by dissolving a nitrogen-containing aromatic compound in a solvent, applying it in an arbitrary substrate shape to form a film, and heating it together with the substrate, a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD), a thin film evaporation heating method, and the like. The thin film generally means a range with a film thickness of 1 μm or less.

[0031] In the heating step, preferably, the nitrogen-containing aromatic compound is heated in the presence of a copper catalyst. Typical examples of the copper catalyst include reduced copper. Reduced copper is prepared, for example, by reducing copper particles under a flowing hydrogen atmosphere. The reduction temperature is, for example, 200°C or higher and 400°C or lower, and the reduction time is, for example, 10 minutes or longer and 3 hours or shorter. The amount of reduced copper used is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and, for example, 100 parts by mass or less, preferably 80 parts by mass or less, per 1 part by mass of the nitrogen-containing aromatic compound.

[0032] The heating temperature (carbonization temperature) in the heating step is typically 1000°C (1273K) or lower, preferably 800°C (1073K) or lower, more preferably 700°C (973K) or lower, still more preferably 600°C (873K) or lower, particularly preferably 550°C (823K) or lower, and especially preferably 500°C (773K) or lower. Note that the heating temperature (carbonization temperature) in the heating step is, for example, 300°C (573K) or higher, preferably 350°C (623K) or higher. In this embodiment, since the nitrogen-containing aromatic compound as the raw material contains a halogen atom, even if the heating temperature is reduced as described above, the nitrogen-containing aromatic compound can be smoothly carbonized, and the structural control rate of the nitrogen-containing carbon material can be improved.

[0033] The heating time in the heating step is, for example, 1 minute to 120 hours, preferably 10 minutes to 96 hours, more preferably 30 minutes to 72 hours, and still more preferably 1 hour to 24 hours. By controlling the heating time in the heating step within the above range, a nitrogen-containing carbon material with nitrogen atoms introduced and its structure precisely controlled can be easily produced under mild conditions.

[0034] As the heating method in the heating step, a firing furnace such as a tubular furnace or a box furnace, a heating reaction apparatus using a heat medium, a heating reaction apparatus using microwaves, etc. can be used.

[0035] The heating pressure conditions in the heating step can be carried out under vacuum, normal pressure, increased pressure, etc. Also, it can be carried out under reduced pressure.

[0036] As heating atmosphere conditions in the heating step, it can be carried out under the atmosphere, in an inert gas atmosphere, etc. Examples of the inert gas atmosphere include under nitrogen, under argon, etc.

[0037] When the nitrogen-containing aromatic compound is heated in the heating step, a condensation reaction of the nitrogen-containing aromatic compound occurs, resulting in a nitrogen-containing carbon material. When there is one type of nitrogen-containing aromatic compound, it can be a condensation reaction between the same type of molecules. When there are two or more types of nitrogen-containing aromatic compounds, a condensation reaction between the same type of molecules and a condensation reaction between different types of molecules can coexist.

[0038] Due to the condensation reaction of the nitrogen-containing aromatic compound and, in some cases, other reactions that occur subsequent to or concurrently with the condensation reaction, a new bond (e.g., C-C bond, etc.) can be formed between two or more nitrogen-containing aromatic compounds, the molecular weight can increase, and a ring condensation reaction can occur between two or more ring structures.

[0039] ≪≪2. Nitrogen-containing carbon material≫≫ The nitrogen-containing carbon material obtained by the production method according to the embodiment of the present invention is a nitrogen-containing carbon material in which nitrogen atoms are introduced and the structure is precisely controlled. Since the nitrogen-containing carbon material obtained by the production method according to the embodiment of the present invention is a nitrogen-containing carbon material obtained by a characteristic production method, it can be a novel carbon material different from conventionally known carbon materials. Examples of conventionally known carbon materials include carbon nanotubes, fullerenes, graphite films, graphene, graphene oxide, reduced graphene oxide, artificial graphite, carbon black, etc. Specific examples of such nitrogen-containing carbon materials include basal nitrogen-containing carbon materials containing nitrogen atoms present on the basal plane (basal nitrogen atoms), and pyridinic nitrogen-containing carbon materials containing nitrogen atoms present on the edge (pyridinic nitrogen atoms).

[0040] Here, the "basal plane" and "edge" refer to the "basal plane" and "edge" commonly used in the field of carbon materials. In a one-layer or multi-layer structure such as graphite, the plane side is the "basal plane", and the plane substantially perpendicular to the basal plane (the plane where the cross-section of the layer appears) is called the "edge plane" or "edge". That is, for example, in a carbon material having a hollow structure (a structure in which a part of the basal plane is punched out) when viewed from the plane side, the cross-sectional part exposed in the hollow part is also an "edge".

