Carbon supports, metal-supported catalysts, electrodes and batteries

Abstract

To provide a carbon carrier simultaneously realizing durability and catalytic activity of a metal carrier catalyst, a metal carrier catalyst, an electrode, and an electric cell.SOLUTION: A carbon carrier is for carrying a catalyst metal particle. The carbon carrier has a BET specific surface area of 300 m2 / g or more, real density is 2.1 g / cm3 or more, and has a carbon structure showing, in a Raman spectrum obtained by Raman spectroscopy, one or more characteristics selected from a group of characteristics (i) and (ii): (i) a ratio of intensity of D-band having a peak top in a vicinity of Raman shift 1340 cm-1 to intensity of G-band having a peak top in a vicinity of Raman shift 1580 cm-1 is 1.6 or more; and (ii) a ratio of intensity of 2D-band having a peak top in a vicinity of Raman shift 2700 cm-1 to intensity of G-band having a peak top in a vicinity of Raman shift 1580 cm-1 is 0.3 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a carbon support, a metal-supported catalyst, an electrode, and a battery. [Background technology]

[0002] Patent Document 1 describes a method for producing a carbon black or activated carbon by heat treating the carbon black or activated carbon at 1800 to 2500°C, which has an average lattice spacing d of the

[0002] plane. 002 is 0.337~0.348nm, crystallite size Lc (002) is 3 to 18 nm, and the specific surface area is 70 to 800 m 2 / g of a carbon support and an electrode catalyst comprising platinum or a platinum alloy supported on the carbon support.

[0003] Patent Document 2 describes graphitized carbon black obtained by heat treating a mixture containing carbon black and a graphitization promoter at 2000 to 2500°C, and a catalyst for phosphoric acid fuel cells in which platinum is supported on the graphitized carbon black. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-268828 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-273351 Summary of the Invention [Problem to be solved by the invention]

[0005] The inventors of the present invention have focused on the problem that when a graphitized carbon material is used as a carbon support for a metal-supported catalyst, the durability (e.g., corrosion resistance and / or load fluctuation resistance) of the metal-supported catalyst is improved, but the initial catalytic activity of the metal-supported catalyst is reduced.

[0006] The present invention has been made in view of the above-mentioned problems, and one of its objects is to provide a carbon support, a metal-supported catalyst, an electrode, and a battery that achieve both durability and catalytic activity of the metal-supported catalyst. [Means for solving the problem]

[0007] [1] A carbon support according to one embodiment of the present invention for solving the above problems is a carbon support for supporting catalytic metal particles, and has a BET specific surface area of ​​300 m 2 / g or more, and the true density is 2.1g / cm 3 The Raman spectrum obtained by Raman spectroscopy has the following characteristics (i) and (ii): (i) Raman shift 1580 cm -1 Raman shift of the G band intensity with a peak top near 1340 cm -1 (ii) The ratio of the D band intensities with peak tops near 1580 cm is 1.6 or more; -1 Raman shift of the G band intensity with a peak top near 2700 cm -1 The carbon structure exhibits one or more of the following: a ratio of the intensities of 2D bands having peak tops near 0.3 or more; and a ratio of the intensities of 2D bands having peak tops near 0.3 or more. The present invention provides a carbon support that achieves both durability and catalytic activity of a metal-supported catalyst.

[0008] [2] The carbon support of [1] may have the carbon structure exhibiting the characteristic (i). [3] The carbon support of [1] or [2] may have the carbon structure exhibiting the characteristic (ii).

[0009] [4] The carbon support of any one of [1] to [3] may have an oxygen content of 1.0 wt % or more. [5] The carbon support of any one of [1] to [4] may have a Raman shift of 1580 cm in a Raman spectrum obtained by Raman spectroscopy. -1 The half-width at half maximum of the G band, which has a peak top near -1[6] The carbon support may have the carbon structure as described below: [1] Any of the carbon supports described above in [1] to [5] may have a Raman shift of 1340 cm in a Raman spectrum obtained by Raman spectroscopy. -1 The half-width at half maximum of the D band, which has a peak top near -1 [7] The carbon support according to any one of [1] to [6] may have the carbon structure shown below: [7] The carbon support according to any one of [1] to [6] may have a Raman shift of 2700 cm in a Raman spectrum obtained by Raman spectroscopy. -1 The half-width at half maximum of the 2D band with a peak top near -1 The carbon structure may be as follows:

[0010] [8] In any one of the carbon supports [1] to [7], the volume of pores having a pore diameter of 5 nm or more and 70 nm or less is 0.50 cm 3 [9] The carbon support according to any one of [1] to [8] may have a pore volume of 0.20 cm3 / g or less, the pore diameter of which is less than 5 nm. 3 / g or more.

[10] The carbon support according to any one of [1] to [9] above may have a ratio of the volume of pores having a pore diameter of less than 5 nm to the volume of pores having a pore diameter of 5 nm to 70 nm of 4.0 or more.

[11] The carbon support according to any one of [1] to

[10] above may have a pore mode diameter of 7.0 nm or less.

[0011]

[12] In any of the carbon supports [1] to

[11] , in a nitrogen adsorption isotherm obtained at a temperature of 77 K by a nitrogen adsorption method, the difference obtained by subtracting the amount of nitrogen adsorption from the amount of nitrogen desorption at a relative pressure (P / P) of 0.5 (-), which is the ratio of the adsorption equilibrium pressure (P) to the saturated vapor pressure (P), is 40 cm 3

[13] The carbon support of any one of [1] to

[12] may have a carbon structure that exhibits a nitrogen adsorption isotherm obtained at a temperature of 77 K by a nitrogen adsorption method, in which the difference obtained by subtracting the nitrogen adsorption amount from the nitrogen desorption amount at a relative pressure (P / P0) of 0.8(-), which is the ratio of the adsorption equilibrium pressure (P) to the saturated vapor pressure (P0), is 20 cm 3 / g or less.

[0012]

[14] A metal-supported catalyst according to one embodiment of the present invention for solving the above problems includes the carbon support according to any one of [1] to

[13] above and catalytic metal particles supported on the carbon support. According to the present invention, a metal-supported catalyst having both durability and catalytic activity is provided.

[0013]

[15] An electrode according to one embodiment of the present invention for solving the above problems includes the metal-supported catalyst according to

[14] . According to the present invention, an electrode having both durability and catalytic activity is provided.

[0014]

[16] A battery according to one embodiment of the present invention for solving the above problems includes the electrode according to

[15] . According to the present invention, a battery having both durability and catalytic activity is provided. [Effects of the Invention]

[0015] According to the present invention, there are provided a carbon support, a metal-supported catalyst, an electrode, and a battery that achieve both durability and catalytic activity of the metal-supported catalyst. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 2 is an explanatory diagram showing a Raman spectrum obtained for the carbon support of Example 1 in an example according to the present embodiment. [Figure 2] FIG. 2 is an explanatory diagram showing a nitrogen adsorption isotherm obtained for the carbon support of Example 1 in an example according to the present embodiment. [Figure 3A] FIG. 2 is an explanatory diagram showing the pore size distributions obtained for the carbon supports of Examples C1 and C3 in the examples according to the present embodiment. [Figure 3B] FIG. 2 is an explanatory diagram showing the pore size distributions obtained for the carbon supports of Examples C5, C7, and 2 in the examples according to the present embodiment. [Figure 4A] FIG. 1 is an explanatory diagram showing an example of the results of evaluating the characteristics of a carbon support in an example according to the present embodiment. [Figure 4B] FIG. 10 is an explanatory diagram showing another example of the results of evaluating the characteristics of the carbon support in an example according to the present embodiment. [Figure 4C] FIG. 2 is an explanatory diagram showing the results of evaluating the performance of metal-supported catalysts in examples according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0017] An embodiment of the present invention will be described below, but the present invention is not limited to the example shown in this embodiment.

[0018] The carbon support according to this embodiment (hereinafter referred to as "the support") is a porous carbon material composed mainly of carbon. The carbon content of the support is not particularly limited as long as the effects of the present invention can be obtained, but may be, for example, 70% by weight or more, preferably 75% by weight or more, more preferably 80% by weight or more, and particularly preferably 85% by weight or more.

[0019] The carbon content of the present support may be, for example, 100% by weight or less, 95% by weight or less, or 90% by weight or less. The carbon content of the present support may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values. The carbon content of the carbon support is obtained by elemental analysis (specifically, combustion method).

[0020] The true density of the carrier is not particularly limited as long as the effects of the present invention can be obtained. For example, it is 1.8 g / cm 3 It may be 1.9 g / cm or more. 3 It is preferable that the concentration is 2.0 g / cm or more. 3 More preferably, it is 2.1 g / cm or more. 3 More preferably, it is 2.2 g / cm or more. 3 More preferably, it is 2.3 g / cm or more. 3 More preferably, it is equal to or greater than this.

[0021] The true density of the carrier is, for example, 2.6 g / cm3 It may be less than 2.5 g / cm 3 It may be less than 2.4 g / cm 3 It may be less than 2.3 g / cm 3 may be less than 2.2 g / cm 3 may be less than 2.1 g / cm 3 The true density of the support may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values. The true density of the carbon support is obtained by a constant volume expansion method.

[0022] Here, the measured true density of a porous carbon material obtained by the constant volume expansion method will be smaller than that of a solid carbon material if the carbon material has closed pores. Furthermore, for example, by subjecting a porous carbon material to a graphitization treatment, some of the pores are closed, and the volume of the closed pores increases. As a result, the measured true density of the carbon material after the graphitization treatment is smaller than that before the graphitization treatment. In this way, the true density of a carbon material reflects the volume of the closed pores contained in the carbon material.

[0023] On the other hand, when a porous carbon material is used as a carbon support for supporting catalytic metal particles, the blocked pores in the carbon material are wasted space that cannot support the catalytic metal particles. Therefore, the relatively large true density of the support, reflecting the small volume of blocked pores, means that the support has a porous structure suitable for use as a carbon support for supporting catalytic metal particles. Specifically, for example, when the support is a carbon material that has been subjected to an oxidation treatment after graphitization, the pores that were blocked by the graphitization treatment are reopened by the oxidation treatment, resulting in the support having a higher true density than the carbon material before the oxidation treatment. This increase in true density due to the oxidation treatment increases the surface and space available for supporting catalytic metal particles in the support, thereby contributing to improved catalytic activity of metal-supported catalysts containing catalytic metal particles supported on the support.

[0024] This carrier exhibits a Raman shift of 1580 cm in the Raman spectrum obtained by Raman spectroscopy.-1 (specifically, for example, 1550 cm -1 Over, 1610cm -1 The half-width at half maximum of the G band (hereinafter referred to as "Raman G half-width at half maximum") having a peak top within the range of 37 cm -1 It is preferred to have the carbon structure shown below:

[0025] In this case, the Raman G half-width at half maximum of this support is 36 cm -1 Preferably less than 35cm -1 The Raman G half width at half maximum of the carrier is more preferably 34 cm or less. -1 More preferably, it is 33 cm or less. -1 More preferably, it is 32 cm or less. -1 More preferably, it is 31 cm or less. -1 More preferably, it is 30 cm or less. -1 More preferably, it is 29 cm or less. -1 More preferably, it is 28cm or less. -1 It is particularly preferred that:

[0026] The Raman G half width at half maximum of this carrier is, for example, 10 cm -1 It may be more than 15cm -1 It may be more than 18cm -1 It may be more than 20cm -1 It can be more than 22cm -1 It can be more than 24cm -1 It can be more than 26cm -1 It can be more than 27cm -1 It can be more than 28cm -1 The Raman G half width at half maximum of the present carrier may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values.

[0027] Here, in the Raman spectrum of a carbon material, the G band is a component derived from the carbon atoms that constitute graphene. The half-width at half maximum of the G band indicates the degree of graphene development. That is, as the graphene contained in a carbon structure develops, the Raman G half-width at half maximum of the carbon structure becomes smaller. In this regard, as graphene develops, the stability of the carbon structure increases. Therefore, a carbon structure that exhibits a Raman G half-width at half maximum that is equal to or less than the above-mentioned upper limit contributes to improving the durability of a metal-supported catalyst that includes catalytic metal particles supported on this support.

[0028] On the other hand, a carbon structure exhibiting a too small Raman G half width at half maximum has an excessively developed graphene and is therefore less suitable for supporting catalytic metal particles. In contrast, a carbon structure exhibiting a moderately large Raman G half width at half maximum has an insufficient graphene and contains an appropriate amount of strain and / or heteroatoms, and is therefore more suitable for supporting catalytic metal particles.

