Method for manufacturing template carbon material, method for manufacturing catalyst, method for manufacturing catalyst layer for polymer electrolyte fuel cell, and method for manufacturing fuel cell

Abstract

To provide a method for producing templated carbon material with high carbon yields and good yields, a method for producing a catalyst using the same, a method for producing a catalyst layer for a polymer electrolyte fuel cell, and a method for producing a fuel cell.SOLUTION: The present invention provides a method for producing templated carbon material using a carbon source satisfying the following requirement (A) and a template source satisfying the following requirement (B). The (A) carbon source comprises an aromatic compound that comprises two or more oxygen-containing functional groups and / or two or more nitrogen-containing functional groups, wherein, in a thermogravimetric analysis in an inert atmosphere, it reaches a 5 mass% loss at a temperature T0.05 of 200°C or lower. The (B) template source is at least one selected from oxide, carbonate, sulfate, and hydroxide of magnesium, alkaline-earth metal and aluminum.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a template carbon material, a method for producing a catalyst, a method for producing a catalyst layer for a polymer electrolyte fuel cell, and a method for producing a fuel cell. [Background technology]

[0002] Template carbon materials are carbon materials characterized by the shape in which the shape of the template is inverted by coating the surface of a compound that serves as a template with carbon and then removing the template component. A method for producing a template carbon material is a process in which a general-purpose resin, such as polyvinyl alcohol, is used as a carbon source, and a compound of an alkaline earth metal, such as magnesium oxide, is used as a template source, and these are thoroughly mixed together. The mixture is then heat-treated at 600°C to 1500°C in a non-oxidizing atmosphere, and the template source is then dissolved and removed with an acid, or in some other way, to carbonize the carbon source and remove the template source. Magnesium oxide and calcium oxide can be easily dissolved in hydrochloric acid, sulfuric acid, etc., and therefore template carbon materials using these compounds as template sources are often investigated.

[0003] Furthermore, since the carbon coating process typically involves heat treatment at temperatures of 600°C to 1500°C, it is also possible to use, as the template source, compounds that chemically change into magnesium oxide or calcium oxide during the heat treatment process (e.g., carbonates, hydroxides, sulfates, etc.).

[0004] The temperature of the heat treatment for carbon coating is selected depending on the purpose. For example, if a highly amorphous porous carbon material containing a large amount of functional groups is to be prepared, a temperature of 600°C to 900°C is selected. If a highly crystalline porous carbon material is to be obtained, the material is prepared at a temperature exceeding 1000°C. However, high-temperature treatment that involves the formation of carbides such as calcium carbide or metal acetylides must be avoided. In practice, the heat treatment temperature for carbon coating is limited to around 1800°C.

[0005] Templated carbon materials are classified as one type of porous carbon material that corresponds to porous carbon materials (such as activated carbon) produced by a so-called activation method. The structural feature of templated carbon materials is that, while the pores of activated porous carbon materials grow from the outside toward the inside through oxidative attrition, the pore structure of templated carbon materials is essentially homogeneous within the material, although the outermost surface is affected by the manufacturing method, etc., and the pores are generally isotropically connected. This is a structural feature of templated carbon materials that is particularly in contrast to the pore structure of activated porous carbon materials.

[0006] Templated carbon materials with isotropic interconnected pores are sometimes referred to as interconnected pores in the field of polymer electrolyte fuel cells, and it is believed that the good gas flow (fast diffusion) within the material will improve power generation performance when used as a catalyst support, making them a promising material. Furthermore, in principle, templated carbon materials can produce pores that are an inverse copy of the template, making it possible to obtain highly uniform pore structures ranging from micropores to several tens of nanometers in size, in contrast to the pores formed by activation methods, which are inevitably distributed widely from micropores to mesopores.

[0007] The thickness of the carbon layer in the template carbon material can be freely controlled by changing the mixture ratio of the template source and the carbon source, so there is a high degree of freedom in the specific surface area per mass.

[0008] Because templated carbon materials are porous carbon materials, they are applicable to fields in which carbon materials known as activated carbons are used (for example, in the field of adsorbents for selective adsorption of specific gases or molecules with specific structures in the liquid phase), in fields such as catalyst supports for polymer electrolyte fuel cells in which Ketjen black is used, and in fields such as electrodes for supercapacitors. One area that seems to be unique to templated carbon materials is their use in taking advantage of the high diffusivity within the material, which is achieved by taking advantage of the interconnected isotropic pores.

[0009] For example, a porous carbon material consisting only of micropores using zeolite as a template can achieve an astonishing surface area of ​​4,000 m by selecting the type of template and optimizing the conditions for carbon coating inside the pores using CVD with propylene gas as the raw material. 2 It has been reported that the solubility of HCl reaches up to / g (Non-Patent Document 1). Because the pore diameter is on the order of a few tenths of a nanometer at the atomic level, the carbon walls that coat the pores are formed as a single atomic layer, and the pore walls contain five-membered rings, seven-membered rings, etc. to maintain curvature. Therefore, as mentioned above, the pore volume and pore surface area per mass are large, but on the other hand, the carbon structure with curvature tends to be inferior in mechanical strength and chemical stability compared to aromatic structures.

[0010] On the other hand, a method for producing a template carbon material is also known in which magnesium citrate is heat-treated at 900°C for 1 hour in a nitrogen atmosphere, the resulting MgO powder is mixed with polyvinyl alcohol powder, and then the mixture is treated at 900°C for 1 hour in a nitrogen atmosphere (Non-Patent Document 2).

[0011] Also known is a method for producing activated carbon, which uses organic acid magnesium having a carbon number of 6 or more as a raw material, heats the raw material to 300°C or higher in an inert atmosphere, and then cools and washes the raw material with acid (Patent Document 1). In this method for producing activated carbon, citric acid and polyvinyl alcohol (PVA) are used as carbon sources.

[0012] Also known is a method for producing activated carbon that includes a step of mixing an organic resin with at least one alkaline earth metal compound selected from the group consisting of alkaline earth metal oxides, hydroxides, carbonates, and organic acid salts, and then heating and firing the mixture in a non-oxidizing atmosphere, in which the pore size of the activated carbon is adjusted depending on the crystallite size of the alkaline earth metal oxide produced after firing and carbonization (Patent Document 2).In this method for producing activated carbon, resin materials such as polyvinyl alcohol (PVA), polyethylene terephthalate (PET), and hydroxypropyl cellulose (HPC) are used as carbon sources.