[0041] By selecting a nitrogen-containing aromatic compound as a raw material, a nitrogen-containing carbon material having a desired structure can be produced. When producing a basal nitrogen-containing carbon material, among the above-mentioned nitrogen-containing aromatic compounds, a nitrogen-containing aromatic compound having a nitrogen-containing condensed ring (a 6-5 membered nitrogen-containing condensed ring or a 6-6 membered nitrogen-containing condensed ring) containing a nitrogen atom in the shared part of the condensed ring is selected. Preferably, a nitrogen-containing aromatic compound having an indolizine ring is selected. The basal nitrogen-containing carbon material is typically a nitrogen-containing carbon material in which the ratio of basal nitrogen atoms is higher than the ratio of other nitrogen atoms. Examples of other nitrogen atoms include the above-mentioned basal nitrogen atoms, the above-mentioned pyridinic nitrogen atoms, and pyrrole nitrogen atoms. In N1s XPS analysis, the ratio of the peak of basal nitrogen atoms to the peak of all nitrogen atoms in the basal nitrogen-containing carbon material is, for example, 40% or more, preferably 60% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the above ratio is preferably 100% or less. In the basal nitrogen-containing carbon material, if the ratio of the peak of basal nitrogen atoms to the peak of all nitrogen atoms by N1s XPS analysis is within the above range, the basal nitrogen atoms are precisely controlled in structure in the nitrogen-containing carbon material (that is, it has excellent structure control rate), and it can become a novel carbon material having various physical properties and may be widely applied to various uses.

[0042] When producing a pyridinic or pyrrolic nitrogen-containing carbon material, among the nitrogen-containing aromatic compounds described above, a nitrogen-containing aromatic compound having a nitrogen-containing aromatic ring selected from the group consisting of a 6-membered monocyclic nitrogen-containing aromatic ring, a carbazole ring, and a nitrogen-containing condensed ring (6-5 membered nitrogen-containing condensed ring or 6-6 membered nitrogen-containing condensed ring) containing a nitrogen atom other than the shared portion of the condensed ring is selected. Preferably, a nitrogen-containing aromatic compound having a nitrogen-containing aromatic ring selected from the group consisting of a triazine ring, a quinoline ring, an isoquinoline ring, a naphthyridine ring, and a carbazole ring is selected. The pyridinic or pyrrolic nitrogen-containing carbon material is, more specifically, a nitrogen-containing carbon material in which the proportion of pyridinic or pyrrolic nitrogen atoms is larger than the proportion of other nitrogen atoms. In N1s XPS analysis, the ratio of the peak of pyridinic nitrogen atoms to the peak of all nitrogen atoms in the pyridinic nitrogen-containing carbon material is, for example, 60% or more, preferably 70% or more. The upper limit of the above ratio is preferably 100% or less. In N1s XPS analysis, with respect to the peak of all nitrogen atoms in the pyrrolic nitrogen-containing carbon material, Pyrrole the ratio of the peak of nitrogen atoms is, for example, 80% or more, preferably 90% or more. The upper limit of the above ratio is preferably 100% or less. In the pyridinic or pyrrolic nitrogen-containing carbon material, if the ratio of the peak of pyridinic or pyrrolic nitrogen atoms to the peak of all nitrogen atoms by N1s XPS analysis is within the above range, the pyridinic or pyrrolic nitrogen atoms are precisely structured and present in the nitrogen-containing carbon material (that is, it has excellent structure control rate), and can become a novel carbon material with various physical properties, and may be widely applied to various uses.

[0043] The nitrogen-containing carbon material obtained by the production method according to the embodiment of the present invention preferably has a honeycomb structure (graphene structure) derived from a benzene ring in its structure. The presence or absence of the graphene structure can be confirmed by Raman spectroscopic analysis.

[0044] The nitrogen-containing carbon material usually has a total metal component content of preferably 5 atomic% or less, more preferably 1 atomic% or less, and particularly preferably substantially zero, based on 100 atomic% of carbon atoms. These can be confirmed by analyzing the nitrogen-containing carbon material by X-ray fluorescence elemental analysis (XRF), elemental analysis by combustion method, or XPS. When no metal catalyst is used, it is considered to be substantially zero. Even when a metal catalyst (e.g., copper) is used, it can be easily removed in the form of the present invention.

[0045] The nitrogen-containing carbon material essentially contains carbon and nitrogen as its constituent elements, and may contain elements other than carbon and nitrogen. Such elements other than carbon and nitrogen are, for example, at least one element selected from the above-mentioned halogen elements, oxygen, hydrogen, boron, and sulfur. More preferably, it is at least one element selected from chlorine, bromine, oxygen, hydrogen, boron, and sulfur. Even more preferably, it is at least one element selected from bromine, oxygen, and hydrogen. When the total amount of elements other than hydrogen among the elements constituting the nitrogen-containing carbon material is taken as 100 atomic%, the total amount of carbon and nitrogen is preferably 60 atomic% or more, more preferably 70 atomic% or more, and even more preferably 75 atomic% or more. Also, elements other than carbon, nitrogen, and hydrogen are preferably 10 atomic% or less. By the proportion of each element falling within this range, it becomes possible to exhibit a high structure control rate while being a nitrogen-containing carbon material. These can be confirmed by quantifying the nitrogen-containing carbon material by X-ray photoelectron spectroscopy (C1s XPS).

[0046] The nitrogen-containing carbon material preferably has at least one mode selected from the group consisting of the following (i) to (iv) by Raman spectroscopic analysis.

