Porous carbon material and production method therefor

Abstract

This porous carbon material has, in a pore size distribution measured by mercury porosimetry, a first peak positioned in a pore diameter range from equal to or greater than 3 nm to less than 10 nm and a second peak positioned in a pore diameter range from equal to or greater than 10 nm to equal to or less than 1 µm, and satisfies at least one of the following (A), (B), and (C).　(A) The X-ray diffraction pattern has a peak (i) that has a half-value width of 0.6° or less and a peak top in the range of 2θ = 25° to 27°.　(B) In measurement of the nitrogen adsorption, the amount of nitrogen adsorption when the relative pressure is 0.2 is 10 cm3 / g to 250 cm3 / g.　(C) The surface oxygen concentration measured by XPS is not more than 6 at%.

Description

Porous carbon material and method for producing the same

[0001] The present disclosure relates to a porous carbon material and a method for producing the same.

[0002] Carbon materials, particularly porous carbon materials having fine pores, are useful for applications such as catalyst supports and electrode materials, and various production methods have been investigated. For example, Patent Document 1 discloses a method of obtaining activated carbon by heating a mixture of a block copolymer having a hydrophilic block and a hydrophobic block, a phenol, formaldehyde, and a solvent to obtain porous carbon, and then activating the porous carbon.

[0003] JP 2014-034475 A

[0004] In recent years, due to the expansion of applications, porous carbon materials with superior oxidation resistance are desired.

[0005] An object of the present disclosure is to provide a porous carbon material that has excellent oxidation resistance and is suitable as a catalyst support, and a method for easily producing the porous carbon material.

[0006] The present disclosure relates to, for example, the following items [1] to

[20] . [1] A porous carbon material having, in a pore size distribution measured by mercury intrusion porosimetry, a first peak located in a pore size range of 3 nm or more and less than 10 nm, and a second peak located in a pore size range of 10 nm or more and 1 μm or less, and satisfying at least one of the following (A), (B), and (C): (A) In an X-ray diffraction pattern, the material has a peak (i) having a half-width of 0.6° or less and a peak top within a range of 2θ = 25° to 27°; (B) In a nitrogen adsorption measurement, the amount of nitrogen adsorption at a relative pressure of 0.2 is 10 cm ３ / g or more 250cm ３ / g or less. (C) The surface oxygen concentration measured by XPS is 6 at% or less. [2] The porous carbon material according to [1], which satisfies (A). [3] The porous carbon material according to [2], which further has a peak (ii) in an X-ray diffraction pattern having a half-width of 9° or less and partly overlapping with the peak (i). [4] The porous carbon material according to [1], which satisfies (B). [5] The porous carbon material according to [1], which satisfies (B). [6] The porous carbon material according to [1], which further has a nitrogen adsorption capacity of 10 cm ３ / g or more 200cm ３ / g or less. [6] The porous carbon material according to [1], which satisfies (C). [7] The porous carbon material according to [6], which has a surface oxygen concentration measured by XPS of 2 at% or less and a surface carbon concentration measured by XPS of 98 at% or more. [8] The porous carbon material according to [1], which has a specific surface area of ​​200 m ２ / g or more 1800m ２ / g or less. [9] The porous carbon material according to any one of [1] to [7], wherein the first peak is located in a pore diameter range of 4 nm or more and 7 nm or less.

[10] The porous carbon material according to any one of [1] to [7], wherein the second peak is located in a pore diameter range of 20 nm or more and 700 nm or less.

[11] A method for producing a porous carbon material, comprising: a preparation step of preparing a resin molded body containing a resin material as a carbon source, a first template, and a second template; and a calcination step of calcining the resin molded body to obtain the porous carbon material according to [2] or [3], wherein the calcination step comprises calcining at 1200°C or more, wherein the first template comprises amphiphilic molecules, and the second template comprises latex particles.

[12] The method for producing a porous carbon material according to

[11] , wherein the firing step comprises: a first firing step of firing the resin molded body at a firing temperature of less than 1200°C to obtain a first fired body; and a second firing step of firing the first fired body at a firing temperature of 1500°C or higher.

[13] The method for producing a porous carbon material according to

[11] , wherein the firing step comprises: a first firing step of firing the resin molded body at a firing temperature of less than 1200°C to obtain a first fired body; a crushing step of crushing the first fired body; and a second firing step of firing the first fired body crushed in the crushing step at a firing temperature of 1500°C or higher.

[14] The method for producing a porous carbon material according to

[11] , wherein the firing step comprises firing at 2000°C or higher.

[15] The method for producing a porous carbon material according to

[11] , wherein the firing at 1500°C or higher in the firing step is performed in an argon atmosphere.

[16] A method for producing a porous carbon material, comprising: a preparation step of preparing a resin molded body containing a resin material as a carbon source, a first template, and a second template; and a firing step of firing the resin molded body to obtain the porous carbon material according to any one of [4] to [7], wherein the firing step comprises firing at 1100°C or higher, the first template comprises amphiphilic molecules, and the second template comprises latex particles.

[17] The method for producing a porous carbon material according to

[16] , wherein the firing step comprises: a first firing step of firing the resin molded body at a firing temperature of less than 1100°C to obtain a first fired body; and a second firing step of firing the first fired body at a firing temperature of 1100°C or higher.

[18] The method for producing a porous carbon material according to

[16] , wherein the firing step comprises: a first firing step of firing the resin molded body at a firing temperature of less than 1100°C to obtain a first fired body, a crushing step of crushing the first fired body, and a second firing step of firing the first fired body crushed in the crushing step at a firing temperature of 1100°C or higher.

[19] The method for producing a porous carbon material according to

[16] , wherein the firing step comprises firing at 2000°C or higher.

[20] The method for producing a porous carbon material according to

[16] , wherein the firing at 1100°C or higher in the firing step is performed in an argon atmosphere.

[0007] According to the present disclosure, there is provided a porous carbon material having excellent oxidation resistance and suitable as a catalyst support. Furthermore, according to the present disclosure, there is provided a method for easily producing the porous carbon material.

[0008] Fig. 1(a) is a cross-sectional view schematically showing an example of a resin molded body, and Fig. 1(b) is a cross-sectional view schematically showing an example of a porous carbon material. Fig. 2 is a diagram showing a pore distribution curve of the porous carbon material obtained in Example A-1. Fig. 3 is a diagram showing an X-ray diffraction pattern of the porous carbon material obtained in Example A-1.

[0009] In the present disclosure, a porous carbon material is a carbon material having a plurality of pores. The porous carbon material satisfies at least one of the following (A), (B), and (C): (A) in an X-ray diffraction pattern, the material has a peak (i) whose half-width is 0.6° or less and whose peak top is in the range of 2θ=25° to 27°; (B) in a nitrogen adsorption measurement, the amount of nitrogen adsorption at a relative pressure of 0.2 is 10 cm ３ / g or more 250cm ３ (C) The surface oxygen concentration measured by XPS is 6 at % or less.

[0010] The porous carbon material may satisfy two or more of (A), (B), and (C), or may satisfy all three.