[0013] Another known method for producing a porous carbon material involves thermal CVD treatment of alumina nanoparticles (average crystallite size 10 nm, commercially available product) using methane as a carbon source gas (Patent Document 3). In this method for producing a porous carbon material, experimental conditions such as the heat treatment temperature, gas concentration, and treatment time are thoroughly optimized to obtain alumina nanoparticles coated with a carbon film in which the carbon layer is controlled to two or less layers. The alumina is then dissolved in a hydrofluoric acid solution, diluted with distilled water, filtered, dispersed again in distilled water, filtered, and the resulting powder is vacuum-dried to obtain porous carbon.

[0014] Furthermore, a method for producing a template carbon material using an alkaline earth metal salt of benzenedicarboxylic acid as a template source is known (Patent Document 4). This method for producing template carbon is a method for obtaining a template carbon material that has mesopores and has high oxidation resistance and electrical conductivity. [Prior art documents] [Patent documents]

[0015] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-013394 [Patent Document 2] Patent No. 4955952 [Patent Document 3] Japanese Patent Application Laid-Open No. 2015-164889 [Patent Document 4] Patent Publication No. 2021-034128 [Non-patent literature]

[0016] [Non-Patent Document 1] Formation of new type of porous carbon by carbonization in zeolite nanochannels, Chemistry of materials, 2, 609-615(1997) [Non-patent document 2] A review of the controle of pore structure in MgO-templated nanoporous carbons, Carbon, 48, 2690-2707(2010)) Summary of the Invention [Problem to be solved by the invention]

[0017] In the above-mentioned example, for example, in the case of carbon materials using zeolite as a template, the zeolite used as the template itself has a molecular sieve function, i.e., the pore diameter is on the order of several angstroms. Therefore, the thickness of the carbon covering the pores is also 1 nm or less per atomic layer, so a synthesis method using a gas phase method such as CVD (Chemical Vapor Deposition) must be used. In this case, the material is unsuitable for industrial-scale mass production. On the other hand, the methods for producing template carbon materials using MgO or the like as a template source, as exemplified in Patent Documents 1 to 3, are simple production methods and are therefore suitable for industrial materials in terms of production process and production scale. However, as a result of extensive investigations by the present inventors, there is a problem in that the yield of carbon that constitutes the template carbon relative to the weight of the resin used as the carbon source is at most just over 10%.

[0018] Generally, activated porous carbon materials, such as activated carbon and Ketjen black, experience a significant reduction in pore volume and specific surface area when heated in a non-oxidizing atmosphere at temperatures above 1500°C. Heat treatment in a non-oxidizing atmosphere is a common processing method for ensuring the chemical stability and controlling the strength of carbon materials, and it is desirable for the heat treatment to cause minimal changes in the pore structure. From this perspective, templated carbon materials are preferred.

[0019] Therefore, there is currently a demand for a method for producing template carbon materials with high carbon yield and good production yield. Although Patent Document 4 describes the method for producing a templated carbon material as being excellent in oxidation-depletion resistance, it does not describe that the pore structure can be freely controlled and that a templated carbon material with a high carbon yield and good yield can be obtained. In particular, to achieve both improved carbon yield and oxidation-depletion resistance, it is equally or more important to increase the average thickness of the carbon walls that form the pores, i.e., the number of layers of the aromatic carbon network, as important as increasing the aromaticity. The complex-based raw material described in Patent Document 4 does not allow for an increase in the number of carbon atoms relative to the metal atoms, and therefore presents a fundamental problem in improving carbon yield and oxidation-depletion resistance.

[0020] Therefore, the object of the present invention is to provide a method for producing a template carbon material with high carbon yield and good production yield, a method for producing a catalyst using the same, a method for producing a catalyst layer for a polymer electrolyte fuel cell, and a method for producing a fuel cell. [Means for solving the problem]

[0021] The means for solving the problem include the following aspects. <1> A method for producing a template carbon material using, as raw materials, a carbon source that satisfies the following requirement (A) and a template source that satisfies the following requirement (B). (A) The carbon source has at least two or more oxygen-containing functional groups and two or more nitrogen-containing functional groups. In addition, the temperature T at which a 5% weight loss is reached in thermogravimetric analysis under an inert atmosphere 0.05 Contains aromatic compounds with a temperature of 200°C or less. (B) Template source But, A The base material is at least one selected from oxides, carbonates, sulfates, and hydroxides of alkaline earth metals and aluminum. <2> In the carbon source, the aromatic compound is a compound in which at least two of the oxygen-containing functional groups are separated by two or more carbon atoms. <1> A method for producing the template carbon material described in 1. <3> In the carbon source, the aromatic compound is at least one selected from a monocyclic aromatic compound and a bicyclic aromatic compound, the oxygen-containing functional group is a carboxyl group, and the nitrogen-containing functional group is an amino group. <1> or <2> A method for producing the template carbon material described in 1. <4> The bicyclic aromatic compound is a compound having a naphthalene skeleton. <3> A method for producing the template carbon material described in 1. <5> In the carbon source, the aromatic compound is an aromatic compound having three or more rings, the oxygen-containing functional group is a carboxyl group or a hydroxyl group, and the nitrogen-containing functional group is an amino group. <1> or <2> A method for producing the template carbon material described in 1. <6> The aromatic compound having a fused ring structure of three or more rings is at least one selected from a compound having an anthraquinone skeleton and a compound having an anthracene skeleton. <5> A method for producing the template carbon material described in 1. <7> The template source is at least one selected from oxides, carbonates, sulfates, and hydroxides of magnesium and calcium. <1> ~ <6> 1. A method for producing the template carbon material according to any one of claims 1 to 9. <8> The template source is at least one selected from magnesium carbonate and magnesium sulfate. <1> ~ <7> 1. A method for producing the template carbon material according to any one of claims 1 to 9. <9> <1> ~ <8> 1. A method for producing a catalyst, comprising using the carbon material obtained by the method for producing a template carbon material according to any one of the above items as a support, and supporting a catalyst component on the surface of the support. <10> <9> 2. A method for producing a catalyst layer for a polymer electrolyte fuel cell, using a catalyst obtained by the method for producing a catalyst according to claim 1. <11> <10> 1. A method for producing a fuel cell, which uses a catalyst layer obtained by the method for producing a catalyst layer for a polymer electrolyte fuel cell according to claim 1. <12> The catalyst layer for a polymer electrolyte fuel cell is a catalyst layer on the cathode side. <11> A method for manufacturing the fuel cell according to claim 1. [Effects of the Invention]

[0022] According to the present invention, it is possible to provide a method for producing a template carbon material with a high carbon yield and good yield, a method for producing a catalyst using the same, a method for producing a catalyst layer for a polymer electrolyte fuel cell, and a method for producing a fuel cell. [Brief explanation of the drawings]

[0023] [Figure 1] 1 is a schematic diagram showing a general configuration of a fuel cell according to an embodiment of the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0024] The present invention will be described below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In numerical ranges described in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In a numerical range, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. The term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved. A "combination of preferred embodiments" is a more preferred embodiment.