[0029] Furthermore, as graphene develops, the hydrophilicity of the carbon structure decreases. Therefore, for example, when a metal-supported catalyst is applied to a fuel cell, a carbon structure with a too small Raman G half-width at half maximum is poorly suited to retaining the generated water. In contrast, a carbon structure with an appropriate Raman G half-width at half maximum has appropriate hydrophilicity and is therefore excellently suited to retaining the generated water.

[0030] Therefore, a carbon structure exhibiting a Raman G half width at half maximum equal to or greater than the above-mentioned lower limit contributes to improving the durability and / or catalytic activity of a metal-supported catalyst containing catalytic metal particles supported on the support (for example, power generation performance (including power generation performance under low humidification conditions) when the metal-supported catalyst is applied to a battery).

[0031] This carrier exhibits a Raman shift of 1340 cm in the Raman spectrum obtained by Raman spectroscopy. -1 Around (specifically, for example, 1320 cm -1 Above, 1360cm -1 The half-width at half maximum of the D band (hereinafter referred to as "Raman D half-width at half maximum") having a peak top within the range of 38 cm-1 It is preferred to have the carbon structure shown below:

[0032] In this case, the Raman D half width at half maximum of this support is 36 cm -1 Preferably less than 34cm -1 The Raman D half width at half maximum of the carrier is more preferably 32 cm or less. -1 More preferably, it is 30 cm or less. -1 More preferably, it is 29 cm or less. -1 More preferably, it is 28cm or less. -1 More preferably, it is 27cm or less. -1 More preferably, it is 26 cm or less. -1 More preferably, it is 25 cm or less. -1 More preferably, it is 24 cm or less. -1 More preferably, it is 23 cm or less. -1 It is particularly preferred that:

[0033] The Raman D half width at half maximum of this carrier is, for example, 10 cm -1 It may be more than 15cm -1 It may be more than 18cm -1 It may be more than 20cm -1 It may be more than 21cm -1 It can be more than 22cm -1 It may be more than 23cm -1 The Raman D half width at half maximum of the carrier may be, for example, 24 cm or more. -1 May be more than 25cm -1 It can be more than 26cm -1 It can be more than 27cm -1 It can be more than 28cm -1 It may be more than 29cm -1 The Raman D half width at half maximum of the present carrier may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values.

[0034] According to a reference (A. Sadezky et al., Carbon 43 (2005) 1731-1742), in the Raman spectrum of a carbon material, the D band is a component derived from carbon atoms adjacent to disordered lattices such as edges and defects in graphene layers. The half-width at half maximum of the D band indicates the crystallinity of the carbon around the edges and defects. That is, as the crystallinity of the carbon around the edges and defects in a carbon structure increases, the Raman D half-width at half maximum of the carbon structure decreases. Furthermore, as the crystallinity of the carbon increases, the stability of the carbon structure increases. Therefore, a carbon structure exhibiting a Raman D half-width at half maximum equal to or less than the above-mentioned upper limit contributes to improving the durability of metal-supported catalysts containing catalytic metal particles supported on this support.

[0035] On the other hand, a carbon structure that exhibits a Raman D half width at half maximum that is too small has too high a crystallinity of carbon around edges and defects, making it less suitable for supporting catalytic metal particles.In contrast, a carbon structure that exhibits a moderately large Raman D half width at half maximum has excellent suitability for supporting catalytic metal particles, because the crystallinity of carbon around edges and defects is not too high.

[0036] Furthermore, as the crystallinity of carbon increases, the hydrophilicity of the carbon structure decreases. Therefore, for example, when a metal-supported catalyst is applied to a fuel cell, a carbon structure with a too small Raman D half-width at half maximum is less suitable for retaining the generated water. In contrast, a carbon structure with an appropriate Raman D half-width at half maximum has appropriate hydrophilicity and is therefore excellent in its suitability for retaining the generated water.

[0037] Therefore, a carbon structure exhibiting a Raman D half width at half maximum equal to or greater than the above-mentioned lower limit contributes to improving the durability and / or catalytic activity of a metal-supported catalyst containing catalytic metal particles supported on the support (for example, power generation performance (including power generation performance under low humidification conditions) when the metal-supported catalyst is applied to a battery).

[0038] This carrier exhibits a Raman shift of 2700 cm in the Raman spectrum obtained by Raman spectroscopy. -1 around (specifically, for example, 2670 cm-1 Above, 2730cm -1 The half-width at half maximum of the 2D band having a peak top within the range below (hereinafter referred to as "Raman 2D half-width at half maximum") is 57 cm -1 It is preferred to have the carbon structure shown below:

[0039] In this case, the Raman 2D half-width at half maximum of this support is 55 cm -1 Preferably less than 54cm -1 More preferably, it is 53 cm or less. -1 The Raman 2D half width at half maximum of the carrier is more preferably 52 cm or less. -1 More preferably, it is 51 cm or less. -1 More preferably, it is 50 cm or less. -1 More preferably, it is 49 cm or less. -1 More preferably, it is 48cm or less. -1 More preferably, it is 47cm or less. -1 More preferably, it is 46 cm or less. -1 More preferably, it is 45 cm or less. -1 More preferably, it is 44 cm or less. -1 More preferably, it is 43 cm or less. -1 More preferably, it is 42 cm or less. -1 More preferably, it is 41 cm or less. -1 More preferably, it is 40 cm or less. -1 More preferably, it is 39 cm or less. -1 It is particularly preferred that:

[0040] The Raman 2D half width at half maximum of this carrier is, for example, 10 cm -1 It may be more than 15cm -1 It may be more than 20cm -1 May be more than 25cm -1 It may be more than 30cm -1 It may be more than 32cm -1 The Raman 2D half width at half maximum of this carrier may be 34 cm or more.-1 It can be more than 36cm -1 It can be more than 38cm -1 It may be more than 40cm -1 It can be more than 42cm -1 It may be more than 44cm -1 It can be more than 46cm -1 It can be more than 48cm -1 It may be more than 50cm -1 The Raman 2D half width at half maximum of the present carrier may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values.

[0041] In the Raman spectrum of a carbon material, the 2D band is a component derived from the carbon atoms constituting the graphene layer. The half-width at half maximum of the 2D band indicates the uniformity of the graphene layer. That is, as the graphene layer contained in a carbon structure becomes more uniform, the Raman 2D half-width at half maximum of the carbon structure becomes smaller. Furthermore, as the graphene layer becomes more uniform, the stability of the carbon structure increases. Therefore, a carbon structure exhibiting a Raman 2D half-width at half maximum of the above-mentioned upper limit or less contributes to improving the durability of a metal-supported catalyst including catalytic metal particles supported on this support.

[0042] On the other hand, carbon structures with too small Raman 2D FWHMs have too high a uniformity of the graphene layer and are therefore less suitable for supporting catalytic metal particles.In contrast, carbon structures with an appropriate Raman 2D FWHM have an appropriate amount of defects and distortion in the graphene layer and are therefore more suitable for supporting catalytic metal particles.

[0043] Furthermore, as the graphene layer becomes more uniform, the hydrophilicity of the carbon structure decreases. Therefore, for example, when a metal-supported catalyst is applied to a fuel cell, a carbon structure with a too small Raman 2D FWHM is less suitable for retaining the generated water. In contrast, a carbon structure with an appropriate Raman 2D FWHM has an appropriate hydrophilicity and is therefore more suitable for retaining the generated water.

[0044] Therefore, a carbon structure exhibiting a Raman 2D half width at half maximum that is equal to or greater than the above-mentioned lower limit contributes to improving the durability and / or catalytic activity of a metal-supported catalyst containing catalytic metal particles supported on the support (for example, power generation performance (including power generation performance under low humidification conditions) when the metal-supported catalyst is applied to a battery).

[0045] The carrier preferably has a carbon structure in which the ratio of the intensity of the D band to the intensity of the G band in a Raman spectrum obtained by Raman spectroscopy (hereinafter referred to as "Raman D / G ratio") is 1.6 or more.

[0046] In this case, the Raman D / G ratio of the present carrier is more preferably 1.7 or more, even more preferably 1.8 or more, even more preferably 1.9 or more, and even more preferably 2.0 or more. The Raman D / G ratio of the present carrier is more preferably 2.1 or more, even more preferably 2.2 or more, and particularly preferably 2.3 or more.

[0047] The Raman D / G ratio of the carrier may be, for example, 4.0 or less, 3.5 or less, 3.0 or less, 2.8 or less, 2.6 or less, 2.5 or less, 2.4 or less, or 2.3 or less. The Raman D / G ratio of the carrier may be, for example, 2.2 or less, or 2.1 or less. The Raman D / G ratio of the carrier may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values.

[0048] Here, the Raman D / G ratio of a carbon material indicates the amount of edges and defects contained in the graphene layers in the carbon structure. That is, the more edges and defects there are in the graphene layers, the higher the Raman D / G ratio of the carbon structure. In this regard, the edges and defects function as support sites for catalytic metal particles. Therefore, as the number of edges and defects in the graphene layers increases, the suitability of the carbon structure for supporting catalytic metal particles improves.

[0049] Furthermore, as the number of edges and defects in the graphene layers increases, the hydrophilicity of the carbon structure increases, which improves its suitability for retaining produced water, for example, when the supported metal catalyst is applied to a fuel cell.

[0050] Therefore, a carbon structure exhibiting a Raman D / G ratio equal to or greater than the above-mentioned lower limit contributes to improving the durability and / or catalytic activity of a metal-supported catalyst containing catalytic metal particles supported on the support (for example, power generation performance (including power generation performance under low humidification conditions) when the metal-supported catalyst is applied to a battery).

[0051] On the other hand, a carbon structure with a Raman D / G ratio that is too large has too many edges and defects, resulting in reduced durability. In contrast, a carbon structure with a moderate Raman D / G ratio has a moderate amount of edges and defects. Therefore, a carbon structure with a Raman D / G ratio that is equal to or less than the above-mentioned upper limit contributes to improving the durability of a metal-supported catalyst containing catalytic metal particles supported on this support.

[0052] The carrier preferably has a carbon structure in which the ratio of the intensity of the 2D band to the intensity of the G band in a Raman spectrum obtained by Raman spectroscopy (hereinafter referred to as "Raman 2D / G ratio") is 0.3 or more.

[0053] In this case, the Raman 2D / G ratio of the present support is more preferably 0.4 or more, even more preferably 0.5 or more, still more preferably 0.6 or more, and particularly preferably 0.7 or more.

[0054] The Raman 2D / G ratio of the present carrier may be, for example, 1.5 or less, 1.2 or less, 1.0 or less, 0.9 or less, 0.8 or less, or 0.7 or less. The Raman 2D / G ratio of the present carrier may be, for example, 0.6 or less, 0.5 or less, 0.4 or less, or 0.3 or less. The Raman 2D / G ratio of the present carrier may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values.

[0055] Here, the Raman 2D / G ratio of a carbon material indicates the number of layers constituting the graphene stack contained in the carbon structure of the carbon material. That is, when the intensity of the 2D band is greater than the intensity of the G band (Raman 2D / G ratio > 1), the graphene is a single layer. When the intensity of the 2D band is the same as the intensity of the G band (Raman 2D / G ratio = 1), the number of layers of the graphene stack is approximately two. When the intensity of the 2D band is smaller than the intensity of the G band (Raman 2D / G ratio < 1), the number of layers of the graphene stack is three or more. The specific number of layers can be determined from the ratio of the intensity of the 2D band (peak top height) to the intensity of the G band (peak top height).

[0056] Carbon structures with too small a Raman 2D / G ratio, i.e., carbon structures with too many graphene stack layers, have too many edges and defects relative to the basal plane, which are the starting points for oxidative degradation, resulting in reduced durability (particularly corrosion resistance). In contrast, carbon structures with a Raman 2D / G ratio equal to or greater than the above-mentioned lower limit contain few-layer graphene in which the number of graphene stack layers is controlled within an appropriate range (e.g., about two to three layers), and the relative amount of edges and defects relative to the exposed basal plane is controlled within an appropriate range, contributing to improved durability (particularly corrosion resistance).

[0057] On the other hand, edges and defects also function as support sites for catalytic metal particles. Therefore, carbon structures with a Raman 2D / G ratio that is too large have too few edges and defects relative to the basal plane, making them less suitable for supporting catalytic metal particles. In contrast, carbon structures with a moderate Raman 2D / G ratio have a moderate number of edges and defects, making them more suitable for supporting catalytic metal particles.