[0047] The nitrogen-containing carbon material preferably has, in the Raman spectrum obtained by Raman spectroscopic analysis, a G band (generally 1550 cm -1 ~1650 cm -1shows a peak within the range of). Therefore, that the nitrogen-containing carbon material has a peak in the G band (generally within the range of 1550 cm -1 ~1650 cm -1 in the Raman spectrum obtained by Raman spectroscopy means that the nitrogen-containing carbon material has a graphene structure or a structure similar to the graphene structure. If the G band has high intensity and is sharp, it can be said that it has a cleaner graphene structure or a structure similar to the graphene structure.

[0048] The nitrogen-containing carbon material preferably (ii) shows a peak in the D band (generally within the range of 1300 cm -1 ~1400 cm -1 in the Raman spectrum obtained by Raman spectroscopy. The nitrogen-containing carbon material having a structure derived from the defect of the graphene structure shows a peak in the D band (generally within the range of 1300 cm -1 ~1400 cm -1 in the Raman spectrum obtained by Raman spectroscopy. Therefore, that the nitrogen-containing carbon material has a peak in the D band (generally within the range of 1300 cm -1 ~1400 cm -1 in the Raman spectrum obtained by Raman spectroscopy means that the nitrogen-containing carbon material contains a functional group, contains edges, has a structure derived from the defect of the graphene structure or a structure similar to the structure derived from the defect of the graphene structure. If the D band has low intensity, it can be said that it has a cleaner graphene structure or a structure similar to the graphene structure. Also, the fact that the D band can be confirmed means that the nitrogen-containing carbon material may have a functional group, suggesting that the structure is controlled.

[0049] The nitrogen-containing carbon material preferably (i) has a peak in the G band (generally within the range of 1550 cm -1 ~1650 cm -1shows a peak within the range of), and further, (ii) in the Raman spectrum obtained by Raman spectroscopic analysis, the D band (generally within the range of 1300 cm -1 ~1400 cm -1 shows a peak within the range of).

[0050] The nitrogen-containing carbon material preferably (iii) shows a peak in the G′ band (generally within the range of 2650 cm -1 ~2750 cm -1 in the Raman spectrum obtained by Raman spectroscopic analysis. Therefore, the fact that the nitrogen-containing carbon material has a peak in the G′ band (generally within the range of 2650 cm -1 ~2750 cm -1 means that the nitrogen-containing carbon material has a graphene structure or a structure similar to the graphene structure. The intensity of the G′ band is the strongest when the graphene structure is one layer, and gradually decreases as the number of stacked layers of the graphene structure increases. However, even if the intensity of the G′ band gradually decreases as the number of stacked layers of the graphene structure increases, the peak can still be observed. Therefore, it can be said that having a peak in the G′ band means that the nitrogen-containing carbon material has a graphene structure or a structure similar to the graphene structure. The G′ band is sometimes also called the 2D band.

[0051] The nitrogen-containing carbon material preferably (i) shows a peak in the G band (generally within the range of 1550 cm -1 ~1650 cm -1 in the Raman spectrum obtained by Raman spectroscopic analysis, and further, (ii) shows a peak in the D band (generally within the range of 1300 cm -1 ~1400 cm -1 in the Raman spectrum obtained by Raman spectroscopic analysis, and further, (iii) shows a peak in the G′ band (generally within the range of 2650 cm -1 ~2750 cm -1 in the Raman spectrum obtained by Raman spectroscopic analysis.

[0052] The nitrogen-containing carbon material preferably shows a peak in the D+D′ band (generally in the range of 2800 cm -1 to 3000 cm -1 ), as obtained by Raman spectroscopic analysis. A nitrogen-containing carbon material having a structure derived from defects in the graphene structure shows a peak in the D+D′ band (generally in the range of 2800 cm -1 to 3000 cm -1 ), as obtained by Raman spectroscopic analysis. Therefore, the fact that the nitrogen-containing carbon material has a peak in the D+D′ band (generally in the range of 2800 cm -1 to 3000 cm -1 ), as obtained by Raman spectroscopic analysis, means that the nitrogen-containing carbon material contains a functional group or has a structure similar to the structure derived from defects in the graphene structure or a structure derived from defects in the graphene structure. If the intensity of the D+D′ band is low, it can be said that it has a cleaner graphene structure or a structure similar to the graphene structure. The D+D′ band is sometimes also called the D+G band. Also, the fact that the D+D′ band can be confirmed also means that the nitrogen-containing carbon material has a functional group and suggests that the structure is controlled.

[0053] The nitrogen-containing carbon material preferably shows a peak in the G band (generally in the range of 1550 cm -1 to 1650 cm -1 ), as obtained by Raman spectroscopic analysis, and further shows a peak in the D band (generally in the range of 1300 cm -1 to 1400 cm -1 ), as obtained by Raman spectroscopic analysis, and further shows a peak in the G′ band (generally in the range of 2650 cm -1 to 2750 cm -1 ), as obtained by Raman spectroscopic analysis, and further shows a peak in the D+D′ band (generally in the range of 2800 cm -1 to 3000 cm -1shows a peak within the range of

[0054] According to elemental analysis, the nitrogen atom content ratio of the nitrogen-containing carbon material is preferably 0.5 atom% to 70 atom%, more preferably 0.7 atom% to 60 atom%, still more preferably 1 atom% to 55 atom%, particularly preferably 1.5 atom% to 50 atom%, and most preferably 2 atom% to 20 atom%.