[0025] The method for producing a template carbon material of the present invention is a production method using, as raw materials, a carbon source that satisfies the following requirement (A) and a template source that satisfies the following requirement (B). (A) A carbon source having at least two or more oxygen-containing functional groups and two or more nitrogen-containing functional groups, and a temperature T at which a weight loss of 5% by mass is reached in a thermogravimetric analysis under an inert atmosphere. 0.05 Contains aromatic compounds with a temperature of 200°C or less. (B) Template source But, AThe base material is at least one selected from oxides, carbonates, sulfates, and hydroxides of alkaline earth metals and aluminum.

[0026] The method for producing a template carbon material of the present invention is a method for producing a template carbon material with a high carbon yield and good production yield. The method for producing a template carbon material of the present invention was discovered based on the following findings.

[0027] First, conventional methods for producing template carbon materials typically use ceramics (MgO, CaO, alumina, etc.) as the template source and resin as the carbon source. The gaseous components generated by the thermal decomposition of the resin formed a carbon film on the ceramic surface, which is thought to be a phenomenon unique to the decomposition products of the resin, and this is thought to be the reason why resin was used exclusively as the carbon source. Meanwhile, carbon coating of ceramics by thermal CVD using propylene gas is also well known as a common technique, and these two phenomena led to the idea that the gaseous low-molecular-weight compounds generated by thermal decomposition are essentially important for carbon coating of ceramics. Many resins contain oxygen in the monomer structure, typically the formula (-(CH2-CHOH) n -) is a polyvinyl alcohol. When these resins are simply heated in a non-oxidizing atmosphere, for example at temperatures above 600°C, they undergo thermal decomposition, leaving no solid material behind. However, when they coexist with ceramics such as MgO, CaO, or alumina, the differentiated gaseous compounds are adsorbed onto the ceramic and remain as a carbon film. This phenomenon has previously been considered similar to thermal CVD and therefore unique to radical compounds.

[0028] Meanwhile, the present inventors have investigated at the atomic level the mechanism by which the material used as the carbon source is carbonized and deposited on the surface of the template source through the elementary processes, and have obtained the following findings. First, decomposition of resin as a carbon source is not necessarily required. By using a low molecular weight compound having multiple oxygen-containing or nitrogen-containing functional groups instead of resin, it is possible to obtain a much higher carbon yield than resin. ,a This is because when at least one selected from oxides, carbonates, sulfates, and hydroxides of alkaline earth metals and aluminum is used as the template source, the carbon yield increases due to the mechanism described below.

[0029] The oxygen-containing functional group or the nitrogen-containing functional group is a template source (template source But, A CaCO3-Earth Gold The template source has a strong affinity for metals and aluminum (at least one selected from oxides, carbonates, sulfates, and hydroxides). Therefore, when an aromatic compound having a molecular structure containing two or more oxygen-containing or nitrogen-containing functional groups that have an affinity for the template source is used as a carbon source and heated together with the template source in a non-oxidizing atmosphere, the carbon yield increases. Although the elementary process of the carbon fixation reaction of a carbon source at the atomic level is not clear, it is presumed that at least two or more oxygen-containing functional groups in the molecular structure of the carbon source fix the carbon source to the surface of the template source, and when oxygen is released in the form of carbon dioxide during a thermal process, the molecular structure between the two oxygen-containing functional groups is fixed. Similarly, when nitrogen is released during a thermal process for two or more nitrogen-containing functional groups, the molecular structure between the two nitrogen-containing functional groups is presumed to be fixed.

[0030] Formula (-(CH2-CHOH) n Even when a typical resin material such as polyvinyl alcohol represented by the formula (I-) is used as a carbon source, the gaseous compound produced by thermal decomposition necessarily contains oxygen atoms in its structure. Therefore, only compounds containing multiple oxygen-containing functional groups or multiple nitrogen-containing functional groups will have a high carbon yield, and it is presumed that the overall carbon yield will be low because the probability of this occurring is low.

[0031] From the above findings, it has been found that the method for producing a template carbon material of the present invention provides a high carbon yield and is a method for producing a template carbon material with good yield.

[0032] The method for producing the template carbon material of the present invention will be described in detail below.

[0033] The method for producing a template carbon material of the present invention includes, for example, a mixing step of mixing a carbon source and a template source, a first heating step, a template source removal step, and a second heating step. Each step will be described in detail below.

[0034] (Mixing process) In this step, a carbon source and a template source are mixed together.

[0035] -Carbon source- The carbon source has at least two or more oxygen-containing functional groups and two or more nitrogen-containing functional groups, and has a temperature T at which a 5% weight loss is reached in thermogravimetric analysis under an inert atmosphere. 0.05 At least aromatic compounds with a melting point of 200°C or less are applicable.

[0036] The aromatic compound has two or more oxygen-containing functional groups and nitrogen-containing functional groups, but from the viewpoint of improving the carbon yield, it preferably has two to six, more preferably two to six. Examples of oxygen-containing functional groups include carboxyl groups, hydroxyl groups, etc. Examples of nitrogen-containing functional groups include amino groups, etc.