[0058] Furthermore, the hydrophilicity of the carbon structure decreases as the relative number of edges and defects relative to the basal plane decreases. Therefore, for example, when a metal-supported catalyst is applied to a fuel cell, a carbon structure with a too large Raman 2D / G ratio is less suitable for retaining the generated water. In contrast, a carbon structure with a moderate Raman 2D / G ratio has moderate hydrophilicity and is therefore excellent in its suitability for retaining the generated water.

[0059] Therefore, a carbon structure exhibiting a Raman 2D / G ratio equal to or less than the upper limit described above contributes to improving the durability and / or catalytic activity of a metal-supported catalyst containing catalytic metal particles supported on the support (for example, power generation performance (including power generation performance under low humidification conditions) when the metal-supported catalyst is applied to a battery).

[0060] The oxygen content of the carrier is not particularly limited as long as the effects of the present invention are obtained, but is preferably 1.0 wt% or more, more preferably 1.5 wt% or more, even more preferably 2.0 wt% or more, even more preferably 2.4 wt% or more, even more preferably 2.6 wt% or more, and even more preferably 2.8 wt% or more. The oxygen content of the carrier is preferably 3.0 wt% or more, even more preferably 3.1 wt% or more, even more preferably 3.2 wt% or more, even more preferably 3.3 wt% or more, even more preferably 3.4 wt% or more, even more preferably 3.5 wt% or more, even more preferably 3.6 wt% or more, even more preferably 3.7 wt% or more, even more preferably 3.8 wt% or more, even more preferably 3.9 wt% or more, and particularly preferably 4.0 wt% or more.

[0061] The oxygen content of the carrier may be, for example, 20.0 wt% or less, 15.0 wt% or less, 12.0 wt% or less, 10.0 wt% or less, 9.5 wt% or less, 9.0 wt% or less, 8.5 wt% or less, 8.0 wt% or less, 7.5 wt% or less, 7.0 wt% or less, 6.5 wt% or less, 6.0 wt% or less, 5.5 wt% or less, 5.0 wt% or less, 4.8 wt% or less, 4.6 wt% or less, 4.4 wt% or less, 4.2 wt% or less, 4.0 wt% or less, 3.8 wt% or less, or 3.6 wt% or less. The oxygen content of the carrier may be, for example, 3.5% by weight or less, 3.4% by weight or less, 3.3% by weight or less, 3.2% by weight or less, or 3.1% by weight or less. The oxygen content of the carrier may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values. The oxygen content of the carrier is obtained by elemental analysis (specifically, pyrolysis).

[0062] Here, the oxygen content obtained by elemental analysis of a carbon material affects the hydrophilicity of the carbon material. That is, as the oxygen content of a carbon material increases, the hydrophilicity of the carbon material increases. In general, as the Raman G half-width at half maximum, Raman D half-width at half maximum, and Raman 2D half-width at half maximum of a carbon structure decrease, or as the Raman 2D / G ratio of the carbon structure increases, the hydrophilicity of the carbon structure decreases. However, even for carbon structures that exhibit small Raman G half-width at half maximum, Raman D half-width, or Raman 2D half-width at half maximum, and / or large Raman 2D / G ratios, the hydrophilicity increases as the oxygen content increases. Furthermore, carbon materials with high hydrophilicity are excellently suited to retaining generated water, for example, when metal-supported catalysts are applied to fuel cells.

[0063] Therefore, a carbon structure exhibiting an oxygen content equal to or greater than the above-mentioned lower limit contributes to improving the catalytic activity of the metal-supported catalyst containing catalytic metal particles supported on the support (for example, the power generation performance (including the power generation performance under low humidification conditions) when the metal-supported catalyst is applied to a battery).

[0064] On the other hand, a carbon structure with an excessively large oxygen content has too many oxidation initiation points, resulting in a decrease in durability (particularly corrosion resistance).In contrast, a carbon structure with an oxygen content equal to or less than the upper limit described above does not have too many oxidation initiation points, contributing to an improvement in durability (particularly corrosion resistance).

[0065] The BET specific surface area of ​​the carrier is not particularly limited as long as the effects of the present invention can be obtained. For example, 2 The BET specific surface area of ​​the carrier is preferably 400 m 2 / g or more is more preferable, and 500m 2 / g or more is more preferable, and 600m 2 / g or more is more preferable, and 700m 2 / g or more is more preferable, and 2 / g or more is more preferable, and 2 / g or more. The BET specific surface area of ​​the carrier is preferably 1000 m 2 / g or more is more preferable, and 2 / g or more is more preferable, and 2 / g or more is more preferable, and 1200m 2 / g or more is more preferable, and 1250m 2 / g or more is more preferable, and 1300m 2 / g or more is more preferable, and 1350m 2 / g or more is more preferable, and 1400m 2 It is particularly preferable that the saturation coefficient is 1 / g or more.

[0066] The BET specific surface area of ​​the carrier is, for example, 3300 m 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 The BET specific surface area of ​​the carrier may be, for example, 1500 m 2 / g or less, and 1450m 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 / g or less, and 2 / g or less. The BET specific surface area of ​​the present support may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values. The BET specific surface area of ​​the present support is obtained by the BET method from a nitrogen adsorption isotherm obtained at a temperature of 77 K by the nitrogen adsorption method.

[0067] An increase in the BET specific surface area of ​​the carbon support increases the number of support sites for catalytic metal particles, thereby contributing to an improvement in the durability and / or catalytic activity of the metal-supported catalyst containing catalytic metal particles supported on the carbon support.

[0068] The carrier has a pore volume of 5 nm or more and 70 nm or less (hereinafter referred to as "pore volume (5-70 nm)") of 0.50 cm 3 In this case, the pore volume (5-70 nm) of the carrier is preferably 0.45 cm 3 / g or less is more preferable, and 0.40 cm 3 / g or less is more preferable, and 0.35 cm 3 / g or less is more preferable, and 0.30 cm 3 / g or less is more preferable, and 0.25 cm 3 / g or less is more preferable, and 0.20 cm 3 / g or less is more preferable, and 0.15 cm 3 / g or less is more preferable, and 0.12 cm 3 / g or less, and 3 / g or less is more preferable, and 0.09 cm 3 / g or less is more preferable, and 0.08 cm 3 / g or less. The pore volume (5-70 nm) of the carrier is 0.07 cm 3 / g or less is more preferable, and 0.06 cm 3 / g or less is more preferable, and 0.05 cm 3 It is particularly preferable that the saturation coefficient is 1 / g or less.

[0069] The pore volume (5-70 nm) of the carrier is, for example, 0.00 cm 3 / g or more, and 3 / g or more, and 3 / g or more, and 3 The pore volume (5-70 nm) of the carrier may be 0.04 cm 3 / g or more, and 3 / g or more, and 3 / g or more, and 3 / g or more, and 3 / g or more. The pore volume (5-70 nm) of the present support may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values. The pore volume (5-70 nm) of the present support is obtained by the DFT method from a nitrogen adsorption isotherm obtained at a temperature of 77 K by the nitrogen adsorption method.

[0070] Pores with a relatively large pore size of 5 nm or more and 70 nm or less in a carbon support are less suitable for retaining generated water when a metal-supported catalyst containing catalytic metal particles supported on the carbon support is applied to a fuel cell, for example, and therefore proton paths for the generated water are less likely to form within the pores. Furthermore, catalytic metal particles supported in pores with a pore size of 5 nm or more and 70 nm or less are easily covered by the electrolyte, which reduces their catalytic activity. Therefore, a porous carbon structure with a pore volume (5-70 nm) below the upper limit mentioned above contributes to improving the catalytic activity of a metal-supported catalyst containing catalytic metal particles supported on this support (e.g., power generation performance (particularly power generation performance under low humidification conditions) when the metal-supported catalyst is applied to a cell).

[0071] The carrier has a pore volume of 0.20 cm with a pore diameter of less than 5 nm (hereinafter referred to as "pore volume (less than 5 nm)"). 3 In this case, the pore volume of the carrier (less than 5 nm) is preferably 0.30 cm 3 / g or more is more preferable, and 0.35 cm 3 / g or more is more preferable, and 0.40 cm 3 / g or more. The pore volume (less than 5 nm) of the carrier is 0.45 cm 3 / g or more is more preferable, and 0.50 cm 3 / g or more is more preferable, and 0.55 cm 3 / g or more is more preferable, and 0.60 cm 3 / g or more is more preferable, and 0.65 cm 3 It is particularly preferable that the saturation coefficient is 1 / g or more.

[0072] The pore volume of the carrier (less than 5 nm) is, for example, 1.20 cm 3 / g or less, and 3 / g or less, and 3 / g or less, and 3 / g or less, and 3 / g or less, and 3 / g or less, and 3 / g or less, and 3 The pore volume of the carrier (less than 5 nm) may be 0.70 cm 3 / g or less, and 3 / g or less, and 3 / g or less, and 3 / g or less, and 3 / g or less. The pore volume (less than 5 nm) of the present support may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values. The pore volume (less than 5 nm) of the present support is obtained by the DFT method from a nitrogen adsorption isotherm obtained at a temperature of 77 K by the nitrogen adsorption method.

[0073] Pores with a relatively small pore size of less than 5 nm are highly suitable for supporting catalytic metal particles with a relatively small particle size and high catalytic activity. Furthermore, when a metal-supported catalyst containing catalytic metal particles supported on the carbon support is applied to a fuel cell, for example, pores with a pore size of less than 5 nm in the carbon support are highly suitable for retaining generated water, and therefore a proton path is easily formed within the pores by the generated water. Furthermore, catalytic metal particles supported in pores with a pore size of less than 5 nm are not easily coated with an electrolyte. Therefore, a porous carbon structure with a pore volume (less than 5 nm) equal to or greater than the above-mentioned lower limit contributes to improving the catalytic activity of a metal-supported catalyst containing catalytic metal particles supported on this support (for example, power generation performance (particularly power generation performance under low humidification conditions) when the metal-supported catalyst is applied to a cell).

[0074] On the other hand, a carbon support having a pore volume that is too large (less than 5 nm) has a sparse carbon structure, resulting in poor corrosion resistance. In contrast, a carbon support having a pore volume (less than 5 nm) equal to or less than the upper limit mentioned above contributes to improving the corrosion resistance of the support due to its dense structure.

[0075] The carrier has a pore volume of 5-70 nm (cm 3 / g) to the pore volume (less than 5 nm) (cm 3 / g) (hereinafter referred to as "pore volume ratio (5 / (5-70))") (-) is preferably 4.0 or more. In this case, the pore volume ratio (5 / (5-70)) of the present carrier is more preferably 4.5 or more, even more preferably 5.0 or more, and even more preferably 6.0 or more. The pore volume ratio (5 / (5-70)) of the present carrier is also more preferably 6.5 or more, even more preferably 7.0 or more, even more preferably 7.5 or more, even more preferably 8.0 or more, even more preferably 8.5 or more, even more preferably 9.0 or more, even more preferably 9.5 or more, even more preferably 10.0 or more, even more preferably 10.5 or more, even more preferably 11.0 or more, even more preferably 11.5 or more, and particularly preferably 12.0 or more.

[0076] The pore volume ratio (5 / (5-70)) of the present carrier may be, for example, 50.0 or less, 40.0 or less, 35.0 or less, or 30.0 or less. The pore volume ratio (5 / (5-70)) of the present carrier may be 25.0 or less, 20.0 or less, 15.0 or less, 10.0 or less, 9.0 or less, or 8.0 or less. The pore volume ratio (5 / (5-70)) of the present carrier may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values.

[0077] In a carbon support having a too small pore volume ratio (5 / (5-70)), i.e., a pore volume (5-70 nm) that is too large compared to the pore volume (less than 5 nm), for example, when a metal-supported catalyst containing catalytic metal particles supported on the carbon support is applied to a fuel cell, proton paths are unlikely to form within the pores, and the catalytic metal particles supported within the pores are likely to be covered by the electrolyte. In contrast, in a carbon support having a large pore volume ratio (5 / (5-70)), proton paths are likely to form within the pores, and the catalytic metal particles supported within the pores are unlikely to be covered by the electrolyte. Therefore, a porous carbon structure having a pore volume ratio (5 / (5-70)) equal to or greater than the above-mentioned lower limit contributes to improving the catalytic activity of a metal-supported catalyst containing catalytic metal particles supported on this support (e.g., improving the power generation performance (particularly under low-humidity conditions) when the metal-supported catalyst is applied to a cell).