[0055] According to elemental analysis, the hydrogen atom content ratio of the nitrogen-containing carbon material is preferably 0 atom% to 45 atom%, more preferably 0 atom% to 40 atom%, still more preferably 0 atom% to 35 atom%, particularly preferably 1 atom% to 35 atom%, and most preferably 5 atom% to 35 atom%. When the hydrogen atom content ratio in the nitrogen-containing carbon material is within this range, the effects of the nitrogen-containing carbon material of the present invention can be preferably exerted.

[0056] According to elemental analysis, the halogen atom content ratio of the nitrogen-containing carbon material is preferably 0 atom% to 75 atom%, more preferably 0 atom% to 70 atom%, still more preferably 0 atom% to 60 atom%, particularly preferably 0.1 atom% to 60 atom%, and most preferably 0.5 atom% to 55 atom%. A lower halogen atom content ratio in the nitrogen-containing carbon material means that carbonization is progressing, which is preferable.

[0057] If the content ratios of carbon atoms, nitrogen atoms, hydrogen atoms, halogen atoms, and oxygen atoms in the elemental analysis of the nitrogen-containing carbon material are within the above ranges, the structure of the nitrogen-containing carbon material can be precisely controlled. Elemental analysis can be performed, for example, using a commercially available elemental analyzer or XPS, and can be obtained based on the results obtained. As such an analyzer, for example, an elemental analyzer (CE-440F) manufactured by Exeter Analytical, Inc. can be employed.

[0058] As described above, the carbonization described in the present specification can be confirmed not only by Raman analysis but also by the degree of decrease in hydrogen element by elemental analysis. The degree of carbonization can be understood from how much the hydrogen element / carbon element ratio (atomic ratio) contained in the raw material compound is reduced by carbonization. For example, sufficient carbonization means that when the hydrogen element / carbon element ratio of the raw material is set to 100%, it decreases by 10% or more by heating. As sufficient carbonization, more preferably, it is a decrease of 20% or more, still more preferably a decrease of 30% or more, and most preferably a decrease of 40% or more.

[0059] The nitrogen-containing carbon material preferably has no peak due to C=O stretching vibration between 1660 cm -1 ~1800 cm -1 in IR analysis. When no peak due to C=O stretching vibration is observed between 1660 cm -1 ~1800 cm -1 in the IR analysis of the nitrogen-containing carbon material, the nitrogen-containing carbon material may be one in which side reactions are suppressed. The fact that no peak due to C=O stretching vibration is observed between 1660 cm -1 ~1800 cm -1 in the IR analysis of the nitrogen-containing carbon material means that the ratio of C=O bonds derived from side reactions such as decomposition reactions is small, and it can be said that the nitrogen-containing carbon material is obtained by suppressing the decomposition reaction.

Examples

[0060] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". In addition, in this specification, "mass" may be read as "weight". However, the % in the part related to N1s XPS in this specification means atomic %. The temperature in the examples is expressed in K (absolute temperature). It can be read as °C (Celsius temperature) by the formula of absolute temperature -273.

[0061] The nitrogen-containing aromatic compounds used in the examples and their abbreviations are as follows. Cyanuric chloride: CyanCl (pyridinic) Indolizine: ID (basal) 8-Bromo-indolizine: 8-BrID (basal) 3,6-Dibromo-9H-carbazol: 36-DBC (pyrrole) Isoquinoline: IQ (pyridinic) 1-Bromoisoquinoline: 1-BrIQ (pyridinic) 4-Bromoisoquinoline: 4-BrIQ (pyridinic) 5-Bromoisoquinoline: 5-BrIQ (pyridinic) 8-Bromoisoquinoline: 8-BrIQ (pyridinic) 1,4,8-Tribromoisoquinoline: 1,4,8-BrIQ (pyridinic) 1,5-Naphthyridine: 15-NAP (pyridinic) 3,7-Dibromo-1,5-naphthyridine: 37-Br-15-NAP (pyridinic) 2,4-Dibromoquinoline: 24-BrQ (pyridinic) 3,6-Dibromoquinoline: 36-BrQ (pyridinic) 4,8-Dibromoquinoline: 48-BrQ (pyridinic) 5,8-Dibromoquinoline: 58-BrQ (pyridinic)

[0062] In addition, in the following, the nitrogen-containing carbon materials obtained in each example and each comparative example may be referred to as "abbreviation of nitrogen-containing aromatic compound_T" using the abbreviation of the above-mentioned nitrogen-containing aromatic compound and the heating temperature T [K].

[0063] <Elemental analysis> Elemental analysis of C, H, and N was performed using an elemental analyzer (CE-440F) manufactured by Exeter Analytical, Inc., and the atomic ratio was determined based on the obtained results.