[0037] In the aromatic compound, the number of carbon atoms interposed between at least two of the two or more oxygen-containing functional groups or nitrogen-containing functional groups is preferably 2 or more, more preferably 2 to 5, and more preferably 2 to 4, from the viewpoint of improving the carbon yield. Here, the number of carbon atoms intervening between two oxygen-containing functional groups or nitrogen-containing functional groups does not include the carbon atoms of the oxygen-containing functional groups or nitrogen-containing functional groups (e.g., the carbon atoms of a carboxyl group), but refers to the number of carbon atoms connected in a linear chain between the two oxygen-containing functional groups or nitrogen-containing functional groups. In other words, when the carbon atom intervening between two oxygen-containing functional groups or nitrogen-containing functional groups has a substituent (e.g., an alkyl group), the number of carbon atoms intervening between the two oxygen-containing functional groups or nitrogen-containing functional groups does not include the number of carbon atoms of the substituent. Furthermore, the number of carbon atoms between two oxygen-containing functional groups or nitrogen-containing functional groups is the number of carbon atoms between the nearest oxygen-containing functional groups or nitrogen-containing functional groups.

[0038] The functional groups on the aromatic compounds are the template source. Rua They strongly adsorb to oxides, carbonates, sulfates, or hydroxides of alkaline earth metals, and when the carbon source is thermally decomposed during the carbonization process, the inorganic compound of the template source binds strongly to the oxygen- or nitrogen-containing functional groups, preventing the carbon source decomposition products from disappearing in the gas phase. Therefore, it is a prerequisite that the carbon source is thermally decomposed during the carbonization process. In other words, aromatic compounds are decomposed at the temperature T 0.05 However, it must be filled at 200°C or less. In this regard, for example, anthraquinone and phenanthrenequinone have two quinone-type oxygen-containing functional groups, but at temperature T 0.05 It does not fall under the category of aromatic compounds at temperatures below 200°C. This is because quinone functional groups are extremely stable and do not undergo thermal decomposition during the carbonization process, but rather sublimate, resulting in a carbonization yield of essentially zero. In thermogravimetric analysis under an inert atmosphere, the temperature T 0.05 The measurement method is as described in the Examples below.

[0039] Here, examples of aromatic compounds include monocyclic aromatic compounds and aromatic compounds with two or more rings (condensed polycyclic aromatic compounds with two or more rings, and non-condensed polycyclic aromatic compounds with two or more rings). Note that aromatic compounds also include aromatic heterocyclic compounds. Examples of the monocyclic aromatic compound include compounds having a benzene skeleton and heterocyclic rings (compounds having a pyridine skeleton, compounds having a pyrimidine skeleton, compounds having a triazine skeleton, compounds having a pyrrole skeleton, compounds having a furan skeleton, compounds having a triazine skeleton, etc.). The fused polycyclic aromatic compound having two or more rings is a compound in which two or more aromatic rings are fused, and examples thereof include compounds having a naphthalene skeleton, compounds having an anthracene skeleton, compounds having an anthraquinone skeleton, compounds having a phenanthrenequinone skeleton, compounds having a nitrogen-containing three-ring skeleton (e.g., 1-azaphenanthrene, 4-azaphenanthrene, 9-azaphenanthrene, 1,10-phenanthroline, 9-azaanthracene, 9,10-diazaanthracene, etc.), compounds having a pyrene skeleton, compounds having a perylene skeleton, compounds having a phenanthrene skeleton, compounds having a pentacene skeleton, and compounds having a coronene skeleton. Non-condensed polycyclic aromatic compounds having two or more rings are compounds in which two or more aromatic rings are linked to each other directly or via a bridging member (such as an aliphatic hydrocarbon group, a nitrogen atom, or a sulfur atom), and examples thereof include compounds having a biphenyl skeleton, compounds having a terphenyl skeleton, and compounds having a triphenylmethane skeleton.

[0040] From the viewpoint of improving carbon yield, the aromatic compound is preferably at least one selected from monocyclic aromatic compounds and bicyclic aromatic compounds (preferably bicyclic condensed polycyclic aromatic compounds), and is preferably a compound in which the oxygen-containing functional group is a carboxyl group and the nitrogen-containing functional group is an amino group. As the bicyclic aromatic compound, a bicyclic condensed polycyclic aromatic compound is preferred, and naphthalene is preferred.

[0041] From the viewpoint of improving carbon yield, the aromatic compound is preferably an aromatic compound having three or more rings, in which the oxygen-containing functional group is a carboxyl group or a hydroxyl group, and the nitrogen-containing functional group is an amino group. The aromatic compound having three or more rings is preferably a condensed polycyclic aromatic compound having three or more rings, and is preferably at least one selected from compounds having an anthraquinone skeleton and compounds having an anthracene skeleton.

[0042] From the viewpoint of improving the carbon yield, the total number of oxygen atoms in all oxygen-containing functional groups in the aromatic compound is preferably 4 or more, and more preferably 4 to 8. The total number of nitrogen atoms in all nitrogen-containing groups is preferably 2 or more, and more preferably 2 to 4. Two or more carboxyl groups may form an anhydride. Two or more carboxyl groups may form an alkyl metal salt. That is, for example, an aromatic compound having one carboxylic acid anhydride group corresponds to an aromatic compound having two carboxyl groups. The amino group may be a primary amino group, a secondary amino group, or a tertiary amino group. The secondary amino group may be -NR 1 H(R 11 is an alkyl group having 1 to 6 carbon atoms). Examples of the tertiary amino group include -NR 2 R 3 (R 2 , R 3 and each independently represent an alkyl group having 1 to 6 carbon atoms. Of these, the amino group is preferably a primary amino group.

[0043] The aromatic compound preferably has 6 to 30 carbon atoms, more preferably 6 to 24 carbon atoms, and even more preferably 10 to 20 carbon atoms, from the viewpoint of improving the carbon yield. Here, the number of carbon atoms in the aromatic compound is the number of carbon atoms including the carbon atoms in the oxygen-containing functional group and the nitrogen-containing functional group.

[0044] Among aromatic compounds, examples of monocyclic or bicyclic aromatic compounds having two or more carboxyl groups include benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetetracarboxylic anhydride, naphthalenetetracarboxylic anhydride, etc. Also included are nitrogen-containing heterocyclic dicarboxylic acids of benzene, nitrogen-containing heterocyclic dicarboxylic acids of naphthalene, and anhydrides thereof.

[0045] Examples of aromatic compounds having two or more carboxyl groups and three or more rings include polycarboxylic acids of phenanthrene, anthracene, pyrene, and coronene, as well as nitrogen-containing heterocyclic rings of these aromatic compounds having three or more rings.

[0046] Examples of aromatic compounds having two or more hydroxyl groups and three or more rings include anthraquinone, phenanthrenequinone, dihydroxyanthraquinone, tetrahydroxyanthraquinone, and dihydroxyanthracene.