[0011] Preferred embodiments of a porous carbon material that satisfies (A), a porous carbon material that satisfies (B), and a porous material that satisfies (C) will be described in detail below.

[0012] [Porous carbon material satisfying (A)] The porous carbon material of this embodiment has a pore size distribution measured by mercury intrusion porosimetry, in which a first peak is located in a pore size range of 3 nm or more and less than 10 nm, and a second peak is located in a pore size range of 10 nm or more and 1 μm or less. １ ~A ２ "having a peak in the range of pore diameter A １ ~A ２ This means that a peak having a peak top in the range of

[0013] The porous carbon material of this embodiment can also be said to have a first group of pores forming a first peak and a second group of pores forming a second peak. The porous carbon material of this embodiment can also be said to have a microstructure formed by the first group of pores and a higher-order structure formed by the second group of pores.

[0014] The porous carbon material of this embodiment allows the reaction substrates to move efficiently through the wide pores of the higher-order structure, so that the reaction substrates can be efficiently transported to the reaction sites and the reaction products can be efficiently discharged. Furthermore, the porous carbon material of this embodiment has a first group of pores, which allows a high specific surface area and efficient support of the active metal. Furthermore, in this embodiment, by coating the higher-order structure with a coating material, the coating material can be provided on the porous carbon material without poisoning or burying the active metal supported within the microstructure. Thus, the porous carbon material of this embodiment allows the reaction substrates to easily reach the reaction sites, and the reaction sites can function effectively even when coated with a coating material. Therefore, the porous carbon material of this embodiment is suitable as a catalyst support.

[0015] The first peak is located in the pore diameter range of 3 nm or more and less than 10 nm, and preferably in the pore diameter range of 4 nm or more and 7 nm or less. The second peak is located in the pore diameter range of 10 nm or more and 1 μm or less, and preferably in the pore diameter range of 20 nm or more and 200 nm or less. This makes the above-mentioned effects more pronounced.

[0016] The first peak and the second peak may each have a peak value of 0.1 mL / g or more, preferably 0.5 mL / g or more, and may each have a peak value of 4 mL / g or less, or 2 mL / g or less.

[0017] The first peak and the second peak are preferably the peak with the highest peak value (Peak A) or the peak with the second highest peak value (Peak B) among the peaks located in the pore diameter range of 3 nm to 1 μm. That is, when the first peak is Peak A, the second peak is preferably Peak B, and when the first peak is Peak B, the second peak is preferably Peak A.

[0018] In this specification, the pore size distribution of the porous carbon material is measured by mercury intrusion porosimetry. More specifically, it is measured by the following method. The pore size distribution is represented by a pore size distribution curve with the horizontal axis representing the pore size (pore diameter) (logarithmic scale) and the vertical axis representing the log differential pore volume (linear scale). <Measurement of Pore Size Distribution> First, 40 to 80 mg of the porous carbon material is collected in a 5 cc measurement cell. Next, using an automatic mercury porosimeter (Shimadzu Corporation-Micromeritics Autopore V9620), the mercury pressure is increased from 1 psia to 60,000 psia, and the amount of mercury intrusion is measured. The pore size distribution is then determined from the obtained pressure vs. intrusion amount curve. The mercury contact angle is 130 degrees, and the mercury surface tension is 485 dynes / cm.

[0019] The porous carbon material of this embodiment has, in its X-ray diffraction pattern, a peak (i) having a half-width of 0.6° or less and a peak top within the range of 2θ=25° to 27°.

[0020] It can be said that a porous carbon material having the above peak (i) has a region with high crystallinity formed in part. In this embodiment, it is considered that the porous carbon material has a region with high crystallinity, thereby realizing excellent oxidation resistance. Such a porous carbon material can be formed, for example, by a firing step including firing at 1500°C or higher, as shown in the manufacturing method described below.

[0021] The half width of peak (i) may be, for example, 0.5° or less. Alternatively, the half width of peak (i) may be, for example, 0.1° or more, 0.2° or more, or 0.3° or more.

[0022] The crystallite diameter of peak (i) may be, for example, 60 nm or less, 55 nm or less, 50 nm or less, or 45 nm or less. The crystallite diameter of peak (i) may be, for example, 20 nm or more.

[0023] The porous carbon material of this embodiment may further have a peak (ii) in its X-ray diffraction pattern, which has a half-width of 9° or less and partially overlaps with the peak (i). In other words, the peak (i) can be said to be a peak that exists at a position overlapping with the peak (ii).

[0024] The half width of peak (ii) may be, for example, 8.5° or less. The half width of peak (ii) may be, for example, 1.0° or more, 4.0° or more, or 7.0° or more. The peak height ratio of peak (i) to peak (ii) may be, for example, 0.1 or more, 0.2 or more, or 0.3 or more. The peak height ratio of peak (i) to peak (ii) may be, for example, 5.0 or less, 3.0 or less, or 1.5 or less.

[0025] In this specification, the X-ray diffraction pattern of a porous carbon material is measured by the following method. <Measurement of X-ray diffraction pattern> A porous carbon material is placed on a Si anti-reflective sample holder (filled portion: 20 mm × 18 mm × 0.2 mmt), and a measurement sample is obtained by spreading it with a glass plate so that the sample surface (the height of the portion filled with the sample) coincides with the reference plane of the sample holder. The obtained measurement sample is placed in an X-ray diffractometer (Rigaku Corporation, X-ray diffractometer Ultima IV), and the X-ray diffraction pattern is measured at room temperature using a Cu-Kα X-ray source, a standard sample stage, a focusing optical system, a semiconductor detector (D / teX Ultra), and an anti-scatter tube (slit width 4 mm, length approximately 9 cm) with a measurement angle range of 2θ = 10° to 70°, a sampling width of 0.02°, and a scan rate of 5° / min.

[0026] <Calculation of Half-Width, Crystallite Diameter, and Peak Height Ratio> The powder X-ray diffraction pattern comprehensive analysis software Jade 9 was used to calculate the half-width and crystallite diameter. Peaks (i) and (ii) are assumed to exist in the range of 2θ = 10° to 40° in the X-ray diffraction pattern, and peak separation is performed to calculate the half-width (β measured), peak position 2θ (°), and peak height of peaks (i) and (ii) derived from the Cu-Kα1 line. However, when a sharp peak (i) is not observed in the X-ray diffraction pattern, peak separation is performed assuming that only peak (ii) exists. In this case, the peak shape is a pseudo-Voigt function, and the background shape is a Cubic Spline (fixed). The background is drawn by manually specifying six points as binding points (for example, in Figure 3, 2θ = 10°, 11°, 12.3°, 15°, 35°, and 40°). When calculating the half width and crystallite diameter, the half width derived from the instrument is corrected using the following method. Specifically, the same measurement as in the above <X-ray diffraction pattern measurement> is performed on Si powder (NIST SRM 640c), and full pattern fitting (WPPF) is performed on the measurement results using Jade 9 to obtain the half width curve of Si. Using the obtained half width curve of Si, the half width of Si at the peak position 2θ of peak (i) in the porous carbon material is calculated, and this is taken as the half width derived from the instrument corresponding to peak (i) (β instrument). This value is substituted into the following formula for correction, and the half width derived from the sample of peak (i) (β sample) is calculated. Similarly, in the case of peak (ii), the half width of Si at the peak position 2θ of peak (ii) is calculated, and this is taken as the half width derived from the instrument corresponding to peak (ii) (β instrument). This value is substituted into the following formula for correction, and the half width derived from the sample of peak (ii) (β sample) is calculated. (β sample) ２ = [(β measured) ２ - (β device) ２] Next, the half width of peak (i) (β sample) is substituted into the following Scherrer formula to calculate the crystallite size. At this time, the Scherrer constant K is 1, the measurement X-ray wavelength λ is 0.154 nm, and the peak position of peak (i) obtained by peak separation in Jade 9 is used as the value of the diffraction angle 2θ (°). Crystallite size = (K × λ) / (β × cos θ) The peak height ratio is calculated by substituting the peak height of peak (i) and the peak height of peak (ii) obtained by the above peak separation into the following formula. (Peak height ratio) = (peak height of peak (i)) / (peak height of peak (ii))