[0064] <XPS Analysis> XPS measurement was performed using JPS9030 of JEOL under the following conditions. Source: MgKα Emission: 10 mA Anode: 10 kV Pass Energy: 30 eV Aperture: 6 mm Integration times: 10 - 40 times The sample was measured on a quartz substrate or in powder form during measurement. This quartz substrate was oxidized at 700 °C under oxygen flow (flow rate: 20 mL / min) as a pretreatment, and then reduced at 700 °C under hydrogen flow (flow rate: 20 mL / min). The conditions for Br340_ID, Br340_ID623, and Br340_ID673 described later were performed under the following conditions. Pass Energy: 10 eV Neutralizing gun: Current value 5 mA, voltage value: 5 V <Element Composition Ratio> The element composition ratios of the nitrogen-containing carbon material and the nitrogen-containing aromatic compound as its raw material are summarized in Table 1 below. The CHN composition ratio was obtained from the results of elemental analysis by combustion method, and the content ratio of halogen elements was calculated from the ratio to C by XPS. Furthermore, each element's atomic weight was multiplied by the obtained CHN composition ratio and the content ratio of halogen elements to convert them to mass ratios, and the mass % of each element was calculated from the mass ratios. The atom % of each element was calculated by dividing the obtained mass % of each element by the atomic weight of each element. The results are shown in Table 1.

[0065] <Raman Spectroscopy Analysis> Raman spectroscopy analysis was performed using the following apparatus and conditions. Measuring apparatus: Micro-Raman (JASCO NRS-4500) Measurement conditions: Using a 532.23 nm laser, 100-fold objective lens In Raman analysis, the G’ band and the D+D’ band may appear overlapping, and the D+D’ band may be analyzed as a broad peak with a shoulder in particular. In this case, the inflection point of the shoulder peak is regarded as the peak of the G’ band.

[0066] <IR Analysis> FT-IR analysis was performed under the following apparatus and conditions. Measuring apparatus: Fourier transform infrared spectrophotometer (FT / IR-4200 type A manufactured by JASCO Corporation) Measurement conditions: DRIFT method, MCT_M detector, resolution 4 cm -1 , number of accumulations 32 to 64 times Measurement range: 499.473 cm -1 ~4000.6 cm -1 Sample conditions: A sample prepared by mixing the sample and KBr at a weight ratio of 1:10 to 100 was used.

[0067] [Example 1-2] In a glove box, 1.41 g of reduced copper nanopowder (CNP, 60-80 nm particle, SIGMA-ALDRICH) and 20 mg of cyanuric chloride (CyanCl; >98.0%, Tokyo Chemical Industry Co., Ltd.) were placed in a glass tube, and vacuum drying using a vacuum pump was carried out at room temperature (298 K) for 1 hour to remove impurities such as moisture, and then an ampoule tube was prepared. The ampoule tube was heated at 773 K or 873 K for 1 hour to allow the reaction to proceed. After heating, the ampoule tube was opened and the recovered product was heated at 473 K under reduced pressure for 1 hour to remove unreacted raw materials and low molecular weight compounds to obtain a product (nitrogen-containing carbon material) (Example 1: CuCyanCl_873, Example 2: CuCyanCl_773). The obtained product (nitrogen-containing carbon material) was subjected to the above-described XPS analysis and IR analysis. The XPS analysis results are shown in FIG. 1, and the IR analysis results are shown in FIG. 2. It was found that a high structure control rate (100% pyridinic nitrogen at 773 K and 873 K respectively) was exhibited due to the effect of copper. Also, carbonization did not proceed and decomposition occurred in triazine having no halogen group.

[0068] 〔Examples 3 - 5, Comparative Examples 1 - 3〕 In a glove box filled with nitrogen, about 40 mg of indolizine (ID; >95%, BLD pharm) and about 5 mg of 8 - Bromo - indolizine (8 - BrID; >96%, eNovation Chemicals LLC) were weighed, and each of these reagents was placed in a glass tube with a length of 15 cm and an inner diameter of 8 mm that was closed at one end. Next, in order to remove impurities such as moisture, it was dried under reduced pressure for 1 hour using a vacuum pump. At this time, ID was dried at room temperature, and 8 - BrID was dried while being immersed in liquid nitrogen. Then, the other end of the tube was sealed with a gas burner so that the length of the tube became about 8 cm, and an ampoule tube was prepared. The prepared ampoule tube was placed in a boat - shaped crucible and heated at the center of an electric furnace. The temperature was raised from room temperature (298 K) to the heating temperature T [K] (for ID, T is either 723 K, 773 K, or 823 K; for 8 - BrID, T is either 623 K, 673 K, or 723 K) at a rate of 10 K / min and then heated at T [K] for 1 hour. At this time, in order to keep the temperature in the electric furnace constant, nitrogen was circulated as a carrier gas. After collecting the sample, raw material extraction was performed using a vacuum pump. At this time, ID was heated at 403 K and 8 - BrID was heated at 473 K for 1 hour at a heating rate of 5 K / min to remove the remaining raw materials. As a result, nitrogen - containing carbon materials were obtained (Example 3: 8 - BrID_723, Example 4: 8 - BrID_673, Example 5: 8 - BrID_623, Comparative Example 1: ID_823, Comparative Example 2: ID_773, Comparative Example 3: I_723). The obtained product (nitrogen-containing carbon material) was subjected to the above-described XPS analysis, IR analysis, and Raman analysis. The XPS analysis results are shown in Fig. 3, the IR analysis results are shown in Fig. 4, and the Raman analysis results are shown in Fig. 5. It was found that 8-BrID having a halogen exhibits a low carbonization temperature and a high structure control rate. More specifically, when 8-BrID is used as a raw material, carbonization can proceed smoothly even at a heating temperature of 773 K or lower, and basal nitrogen atoms can be sufficiently formed. In addition, for ID having no halogen group (Comparative Examples 1-3), carbonization did not proceed sufficiently and decomposition occurred, making it difficult to obtain a sample for elemental analysis. This also demonstrates the superiority of the halogen group.