[0047] Examples of monocyclic or bicyclic aromatic compounds having two or more amino groups include diaminobenzene, diaminonaphthalene, diamines having a nitrogen-containing benzene ring, and diamines having a nitrogen-containing naphthalene ring.

[0048] Examples of aromatic compounds having two or more amino groups and two or more rings include diaminoanthraquinone, diaminoanthracene, diaminophenanthrene, and triaminoanthraquinone.

[0049] In addition to the aromatic compound, a resin may be used as the carbon source, provided that the amount of the aromatic compound is, for example, 30% by mass or more (preferably 40% by mass or more) of the total carbon source. Examples of resins that can be used as carbon sources include well-known resins that are used as carbon sources, such as polyvinyl alcohol, polyethylene glycol, and polyacrylic acid.

[0050] -Mold Source- As the template source, the template source is ,a At least one selected from oxides, carbonates, sulfates, and hydroxides of alkaline earth metals and aluminum is used. Here, the alkaline earth metals include calcium, barium, strontium, and the like. ,magnesium etc.

[0051] a Examples of the oxides of alkaline earth metals include magnesium oxide (MgO), calcium oxide, barium oxide, and strontium oxide. a Examples of carbonates of alkaline earth metals include magnesium carbonate, calcium carbonate, barium carbonate, and strontium carbonate. a Examples of the sulfates of alkaline earth metals include magnesium sulfate, calcium sulfate, barium sulfate, and strontium sulfate. a Examples of hydroxides of alkaline earth metals include magnesium hydroxide, calcium hydroxide, barium hydroxide, and strontium hydroxide.

[0052] Among these, from the viewpoint of improving carbon yield, the carbon source is ,a At least one selected from oxides, carbonates, sulfates, and hydroxides of alkaline earth metals and aluminum is preferred, at least one selected from oxides, carbonates, and oxides of magnesium and calcium is more preferred, and at least one selected from magnesium carbonate and magnesium sulfate is more preferred. Among the oxides, carbonates, sulfates and hydroxides of aluminum, aluminum oxide is preferred.

[0053] -Mixing ratio of carbon source and template source- The mixing ratio of the carbon source and the template source (template source / carbon source), in terms of the molar ratio of the template source to carbon C in the carbon source, is preferably 0.1 to 15.0, more preferably 0.5 to 10.0, thereby obtaining a template carbon material (i.e., a porous carbon material) with the desired BET specific surface area and pore distribution.

[0054] (First heating step) In the first heating step, for example, a mixture of a carbon source and a template source is heated to 800 to 1100°C at a rate of 5 to 30°C / min in an inert gas atmosphere, and is maintained at that temperature for 10 to 200 minutes. This heat treatment allows the template source to be thermally decomposed and oxidized in parallel with the carbonization of the carbon source, resulting in the carbon and template (i.e. Ria A complex with an oxide of an alkaline earth metal or aluminum is obtained.

[0055] (Mold source removal process) In the template removal process, carbon and the template ( RiaThe composite of carbon and the template (oxide of an alkaline earth metal or aluminum) is pickled to dissolve the template in the pickling solution. This removes the template from the composite of carbon and the template, thereby obtaining a porous carbon material intermediate. The acid used for pickling may be any acid as long as it dissolves the template, and a preferred example is sulfuric acid. After pickling, the carbon material is washed with water and dried.

[0056] (Second heating step) In the second heating step, for example, the obtained intermediate template carbon material is held in an inert gas atmosphere at 2300 to 2600° C. for 0.5 to 3.0 hours. This heat treatment increases the crystallinity of the template carbon material and improves its durability (resistance to oxidation and wear) at high temperatures. After the second heating step, the intermediate template carbon material may be subjected to graphitization treatment at 2400° C. or higher.

[0057] Through the above steps, the desired template carbon material (that is, porous carbon material) is obtained.

[0058] The method for producing a templated carbon material of the present invention is applicable to fields in which a carbon material called activated carbon is used (for example, the field of adsorbents for selective adsorption of specific gases and molecules with specific structures in the liquid phase), fields in which Ketjen black is used as a catalyst support for solid polymer fuel cells, and fields in which supercapacitor electrodes are used.

[0059] <Catalyst manufacturing method> The method for producing a templated carbon material of the present invention can be applied to a method for producing a catalyst, which involves supporting a catalyst component on the surface of the carbon material obtained by the method for producing a templated carbon material of the present invention as a support. A typical catalyst component is a catalyst for solid polymer fuels. Examples of catalyst components include platinum and platinum alloys. Examples of alloy components of platinum alloys include gold, silver, chromium, iron, titanium, manganese, cobalt, nickel, molybdenum, tungsten, aluminum, silicon, zinc, tin, ruthenium, rhodium, palladium, osmium, and iridium. Other typical catalyst components include catalysts for polymer electrolyte fuels. Examples of catalyst components include platinum and platinum alloys. Examples of alloy components of platinum alloys include Au, Ag, Cr, Fe, Ti, Mn, Co, Ni, Mo, W, Al, Si, Zn, Sn, Ru, Rh, Pd, Os, and Ir.

[0060] The catalyst production method of the present invention can be applied to the production of electrodes that provide a large reaction surface area and are required to have high chemical and electrochemical stability, such as catalyst layers for polymer electrolyte fuel cells, air electrodes for metal-air batteries such as Li-air batteries, and electrodes for redox flow batteries.

[0061] <Method of manufacturing a polymer electrolyte fuel cell> The method for producing a template carbon material of the present invention is applicable to a method for producing a polymer electrolyte fuel cell (or a catalyst layer thereof). An example of the solid polymer fuel cell to be manufactured is a solid polymer fuel cell 100 shown in Figure 1. The solid polymer fuel cell 100 includes separators 110, 120, gas diffusion layers 130, 140, catalyst layers 150, 160, and an electrolyte membrane 170, for example.

[0062] Separator 110 is an anode-side separator that introduces a fuel gas such as hydrogen into gas diffusion layer 130. Separator 120 is a cathode-side separator that introduces an oxidizing gas such as oxygen gas or air into the gas diffusion condensation layer. There is no particular restriction on the type of separators 110 and 120, and they may be any separators used in conventional fuel cells, such as solid polymer fuel cells.