[0078] On the other hand, in a carbon support having a pore volume ratio that is too large (5 / (5-70)), i.e., a pore volume (less than 5 nm) that is too large compared to the pore volume (5-70 nm), the catalytic metal particles are more likely to be supported on the outer surface of the carbon support than inside the pores, resulting in reduced durability. In contrast, a porous carbon structure having a pore volume ratio (5 / (5-70)) below the upper limit mentioned above allows the catalytic metal particles to be effectively supported in the pores, contributing to improved durability of the metal-supported catalyst including the catalytic metal particles supported on this support.

[0079] The carrier preferably has a pore mode diameter of 7.0 nm or less, more preferably 6.0 nm or less, even more preferably 5.0 nm or less, even more preferably 4.5 nm or less, even more preferably 4.0 nm or less, even more preferably 3.5 nm or less, and particularly preferably 3.0 nm or less.

[0080] The pore mode diameter of the present support may be, for example, 0.5 nm or more, 1.0 nm or more, 1.5 nm or more, or 2.0 nm or more. The pore mode diameter of the present support may be 2.5 nm or more, or 3.0 nm or more. The pore mode diameter of the present support may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values. The pore mode diameter of the present support is obtained by the DFT method from a nitrogen adsorption isotherm obtained at a temperature of 77 K by the nitrogen adsorption method.

[0081] In a carbon support having a pore mode diameter that is too large, for example, when a metal-supported catalyst containing catalytic metal particles supported on the carbon support is applied to a fuel cell, the electrolyte easily penetrates into the pores, and the catalytic metal particles supported in the pores are easily coated with the electrolyte, which reduces the utilization rate of the catalytic metal particles. In contrast, in a carbon support having a small pore mode diameter, the electrolyte is less likely to penetrate into the pores, and the catalytic metal particles supported in the pores are less likely to be coated with the electrolyte. Therefore, a porous carbon structure having a pore mode diameter equal to or less than the above-mentioned upper limit contributes to improving the catalytic activity of a metal-supported catalyst containing catalytic metal particles supported on this support (e.g., power generation performance when the metal-supported catalyst is applied to a battery).

[0082] On the other hand, in a carbon support having a pore mode diameter that is too small, the catalytic metal particles are insufficiently supported in the pores, and the catalytic metal particles tend to be supported on the outer surface of the carbon support, resulting in reduced durability. In contrast, a porous carbon structure having a pore mode diameter equal to or greater than the above-mentioned lower limit effectively supports the catalytic metal particles in its pores, thereby contributing to improving the durability of the metal-supported catalyst including the catalytic metal particles supported on this support.

[0083] In the nitrogen adsorption isotherm obtained at a temperature of 77K by the nitrogen adsorption method, this carrier exhibits a difference (hereinafter referred to as "hysteresis (0.5P / P0")) of 40 cm when the relative pressure (P / P0), which is the ratio of the adsorption equilibrium pressure (P) to the saturated vapor pressure (P0), is 0.5(-). 3It is preferred that the carbon structure exhibits a .DELTA. ...

[0084] In this case, the hysteresis (0.5P / P0) of this carrier is 45cm 3 / g or less is more preferable, and 40cm 3 / g or less is more preferable, and 3 / g or less is more preferable, and 3 / g or less is more preferable, and 3 / g or less is more preferable, and 3 / g or less is more preferable, and 3 / g or less is more preferable, and 3 It is particularly preferable that the saturation coefficient is 1 / g or less.

[0085] In addition, the hysteresis (0.5P / P0) of this carrier is, for example, 0 cm 3 / g or more, and 3 / g or more. The hysteresis (0.5P / P0) of the carrier is 5 cm 3 / g or more, and 3 / g or more, and 3 / g or more, and 3 / g or more, and 3 The hysteresis (0.5P / P0) of the carrier may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values.

[0086] In the nitrogen adsorption isotherm obtained at a temperature of 77K by the nitrogen adsorption method, the difference obtained by subtracting the amount of nitrogen adsorption from the amount of nitrogen desorption at a relative pressure (P / P) of 0.8 (-) (hereinafter referred to as "hysteresis (0.8P / P)") of 20 cm 3 It is preferred that the carbon structure exhibits a .DELTA. ...

[0087] In this case, the hysteresis (0.8P / P0) of the carrier is, for example, 15 cm 3 / g or less is more preferable, and 3 / g or less. The hysteresis (0.8P / P0) of the carrier is 9 cm 3 / g or less is more preferable, and 3 / g or less is more preferable, and 3 / g or less is more preferable, and 3 / g or less is more preferable, and 3 / g or less is more preferable, and 3 / g or less is more preferable, and 3 It is particularly preferable that the saturation coefficient is 1 / g or less.

[0088] In addition, the hysteresis (0.8P / P0) of this carrier is, for example, 0 cm 3 / g or more, and 3 / g or more, and 3 / g or more, and 3 The hysteresis (0.8P / P0) of the carrier is 4 cm / g or more. 3 / g or more, and 3 The hysteresis (0.8P / P0) of the carrier may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values.

[0089] Here, as the interconnectivity of the pores contained in the carbon support increases, the hysteresis of the nitrogen adsorption isotherm of the carbon support decreases, and the hysteresis (0.5P / P) and hysteresis (0.8P / P) of the carbon support decrease. Therefore, in a porous carbon structure (i.e., a porous carbon structure with high interconnectivity) exhibiting a hysteresis (0.5P / P) equal to or less than the above-mentioned upper limit and / or a hysteresis (0.8P / P) equal to or less than the above-mentioned upper limit, for example, when a metal-supported catalyst containing catalytic metal particles supported on the support is applied to a fuel cell, water generated in the pores is effectively discharged, contributing to improved durability and / or catalytic activity of the metal-supported catalyst. Note that the hysteresis (0.5P / P) indicates the interconnectivity of pores with relatively small pore diameters, and the hysteresis (0.8P / P) indicates the interconnectivity of pores with relatively large pore diameters.

[0090] The present support is preferably specified as a carbon material having any combination of two or more of the above-mentioned properties. That is, for example, the present support according to one aspect of the present embodiment preferably has a carbon structure that exhibits, in addition to a BET specific surface area and a true density within a specific range, one or more of the following properties (i) to (iii) in a Raman spectrum obtained by Raman spectroscopy: (i) a Raman G half width at half maximum within a specific range; (ii) a Raman D half width at half maximum within a specific range; and (iii) a Raman 2D half width at half maximum within a specific range.

[0091] In this case, the support may have a carbon structure that exhibits only one selected from the group consisting of characteristics (i) to (iii), or may have a carbon structure that exhibits a combination of any two selected from the group (characteristics (i) and (ii), characteristics (i) and (iii), or characteristics (ii) and (iii)), or may have a carbon structure that exhibits all of the characteristics (i) to (iii).

[0092] Specifically, the present carrier has a BET specific surface area of ​​300 m 2 / g or more, and the true density is 2.1g / cm 3The Raman spectrum obtained by Raman spectroscopy has the following characteristics (i) to (iii): (i) a Raman G half width at half maximum of 37 cm -1 (ii) a Raman D half-width at half maximum of 38 cm -1 and (iii) a Raman 2D half-width at half maximum of 57 cm -1 The carbon structure may be one or more selected from the group consisting of:

[0093] When the support has a relatively large BET specific surface area, a relatively large true density, and a relatively small Raman half width at half maximum (one or more selected from the group consisting of Raman G half width at half maximum, Raman D half width at half maximum, and Raman 2D half width at half maximum), the support has a surface area that allows catalytic metal particles to be effectively supported, a small volume of blocked pores that cannot support catalytic metal particles, and a highly crystalline carbon structure, and therefore effectively contributes to achieving both durability and catalytic activity of the metal-supported catalyst.

[0094] Furthermore, for example, the carrier according to another aspect of this embodiment preferably has a carbon structure that exhibits, in addition to a BET specific surface area within a specific range and a true density within a specific range, one or more of the following characteristics (iv) and (v) in a Raman spectrum obtained by Raman spectroscopy: (iv) a Raman D / G ratio within a specific range; and (v) a Raman 2D / G ratio within a specific range.

[0095] In this case, the support may have a carbon structure that exhibits only one selected from the group consisting of properties (iv) and (v), or may have a carbon structure that exhibits properties (iv) and (v).

[0096] Specifically, the present carrier has a BET specific surface area of ​​300 m 2 / g or more, and the true density is 2.1g / cm 3 and may have a carbon structure that exhibits one or more of the following characteristics (iv) and (v) in a Raman spectrum obtained by Raman spectroscopy: (iv) a Raman D / G ratio of 1.6 or more; and (v) a Raman 2D / G ratio of 0.3 or more.

[0097] When the support has a relatively large BET specific surface area, a relatively large true density, and a relatively large Raman D / G ratio and / or 2D / G ratio, the support has a surface area that can effectively support catalytic metal particles, a small volume of blocked pores that cannot support catalytic metal particles, and a carbon structure that is advantageous for supporting catalytic metal particles, and therefore effectively contributes to achieving both durability and catalytic activity of the metal-supported catalyst.

[0098] Furthermore, for example, the carrier according to yet another aspect of the present embodiment preferably has a carbon structure that, in addition to a BET specific surface area within a specific range and a true density within a specific range, exhibits, in a Raman spectrum obtained by Raman spectroscopy, one or more of the following properties (i) to (iii) selected from the group consisting of: (i) a Raman G half width at half maximum within a specific range; (ii) a Raman D half width at half maximum within a specific range; and (iii) a Raman 2D half width at half maximum within a specific range; and one or more of the following properties (iv) and (v): (iv) a Raman D / G ratio within a specific range; and (v) a Raman 2D / G ratio within a specific range.

[0099] In this case, the support may have a carbon structure that exhibits only one selected from the group consisting of characteristics (i) to (iii) and one or both of characteristics (iv) and (v). Alternatively, the support may have a carbon structure that exhibits a combination of any two selected from the group consisting of characteristics (i) to (iii) (characteristics (i) and (ii), characteristics (i) and (iii), or characteristics (ii) and (iii)) and one or both of characteristics (iv) and (v). Alternatively, the support may have a carbon structure that exhibits all of characteristics (i) to (iii) and one or both of characteristics (iv) and (v).

[0100] Specifically, the present carrier has a BET specific surface area of ​​300 m 2 / g or more, and the true density is 2.1g / cm 3 The Raman spectrum obtained by Raman spectroscopy has the following characteristics (i) to (iii): (i) a Raman G half width at half maximum of 37 cm -1(ii) a Raman D half-width at half maximum of 38 cm -1 and (iii) a Raman 2D half-width at half maximum of 57 cm -1 and one or more selected from the group consisting of the following properties (iv) and (v): (iv) a Raman D / G ratio of 1.6 or more; and (v) a Raman 2D / G ratio of 0.3 or more.

[0101] Furthermore, for example, the carrier according to yet another aspect of the present embodiment preferably has a carbon structure that, in addition to an oxygen content within a specific range, exhibits, in a Raman spectrum obtained by Raman spectroscopy, one or more of the following characteristics (i) to (iii) selected from the group consisting of: (i) a Raman G half width at half maximum within a specific range; (ii) a Raman D half width at half maximum within a specific range; (iii) a Raman 2D half width at half maximum within a specific range; (iv) a Raman D / G ratio within a specific range; and (v) a Raman 2D / G ratio within a specific range.

[0102] In this case, the support may have a carbon structure that exhibits only one of the characteristics (i) to (v), a carbon structure that exhibits a combination of any two of the characteristics (i) to (v), a carbon structure that exhibits a combination of any three of the characteristics (i) to (v), a carbon structure that exhibits a combination of any four of the characteristics (i) to (v), or a carbon structure that exhibits all of the characteristics (i) to (v).

[0103] Specifically, the present carrier has, for example, an oxygen content of 2.6% by weight or more, and exhibits the above-mentioned characteristics (i) to (v) in a Raman spectrum obtained by Raman spectroscopy: (i) a Raman G half width at half maximum of 37 cm -1 (ii) a Raman D half-width at half maximum of 38 cm -1 (iii) a Raman 2D half-width at half maximum of 57 cm -1or less; (iv) a Raman D / G ratio of 1.6 or more; and (v) a Raman 2D / G ratio of 0.3 or more.

[0104] In addition to the oxygen content within a specific range, the support may have a carbon structure that exhibits one or more of the above characteristics (i) to (iii) in a Raman spectrum obtained by Raman spectroscopy: (i) a Raman G half width at half maximum within a specific range; (ii) a Raman D half width at half maximum within a specific range; and (iii) a Raman 2D half width at half maximum within a specific range.