[0027] The porous carbon material of this embodiment has a relative pressure (P / P ０ ) is 0.2, the amount of nitrogen adsorption is, for example, 10 to 250 cm ３ / g.

[0028] Relative pressure (P / P ０ When the nitrogen adsorption amount is 250 cm or less, the porous carbon material having a low nitrogen adsorption amount can be said to have a small number of micropores. ３ / g or less, there are fewer fine pores that are likely to be the starting points for deterioration, and therefore the porous carbon material tends to have better oxidation resistance. ３ A porous carbon material having a porosity of 1 / g or more tends to be more suitable as a catalyst support because the presence of fine pores makes it easier to support a catalyst. Such a porous carbon material can be formed, for example, by a calcination step including calcination at 1500°C or higher, as shown in the production method described below.

[0029] Relative pressure (P / P ０ ) is 0.2, the amount of nitrogen adsorption is, for example, 250 cm ３ / g or less, and from the viewpoint of more significantly exhibiting the above-mentioned effect, it is preferable that the ３ / g or less, 170cm ３ / g or less, 150cm ３ / g or less, 130cm ３ / g or less or 110 cm ３ / g or less.

[0030] Relative pressure (P / P ０) is 0.2, the amount of nitrogen adsorption is, for example, 10 cm ３ / g or more, and from the viewpoint of more significantly exhibiting the above-mentioned effect, ３ / g or more, 30cm ３ / g or more, 40cm ３ / g or more or 50 cm ３ / g or more.

[0031] In the porous carbon material of this embodiment, the relative pressure (P / P ０ ) is 0.8, the nitrogen adsorption amount (N ０ ) relative pressure (P / P ０ The nitrogen adsorption amount (N １ ) ratio (N １ / N ０ ) may be, for example, 0.6 or less, and from the viewpoint of more significantly achieving the above-mentioned effect, it may be 0.5 or less or 0.4 or less.

[0032] In this specification, the nitrogen adsorption amount of a porous carbon material is measured by the following method. <Measurement of nitrogen adsorption amount> A porous carbon material is dried under vacuum at 300°C for 3 hours using a pretreatment device (BELPREP-VAC II manufactured by Microtrac-Bel). Next, a nitrogen adsorption isotherm is measured using a high-precision gas / vapor adsorption amount measuring device (BELSORP MAX II manufactured by Microtrac-Bel). The nitrogen adsorption amount at a predetermined relative pressure is then calculated from the obtained nitrogen adsorption isotherm.

[0033] The porous carbon material of this embodiment may have a surface oxygen concentration of 2.5 at % or less as measured by XPS.

[0034] A porous carbon material with a low surface oxygen concentration can be said to be a porous carbon material with a small amount of surface functional groups. When the surface oxygen concentration is low, the amount of surface functional groups in the porous carbon material is small, and the surface of the porous carbon material becomes more hydrophobic. As a result, when the porous carbon material is used as a catalyst support, reaction products are more likely to be discharged from the inside of the porous carbon material. Such a porous carbon material can be formed, for example, by a calcination step including calcination at 1500°C or higher, as shown in the manufacturing method described below.

[0035] The surface oxygen concentration of the porous carbon material of this embodiment may be, for example, 2.5 at% or less, and from the viewpoint of more significantly achieving the above-mentioned effect, it may be 2 at% or less, 1.5 at% or less, 1 at% or less, or 0.5 at% or less. The lower limit of the surface oxygen concentration of the porous carbon material of this embodiment is not particularly limited, and may be 0 at%.

[0036] The porous carbon material of this embodiment may have a surface carbon concentration of 95 at % or more as measured by XPS.

[0037] A porous carbon material with a high surface carbon concentration can be said to have a small amount of surface functional groups. When the surface carbon concentration is high, the amount of surface functional groups in the porous carbon material is small, and the surface of the porous carbon material becomes more hydrophobic. As a result, when the porous carbon material is used as a catalyst support, reaction products are more likely to be discharged from the inside of the porous carbon material. Such a porous carbon material can be formed, for example, by a calcination step including calcination at 1500°C or higher, as shown in the manufacturing method described below.

[0038] The surface carbon concentration of the porous carbon material of this embodiment may be, for example, 95 at% or more, and from the viewpoint of more significantly achieving the above-mentioned effect, it may be 97.5 at% or more, 98 at% or more, 98.5 at% or more, 99 at% or more, or 99.5 at% or more. The upper limit of the surface carbon concentration of the porous carbon material of this embodiment is not particularly limited, and may be 100 at%.

[0039] In the porous carbon material of this embodiment, the sum of the surface oxygen concentration and the surface carbon concentration is 100 at %, and for example, when the surface oxygen concentration is 2 at %, the surface carbon concentration is 98 at %.

[0040] In this specification, the surface oxygen concentration and surface carbon concentration of a porous carbon material are measured by the following method. <Measurement of Surface Oxygen Concentration and Surface Carbon Concentration> The surface oxygen concentration and surface carbon concentration are determined by XPS measurement using an X-ray photoelectron spectrometer (K-Alpha type X-ray photoelectron spectrometer manufactured by Thermo Instruments). Specifically, the porous carbon material is filled into a recess (φ3 mm × 1 mm thick) of a powder sample holder, and the sample surface is flattened and crushed for measurement. The excitation source used for the measurement is an Al-Kα with a monochromator, the X-ray irradiation area is 400 × 200 μm (elliptical in shape), the detection angle is 90° (perpendicular to the sample surface), the pass energy is 50 eV, and the number of scans is 5. The elements to be detected are oxygen (O) and carbon (C), and their narrow spectra are measured. The surface oxygen concentration and the surface carbon concentration are calculated by integrating O in the O1s range (approximately 540 to 527 eV) and C in the C1s range (approximately 293 to 280 eV). Charge correction is performed using the C1s peak (284.8 eV) as the reference peak, and the background is specified by Shirley. The surface oxygen concentration and the surface carbon concentration are normalized so that the sum of them is 100 at%.