[0063] The gas diffusion layer 130 is an anode-side gas diffusion layer that diffuses the fuel gas supplied from the separator 110 and then supplies it to the catalyst layer 150. The gas diffusion layer 140 is a cathode-side gas diffusion layer that diffuses the oxidizing gas supplied from the separator 120 and then supplies it to the catalyst layer 160. There is no particular restriction on the type of gas diffusion layers 130 and 40, as long as they are gas diffusion layers used in conventional fuel cells, such as solid polymer fuel cells. Examples of gas diffusion layers 130 and 40 include porous carbon materials (carbon cloth, carbon paper, etc.), porous metal materials (metal mesh, metal wool, etc.), etc. A preferred example of the gas diffusion layers 130 and 140 is a two-layer gas diffusion layer in which the layer on the separator side of the gas diffusion layer is a gas diffusion fiber layer mainly composed of a fibrous carbon material, and the layer on the catalyst layer side is a micropore layer mainly composed of carbon black.

[0064] The catalyst layer 150 is a so-called anode. An oxidation reaction of the fuel gas occurs in the catalyst layer 150, producing protons and electrons. For example, when the fuel gas becomes hydrogen gas, the following oxidation reaction occurs. H2→2H + +2e - (E0=0V)

[0065] Protons produced by the oxidation reaction pass through catalyst layer 150 and electrolyte membrane 170 to reach catalyst layer 160. Electrons produced by the oxidation reaction pass through catalyst layer 150, gas diffusion layer 130, and separator 110 to reach the external circuit. After performing work in the external circuit, the electrons are introduced into separator 120. The electrons then pass through separator 120 and gas diffusion layer 140 to reach catalyst layer 160.

[0066] The configuration of the catalyst layer 150 that serves as the anode is not particularly limited. That is, the configuration of the catalyst layer 150 may be the same as that of a conventional anode, may be the same as that of the catalyst layer 160, or may be more hydrophilic than the catalyst layer 160.

[0067] The catalyst layer 160 is a so-called cathode. Within the catalyst layer 160, a reduction reaction of the oxidizing gas occurs, producing water. For example, when the oxidizing gas becomes oxygen gas or air, the following reduction reaction occurs: The water produced by the oxidation reaction is discharged to the outside of the polymer electrolyte fuel cell 100 together with the unreacted oxidizing gas. O2+4H + +4e - →2H2O (E0=1.23V)

[0068] In this way, the energy difference (potential difference) between the oxidation reaction and the reduction reaction is utilized to generate electricity in the polymer electrolyte fuel cell 100. In other words, the electrons generated in the oxidation reaction perform work in an external circuit.

[0069] The catalyst layer 160 contains the template carbon material of the present invention. That is, the catalyst layer 160 contains the template carbon material of the present invention, an electrolyte material, and a fuel cell catalyst. This can increase the catalyst utilization rate in the catalyst layer 160. As a result, the catalyst utilization rate of the polymer electrolyte fuel cell 100 can be increased.

[0070] The fuel cell catalyst loading rate in the catalyst layer 160 is not particularly limited, but is preferably 30% by mass or more and less than 80% by mass. The fuel cell catalyst loading rate is preferably the mass % of the fuel cell catalyst relative to the total mass of the catalyst-loaded particles (particles in which the fuel cell catalyst is loaded on a template carbon material). In this case, the catalyst utilization rate is further increased. If the fuel cell catalyst loading rate is less than 30% by mass, it may be necessary to thicken the catalyst layer 160 to make the polymer electrolyte fuel cell 100 practical. On the other hand, if the fuel cell catalyst loading rate is 80% by mass or more, catalyst aggregation is likely to occur. Furthermore, if the catalyst layer 160 becomes too thin, flooding may occur.

[0071] The mass ratio I / C of the mass I (g) of the electrolyte material in the catalyst layer 160 to the mass C (g) of the catalyst support carbon material is not particularly limited, but is preferably greater than 0.5 and less than 5.0. In this case, both the pore network and the electrolyte material network can be achieved, resulting in a high catalyst utilization rate. On the other hand, if the mass ratio I / C is 0.5 or less, the electrolyte material network tends to be weak and the proton conduction resistance tends to increase. If the mass ratio I / C is 5.0 or more, the pore network may be disrupted by the electrolyte material. In either case, the catalyst utilization rate may decrease.

[0072] Furthermore, the thickness of the catalyst layer 160 is not particularly limited, but is preferably more than 5 μm and less than 20 μm. In this case, oxidizing gas is more likely to diffuse within the catalyst layer 160, and flooding is less likely to occur. If the thickness of the catalyst layer 160 is 5 μm or less, flooding is more likely to occur. If the thickness of the catalyst layer 160 is 20 μm or more, oxidizing gas is less likely to diffuse within the catalyst layer 160, and the fuel cell catalyst near the electrolyte membrane 170 becomes less effective. In other words, the catalyst utilization rate may decrease.

[0073] The electrolyte membrane 170 is made of an electrolyte material having proton conductivity. The electrolyte membrane 170 introduces protons generated in the oxidation reaction to the catalyst layer 160, which serves as the cathode. The type of electrolyte material is not particularly limited, and any electrolyte material used in conventional fuel cells, such as solid polymer fuel cells, may be used. A suitable example is an electrolyte material used in solid polymer fuel cells, i.e., an electrolyte resin. Examples of the electrolyte resin include polymers having phosphate groups, sulfonic acid groups, or the like introduced therein (e.g., perfluorosulfonic acid polymers or polymers having benzenesulfonic acid introduced therein). Of course, other types of electrolyte materials may also be used. Examples of such electrolyte materials include inorganic and inorganic-organic hybrid electrolyte materials. The solid polymer fuel cell 100 may be a fuel cell that operates within a temperature range from room temperature to 150°C. [Example]