[0105] Specifically, for example, the carrier has an oxygen content of 1.0% by weight or more, and the above-mentioned characteristic (iii) is a Raman 2D half width at half maximum of 57 cm -1 It may have the following carbon structure:

[0106] In addition to the oxygen content within a specific range, the support may have a carbon structure that exhibits one or more of the above properties (iv) and (v) in a Raman spectrum obtained by Raman spectroscopy: (iv) a Raman D / G ratio within a specific range; and (v) a Raman 2D / G ratio within a specific range.

[0107] Furthermore, the present support may have a carbon structure that, in addition to an oxygen content within a specific range, exhibits, in a Raman spectrum obtained by Raman spectroscopy, one or more of the following properties selected from the group consisting of (i) to (iii): (i) a Raman G half-width at half maximum within a specific range; (ii) a Raman D half-width at half maximum within a specific range; and (iii) a Raman 2D half-width at half maximum within a specific range; and, in a Raman spectrum obtained by Raman spectroscopy, one or more of the following properties (iv) and (v) selected from the group consisting of (iv) a Raman D / G ratio within a specific range; and (v) a Raman 2D / G ratio within a specific range.

[0108] Furthermore, the present support preferably has, for example, a BET specific surface area within a specific range, a true density within a specific range, and an oxygen content within a specific range.

[0109] Furthermore, the carrier may have, for example, as a pore volume characteristic, one or more selected from the group consisting of a pore volume within a specific range (5-70 nm), a pore volume within a specific range (less than 5 nm), and a pore volume ratio within a specific range (5 / (5-70)).

[0110] That is, in this case, the carrier may have only one of the three pore volume characteristics, i.e., a pore volume within a specific range (5-70 nm), a pore volume within a specific range (less than 5 nm), and a pore volume ratio within a specific range (5 / (5-70)), or a combination of any two of them (a pore volume within a specific range (5-70 nm) and a pore volume within a specific range (less than 5 nm), a pore volume within a specific range (5-70 nm) and a pore volume ratio within a specific range (5 / (5-70)), or a pore volume within a specific range (less than 5 nm) and a pore volume ratio within a specific range (5 / (5-70))), or it may have all (three) of the pore volume characteristics.

[0111] The carrier is preferably a carbonized material. The carbonized material is obtained by carbonizing a raw material containing organic matter. The organic matter content in the raw material for carbonization may be, for example, 5% by weight or more and 90% by weight or less, and preferably 10% by weight or more and 80% by weight or less.

[0112] The organic matter contained in the raw material is not particularly limited as long as it can be carbonized. The organic compound contained in the organic matter may be a polymer (e.g., a thermosetting resin and / or a thermoplastic resin) and / or an organic compound with a smaller molecular weight.

[0113] Specific examples of organic substances include polyacrylonitrile, polyacrylonitrile-polyacrylic acid copolymer, polyacrylonitrile-polymethyl acrylate copolymer, polyacrylonitrile-polymethacrylic acid copolymer, polyacrylonitrile-polymethacrylic acid-polymethallylsulfonic acid copolymer, polyacrylonitrile-polymethyl methacrylate copolymer, phenol resin, polyfurfuryl alcohol, furan, furan resin, phenol formaldehyde resin, melamine, melamine resin, epoxy resin, nitrogen-containing chelate resin (e.g., one or more selected from the group consisting of polyamine type, iminodiacetic acid type, aminophosphoric acid type, and aminomethylphosphonic acid type), polyamideimide resin, pyrrole, polypyrrole, polyvinylpyrrole, 3-methylpolypyrrole, acrylonitrile, polyvinylidene chloride, thiophene, oxazole, thiazole, pyrazole, vinylpyridine, polyvinylpyridine, The polymer may be one or more selected from the group consisting of pyridazine, pyrimidine, piperazine, pyran, morpholine, imidazole, 1-methylimidazole, 2-methylimidazole, quinoxaline, aniline, polyaniline, succinic acid dihydrazide, adipic acid dihydrazide, polysulfone, polyaminobismaleimide, polyimide, polyvinyl alcohol, polyvinyl butyral, benzimidazole, polybenzimidazole, polyamide, polyester, polylactic acid, polyether, polyether ether ketone, cellulose, carboxymethyl cellulose, lignin, chitin, chitosan, pitch, silk, wool, polyamino acid, nucleic acid, DNA, RNA, hydrazine, hydrazide, urea, salen, polycarbazole, polybismaleimide, triazine, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polymethacrylic acid, polyurethane, polyamidoamine, and polycarbodiimide.

[0114] The present support preferably contains nitrogen. That is, the present support preferably contains nitrogen atoms (e.g., doped nitrogen atoms) in its carbon structure. The present support containing nitrogen is preferably a nitrogen-containing carbonized material. The nitrogen-containing carbonized material is obtained, for example, by carbonizing a raw material containing a nitrogen-containing organic substance. The nitrogen-containing organic substance preferably contains a nitrogen-containing organic compound. The nitrogen-containing organic compound is not particularly limited as long as it is an organic compound containing a nitrogen atom in its molecule. The nitrogen contained in the present support may be introduced by nitrogen doping treatment.

[0115] The nitrogen content of the present support may be, for example, 0.10 wt% or more, preferably 0.15 wt% or more, more preferably 0.20 wt% or more, even more preferably 0.25 wt% or more, and particularly preferably 0.30 wt% or more. The nitrogen content of the present support may be, for example, 10.00 wt% or less. The nitrogen content of the carbon support is obtained by elemental analysis of the carbon support (specifically, by combustion).

[0116] The present support is preferably a carbonized material obtained by carbonizing a raw material containing an organic substance and a metal. In this case, the present support may be a carbonized material that has been subjected to a metal removal treatment after carbonization. The metal removal treatment is a treatment for reducing the amount of metals derived from the raw material contained in the carbonized material. Specifically, the metal removal treatment is preferably, for example, an acid washing treatment and / or an electrolytic treatment.

[0117] When the present support is a carbonized material obtained by carbonizing a raw material containing an organic substance and a metal, the present support may contain a metal derived from the raw material of the carbonization (hereinafter, sometimes referred to as a "raw material metal"). In this case, the present support contains a metal inside the skeleton that constitutes its porous structure. Even when the present support is a carbonized material produced through a metal removal treatment as described above, the raw material metal remains inside the skeleton of the present support. In this case, the weight of the metal contained inside the skeleton of the present support may be greater than the weight of the metal contained on the surface of the skeleton of the present support.

[0118] The metal contained inside the framework of the present carrier can be detected, for example, by subjecting the framework to a surface etching treatment and analyzing the cross section exposed by the etching treatment. That is, in this case, when one particle of the present carrier is subjected to an etching treatment, the metal is detected on the cross section of the particle exposed by the etching treatment. The metal contained in the present carrier can be detected, for example, by inductively coupled plasma atomic emission spectroscopy of the present carrier.

[0119] The metal content of the carrier (the ratio of the weight of the metal contained in the carrier to the weight of the carrier not yet supporting catalytic metal particles) may be, for example, 0.000% by weight or more, 0.001% by weight or more, 0.002% by weight or more, or 0.003% by weight or more. The metal content of the carrier may be, for example, 1% by weight or less, 0.5% by weight or less, 0.1% by weight or less, 0.05% by weight or less, 0.01% by weight or less, 0.008% by weight or less, or 0.005% by weight or less. The metal content of the carrier may be specified by any combination of the above-mentioned lower limit and the above-mentioned upper limit. The metal content of the carrier can be determined, for example, by inductively coupled plasma atomic emission spectroscopy of the carrier.

[0120] The raw material metal is preferably a transition metal, that is, the raw material metal is preferably a transition metal belonging to Groups 3 to 12 of the periodic table, and particularly preferably a transition metal belonging to the fourth period of Groups 3 to 12 of the periodic table.

[0121] The source metal may be a transition metal other than platinum, or a transition metal other than a noble metal (e.g., ruthenium (Ru), palladium (Pd), rhodium (Rh), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au)).

[0122] Specifically, the raw material metal may be, for example, one or more selected from the group consisting of scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), lanthanides (e.g., gadolinium (Gd)), and actinides, and is preferably one or more selected from the group consisting of Fe, Co, Ni, Cu, and Zn, more preferably one or more selected from the group consisting of Fe, Co, Ni, and Zn, and particularly preferably one or more selected from the group consisting of Co, Ni, and Zn.

[0123] The carrier may not contain platinum (Pt). The carrier may also not contain a precious metal. That is, the carrier may not contain, for example, ruthenium (Ru), palladium (Pd), rhodium (Rh), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), or gold (Au).

[0124] Carbonization in the production of a carbonized material is carried out by heating the raw material at a temperature at which the organic matter contained in the raw material is carbonized. The carbonization temperature is not particularly limited as long as it is a temperature at which the raw material is carbonized, and is, for example, preferably 1200°C or higher, more preferably 1300°C or higher, even more preferably 1400°C or higher, and particularly preferably 1500°C or higher.

[0125] The carbonization temperature may be, for example, 3000°C or lower, and preferably 2500°C or lower. The carbonization temperature may be 2400°C or lower, 2300°C or lower, 2200°C or lower, 2100°C or lower, 2000°C or lower, 1900°C or lower, 1800°C or lower, 1700°C or lower, or 1600°C or lower. The carbonization temperature may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values. The rate of temperature rise to the carbonization temperature is not particularly limited and may be, for example, 0.5°C / min or higher and 300°C / min or lower. Carbonization is preferably performed in an inert atmosphere such as a nitrogen atmosphere.

[0126] Carbonization may be carried out under normal pressure (atmospheric pressure), but is preferably carried out under pressure (under pressure higher than atmospheric pressure). When carbonization is carried out under pressure, the pressure of the atmosphere in which the carbonization is carried out may be, for example, 0.05 MPa or more in gauge pressure, preferably 0.15 MPa or more in gauge pressure, more preferably 0.20 MPa or more, even more preferably 0.40 MPa or more, and particularly preferably 0.50 MPa or more. The upper limit of the pressure of the atmosphere in which the carbonization is carried out is not particularly limited, but the pressure may be, for example, 10 MPa or less in gauge pressure.

[0127] The present support is preferably a carbonized material that has been subjected to a graphitization treatment after carbonization, i.e., the present support is preferably a carbonized material obtained by, for example, carbonizing a raw material containing an organic substance and then further graphitizing the carbonized material.

[0128] The graphitization treatment is carried out by heating the carbonized material at a temperature at which graphitization proceeds. The heating temperature at which the carbonized material is heated in the graphitization treatment is not particularly limited as long as it is a temperature at which graphitization proceeds in the carbonized material, but is preferably a temperature higher than the carbonization temperature for obtaining the carbonized material.

[0129] Specifically, the heating temperature in the graphitization treatment may be, for example, 1300°C or higher, preferably 1400°C or higher, more preferably 1500°C or higher, even more preferably 1600°C or higher, still more preferably 1650°C or higher, and particularly preferably 1700°C or higher.

[0130] Furthermore, the heating temperature in the graphitization treatment may be, for example, 1750°C or higher, 1800°C or higher, 1850°C or higher, 1900°C or higher, 1950°C or higher, 2000°C or higher, 2050°C or higher, 2100°C or higher, 2150°C or higher, or 2200°C or higher.

[0131] Furthermore, the heating temperature in the graphitization treatment may be, for example, 3000°C or less, 2500°C or less, 2400°C or less, 2300°C or less, 2250°C or less, or 2200°C or less.

[0132] Furthermore, the heating temperature in the graphitization treatment may be, for example, 2150°C or less, 2050°C or less, 2000°C or less, 1950°C or less, 1900°C or less, 1850°C or less, 1800°C or less, 1750°C or less, or 1700°C or less.

[0133] The heating temperature in the graphitization treatment may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values. The rate of temperature increase up to the heating temperature in the graphitization treatment is not particularly limited and may be, for example, 0.5°C / min or more and 300°C / min or less. The graphitization treatment is preferably performed in an inert atmosphere such as a nitrogen atmosphere.

[0134] When the present support is a carbonized material that has been graphitized after carbonization, it is preferable that the carbonized material after the graphitization is not subjected to a pulverization treatment. That is, in the production of the present support, for example, the carbonized material obtained by carbonizing a raw material is pulverized to adjust its particle size (e.g., median diameter), and then the pulverized carbonized material is graphitized, but the carbonized material after the graphitization is not subjected to a pulverization treatment.