[0069] 〔Examples 6-8〕 In a glove box filled with nitrogen, about 40 mg of 3,6-Dibromo-9H-carbazole (36-DBC; >99.5%, BLD pharm) was weighed, and the weighed 36-DBC was placed in a glass tube with a length of 15 cm and an inner diameter of 8 mm, one end of which was closed. Next, in order to remove impurities such as moisture, it was dried under reduced pressure at a heating rate of 5 K / min and 428 K for 1 hour using a vacuum pump. Thereafter, the other end of the tube was sealed with a gas burner so that the length of the tube became about 8 cm, and an ampoule tube was prepared. The prepared ampoule tube was placed in a boat-shaped crucible and heated at the center of an electric furnace. After heating from room temperature (298 K) to a heating temperature T [K] (any one of 773 K, 823 K, and 873 K) at a rate of 10 K / min, it was heated at T [K] for 1 hour. At this time, in order to keep the temperature in the electric furnace constant, nitrogen was passed as a carrier gas. After collecting the sample, a raw material draw was performed using a vacuum pump. At this time, it was heated at a heating rate of 5 K / min and 528 K for 1 hour to remove the remaining raw material. Thereby, a nitrogen-containing carbon material was obtained (Example 6: 36-DBC_773, Example 7: 36-DBC_823, Example 8: 36-DBC_873). The nitrogen-containing carbon material was subjected to the above XPS analysis and IR analysis. The XPS analysis results are shown in Fig. 6, and the IR analysis results are shown in Fig. 7. It was found that 36-DBC having a halogen exhibits a low carbonization temperature and a high structure control rate. More specifically, when 36-DBC is used as a raw material, carbonization can proceed smoothly even at a heating temperature of 873 K or lower, and pyrrole nitrogen atoms can be formed. In addition, in the case of carbazole having no halogen group, carbonization did not proceed sufficiently and decomposition occurred, making it difficult to obtain a sample for elemental analysis. This also shows the superiority of the halogen group.

[0070] 〔Examples 9 and 10〕 <Bromination step> Indolizine (40 mg) and the solvent 1,2-dichlorobenzene (27.0 ml) were placed in a three-necked flask and completely dissolved by ultrasonic treatment for about 10 minutes. Then, the solution in the three-necked flask and 5 g of liquid bromine were placed in a Teflon container (70 ml) in a fume hood. In order to fill the gas phase in the Teflon container with nitrogen, the lid of the Teflon container was opened in a glove box and the air in the container was replaced by tilting it by hand. Then, the Teflon container was placed in a hydrothermal container and heated at 340 K for 24 hours. There were precipitates in the Teflon container after heating, and it is considered that the solubility decreased due to the introduction of bromine into indolizine. All of the solution and precipitates in the Teflon container were transferred to an eggplant flask and evaporated while heating in a water bath (353 K). It was confirmed that the surface of the sample was dry, and then it was left in the water bath for about 1 hour for further drying. As much as possible of the obtained green sample was transferred to a 15 cm long glass tube and dried under reduced pressure at 463 K for about 1 hour to remove the solvent and adsorbed bromine (brominated sample: Br340_ID). <Carbonization step> Weighed about 30 mg of Br340_ID, quartz plate [6x6x1(mm) 3It was added to a glass tube. Thereafter, it was dried under reduced pressure at 393 K for 1 hour. After drying under reduced pressure, the glass tube was heated with a gas burner and sealed. The ampoule tube was placed in a boat-shaped crucible, placed in the central part of an electric furnace, and heated. The heating conditions were as follows: the temperature was raised from room temperature (298 K) to 623 K at 8 K / min, and 623 K was maintained for 1 hour. After collecting the sample, it was heated under vacuum at 513 K for 1 hour to remove the remaining raw materials. The same operation was also performed at 673 K. As a result, a nitrogen-containing carbon material was obtained (Example 9: Br340_ID_673, Example 10: Br340_ID_623). The obtained nitrogen-containing carbon material was subjected to the above-described XPS analysis, IR analysis, and Raman analysis. The XPS analysis results are shown in FIG. 8, the IR analysis results are shown in FIG. 9, and the Raman analysis results are shown in FIG. 10. It was found that Br340_ID having a halogen exhibits a low carbonization temperature and a high structure control rate. More specifically, when Br340_ID is used as a raw material, carbonization can proceed smoothly even at a heating temperature of 773 K or lower, and basal nitrogen atoms can be formed. 1400 - 1510 cm -1 It can be seen that there is a peak derived from a 5-membered ring C=C bond. In the sample (Br340_ID) before heating, a peak at 1503 cm -1 appeared sharply, so it was confirmed that the 5-membered ring structure was not destroyed by the bromination reaction. This peak at 1503 cm -1 was also confirmed during heating at each temperature of 623 and 673 K, suggesting that it has a 5-membered ring structure. Also, as bromination and carbonization proceed, the structure becomes more complex, and a new peak derived from a 5-membered ring C=C bond appears in the vicinity of 1400 cm -1 .