[0074] <Experimental Example> The carbon source and template source were mixed in the types and amounts shown in Tables 1 to 4. Since particles with as small a particle size as possible will form a uniform fired product in the first heating step, the carbon source and template source were pulverized in a mortar, planetary ball mill, or the like before testing to a volume average particle size of 1.0 to 10.0 μm. The mixture was mixed in a mortar for at least several minutes before use. The compounds used as carbon sources were evaluated by thermogravimetric analysis under an inert atmosphere. For the thermogravimetric analysis, a Rigaku TG-DTA8122 was used, and the temperature was raised from room temperature (25°C) to 500°C at a rate of 10°C / min. Under argon gas flow conditions, the temperature T 0.05 was calculated. 0.05 The results are shown in Tables 1 to 4, with ◯ indicating that the temperature was 200°C or less, and × indicating that the temperature did not meet this requirement. Next, the mixture was fired (first heat treatment) in a gas-flow type horizontal tubular electric furnace while flowing argon gas to obtain a composite of carbon and the template. Specifically, argon was flowed at a linear velocity of 3 cm / min, and the temperature was raised from room temperature to 900°C at a rate of 20°C / min, held at 900°C for 1 hour, and then allowed to cool until it reached 100°C or below, at which point the mixture was removed to obtain a composite of carbon and the template. Next, the composite was lightly crushed in a mortar, dispersed in a 20% by mass aqueous solution of sulfuric acid, stirred at 90°C for 40 hours, and then suction filtered through a membrane filter. This was then dispersed in distilled water and filtered twice more, followed by washing, to remove the template. Next, the washed material was dried in a hot air dryer at 100°C to remove moisture, and then vacuum dried at 90°C for 5 hours to obtain an intermediate for the template carbon material. Next, in order to enhance the crystallinity of the resulting template carbon material, the intermediate of the template carbon material was subjected to a second heat treatment in an inert gas atmosphere at 1500°C for 1.0 hour, after which the intermediate of the template carbon material was subjected to a graphitization treatment (heat treatment). Through the above steps, a template carbon material (that is, a porous carbon material) was obtained.

[0075] Benzene-1,4-dicarboxylic acid calcium salt was obtained by reproducing the description of Example 1 of Patent Document 4 (Experimental Example No. Ar1-12). Specifically, 2 L of pure water, 1 mol of calcium hydroxide, and 1 mol of terephthalic acid were placed in a reaction vessel and mixed at 80°C for 3 hours to prepare calcium terephthalate. The prepared calcium terephthalate was allowed to stand for 24 hours. The calcium terephthalate was then filtered, dried at 115°C for 24 hours, and coarsely pulverized. A template carbon material (i.e., a porous carbon material) was obtained from the obtained benzene-1,4-dicarboxylic acid calcium salt by the same procedure as above, including the first heat treatment.

[0076] <Evaluation> The obtained template carbon material (that is, the porous carbon material) was evaluated as follows.

[0077] (carbon yield) The carbon yield in the manufacturing method of the template carbon material of each example was determined as follows. The mass ratio of the mass of carbon after the template source removal step to the mass of the carbon source used as the raw material was defined as the carbon yield, and was measured by the following method. That is, after the first heat treatment described above, the sample was held at 900°C for 1 hour, and then the template was removed by a sulfuric acid solution treatment and a subsequent washing treatment. The template carbon intermediate obtained by further performing a vacuum tube treatment was weighed, and the mass was divided by the mass of the carbon source used as the raw material to calculate the carbon yield in %.

[0078] (Catalyst preparation, catalyst layer fabrication, MEA fabrication, fuel cell assembly, and cell performance evaluation) Using the obtained template carbon material, a catalyst for a polymer electrolyte fuel cell carrying a catalytic metal was prepared as follows: the obtained catalyst was used to prepare a catalyst layer ink liquid, which was then used to form a catalyst layer, which was then used to fabricate a membrane electrode assembly (MEA), which was then incorporated into a fuel cell, and a power generation test was performed using a fuel cell measuring device. The preparation of each component and the cell evaluation through the power generation test are described in detail below.

[0079] (1) Preparation of catalysts (platinum-supported carbon materials) for polymer electrolyte fuel cells The resulting template carbon material was dispersed in distilled water, and formaldehyde was added to the dispersion. The dispersion was then placed in a water bath set at 40°C. Once the temperature of the dispersion reached the same temperature as the bath (40°C), an aqueous solution of dinitrodiamine platinum complex nitric acid was slowly poured into the dispersion while stirring. Stirring was continued for approximately 2 hours, followed by filtration and washing of the resulting solid. The solid thus obtained was vacuum dried at 90°C, crushed in a mortar, and then heat-treated for 1 hour at 200°C in an argon atmosphere containing 5% hydrogen by volume to produce a platinum catalyst particle-supported carbon material. The amount of platinum carried in this platinum-supported carbon material was adjusted to 40 mass % relative to the total mass of the template carbon material and platinum particles, and was confirmed by measurement using inductively coupled plasma atomic emission spectrometry (ICP-AES).

[0080] (2) Preparation of the catalyst layer Using the platinum-supported carbon material (Pt catalyst) prepared as described above, and Nafion (registered trademark: Nafion; a persulfonic acid-based ion exchange resin) manufactured by DuPont as the electrolyte resin, the Pt catalyst and Nafion were mixed under an Ar atmosphere in a ratio of 1.0 times the mass of the Nafion solids relative to the mass of the platinum catalyst particle-supported carbon material, and 0.5 times the mass of the non-porous carbon. After light stirring, the Pt catalyst was crushed using ultrasound, and ethanol was added so that the total solid concentration of the Pt catalyst and electrolyte resin combined was adjusted to 1.0 mass %, thereby preparing a catalyst layer ink liquid in which the Pt catalyst and electrolyte resin were mixed.

[0081] Ethanol was further added to each catalyst layer ink liquid thus prepared, each having a solids concentration of 1.0% by mass, to prepare a catalyst layer ink liquid for spray application with a platinum concentration of 0.5% by mass. The spray conditions were adjusted so that the mass of platinum per unit area of ​​the catalyst layer (hereinafter referred to as "platinum coverage") was 0.2 mg / cm2. The catalyst layer ink for spray application was sprayed onto a Teflon (registered trademark) sheet, which was then dried in argon at 120°C for 60 minutes to prepare a catalyst layer.

[0082] (3) Preparation of MEA Using the catalyst layer prepared as above, an MEA (membrane electrode assembly) was prepared by the following method. A square electrolyte membrane with sides of 6 cm was cut out from a Nafion membrane (NR211 manufactured by DuPont). The anode and cathode catalyst layers coated on Teflon (registered trademark) sheets were each cut into a square with sides of 2.5 cm using a cutter knife. The electrolyte membrane was sandwiched between the anode and cathode catalyst layers cut out in this way so that the catalyst layers were in contact with each other, sandwiching the center of the electrolyte membrane, and so that there was no misalignment between them. The mixture was pressed at 120°C and 100 kg / cm for 10 minutes, and then cooled to room temperature. After that, the Teflon sheets were carefully peeled off from both the anode and cathode, thereby preparing a catalyst layer-electrolyte membrane assembly in which the anode and cathode catalyst layers were fixed to the electrolyte membrane.