[0135] The present support is preferably a carbonized material that has been subjected to an oxidation treatment after graphitization, i.e., the present support is preferably a carbonized material obtained, for example, by carbonizing a raw material containing an organic substance, subjecting the carbonized material to a graphitization treatment, and then further subjecting the carbonized material to an oxidation treatment.

[0136] The oxidation treatment is carried out by heating the carbonized material in an oxygen-containing atmosphere at a temperature at which oxidation proceeds. The atmosphere in which the oxidation treatment is carried out is not particularly limited as long as it contains oxygen, but is preferably, for example, air (atmospheric air). The heating temperature at which the carbonized material is heated in the oxidation treatment is not particularly limited as long as it is a temperature at which oxidation proceeds in the carbonized material, but is preferably a temperature lower than the carbonization temperature for obtaining the carbonized material.

[0137] Specifically, the heating temperature in the oxidation treatment may be, for example, 300°C or higher, preferably 320°C or higher, more preferably 350°C or higher, even more preferably 380°C or higher, even more preferably 400°C or higher, and particularly preferably 420°C or higher.

[0138] The heating temperature in the oxidation treatment may be, for example, 650° C. or lower, preferably 600° C. or lower, more preferably 550° C. or lower, even more preferably 500° C. or lower, and particularly preferably 480° C. or lower. The heating temperature in the oxidation treatment may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values.

[0139] The present support is preferably a carbon material that exhibits catalytic activity. That is, in this case, the present support is a carbon catalyst that exhibits catalytic activity by itself. The present support, which is a carbon catalyst, is preferably a carbonized material obtained by carbonizing a raw material containing an organic substance and a metal, as described above.

[0140] The catalytic activity exhibited by the present support is preferably, for example, reduction activity and / or oxidation activity, more preferably oxygen reduction activity and / or hydrogen oxidation activity, and particularly preferably at least oxygen reduction activity.

[0141] The present support is preferably used as a carbon support for supporting catalytic metal particles. In this regard, the metal-supported catalyst according to this embodiment (hereinafter referred to as "the present catalyst") includes the present support and catalytic metal particles supported on the present support.

[0142] The catalyst is produced by supporting catalytic metal particles on the support, i.e., by impregnating the support with a precursor of the metal that constitutes the catalytic metal particles, and then subjecting the support impregnated with the precursor to a reduction treatment, thereby supporting catalytic metal particles containing the metal on the support.

[0143] The catalytic metal particles are not particularly limited as long as they are metal particles that exhibit catalytic activity, but for example, they are preferably metal particles that exhibit reduction activity and / or oxidation activity, more preferably metal particles that exhibit oxygen reduction activity and / or hydrogen oxidation activity, and particularly preferably metal particles that exhibit at least oxygen reduction activity.

[0144] Specifically, the catalytic metal particles are preferably metal particles containing a precious metal (hereinafter referred to as "precious metal particles"). The precious metal particles contain a pure precious metal (a precious metal that is not alloyed) and / or a precious metal alloy (an alloy of a precious metal and a metal other than a precious metal (hereinafter referred to as "non-precious metal"). The precious metal alloy is an alloy of one or more precious metals and one or more non-precious metals.

[0145] The noble metal is preferably at least one selected from the group consisting of ruthenium (Ru), palladium (Pd), rhodium (Rh), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au), more preferably at least one selected from the group consisting of Ru, Pd, Rh, Ir, and Pt, and particularly preferably Pt. That is, the noble metal particles are particularly preferably platinum particles (metal particles containing platinum). The platinum particles include pure platinum (unalloyed platinum) and / or a platinum alloy (an alloy of platinum and a non-noble metal).

[0146] The non-precious metal constituting the precious metal alloy is not particularly limited as long as it forms an alloy with the precious metal, but is preferably a transition metal other than a precious metal. Specifically, the non-precious metal contained in the precious metal alloy is preferably one or more selected from the group consisting of titanium (Ti), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium (Nb), and cerium (Ce), more preferably one or more selected from the group consisting of Fe, Co, and Ni, and particularly preferably one or more selected from the group consisting of Co and Ni.

[0147] When the support is a carbonized material of a raw material containing an organic substance and a raw material metal, the catalytic metal particles supported on the support may contain the same type of metal as the raw material metal, or may not contain the same type of metal as the raw material metal.

[0148] In the present catalyst, the ratio of the weight of the precious metal contained in the catalyst (more specifically, the precious metal contained in the catalytic metal particles) to the weight of the present catalyst (hereinafter referred to as "precious metal content") is preferably 10% by weight or more. The precious metal content of the present catalyst is, for example, more preferably 20% by weight or more, even more preferably 30% by weight or more, even more preferably 35% by weight or more, even more preferably 40% by weight or more, and particularly preferably 45% by weight or more.

[0149] The precious metal content of the catalyst may be, for example, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less. The precious metal content of the catalyst may be specified by any combination of any of the above-mentioned lower limit values ​​and any of the above-mentioned upper limit values. The precious metal content of the catalyst is measured by inductively coupled plasma (ICP) atomic emission spectrometry.

[0150] The electrode according to this embodiment (hereinafter referred to as "the electrode") contains the catalyst of the present invention. That is, the electrode of the present invention includes, for example, an electrode substrate and the catalyst of the present invention supported on the electrode substrate. Specifically, the electrode of the present invention includes, for example, an electrode substrate and a catalyst layer containing the catalyst of the present invention formed on the electrode substrate.

[0151] The electrode is preferably a battery electrode, i.e., an electrode of a fuel cell (e.g., a polymer electrolyte fuel cell), an air battery, a water electrolyzer (e.g., a polymer electrolyte water electrolyzer), a redox flow battery, or a halogen battery.

[0152] The electrode may be either a cathode or an anode, but is preferably a cathode, i.e., the electrode is the cathode or anode, preferably a cathode, of a fuel cell, air cell, water electrolyzer, redox flow battery, or halogen battery.

[0153] The battery according to this embodiment (hereinafter referred to as "this battery") includes this electrode. Specifically, this battery is preferably a fuel cell (e.g., a polymer electrolyte fuel cell), an air battery, a redox flow battery, or a halogen battery that includes this electrode. This battery preferably has a membrane electrode assembly (MEA) that includes this electrode.

[0154] The present battery is a battery having the present electrode as a cathode or an anode, preferably a battery having the present electrode as a cathode. That is, the present battery is a fuel cell, air battery, redox flow battery, or halogen battery having the present electrode as a cathode or an anode, preferably a fuel cell, air battery, redox flow battery, or halogen battery having the present electrode as a cathode.

[0155] Next, a specific example according to this embodiment will be described. [Example]

[0156] [Production of carbon supports: Examples C1 to C4] Commercially available Ketjenblack (EC600JD, manufactured by Lion Specialty Chemicals Co., Ltd.) was used as the carbon support KB in Example C1. The carbon support KB was subjected to air oxidation treatment by heating in air at 450 °C for 1 hour. The carbon material obtained by this air oxidation treatment was used as the carbon support KB-AO in Example C2.

[0157] The carbon support KB was graphitized by heating it at 2000°C under normal pressure in a nitrogen atmosphere. The carbon material obtained by this graphitization was used as carbon support KB-G2000 in Example C3. The carbon support KB-G2000 obtained in Example C3 above was heated in air at 450°C for 1 hour to perform an air oxidation treatment. The carbon material obtained by this air oxidation treatment was used as carbon support KB-G2000AO in Example C4.

[0158] [Production of carbon support: Example C5] 1.0 g of polyacrylonitrile, 1.0 g of 2-methylimidazole, 3.3 g of zinc chloride (ZnCl2), and 30 g of dimethylformamide were mixed. The resulting mixture was dried to remove the solvent. The dried mixture was heated in air at 250°C to make it infusible.

[0159] The infusibilized mixture was heated to 1500°C under a gauge pressure (applied pressure) of 0.90 MPa in a nitrogen atmosphere to perform carbonization. Dilute hydrochloric acid was added to the carbonized material obtained by carbonization and stirred. The suspension containing the carbonized material was then filtered using a filter membrane, and the carbonized material was washed with distilled water until the filtrate became neutral. In this way, metal removal treatment by acid washing was performed.

[0160] The carbonized material after the metal removal treatment was pulverized using a fine pulverizer until the median particle size was 0.4 μm or less. The pulverized carbonized material was vacuum dried to remove moisture. The carbonized material thus obtained was used as carbon support C1500 in Example C5.

[0161] [Production of carbon supports: Examples C6 to C9] The carbon support C1500 obtained in Example C5 above was graphitized by heating it in a nitrogen atmosphere under normal pressure at 1700°C, 1900°C, 2000°C, or 2200°C. The carbonized materials thus obtained by the graphitization treatments at 1700°C, 1900°C, 2000°C, and 2200°C were used as carbon support C1500-G1700 in Example C6, carbon support C1500-G1900 in Example C7, carbon support C1500-G2000 in Example C8, and carbon support C1500-G2200 in Example C9, respectively.

[0162] [Production of Carbon Support: Examples 1 to 4] The carbon supports C1500-G1700, C1500-G1900, C1500-G2000, and C1500-G2200 obtained in Examples C6 to C9 were subjected to oxidation treatment by heating in air at 450°C for 1 hour. The carbonized materials thus obtained by oxidation treatment after graphitization were used as carbon support C1500-G1700AO in Example 1, carbon support C1500-G1900AO in Example 2, carbon support C1500-G2000AO in Example 3, and carbon support C1500-G2200AO in Example 4.

[0163] [Constant volume expansion method (true density)] The true density of the carbon support was measured by a constant volume expansion method in accordance with JIS M 8717. Specifically, an ultrapycnometer (UP-1200e, manufactured by Anton Paar) was used to measure the true density of a carbon support with a volume of 1.8 cm. 3 The volume of helium gas displaced by filling the sample chamber with the carbon support was calculated by Boyle's law. Such measurements were carried out three times for each carbon support, and the arithmetic mean value of the volumes obtained in the three measurements was obtained as the volume of the carbon support. The weight (g) of the carbon support measured by the electronic balance was then multiplied by the volume (cm) of the carbon support obtained as described above. 3 ) to obtain the true density (g / cm 3 ) was calculated.

[0164] [Elemental analysis (oxygen content)] The oxygen content of the carbon support was measured by elemental analysis (pyrolysis method). Specifically, 2 mg of the carbon support was pyrolyzed on a carbon-coated platinum plate at 1000°C in a helium / hydrogen atmosphere (5-8% by volume of hydrogen) using an organic trace elemental analyzer (2400II, PerkinElmer Co., Ltd.), and the oxygen-containing compounds (gases) produced by the pyrolysis were analyzed to obtain the oxygen content (wt%) of the carbon support.

[0165] [Raman spectroscopy] The carbon support was analyzed by Raman spectroscopy. The Raman spectrum was measured using a HORIBA laser Raman microscope (LabRAM, HORIBA Jobin Yvon). The laser used for the measurement had an excitation wavelength of 532 nm, an output of 50 mW, and was measured through a neutral density filter D3 under the conditions of 90 seconds of exposure x 2 accumulations.

[0166] The obtained Raman spectra were subjected to baseline correction. -1 ) is 800cm -1 Scattering intensity near 2000cm -1The baseline was determined as a line connecting the scattering intensities at nearby points, and baseline correction was performed by subtracting the baseline from each intensity in the scattering spectrum. As an example of a Raman spectrum, Figure 1 shows the baseline-corrected Raman spectrum obtained for the carbon support C1500-G1700AO in Example 1.

[0167] and Raman shift 1580cm -1 Around (specifically, 1550 cm -1 Over, 1610cm -1 The G band with a peak top within the range of 1000 to 10000 was identified. g Raman shift (cm) corresponding to (peak top intensity of G band) -1 )A g From the above, the intensity of the G band I g The Raman shift (cm) corresponding to half the intensity of -1 )B g By subtracting -1 ) was calculated. That is, the Raman G half-width at half maximum of the carbon support was calculated by the following formula: Raman G half-width at half maximum (cm -1 )=A g (cm -1 )-B g (cm -1 ).

[0168] Next, the Raman shift is 1340 cm -1 Around (specifically, 1320 cm -1 Above, 1360cm -1 The D band with a peak top in the range of 1000 to 15000 was identified. d (D band peak top intensity) -1 )A d From the above, the intensity of the D band I d The Raman shift (cm) corresponding to half the intensity of -1 )B d By subtracting the Raman D half-width at half maximum (cm -1 ) was calculated. That is, the Raman D half-width at half maximum of the carbon support was calculated by the following formula: Raman D half-width at half maximum (cm -1)=A d (cm -1 )-B d (cm -1 ).