[0041] The specific surface area of ​​the porous carbon material of this embodiment is, for example, 200 m ２ / g or more, and ２ / g or more, 300m ２ / g or more or 350m ２ / g or more. This improves the dispersibility of the active metal on the porous carbon material when the active metal is supported, and reaction sites tend to be formed more efficiently. The specific surface area of ​​the porous carbon material of this embodiment may be, for example, 1800 m ２ / g or less, and ２ / g or less, 1000m ２ / g or less, 700m ２ / g or less or 500m ２ / g or less. This tends to further improve the strength of the porous structure of the porous carbon material and make the porous structure more stable.

[0042] In this specification, the specific surface area of ​​a porous carbon material refers to a value measured by a nitrogen adsorption method. More specifically, it is measured by the following method in accordance with JIS Z8830. <Measurement of specific surface area> A porous carbon material is dried under vacuum at 300°C for 3 hours using a pretreatment device (BELPREP-VAC II, manufactured by Microtrac-Bell). Next, a nitrogen adsorption isotherm is measured using a high-precision gas / vapor adsorption measurement device (BELSORP MAX II, manufactured by Microtrac-Bell). The specific surface area is then calculated from the obtained nitrogen adsorption isotherm using the BET method.

[0043] The porous carbon material of the present embodiment may include, for example, a fired product of a resin material. The porous carbon material of the present embodiment may also be, for example, a fired product of a resin molded product containing a resin material.

[0044] Any resin material may be used as long as it can form amorphous carbon upon firing. Examples of the resin material include phenolic resins (novolac-type phenolic resins, resol-type phenolic resins), furan resins, epoxy resins, unsaturated polyester resins, ester resins, urea resins, melamine resins, alkyd resins, xylene resins, polyurethane resins, polyuric acid resins, acrylonitrile resins, polystyrene resins, bismaleimide-triazine resins, divinylbenzene resins, polyimide resins, diallyl phthalate resins, and vinyl ester resins.

[0045] As the resin material, a polymer of a phenol and formaldehyde can be suitably used.

[0046] Phenols are compounds in which at least one hydroxy group is bonded to an aromatic ring. Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, dihydroxybenzene (1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone)), 5-methylresorcinol (orcinol), urushiol, pyrogallol, phloroglucinol, hydroxyhydroquinone, hydroxynaphthalene, hydroxyanthracene, hydroxypyridine, and furfuryl alcohol. Preferred phenols are phenol, resorcinol, phloroglucinol, 1,5-dihydroxynaphthalene, and furfuryl alcohol, with resorcinol being more preferred. One type of phenol may be used alone, or two or more types may be used in combination.

[0047] The polymer may be one obtained by reacting a phenol with formaldehyde, or one obtained by reacting a phenol with a polymer of formaldehyde (for example, paraformaldehyde).

[0048] The polymer may be a polymer produced by an acid catalyst or a polymer produced by a base catalyst, but is preferably a polymer produced by an acid catalyst.

[0049] The fired resin material may be any material that has been fired under conditions that allow amorphous carbon to be formed. By appropriately changing the firing conditions as described below, a porous carbon material having the above-described properties can be obtained.

[0050] The porous carbon material of this embodiment can be produced, for example, by the following production method.

[0051] (Method for Producing Porous Carbon Material) The method for producing a porous carbon material of the present embodiment includes a preparation step of preparing a resin molded body containing a resin material serving as a carbon source, a first template, and a second template, and a firing step of firing the resin molded body to obtain a porous carbon material.

[0052] In this embodiment, the first template includes amphiphilic molecules, and the second template includes latex particles. Also, in this embodiment, the calcination step includes calcination at 1500° C. or higher.

[0053] According to the production method of this embodiment, a first group of pores is formed by the first template, and a second group of pores is formed by the second template. Furthermore, according to the production method of this embodiment, the firing step includes firing at 1500°C or higher, which makes it easier to obtain a porous carbon material that satisfies the above-mentioned requirement regarding peak (i). Therefore, according to the production method of this embodiment, the porous carbon material of this embodiment can be easily produced.

[0054] FIG. 1( a ) is a cross-sectional view schematically showing an example of a resin molded body, and FIG. 1( b ) is a cross-sectional view schematically showing an example of a porous carbon material.

[0055] 1(a) contains a resin material 11 and latex particles 12. The resin material 11 also contains micelles (not shown) of amphipathic molecules. When such a resin material 10 is baked, the micelles in the resin material 11 are burned away, forming micropores corresponding to the first pore group, and the latex particles 12 are burned away, creating voids and forming a branched higher-order structure.

[0056] 1(b) has a higher-order structure formed by the burning of latex particles 12, and micropores formed by the burning of micelles in the porous carbon material 20. Such a porous carbon material 20 has a pore size distribution with a first peak due to the micropores and a second peak due to the higher-order structure.

[0057] Each step of the manufacturing method of this embodiment will be described in detail below.

[0058] In the preparation step, a resin molded body containing a resin material serving as a carbon source, a first template, and a second template is prepared.

[0059] The resin material may be any material that can form amorphous carbon by firing. Examples of the resin material include the same materials as those mentioned above.

[0060] The first template may be any template that contains amphiphilic molecules and is capable of forming a first group of pores that form a first peak.

[0061] The amphiphilic molecule is preferably a molecule capable of forming micelles in water, and the micelles formed by such amphiphilic molecules can be dispersed in a resin material to easily obtain a resin molded product containing the first template.

[0062] Any known amphiphilic molecule capable of forming micelles in water can be used without any particular limitation as the amphiphilic molecule, including, for example, a diblock copolymer having a hydrophilic block-hydrophobic block structure, a triblock copolymer having a hydrophilic block-hydrophobic block-hydrophilic block structure, and a triblock copolymer having a hydrophobic block-hydrophilic block-hydrophobic block structure.

[0063] Examples of hydrophilic blocks include polyethylene oxide blocks, polyvinylpyridine blocks, and polymethyl methacrylate blocks. Of these, polyethylene oxide blocks are preferred. The number of ethylene oxide units in the polyethylene oxide block is preferably 20 to 150, and more preferably 90 to 120. That is, the number of ethylene oxide units in the polyethylene oxide block may be, for example, 20 to 150, 20 to 120, 90 to 150, or 90 to 120.

[0064] Examples of hydrophobic blocks include polypropylene oxide blocks, hydrocarbon blocks, and polystyrene blocks. Among these, polypropylene oxide blocks are preferred. The number of propylene oxide units in the polypropylene oxide block is preferably 30 to 100, and more preferably 60 to 80. That is, the number of propylene oxide units in the polypropylene oxide block may be, for example, 30 to 100, 30 to 80, 60 to 100, or 60 to 80.

[0065] The amphiphilic molecule is preferably a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.

[0066] In this embodiment, the pore diameter of the first pore group (i.e., the peak position of the first peak) can be adjusted by adjusting the particle diameter of the micelles formed by the amphiphilic molecules. In other words, the amphiphilic molecules may be capable of forming micelles that serve as a template (first template) for forming a pore group (first pore group) having a pore diameter peak (first peak) in the range of 3 nm or more and less than 10 nm.