[0071] [Examples 11 - 16, Comparative Example 4] Isoquinoline, 1 - Bromoisoquinoline (>98%), and 8 - Bromoisoquinoline (>97%) were purchased from Tokyo Chemical Industry Co., Ltd., 4 - Bromoisoquinoline (>98%) and 5 - Bromoisoquinoline (>97%) were from Sigma - Aldrich, and 1,4,8 - Tribromoisoquinoline (>95%) was from Enamine. Each reagent was weighed about 40 mg each in a glove box filled with nitrogen and added to a glass tube with a length of 15 cm and an inner diameter of 8 mm with one end closed. Next, in order to remove impurities such as moisture, while the inside of the tube was under reduced pressure with a vacuum pump, 1 - BrIQ, 4 - BrIQ, 5 - BrIQ, 8 - BrIQ were dried under reduced pressure at room temperature (298 K) for 1 hour, and 1,4,8 - BrIQ was dried under reduced pressure at a heating rate of 5 K / min and heated at 373 K for 1 hour. After drying under reduced pressure, the other end of the tube was sealed with a gas burner so that the length of the tube became about 8 cm, and an ampoule tube was prepared. The prepared ampoule tube was placed in a boat - shaped crucible and installed near the center of an electric furnace for heating. The heating rate during heating was 10 K / min, and it was heated at a predetermined heating temperature T [K] (773 K or 873 K) for 1 hour. After heating, the sample was scraped out, ground, and the sample was recovered. In the carbonization by heating, in order to remove small molecules in which polymerization did not proceed even after heating from the obtained sample, while the sample was under reduced pressure with a vacuum pump, at a heating rate of 5 K / min, 1 - BrIQ, 4 - BrIQ, 5 - BrIQ, 8 - BrIQ were heated at 403 K for 1 hour, and 1,4,8 - BrIQ was heated at 573 K for 1 hour for separation. As a result, a nitrogen - containing carbon material was obtained (Example 11: 1 - BrIQ_873, Example 12: 4 - BrIQ_873, Example 13: 5 - BrIQ_873, Example 14: 8 - BrIQ_873, Example 15: 1,4,8 - BrIQ_873, Example 16: 4 - BrIQ_773, Comparative Example 4: IQ_873). The obtained nitrogen-containing carbon material was subjected to the above-described XPS analysis and IR analysis. The XPS analysis results are shown in Fig. 11, and the IR analysis results are shown in Fig. 12. It was found that the samples having a halogen showed a low carbonization temperature and a high structure control rate. More specifically, when 4-BrIQ was used as a raw material, carbonization could proceed smoothly even at a heating temperature of 873 K or lower, and pyridinic nitrogen atoms could be increased. Further, when 1-BrIQ, 5-BrIQ, 8-BrIQ, and 1,4,8-BrIQ were used as raw materials, carbonization could proceed smoothly even at a heating temperature of 873 K or lower, and pyridinic nitrogen atoms could be formed. In addition, in the case of IQ having no halogen group (Comparative Example 4), carbonization did not proceed sufficiently and decomposition occurred, making it difficult to obtain a sample for elemental analysis. This also shows the superiority of the halogen group.

[0072] [Examples 17 - 21, Comparative Examples 5 - 7] For naphthyridines, 3,7-dibromo-1,5-naphthyridine (37-Br-15-NAP, >98%) purchased from BLDpharm was used. For quinolines, 2,4-dibromoquinoline (24-BrQ, >97%) purchased from Aldrich, 3,6-dibromoquinoline (36-BrQ, >95%), 4,8-dibromoquinoline (48-BrQ, >98%), and 5,8-dibromoquinoline (58-BrQ, >98%) purchased from BLDpharm were used. 1,5-naphthyridine (15-NAP) was used for comparison. About 40 mg of each reagent was weighed in a glove box filled with nitrogen and added to a glass tube with a length of 15 cm and an inner diameter of 8 mm with one end closed. For the purpose of removing impurities such as moisture in the tube, while reducing the pressure using a vacuum pump, heating was performed at a rate of 5 K / min at 343 K (37Br-15-NAP) / 316 K (24-BrQ) / 323 K (36-BrQ, 48-BrQ) / 353 K (58-BrQ) for 1 hour for vacuum drying. Then, the other end of the tube was sealed with a gas burner so that the length of the tube became about 8 cm, and an ampule tube was prepared. Next, the ampoule tubes were placed in a boat-shaped crucible, and these were installed in the central part of an electric furnace for heating. The heating was carried out by raising the temperature to 773 K at a rate of 10 K / min and then holding that temperature for 1 hour (15-NAP in the comparative example was heated at 873 and 973 K in the ampoule tube). After heating, the sample was scraped out from the ampoule tube, and the obtained sample was ground. In order to remove the remaining raw materials and small molecules in which polymerization had not proceeded from the sample, the raw material extraction was carried out by drying under reduced pressure at a heating rate of 5 K / min at 473 K (37Br-15-NAP) / 416 K (24-BrQ) / 423 K (36-BrQ, 48-BrQ) / 453 K (58-BrQ) for 1 hour. What remained after the raw material extraction was recovered as a sample. Thereby, nitrogen-containing carbon materials were obtained (Example 17: 37Br-15-NAP_773, Example 18: 24-BrQ_773, Example 19: 36-BrQ_773, Example 20: 48-BrQ_773, Example 21: 58-BrQ_773, Comparative Example 5: 15-NAP_973, Comparative Example 6: 15-NAP_873, Comparative Example 7: 15-NAP_823). The obtained nitrogen-containing carbon materials were subjected to the above-described XPS analysis, IR analysis, and Raman analysis. The XPS analysis results are shown in FIG. 13, the IR analysis results are shown in FIG. 14, and the Raman analysis results are shown in FIG. 15. It was found that the samples having halogen showed a low carbonization temperature and a high structure control rate. More specifically, when 37Br-15-NAP and BrQ were used as raw materials, even at a heating temperature of 773 K or lower, carbonization could proceed smoothly, and pyridinic nitrogen atoms could be formed. From the perspective of only the structure control rate, there are some examples that are inferior to the comparative examples. This is because the comparative examples do not contain halogen, making it difficult to carbonize and resulting in little change in the structure. For example, Comparative Example 5 appears to have a higher structure control rate compared to Example 17, but a higher temperature is required to promote carbonization. As a result, the nitrogen element ratio is lower. At a lower temperature (Comparative Example 6), carbonization does not progress, and the reduction rate of hydrogen elements is low. Thus, it can be seen that by using the raw material having halogen of the present invention, carbonization can progress at a low temperature and the structure control rate can be maintained (compatible) at a high level.