[0169] Furthermore, the Raman shift of 2700 cm -1 Around (specifically, 2670 cm -1 Above, 2730cm -1 The 2D bands with peak tops within the range of I 2d Raman shift (cm) corresponding to (peak top intensity of 2D band) -1 )A 2d from the intensity of the 2D band, I 2d The Raman shift (cm) corresponding to half the intensity of -1 )B 2d By subtracting the Raman 2D half-width at half maximum (cm -1 ) was calculated. That is, the Raman 2D half-width at half maximum of the carbon support was calculated by the following formula: Raman 2D half-width at half maximum (cm -1 )=A 2d (cm -1 )-B 2d (cm -1 ).

[0170] In addition, the D-band intensity I d is the G-band intensity I g The Raman D / G ratio was calculated by dividing the Raman D / G ratio by . That is, the Raman D / G ratio of the carbon support was calculated by the following formula: Raman D / G ratio = I d / I g .

[0171] Also, the intensity of the 2D band I 2d is the G-band intensity I g The Raman 2D / G ratio was calculated by dividing the Raman 2D / G ratio by 1. That is, the Raman 2D / G ratio of the carbon support was calculated by the following formula: Raman 2D / G ratio = I 2d / I g .

[0172] [Nitrogen adsorption method] The specific surface area, pore volume, hysteresis in the nitrogen adsorption isotherm, and pore mode diameter of the carbon support were measured by nitrogen adsorption using a specific surface area and pore size distribution analyzer (TriStar II 3020, Shimadzu Corporation) and the accompanying analysis software (TriStar II 3020).

[0173] First, 0.1 g of carbon support was heated at 100°C for 6.7 × 10 -2 The carbon support was then held at 77 Pa for 3 hours to remove moisture adsorbed to the support. Next, a nitrogen adsorption isotherm at 77 K was obtained by the BET method. This nitrogen adsorption isotherm at 77 K was obtained by measuring the change in the amount of nitrogen adsorbed to the carbon support with a change in nitrogen gas pressure at a temperature of 77 K.

[0174] FIG. 2 shows an example of a nitrogen adsorption isotherm obtained at 77 K by the BET method for the carbon support C1500-G1700AO in Example 1. In the adsorption isotherm shown in FIG. 2, the horizontal axis represents the saturated vapor pressure (P0) (1.01 × 10 for nitrogen at 77 K). 5 The vertical axis shows the relative pressure (P / P0)(-), which is the ratio of the adsorption equilibrium pressure (P) to the adsorption equilibrium pressure (Pa), and the vertical axis shows the nitrogen adsorption amount (cm 3 As shown in Figure 1, the adsorption isotherm (adsorption isotherm measured while increasing the relative pressure) (shown by the filled circle in the figure) and the desorption isotherm (adsorption isotherm measured while decreasing the relative pressure) (shown by the open circle in the figure) were obtained.

[0175] In the nitrogen adsorption isotherm obtained for each carbon support, the hysteresis (0.5P / P) (cm 3 Similarly, the hysteresis (0.8P / P) (cm ) was calculated by subtracting the amount of nitrogen adsorption from the amount of nitrogen desorption at a relative pressure (P / P) of 0.8. 3 / g) was calculated.

[0176] In addition, from the nitrogen adsorption isotherm at a temperature of 77 K, the BET specific surface area (m 2 From the nitrogen adsorption isotherm at 77 K, the volume (cm) of each pore with a pore diameter of less than 5 nm in the carbon support was calculated by the DFT method. 3 / g), the pore volume of pores with a diameter of less than 5 nm (pore volume (less than 5 nm)) (cm 3 Similarly, the volume (cm ) of each pore with a pore diameter of 5 nm or more and 70 nm or less was calculated. 3 / g), the pore volume of pores with diameters of 5 nm or more and 70 nm or less (pore volume (5-70 nm)) (cm 3 / g) was calculated.

[0177] Furthermore, for each carbon support, the pore volume (less than 5 nm) was divided by the pore volume (5-70 nm) to calculate the ratio of the pore volume (less than 5 nm) to the pore volume (5-70 nm) (pore volume ratio (5 / (5-70)))(-).

[0178] In addition, pore size distributions were obtained by DFT from nitrogen adsorption isotherms at a temperature of 77 K. Figure 3A shows the pore size distributions obtained for the carbon support KB (open circles) in Example C1 and the carbon support KB-G2000 (filled circles) in Example C3. Figure 3B shows the pore size distributions obtained for the carbon support C1500 (open circles) in Example C5, the carbon support C1500-G1900 (filled circles) in Example C7, and the carbon support C1500-G1900AO (filled squares) in Example 2.

[0179] In Figures 3A and 3B, the horizontal axis represents the pore diameter D (nm), and the vertical axis represents the log differential pore volume ("dV / dlogD" in the figures) (cm 3 In the pore size distribution of each carbon support, the pore size (nm) at which the Log differential pore volume was greatest was determined as the pore mode diameter (nm) of the carbon support.

[0180] [Production of metal-supported catalysts] Metal-supported catalysts were produced by loading metal catalyst particles onto each of the carbon supports described above. Specifically, 1 g of the carbon support obtained in each of Examples C5 to C9 and Examples 1 to 4 was mixed with 10 g of an aqueous solution containing chloroplatinic acid (HPtCl), a platinum precursor, in an amount sufficient to achieve a platinum concentration of 10 wt% (platinum content per gram). The mixture was stirred for 1 hour under a gauge pressure of -0.1 MPa (reduced pressure), then for 1 hour under a gauge pressure of 0.15 MPa (overpressure), and then for 18 hours under normal pressure. The resulting mixture was then dried at 100°C under a gauge pressure of -0.1 MPa (reduced pressure), and then further maintained at 150°C in nitrogen to volatilize the solvent components.

[0181] The obtained solid was first subjected to a heat treatment (gas phase reduction treatment) at 350°C for 180 minutes in a hydrogen atmosphere (100% by volume of hydrogen gas). The treated solid was then subjected to a heat treatment at 700°C for 180 minutes in a nitrogen atmosphere (100% by volume of nitrogen gas). In this way, a metal-supported catalyst was obtained, which included a carbon support and platinum particles supported on the carbon support as catalytic metal particles.

[0182] [Power generation test and potential cycle test] To evaluate one aspect of the performance of a metal-supported catalyst, a power generation test and a potential cycle test were conducted on a fuel cell having an electrode containing the metal-supported catalyst. The potential cycle test evaluated the durability of the metal-supported catalyst, particularly its resistance to load fluctuations. Specifically, a cell cathode was first fabricated with a catalyst layer containing the metal-supported catalyst. Specifically, 0.25 g of the metal-supported catalyst fabricated as described above was mixed with an amount of electrolyte (equivalent weight EW = 820) such that the weight ratio of the metal-supported catalyst to the carbon support contained in the catalyst was 1.1. An electrolyte solution was then prepared by adding 2 g each of distilled water and 1-propanol. This electrolyte solution and 25 g of balls were placed in a pot and mixed in a ball mill at 200 rpm for 50 minutes to obtain a slurry-like catalyst layer composition containing a uniformly dispersed metal-supported catalyst.

[0183] The resulting slurry composition for catalyst layer was applied to a gas diffusion layer ("29BC", manufactured by SGL Carbon Co., Ltd.) (2.3 cm x 2.3 cm) with an area of ​​5 cm 2 The platinum content per unit area of ​​the battery electrode contained in the catalytic metal particles supported on the metal-supported catalyst is 0.2 mg-Pt / cm 2 The coating was then dried to form a catalyst layer on the gas diffusion layer, thereby obtaining a battery cathode having a catalyst layer containing a metal-supported catalyst formed thereon.

[0184] Next, a fuel cell including an electrode on which a catalyst layer containing a metal-supported catalyst was formed was manufactured. That is, the cell cathode on which a catalyst layer (positive electrode catalyst layer) containing a metal-supported catalyst formed as described above was used as the positive electrode.

[0185] On the other hand, the negative electrode was fabricated as follows. 0.5 g of a commercially available platinum-supported catalyst Pt / C (a catalyst containing platinum particles supported on a carbon support: UNPC40-II, manufactured by Ishifuku Metal Industries Co., Ltd.), 10 g of 5% Nafion (registered trademark), 2 g of distilled water, and 25 g of balls were placed in a pot and mixed in a ball mill at 200 rpm for 50 minutes to prepare a slurry Pt / C composition. This slurry Pt / C composition was then applied to a gas diffusion layer (5 cm 2 ) with a platinum content of 0.1 mg-Pt / cm 2 A battery anode including a catalyst layer (negative electrode catalyst layer) formed from the Pt / C composition was fabricated in the same manner as the positive electrode, except that the above-mentioned condition was satisfied.

[0186] A solid polymer electrolyte membrane (Nafion (registered trademark) 211 manufactured by DuPont) was then placed between the positive electrode catalyst layer and the negative electrode catalyst layer, and these were pressure-bonded at 150°C and 1 MPa for 3 minutes to produce an MEA. A pair of gaskets was attached to this MEA, which was then sandwiched between a pair of separators to produce a single fuel cell cell for power generation tests and potential cycle tests. This single cell was then installed in an automated fuel cell evaluation system (manufactured by Toyo Corporation), and a power generation test was first performed, followed by a potential cycle test.

[0187] The power generation test was carried out by supplying saturated humidified air (oxygen) to the positive electrode side at 2.5 L / min (relative humidity 100%) with a back pressure of 150 kPa and saturated humidified hydrogen to the negative electrode side at 1.0 L / min (relative humidity 100%). The cell temperature was set to 75°C and the open circuit voltage was measured for 5 minutes. After that, the cell current density was increased to 4.0 A / cm. 2 to 0 A / cm 2 The cell voltage was measured while maintaining each current density for 3 minutes until the cell voltage reached 0.2 A / cm under 100% relative humidity. 2 The voltage (mV) measured at the initial stage was used as the "BOL (Beginning of Life)" (0.2A / cm 2 ) (100% RH)" under a relative humidity of 100% and a current density of 1.0 A / cm 2 The voltage (mV) measured at the initial catalyst activity was used as the "BOL (1.0 A / cm 2 )(100%RH)”.

[0188] Next, humidified air (oxygen) was supplied to the positive electrode side at 2.5 L / min (relative humidity 40%) under a back pressure of 150 kPa, and humidified hydrogen was supplied to the negative electrode side at 1.0 L / min (relative humidity 40%). The cell temperature was set to 75°C, and the open circuit voltage was measured for 5 minutes. After that, the cell current density was set to 4.0 A / cm. 2 to 0 A / cm 2 The cell voltage was measured while maintaining each current density for 3 minutes until the temperature reached 40% relative humidity and a current density of 0.2 A / cm. 2 The voltage (mV) measured at the time of the catalyst reaction was used as a measure of the initial catalytic activity under low humidity conditions. 2 ) (40% RH) was obtained. 2 )(100%RH) to "BOL(0.2A / cm 2 ) (40% RH)” was subtracted to obtain the value (mV) that was taken as the “voltage drop (mV)” due to the decrease in humidity.

[0189] The cell temperature was then set to 75°C, saturated humidified nitrogen was supplied to both sides of the single cell at a back pressure of 150 kPa at 0.5 L / min (relative humidity 100%), and saturated humidified hydrogen was supplied to the anode side at 0.5 L / min (relative humidity 100%). A potential cycle test was performed by repeating a square wave cycle in which the potential was first held at 0.6 V for 10 seconds and then at 0.95 V for 10 seconds.

[0190] After the square wave cycle was repeated 10,000 times, a power generation test was conducted again. In the power generation test after the potential cycle test, the relative humidity was 100% and the current density was 0.2 A / cm. 2 The voltage (mV) measured at the EOL (End Of Life) 2 )(100%RH)”.

[0191] [Start-stop test] To evaluate other aspects of the performance of the metal-supported catalyst, a start-stop test was conducted on a fuel cell having electrodes containing the metal-supported catalyst. Specifically, the durability of the metal-supported catalyst, particularly its corrosion resistance (resistance to corrosion), was evaluated based on the change in voltage before and after the start-stop test. Specifically, a solid polymer electrolyte membrane (Nafion® 211, manufactured by DuPont) was placed between a positive electrode catalyst layer and a negative electrode catalyst layer, both of which were prepared in the same manner as in the power generation test and potential cycle test described above. An MEA was then fabricated by compressing the membrane at 150°C and 1 MPa for 3 minutes. A pair of gaskets was attached to the MEA, which was then sandwiched between a pair of separators to fabricate a single fuel cell for the start-stop test. This single cell was then installed in a fuel cell automated evaluation system (manufactured by Toyo Corporation), and a start-stop test was conducted.