[0067] The second template may be any template that contains latex particles and is capable of forming a second group of pores that form a second peak.

[0068] The average particle size of the latex particles is not particularly limited as long as it is within a range that allows the formation of the second group of pores, and may be, for example, 50 nm or more, and preferably 100 nm or more. The average particle size of the latex particles may be, for example, 5 μm or less, and preferably 1 μm or less. In this specification, the average particle size of the latex particles refers to the median diameter measured by a laser diffraction / scattering method. That is, the average particle size of the latex particles may be, for example, 50 nm to 5 μm, 50 nm to 1 μm, 100 nm to 5 μm, or 100 nm to 1 μm.

[0069] In this embodiment, the pore diameter of the second pore group (i.e., the peak position of the second peak) can be adjusted by adjusting the particle diameter of the latex particles. In other words, the latex particles may function as a template (second template) for forming a pore group (second pore group) having a pore diameter peak (second peak) in the range of 10 nm to 1 μm.

[0070] The resin constituting the latex particles is not particularly limited as long as it is burned away when the resin molded body is baked. Examples of the resin constituting the latex particles include polystyrene resin and polymethyl methacrylate resin.

[0071] In the preparation step, the blending amount of the first template may be, for example, 30 parts by mass or more, preferably 40 parts by mass or more, and more preferably 50 parts by mass or more, per 100 parts by mass of the resin material. Furthermore, in the preparation step, the blending amount of the first template may be, for example, 140 parts by mass or less, preferably 120 parts by mass or less, and more preferably 100 parts by mass or less, per 100 parts by mass of the resin material. That is, the blending amount of the first template in the preparation step may be, for example, 30 to 140 parts by mass, 30 to 120 parts by mass, 30 to 100 parts by mass, 40 to 140 parts by mass, 40 to 120 parts by mass, 40 to 100 parts by mass, 50 to 140 parts by mass, 50 to 120 parts by mass, or 50 to 100 parts by mass, per 100 parts by mass of the resin material.

[0072] By adjusting the amount of the first template, it is possible to adjust the pore volume of pores having a pore diameter of 3 nm or more and less than 10 nm. That is, in this embodiment, the amount of the first template may be appropriately adjusted so that the pore volume of pores having a pore diameter of 3 nm or more and less than 10 nm in the porous carbon material falls within the above-mentioned preferred range.

[0073] In the preparation step, the blending amount of the second template may be, for example, 50 parts by mass or more, and preferably 100 parts by mass or more, relative to 100 parts by mass of the resin material. Furthermore, in the preparation step, the blending amount of the second template may be, for example, 1500 parts by mass or less, and preferably 1000 parts by mass or less, relative to 100 parts by mass of the resin material. That is, the blending amount of the second template in the preparation step may be, for example, 50 to 1500 parts by mass, 50 to 1000 parts by mass, 100 to 1500 parts by mass, or 100 to 1000 parts by mass, relative to 100 parts by mass of the resin material.

[0074] By adjusting the amount of the second template, it is possible to adjust the pore volume of pores having a pore diameter of 10 nm or more and 1 μm or less. That is, in this embodiment, the amount of the second template may be appropriately adjusted so that the pore volume of pores having a pore diameter of 10 nm or more and 1 μm or less in the porous carbon material falls within the above-mentioned preferred range.

[0075] In a preferred embodiment (hereinafter referred to as the first embodiment), the preparation step may include a resin material formation step of forming a resin material in a dispersion containing micelles formed by amphipathic molecules, latex particles, and an aqueous solvent to obtain a precipitate containing the micelles, latex particles, and resin material, and a drying step of drying the precipitate to obtain a resin molded product containing the resin material, amphipathic molecules, and latex particles.

[0076] In the resin material formation step, for example, the resin material may be formed from a precursor of the resin material in a dispersion liquid. Here, the precursor of the resin material may be, for example, a monomer that forms the resin material by polymerization, a polymer that forms the resin material by modification, or the like.

[0077] The aqueous solvent is a solvent containing water and may further contain an organic solvent that is compatible with water, such as alcohols such as methanol, ethanol, 1-propanol, and 2-propanol.

[0078] The resin material forming step may be, for example, a step of polymerizing a phenol and formaldehyde in a dispersion liquid to obtain a precipitate containing a polymer of the phenol and formaldehyde, micelles, and latex particles.

[0079] The polymerization of the phenol and formaldehyde may be carried out in the presence of a polymerization catalyst. The polymerization catalyst may be an acid catalyst or a base catalyst, with an acid catalyst being preferred. That is, the dispersion may contain a polymerization catalyst (an acid catalyst or a base catalyst), with an acid catalyst being preferred.

[0080] Examples of acid catalysts include hydrochloric acid, acetic acid, oxalic acid, sulfonic acid, etc. Examples of base catalysts include sodium hydroxide, ammonia, amines, etc.

[0081] Amount C of phenols provided in dispersion １ (mol) and the amount of formaldehyde C ２ (mol) C １ / C ２ may be, for example, 0.1 or more, and preferably 0.3 or more. １ / C ２may be, for example, 1.0 or less, and is 0.9 or less. That is, the ratio C １ / C ２ may be, for example, 0.1 to 1.0, 0.1 to 0.9, 0.3 to 1.0, or 0.3 to 0.9.

[0082] The reaction conditions for the polymerization of phenols and formaldehyde are not particularly limited. For example, the reaction temperature may be 20 to 80° C., and the reaction time may be 10 minutes to 96 hours.

[0083] In the drying step, the precipitate is collected and the aqueous solvent is removed to obtain a resin molded product. The drying conditions in the drying step are not particularly limited, and the drying temperature may be, for example, 20 to 80°C.

[0084] In another preferred embodiment (second embodiment), the preparation step may include an impregnation step of impregnating the latex particle aggregates with a dispersion containing micelles formed by amphiphilic molecules, a resin material (or a precursor thereof), and an aqueous solvent, and a drying step of removing the aqueous solvent.

[0085] The latex particle agglomerates may be randomly aggregated latex particles or regularly arranged latex particles, and may be, for example, colloidal crystals.

[0086] The impregnation step may be, for example, a step of impregnating a mass of latex particles with a dispersion liquid containing micelles, a phenol, formaldehyde, and an aqueous solvent.

[0087] The dispersion may further contain a polymerization catalyst (an acid catalyst or a base catalyst), and preferably further contains an acid catalyst.

[0088] Amount C of phenols provided in dispersion １ (mol) and the amount of formaldehyde C ２ (mol) C １ / C ２ may be the same as in the first embodiment.

[0089] In the second embodiment, the drying step may be a step of removing the aqueous solvent, or a step of forming a resin material from a precursor of the resin material and then removing the aqueous solvent.

[0090] For example, the drying step may be a step of obtaining a resin molded product containing a polymer of phenols and formaldehyde, aggregates of latex particles, and micelles of amphiphilic molecules by polymerizing phenols and formaldehyde and removing the aqueous solvent.

[0091] The firing step is a step of firing the resin molded body to obtain a porous carbon material.