[0083] Next, a pair of square carbon paper sheets with sides of 2.5 cm were cut out from carbon paper (35BC manufactured by SGL Carbon Co., Ltd.) to form gas diffusion layers. The catalyst layer-electrolyte membrane assembly was sandwiched between these carbon paper sheets so that the anode and cathode catalyst layers were aligned with each other without any misalignment, and the sheets were pressed at 120°C and 50 kg / cm2 for 10 minutes to prepare an MEA. The basis weight of each component of the catalytic metal component, carbon material, and electrolyte material in each MEA produced was calculated from the mass of the catalyst layer fixed to the Nafion membrane (electrolyte membrane) obtained from the difference between the mass of the Teflon sheet with the catalyst layer before pressing and the mass of the Teflon sheet peeled off after pressing, and then calculated from the mass ratio of the composition of the catalyst layer.

[0084] (4) Evaluation of fuel cell power generation characteristics (Evaluation of low current characteristics) The MEAs prepared in each test example and fabricated using the prepared porous carbon materials for catalyst supports were each incorporated into a cell, which was then set in a fuel cell measuring device, and the performance of the fuel cell was evaluated according to the following procedure. The reactant gases were supplied at a back pressure of 0.04 MPa, with air supplied to the cathode side and pure hydrogen supplied to the anode side, with the pressure adjusted by a back pressure valve installed downstream of the cell under atmospheric pressure so that the utilization rates were 40% and 70%, respectively. The cell temperature was set to 80°C, and the reactant gas supplied to both the cathode and anode was bubbled with distilled water kept at 60°C in a humidifier, and humidified gas at 60°C was supplied to the cell at 80°C to evaluate power generation.

[0085] Under these conditions, the reaction gas was supplied to the cell, and the load was gradually increased until the current density reached 100 mA / cm. 2 The voltage between the cell terminals at this time was recorded as the output voltage, and the performance of the fuel cell was evaluated and rated according to the following pass / fail ranking criteria. The results are shown in Tables 1 to 4. [Passing rank] ◎: 100mA / cm 2 The output voltage is 0.880V or more. ○: 100mA / cm 2The output voltage is 0.870V or more. [Failure rank] ×:100mA / cm 2 The output voltage is less than 0.870V.

[0086] [Table 1-1]

[0087] [Table 1-2]

[0088] [Table 2-1]

[0089] [Table 2-2]

[0090] [Table 3-1]

[0091] [Table 3-2]

[0092] [Table 4]

[0093] From the above results, it can be seen that the method for producing template carbon material in the example of the present invention is a method for producing template carbon material with a high carbon yield and good yield, equal to or higher than that of the comparative example in which a resin material was used as the carbon source.

[0094] Details of the abbreviations in the table are provided below. ATQ: Anthraquinone PVA: Polyvinyl alcohol (weight average molecular weight = 10,000) PEG: polyethylene glycol (weight average molecular weight = 600) PAA: Polyacrylic acid (weight average molecular weight = 10,000) [Explanation of symbols]

[0095] 100 Polymer electrolyte fuel cell 110, 120 separator 130, 140 Gas diffusion layer 150, 160 catalyst layer 170 Electrolyte membrane

Claims

1. A mixing step of mixing a carbon source and a template source. a first heating step of heat-treating the mixture of the carbon source and the template source to obtain a composite of carbon and the template; a template source removal step of removing the template source from the composite of the carbon and the template to obtain an intermediate of the template carbon material; a second heating step of heat-treating the intermediate of the template carbon material; and A method for producing a template carbon material, wherein the carbon source and the template source in the mixing step satisfy the following requirement (A) and the following requirement (B), respectively: (A) The carbon source is an aromatic compound having at least two or more oxygen-containing functional groups and two or more nitrogen-containing functional groups, and the temperature T0.05 at which a 5% mass loss is reached in thermogravimetric analysis under an inert atmosphere is 200°C or lower. (B) The template source is at least one selected from oxides, carbonates, sulfates, and hydroxides of alkaline earth metals and aluminum.

2. 2. The method for producing a template carbon material according to claim 1, wherein, in the carbon source, the aromatic compound is a compound in which, of the two or more oxygen-containing functional groups, at least two of the oxygen-containing functional groups are separated by two or more carbon atoms.

3. 3. The method for producing a template carbon material according to claim 1 or claim 2, wherein in the carbon source, the aromatic compound is at least one selected from a monocyclic aromatic compound and a bicyclic aromatic compound, the oxygen-containing functional group is a carboxyl group, and the nitrogen-containing functional group is an amino group.

4. 4. The method for producing a template carbon material according to claim 3, wherein the two-ring aromatic compound is a compound having a naphthalene skeleton.

5. 3. The method for producing a template carbon material according to claim 1 or claim 2, wherein in the carbon source, the aromatic compound is an aromatic compound with three or more rings, the oxygen-containing functional group is a carboxyl group or a hydroxyl group, and the nitrogen-containing functional group is an amino group.

6. The aromatic compound having three or more rings is a compound having an anthraquinone skeleton.

6. The method for producing a templated carbon material according to claim 5, wherein the templated carbon material is at least one selected from the group consisting of compounds having an anthracene skeleton and compounds having an anthracene skeleton.

7. The method for producing a template carbon material according to any one of claims 1 to 6, wherein the template source is at least one selected from oxides, carbonates, sulfates, and hydroxides of magnesium and calcium.

8. The method for producing a template carbon material according to any one of claims 1 to 7, wherein the template source is at least one selected from magnesium carbonate and magnesium sulfate.

9. A method for producing a catalyst, comprising using the carbon material obtained by the method for producing a template carbon material according to any one of claims 1 to 8 as a support, and supporting a catalyst component on the surface of the support.

10. A method for producing a catalyst layer for a polymer electrolyte fuel cell, using a catalyst obtained by the method for producing a catalyst according to claim 9.

11. A method for producing a fuel cell, which uses a catalyst layer obtained by the method for producing a catalyst layer for a polymer electrolyte fuel cell according to claim 10.

12. The method for producing a fuel cell according to claim 11, wherein the catalyst layer for a polymer electrolyte fuel cell is a catalyst layer on the cathode side.

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