[0192] That is, the cell temperature was set to 80°C, saturated humidified nitrogen was supplied to both sides of the single cell at a back pressure of 35 kPa at 1.0 L / min (relative humidity 100%), saturated humidified hydrogen was supplied to the anode side at 1.0 L / min (relative humidity 100%), and a start-stop test was performed by repeating a triangular wave cycle in which the potential was scanned from 1.0 V to 1.5 V at a sweep rate of 500 mV / sec.

[0193] After the above triangular wave cycle was repeated 1000 times, a power generation test was conducted. In the power generation test after the start-stop test, the current density was 0.2 A / cm under a relative humidity of 100%. 2 The voltage (mV) measured at the time of start-up / shutdown is calculated as "voltage after start-up / shutdown (0.2A / cm 2 Similarly, in the power generation test after the start-stop test, the current density was 1.0 A / cm under 100% relative humidity. 2 The voltage (mV) measured at the time of start-up / shutdown is calculated as "voltage after start-up / shutdown (1.0A / cm 2 )" was obtained.

[0194] [result] 4A and 4B show the results of evaluating the properties of the carbon support, and Fig. 4C shows the results of evaluating the performance of the metal-supported catalyst.

[0195] As shown in FIG. 4C, the BOL (0.2 A / cm) of the metal-supported catalysts containing the carbon supports of Examples C6 to C9 that had been graphitized but not oxidized was 0.01. 2 ) (100% RH) was significantly smaller than that of Example C5, which was not subjected to the graphitization treatment. In contrast, the BOL (0.2 A / cm) of the metal-supported catalysts containing the carbon supports of Examples 1 to 4, which were subjected to the oxidation treatment after the graphitization treatment, was 2 ) (100% RH) was significantly higher than those of Examples C6 to C9 and was equal to or higher than that of Example C5. Among them, the BOL (0.2 A / cm ) of the metal-supported catalysts containing carbon supports in Examples 2 and 3 was 2 ) (100%RH) was particularly large.

[0196] Examples C6 to C9: BOL (0.2A / cm 2 ) (40% RH) was significantly smaller than that of Example C5. In contrast, the BOL (0.2 A / cm ) of Examples 1 to 4 2 ) (40% RH) was significantly larger than that of Examples C6 to C9 and was equal to or greater than that of Example C5. 2 ) (40% RH) was significantly larger than that of Example C5, and that of Example 1 was particularly large.

[0197] The voltage drop (mV) of Examples C6 to C9 due to a decrease in humidity from 100% RH to 40% RH was equal to or greater than that of Example C5, and was particularly significantly greater in Examples C8 and C9. In contrast, the voltage drop (mV) of Examples 1 to 4 was smaller than that of Example C5, and each was significantly smaller than that of Examples C6 to C9. In particular, the voltage drop (mV) of Examples 1 and 2 was significantly smaller than that of Example C5, and that of Example 1 was particularly small.

[0198] Examples C6 to C9: BOL (1.0A / cm 2 ) (100% RH) was significantly smaller than that of Example C5. In contrast, the BOL (1.0 A / cm 2 ) (100% RH) was equal to or greater than that of Example C5 and significantly greater than that of Examples C6 to C9. 2 ) (100% RH) was significantly larger than that of Example C5, and that of Example 1 was particularly large.

[0199] EOL (0.2A / cm2) of Examples C6 and C7 2 ) (100% RH) was significantly larger than that of Example C5, but those of Examples C8 and C9 were significantly smaller than that of Example C5. In contrast, the EOL (0.2 A / cm 2 ) (100% RH) was significantly larger than that of Example C5. 2 ) (100% RH) were significantly greater than those of Examples C8 and C9, respectively.

[0200] Example: Voltage after start / stop of C6 to C9 (0.2A / cm 2 ) was significantly larger than that of Example C5. 2 ) was significantly larger than that of Example C5, and also larger than those of Examples C6 to C9. 2 ) were significantly larger than those of Examples C7 to C9, respectively, and that of Example 4 was particularly large.

[0201] Example: Voltage after start / stop of C6 to C9 (1.0A / cm 2 ) was larger than that of Example C5. 2 ) was significantly larger than that of Example C5, and significantly larger than that of Examples C6 to C9. 2 ) was significantly larger, and that of Example 4 was particularly large.

[0202] From the above, the metal-supported catalyst containing the carbon support of Example 1 has a small "voltage drop" that indicates a decrease in catalytic activity with decreasing humidity, and a BOL (0.2 A / cm 2 ) (40% RH), the catalyst showed high catalytic activity under low humidity. In addition, the metal-supported catalyst containing the carbon support of Example 1 showed a particularly large BOL (1.0 A / cm 2 ) (100% RH) is also shown.

[0203] The metal-supported catalysts containing carbon supports in Examples 2 and 3 exhibited a BOL (0.2 A / cm 2 ) (100% RH) and BOL (1.0 A / cm 2 ) (100%RH) and the initial catalytic activity reflected in the voltage (0.2A / cm 2 ) and voltage after start / stop (1.0A / cm 2 ) and the corrosion resistance of the carbon support, which is reflected in the

[0204] The metal-supported catalyst containing the carbon support of Example 4 exhibited a voltage after start-stop (0.2 A / cm 2 ) and voltage after start / stop (1.0A / cm 2 ) demonstrated an extremely high level of corrosion resistance of the carbon support.

[0205] As shown in Fig. 4A, the true densities of the carbon supports of Examples 1 to 4, which were subjected to an oxidation treatment after graphitization, were significantly higher than those of the carbon supports of Examples C6 to C9, which were not subjected to the oxidation treatment. That is, the true densities of the carbon supports increased significantly due to the oxidation treatment. Among these, the true densities of Examples 1 to 3 were particularly high. On the other hand, the true densities of Examples C1, C3, and C4 were low.

[0206] The oxygen contents of the carbon supports in Examples 1 to 4 were significantly higher than those in Examples C6 to C9, respectively. That is, the oxygen contents of the carbon supports increased significantly due to the oxidation treatment. Among them, the oxygen content of Example 1 was particularly high. On the other hand, the oxygen contents of Examples C3 and C4 were low.

[0207] The Raman G half width at half maximum of the carbon supports of Examples 1 to 4 was smaller than that of Examples C1 to C5. The Raman D half width at half maximum of the carbon supports of Examples 1 to 4 was significantly smaller than that of Examples C1, C2, and C5. Among them, the Raman D half width at half maximum of Examples 3 and 4 was particularly small. The Raman 2D half width at half maximum of the carbon supports of Examples 1 to 4 was smaller than that of Examples C1 to C6.

[0208] The Raman D / G ratios of the carbon supports in Examples 1 to 4 were higher than those in Examples C6 to C9, respectively. That is, the Raman D / G ratios of the carbon supports increased due to the oxidation treatment. The Raman D / G ratios of Examples C1 to C5 were low. The Raman 2D / G ratios of the carbon supports in Examples 1 to 4 were higher than those of Examples C1, C2, and C5. Among them, the Raman 2D / G ratios of Examples 3 and 4 were particularly high.

[0209] 4B, the BET specific surface areas of the carbon supports in Examples 1 to 4 were larger than those in Examples C6 to C9, respectively. That is, the BET specific surface areas of the carbon supports increased by the oxidation treatment. Among them, the BET specific surface area of ​​Example 1 was particularly large.

[0210] The pore volumes (5-70 nm) of the carbon supports in Examples 1 to 4 were significantly smaller than those in Examples C1 to C4 and comparable to those in Examples C5 to C9. On the other hand, the pore volumes (less than 5 nm) of the carbon supports in Examples 1 to 4 were significantly larger than those in Examples C1 to C4. Furthermore, the pore volumes (less than 5 nm) of Examples 1 to 4 were significantly larger than those in Examples C6 to C9, respectively. That is, the pore volumes (less than 5 nm) of the carbon supports increased significantly by the oxidation treatment.

[0211] The pore volume ratios (5 / (5-70)) of the carbon supports in Examples 1 to 4 were significantly larger than those in Examples C1 to C4. The pore volume ratios (5 / (5-70)) of Examples 1, 3, and 4 were also significantly larger than those in Examples C6, C8, and C9, respectively. Among these, the pore volume ratio (5 / (5-70)) of Example 1 was particularly large.

[0212] The pore mode diameters of the carbon supports in Examples 1 to 4 were significantly smaller than those in Examples C1 to C4. The pore mode diameters of Examples 1 to 3 were similar to those in Examples C5 to C9. On the other hand, the pore mode diameter of Example 4 was larger than those in Examples C5 to C9.

[0213] The hysteresis (0.5P / P0) and hysteresis (0.8P / P0) of the carbon supports in Examples 1 to 4 were significantly smaller than those in Examples C1 to C4. The hysteresis (0.5P / P0) in Examples 1 to 4 was larger than that in Examples C6 to C9. On the other hand, the hysteresis (0.8P / P0) in Examples 1 to 4 was comparable to that in Examples C6 to C9.

Claims

1. A carbon support for supporting catalytic metal particles, BET specific surface area is 300m ２ / g or more, True density is 2.1 g / cm ３ That's all, The Raman spectrum obtained by Raman spectroscopy has the following characteristics (i) and (ii): (i) Raman shift 1580 cm －１ Raman shift of the G band intensity with a peak top near 1340 cm －１ The ratio of the intensity of the D band having a peak top in the vicinity thereof is 1.6 or more; (ii) Raman shift 1580 cm －１ Raman shift of the G band intensity with a peak top near 2700 cm －１ The ratio of the intensities of 2D bands having peak tops in the vicinity is 0.3 or more; having a carbon structure exhibiting one or more selected from the group consisting of: Carbon carrier.

2. The carbon structure exhibits the characteristic (i), The carbon support according to claim 1 .

3. The carbon structure exhibits the property (ii), The carbon support according to claim 1 .

4. The oxygen content is 1.0% by weight or more. The carbon support according to claim 1 .

5. In the Raman spectrum obtained by Raman spectroscopy, the Raman shift was 1580 cm －１ The half width at half maximum of the G band, which has a peak top near －１ having the carbon structure: The carbon support according to claim 1 .

6. In the Raman spectrum obtained by Raman spectroscopy, the Raman shift was 1340 cm －１ The half width at half maximum of the D band with a peak top near －１ having the carbon structure: The carbon support according to claim 1 .

7. In the Raman spectrum obtained by Raman spectroscopy, the Raman shift was 2700 cm －１ The half width at half maximum of the 2D band with a peak top near －１ having the carbon structure: The carbon support according to claim 1 .

8. The volume of pores with a diameter of 5 nm or more and 70 nm or less is 0.50 cm ３ / g or less, The carbon support according to claim 1 .

9. The volume of pores with a diameter of less than 5 nm is 0.20 cm ３ / g or more, The carbon support according to claim 1 .

10. The ratio of the volume of pores having a pore diameter of less than 5 nm to the volume of pores having a pore diameter of 5 nm or more and 70 nm or less is 4.0 or more; The carbon support according to claim 1 .

11. The pore mode diameter is 7.0 nm or less; The carbon support according to claim 1 .

12. In the nitrogen adsorption isotherm obtained at a temperature of 77 K by the nitrogen adsorption method, the saturated vapor pressure (P ０ The relative pressure (P / P) is the ratio of the adsorption equilibrium pressure (P) to the adsorption equilibrium pressure (P). ０ The difference obtained by subtracting the amount of nitrogen adsorption from the amount of nitrogen desorption at 0.5 (-) is 40 cm ３ / g or less, The carbon support according to claim 1 .

13. In the nitrogen adsorption isotherm obtained at a temperature of 77 K by the nitrogen adsorption method, the saturated vapor pressure (P ０ The relative pressure (P / P) is the ratio of the adsorption equilibrium pressure (P) to the adsorption equilibrium pressure (P). ０ The difference obtained by subtracting the amount of nitrogen adsorption from the amount of nitrogen desorption at 0.8 (-) is 20 cm ３ / g or less, The carbon support according to claim 1 .

14. The carbon support according to any one of claims 1 to 13, catalytic metal particles supported on the carbon support; A metal supported catalyst comprising:

15. The catalyst comprises the metal supported catalyst of claim 14. electrode.

16. 16. The electrode of claim 15, battery.

Images