[0092] The firing step may include, for example, a first firing step in which firing is performed at a firing temperature of less than 1200°C, and a second firing step in which firing is performed at a firing temperature of 1500°C or higher.

[0093] The first firing step may be a step of firing the resin molded body to obtain a first fired body. The firing in the first firing step (hereinafter referred to as firing (i)) may be performed under conditions that allow the resin material in the resin molded body to form amorphous carbon, and the firing temperature may be less than 1200°C.

[0094] The firing temperature in firing (i) may be any temperature at which the resin material in the resin molded body can form amorphous carbon, and may be, for example, 400° C. or higher, 600° C. or higher, or 800° C. or higher. The firing temperature in firing (i) may be lower than 1200° C., and may be 1100° C. or lower, or 1000° C. or lower.

[0095] The firing time of firing (i) (the time during which the target is maintained at the firing temperature) is not particularly limited and may be, for example, 30 minutes or more, 1 hour or more, 2 hours or more, or 3 hours or more. The firing time of firing (i) may be, for example, 7 hours or less, 6 hours or less, 5 hours or less, or 4 hours or less.

[0096] The calcination (i) may be calcination under an inert gas atmosphere (for example, under a nitrogen atmosphere, under an argon atmosphere, etc.).

[0097] The first fired body obtained in the first firing step may be a block-shaped porous carbon material, i.e., in the first fired body, amorphous carbon may be formed from the resin material, and the first template and the second template may be burned away.

[0098] The second firing step may be a step of firing the first fired body to obtain the porous carbon material of the present embodiment. The firing in the second firing step (hereinafter referred to as firing (ii)) may be performed at a firing temperature of 1500°C or higher.

[0099] The firing step may further include a pulverization step of pulverizing the first fired body, and in this case, the second firing step may be a step of firing the pulverized product of the first fired body to obtain the porous carbon material of this embodiment. The pulverization method is not particularly limited, and may be, for example, pulverization using a mortar. The degree of pulverization may be appropriately changed depending on the application of the porous carbon material, etc.

[0100] The firing temperature in the firing (ii) is 1500° C. or higher, and from the viewpoint of making it easier to obtain a porous carbon material that satisfies the above-mentioned properties, it may be 1600° C. or higher, 1700° C. or higher, 1800° C. or higher, 1900° C. or higher, or 2000° C. or higher. The firing temperature in the firing (ii) may be, for example, 3000° C. or lower, 2900° C. or lower, 2800° C. or lower, or 2700° C. or lower.

[0101] The calcination time of calcination (ii) (the time during which the target is maintained at the calcination temperature) is not particularly limited and may be, for example, 0.5 hours or more, 1 hour or more, 2 hours or more, or 3 hours or more. The calcination time of calcination (ii) may be, for example, 7 hours or less, 6 hours or less, 5 hours or less, or 4 hours or less.

[0102] The calcination (ii) may be performed under an inert gas atmosphere (e.g., under a nitrogen atmosphere, under an argon atmosphere, etc.), and particularly when the calcination temperature is 2000°C or higher, calcination may be performed under an argon atmosphere from the viewpoint of suppressing gas reactions.

[0103] The use of the porous carbon material of this embodiment is not particularly limited, and it can be used for known uses of carbon materials without particular limitation.

[0104] The porous carbon material of this embodiment can allow the reaction sites to function effectively even when coated with a coating material, and therefore can be particularly suitably used in applications where the material is coated with a coating material.

[0105] For example, the porous carbon material of this embodiment can be suitably used as a cathode catalyst support for a polymer electrolyte fuel cell. A cathode catalyst is used by supporting an active metal (e.g., platinum) on the porous carbon material and coating it with an ionomer. According to the porous carbon material of this embodiment, the active metal supported inside the first group of pores can fully exhibit catalytic activity without being poisoned by the ionomer.

[0106] The porous carbon material of this embodiment can also be suitably used as an electrode material for capacitors, an electrode material for secondary batteries, a gas adsorption material, and the like.

[0107] The porous carbon material of this embodiment has excellent oxidation resistance. The oxidation resistance can be evaluated, for example, by the 5% weight loss temperature. The 5% weight loss temperature of the porous carbon material of this embodiment may be, for example, 500°C or higher, 550°C or higher, 600°C or higher, 620°C or higher, or 650°C or higher.

[0108] In this specification, the 5% weight loss temperature of a porous carbon material is measured by the following method. <Measurement of 5% weight loss temperature> After weighing out about 5 mg of a porous carbon material, the sample is placed in a thermogravimetric / differential calorimeter (STA2500 manufactured by NETZSCH), and the weight loss is measured from 25°C to 1000°C under a heating rate of 10°C / min and an air flow of 20 mL / min. The weight at 25°C on the obtained weight curve is taken as 100%, and the temperature at which 5% weight loss occurs is taken as the 5% weight loss temperature.

[0109] [Porous carbon material satisfying (B)] The porous carbon material of this embodiment has a pore size distribution measured by mercury intrusion porosimetry, in which a first peak is located in a pore size range of 3 nm or more and less than 10 nm, and a second peak is located in a pore size range of 10 nm or more and 1 μm or less. １ ~A ２ "having a peak in the range of pore diameter A１ ~A ２ This means that a peak having a peak top in the range of

[0110] The porous carbon material of this embodiment can also be said to have a first group of pores forming a first peak and a second group of pores forming a second peak. The porous carbon material of this embodiment can also be said to have a microstructure formed by the first group of pores and a higher-order structure formed by the second group of pores.

[0111] The porous carbon material of this embodiment allows the reaction substrates to move efficiently through the wide pores of the higher-order structure, so that the reaction substrates can be efficiently transported to the reaction sites and the reaction products can be efficiently discharged. Furthermore, the porous carbon material of this embodiment has a first group of pores, which allows a high specific surface area and efficient support of the active metal. Furthermore, in this embodiment, by coating the higher-order structure with a coating material, the coating material can be provided on the porous carbon material without poisoning or burying the active metal supported within the microstructure. Thus, the porous carbon material of this embodiment allows the reaction substrates to easily reach the reaction sites, and the reaction sites can function effectively even when coated with a coating material. Therefore, the porous carbon material of this embodiment is suitable as a catalyst support.

[0112] The first peak is located in the pore diameter range of 3 nm or more and less than 10 nm, and preferably in the pore diameter range of 4 nm or more and 7 nm or less. The second peak is located in the pore diameter range of 10 nm or more and 1 μm or less, and preferably in the pore diameter range of 20 nm or more and 200 nm or less. This makes the above-mentioned effects more pronounced.

[0113] The first peak and the second peak may each have a peak value of 0.1 mL / g or more, preferably 0.5 mL / g or more, and may each have a peak value of 4 mL / g or less, or 2 mL / g or less.

[0114] The first peak and the second peak are preferably the peak with the highest peak value (Peak A) or the peak with the second highest peak value (Peak B) among the peaks located in the pore diameter range of 3 nm to 1 μm. That is, when the first peak is Peak A, the second peak is preferably Peak B, and when the first peak is Peak B, the second peak is preferably Peak A.