[0073]

Table 1

Industrial Applicability

[0074] The method of the present invention is suitably used for the production of nitrogen-containing carbon materials that can be applied to various uses.

Claims

A method for producing a nitrogen-containing carbon material including a heating step of heating a nitrogen-containing aromatic compound in a bulk state, wherein the nitrogen-containing carbon material is a pyridinic nitrogen-containing carbon material, the nitrogen-containing aromatic compound is a nitrogen-containing aromatic ring selected from the group consisting of a 6-membered monocyclic nitrogen-containing aromatic ring, a condensed bicyclic nitrogen-containing aromatic ring of a 6-membered ring and a 5-membered ring, and a condensed bicyclic nitrogen-containing aromatic ring of a 6-membered ring and a 6-membered ring, and has a halogen atom bonded to the nitrogen-containing aromatic ring, in the heating step, the nitrogen-containing aromatic compound is heated so that the ratio of the peak of pyridinic nitrogen atoms to the peak of all nitrogen atoms in the pyridinic nitrogen-containing carbon material in N1s XPS analysis is 40% or more, A method for producing a nitrogen-containing carbon material.

2. The method for producing a nitrogen-containing carbon material according to claim 1, wherein the nitrogen-containing aromatic ring is one selected from the group consisting of a triazine ring, a quinoline ring, an isoquinoline ring, and a naphthyridine ring.

3. The nitrogen-containing aromatic ring is a triazine ring, in the heating step, the nitrogen-containing aromatic compound is heated in the presence of a copper catalyst, The method for producing a nitrogen-containing carbon material according to claim 1.

4. The method for producing a nitrogen-containing carbon material according to claim 1, wherein the nitrogen-containing aromatic compound is heated so that the ratio of the peak of pyridinic nitrogen atoms to the peak of all nitrogen atoms in the pyridinic nitrogen-containing carbon material is 60% or more. A method for producing a nitrogen-containing carbon material including a heating step of heating a nitrogen-containing aromatic compound in a bulk state, wherein the nitrogen-containing carbon material is a basal nitrogen-containing carbon material, the nitrogen-containing aromatic compound is a nitrogen-containing aromatic ring selected from the group consisting of a condensed bicyclic nitrogen-containing aromatic ring of a 6-membered ring and a 5-membered ring, and a condensed bicyclic nitrogen-containing aromatic ring of a 6-membered ring and a 6-membered ring, and has a halogen atom bonded to the nitrogen-containing aromatic ring, in the heating step, the nitrogen-containing aromatic compound is heated so that the ratio of the peak of basal nitrogen atoms to the peak of all nitrogen atoms in the basal nitrogen-containing carbon material in N1s XPS analysis is 60% or more, A method for producing a nitrogen-containing carbon material.

6. The method for producing a nitrogen-containing carbon material according to claim 5, wherein the nitrogen-containing aromatic ring is an indolizine ring.

7. A method for producing a nitrogen-containing carbon material including a heating step of heating a nitrogen-containing aromatic compound in a bulk state, wherein The nitrogen-containing carbon material is a pyrrole nitrogen-containing carbon material, The nitrogen-containing aromatic compound, has a carbazole ring, and a halogen atom bonded to the carbazole ring, and in the heating step, the nitrogen-containing aromatic compound is heated so that the ratio of the peak of pyrrole nitrogen atoms to the peak of all nitrogen atoms in the pyrrole nitrogen-containing carbon material in N1s XPS analysis is 80% or more. A method for producing a nitrogen-containing carbon material. **Claim 8**: The method for producing a nitrogen-containing carbon material according to any one of claims 1 to 7, wherein in the heating step, the nitrogen-containing aromatic compound is heated at 300°C to 600°C. **Claim 9**: The method for producing a nitrogen-containing carbon material according to any one of claims 1 to 7, wherein in the heating step, the nitrogen-containing aromatic compound is heated in a sealed container.

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