[0115] In this specification, the pore size distribution of the porous carbon material is measured by mercury intrusion porosimetry. More specifically, it is measured by the following method. The pore size distribution is represented by a pore size distribution curve with the horizontal axis representing the pore size (pore diameter) (logarithmic scale) and the vertical axis representing the log differential pore volume (linear scale). <Measurement of Pore Size Distribution> First, 40 to 80 mg of the porous carbon material is collected in a 5 cc measurement cell. Next, using an automatic mercury porosimeter (Shimadzu Corporation-Micromeritics Autopore V9620), the mercury pressure is increased from 1 psia to 60,000 psia, and the amount of mercury intrusion is measured. The pore size distribution is then determined from the obtained pressure vs. intrusion amount curve. The mercury contact angle is 130 degrees, and the mercury surface tension is 485 dynes / cm.

[0116] The porous carbon material of this embodiment has a relative pressure (P / P ０ ) is 0.2, the amount of nitrogen adsorption is 10 cm ３ / g or more 250cm ３ / g or less.

[0117] Relative pressure (P / P ０ ) is 0.2, the porous carbon material having a small nitrogen adsorption capacity is said to be a porous carbon material having a small number of micropores. ３ / g or less, there are few fine pores that are likely to be the starting points of deterioration, and it is thought that excellent oxidation resistance is realized. ３ / g or more, the presence of fine pores makes it easier to support a catalyst, and it is thought that the porous carbon material can be suitably used as a catalyst support. Such a porous carbon material can be formed, for example, by the production method described below.

[0118] Relative pressure (P / P ０ ) is 0.2, the amount of nitrogen adsorption is 250 cm ３ / g or less, and from the viewpoint of more significantly exhibiting the above-mentioned effect, ３ / g or less, 180cm ３ / g or less, 170cm ３ / g or less, 160cm ３ / g or less, 150cm ３ / g or less, 140cm ３ / g or less, 130cm ３ / g or less or 120 cm ３ / g or less.

[0119] Relative pressure (P / P ０ When the nitrogen adsorption rate is 0.2, the nitrogen adsorption rate is 10 cm ３ / g or more, and from the viewpoint of exhibiting the above effect more significantly, 20 cm ３ / g or more, 30cm ３ / g or more, 40cm ３ / g or more or 50 cm ３ / g or more.

[0120] In the porous carbon material of this embodiment, the relative pressure (P / P ０ ) is 0.8, the nitrogen adsorption amount (N ０ ) relative pressure (P / P ０ The nitrogen adsorption amount (N １ ) ratio (N １ / N ０ ) may be, for example, 0.6 or less, and from the viewpoint of more significantly achieving the above-mentioned effects, it may be 0.5 or less or 0.4 or less.

[0121] In this specification, the nitrogen adsorption amount of a porous carbon material is measured by the following method. <Measurement of nitrogen adsorption amount> A porous carbon material is dried under vacuum at 300°C for 3 hours using a pretreatment device (BELPREP-VAC II manufactured by Microtrac-Bell). Next, a nitrogen adsorption isotherm is measured using a high-precision gas / vapor adsorption amount measuring device (BELSORP MAX II manufactured by Microtrac-Bell). The nitrogen adsorption amount at a predetermined relative pressure is then calculated from the obtained nitrogen adsorption isotherm.

[0122] The porous carbon material of this embodiment may have, in an X-ray diffraction pattern, a peak (i) having a half-width of 0.6° or less and a peak top within the range of 2θ=25° to 27°.

[0123] It can be said that a porous carbon material having the above peak (i) has a highly crystalline region formed in part. The porous carbon material having a highly crystalline region realizes better oxidation resistance. Such a porous carbon material can be formed, for example, by a firing step including firing at 1100°C or higher, as shown in the manufacturing method described below.

[0124] The half width of peak (i) may be, for example, 0.6° or less, 0.5° or less, 0.4° or less, or 0.3° or less. The half width of peak (i) may be, for example, 0.1° or more, 0.2° or more, or 0.3° or more. The crystallite diameter of peak (i) may be, for example, 60 nm or less, 55 nm or less, 50 nm or less, or 45 nm or less. The crystallite diameter of peak (i) may be, for example, 20 nm or more.

[0125] The porous carbon material of this embodiment may further have a peak (ii) in its X-ray diffraction pattern that has a half-width of 9° or less and partially overlaps with the peak (i). That is, peak (i) can also be said to be a peak that exists at a position overlapping with peak (ii). The half-width of peak (ii) may be, for example, 8.5° or less. The half-width of peak (ii) may be, for example, 1.0° or more, 4.0° or more, or 7.0° or more. The peak height ratio of peak (i) to peak (ii) may be, for example, 0.1 or more, 0.2 or more, or 0.3 or more. The peak height ratio of peak (i) to peak (ii) may be, for example, 5.0 or less, 3.0 or less, or 1.5 or less.

[0126] In this specification, the X-ray diffraction pattern of a porous carbon material is measured by the following method. <Measurement of X-ray diffraction pattern> A porous carbon material is placed on a Si anti-reflective sample holder (filled portion: 20 mm × 18 mm × 0.2 mmt), and a measurement sample is obtained by spreading it with a glass plate so that the sample surface (the height of the portion filled with the sample) coincides with the reference plane of the sample holder. The obtained measurement sample is placed in an X-ray diffractometer (Rigaku Corporation, X-ray diffractometer Ultima IV), and the X-ray diffraction pattern is measured at room temperature using a Cu-Kα X-ray source, a standard sample stage, a focusing optical system, a semiconductor detector (D / teX Ultra), and an anti-scatter tube (slit width 4 mm, length approximately 9 cm) with a measurement angle range of 2θ = 10° to 70°, a sampling width of 0.02°, and a scan rate of 5° / min.

[0127] <Calculation of Half-Width, Crystallite Diameter, and Peak Height Ratio> The powder X-ray diffraction pattern comprehensive analysis software Jade 9 was used to calculate the half-width and crystallite diameter. Peaks (i) and (ii) are assumed to exist in the range of 2θ = 10° to 40° in the X-ray diffraction pattern, and peak separation is performed to calculate the half-width (β measured), peak position 2θ (°), and peak height of peaks (i) and (ii) derived from the Cu-Kα1 line. However, when a sharp peak (i) is not observed in the X-ray diffraction pattern, peak separation is performed assuming that only peak (ii) exists. In this case, the peak shape is a pseudo-Voigt function, and the background shape is a Cubic Spline (fixed). The background is drawn by manually specifying six points as binding points (for example, in Figure 3, 2θ = 10°, 11°, 12.3°, 15°, 35°, and 40°). When calculating the half width and crystallite diameter, the half width derived from the instrument is corrected using the following method. Specifically, the same measurement as in the above <X-ray diffraction pattern measurement> is performed on Si powder (NIST SRM 640c), and full pattern fitting (WPPF) is performed on the measurement results using Jade 9 to obtain the half width curve of Si. Using the obtained half width curve of Si, the half width of Si at the peak position 2θ of peak (i) in the porous carbon material is calculated, and this is taken as the half width derived from the instrument corresponding to peak (i) (β instrument). This value is substituted into the following formula for correction, and the half width derived from the sample of peak (i) (β sample) is calculated. Similarly, in the case of peak (ii), the half width of Si at the peak position 2θ of peak (ii) is calculated, and this is taken as the half width derived from the instrument corresponding to peak (ii) (β instrument). This value is substituted into the following formula for correction, and the half width derived from the sample of peak (ii) (β sample) is calculated. (β sample) ２ = [(β measured) ２ - (β device) ２] Next, the half width of peak (i) (β sample) is substituted into the following Scherrer formula to calculate the crystallite size. At this time, the Scherrer constant K is 1, the measurement X-ray wavelength λ is 0.154 nm, and the peak position of peak (i) obtained by peak separation in Jade 9 is used as the value of the diffraction angle 2θ (°). Crystallite size = (K × λ) / (β × cos θ) The peak height ratio is calculated by substituting the peak height of peak (i) and the peak height of peak (ii) obtained by the above peak separation into the following formula. (Peak height ratio) = (peak height of peak (i)) / (peak height of peak (ii))

[0128] The porous carbon material of this embodiment may have a surface oxygen concentration of 6 at % or less as measured by XPS.

[0129] A porous carbon material with a low surface oxygen concentration can be said to be a porous carbon material with a small amount of surface functional groups. When the surface oxygen concentration is low, the amount of surface functional groups in the porous carbon material is small, and the surface of the porous carbon material becomes more hydrophobic. As a result, when the porous carbon material is used as a catalyst support, reaction products are more likely to be discharged from the inside of the porous carbon material. Such a porous carbon material can be formed, for example, by a calcination step including calcination at 1100°C or higher, as shown in the manufacturing method described below.

[0130] The surface oxygen concentration of the porous carbon material of this embodiment may be, for example, 6 at% or less, and from the viewpoint of more significantly achieving the above-mentioned effect, it may be 4.5 at% or less, 3 at% or less, 2 at% or less, 1 at% or less, or 0.5 at% or less. The lower limit of the surface oxygen concentration of the porous carbon material of this embodiment is not particularly limited, and may be 0 at%.

[0131] The porous carbon material of this embodiment may have a surface carbon concentration of 94 at % or more as measured by XPS.

[0132] A porous carbon material with a high surface carbon concentration can be said to have a small amount of surface functional groups. When the surface carbon concentration is high, the amount of surface functional groups in the porous carbon material is small, and the surface of the porous carbon material becomes more hydrophobic. As a result, when the porous carbon material is used as a catalyst support, reaction products are more likely to be discharged from the inside of the porous carbon material. Such a porous carbon material can be formed, for example, by a calcination step including calcination at 1100°C or higher, as shown in the manufacturing method described below.

[0133] The surface carbon concentration of the porous carbon material of this embodiment may be, for example, 94 at% or more, and from the viewpoint of more significantly achieving the above-mentioned effect, it may be 95.5 at% or more, 97 at% or more, 98 at% or more, 99 at% or more, or 99.5 at% or more. The upper limit of the surface carbon concentration of the porous carbon material of this embodiment is not particularly limited, and may be 100 at%.

[0134] In the porous carbon material of this embodiment, the sum of the surface oxygen concentration and the surface carbon concentration is 100 at %, and for example, when the surface oxygen concentration is 2 at %, the surface carbon concentration is 98 at %.

[0135] In this specification, the surface oxygen concentration and surface carbon concentration of a porous carbon material are measured by the following method. <Measurement of Surface Oxygen Concentration and Surface Carbon Concentration> The surface oxygen concentration and surface carbon concentration are determined by XPS measurement using an X-ray photoelectron spectrometer (K-Alpha type X-ray photoelectron spectrometer manufactured by Thermo Instruments). Specifically, the porous carbon material is filled into a recess (φ3 mm × 1 mm thick) of a powder sample holder, and the sample surface is flattened and crushed for measurement. The excitation source used for the measurement is an Al-Kα with a monochromator, the X-ray irradiation area is 400 × 200 μm (elliptical in shape), the detection angle is 90° (perpendicular to the sample surface), the pass energy is 50 eV, and the number of scans is 5. The elements to be detected are oxygen (O) and carbon (C), and their narrow spectra are measured. The surface oxygen concentration and the surface carbon concentration are calculated by integrating O in the O1s range (approximately 540 to 527 eV) and C in the C1s range (approximately 293 to 280 eV). Charge correction is performed using the C1s peak (284.8 eV) as the reference peak, and the background is specified by Shirley. The surface oxygen concentration and the surface carbon concentration are normalized so that the sum of them is 100 at%.

[0136] The specific surface area of ​​the porous carbon material of this embodiment is, for example, 200 m ２ / g or more, and ２ / g or more, 300m ２ / g or more or 350m ２ / g or more. This improves the dispersibility of the active metal on the porous carbon material when the active metal is supported, and reaction sites tend to be formed more efficiently. The specific surface area of ​​the porous carbon material of this embodiment may be, for example, 1800 m ２ / g or less, and ２ / g or less, 1000m ２ / g or less, 700m ２ / g or less or 500m ２ / g or less. This tends to further improve the strength of the porous structure of the porous carbon material and make the porous structure more stable.

[0137] In this specification, the specific surface area of ​​a porous carbon material refers to a value measured by a nitrogen adsorption method. More specifically, it is measured by the following method in accordance with JIS Z8830. <Measurement of specific surface area> A porous carbon material is dried under vacuum at 300°C for 3 hours using a pretreatment device (BELPREP-VAC II, manufactured by Microtrac-Bell). Next, a nitrogen adsorption isotherm is measured using an automatic specific surface area measuring device (BELSORP MAX II, manufactured by Microtrac-Bell). Then, the specific surface area is calculated from the obtained nitrogen adsorption isotherm using the BET method.

[0138] The porous carbon material of the present embodiment may include, for example, a fired product of a resin material. The porous carbon material of the present embodiment may also be, for example, a fired product of a resin molded product containing a resin material.

[0139] The resin material may be any material that can form amorphous carbon by firing. Examples of the resin material include the same resin materials as those described above regarding the porous carbon material that satisfies (A).

[0140] The fired resin material may be any material that has been fired under conditions that allow amorphous carbon to be formed. By appropriately changing the firing conditions as described below, a porous carbon material having the above-described properties can be obtained.

[0141] The porous carbon material of this embodiment can be produced, for example, by the following production method.

[0142] (Method for Producing Porous Carbon Material) The method for producing a porous carbon material of the present embodiment includes a preparation step of preparing a resin molded body containing a resin material serving as a carbon source, a first template, and a second template, and a firing step of firing the resin molded body to obtain a porous carbon material.

[0143] In this embodiment, the first template includes amphiphilic molecules, the second template includes latex particles, and the calcination step includes calcination at 1100° C. or higher.

[0144] According to the production method of this embodiment, a first group of pores is formed by the first template, and a second group of pores is formed by the second template. Furthermore, according to the production method of this embodiment, the firing step includes firing at 1100°C or higher, which makes it easier to obtain a porous carbon material that satisfies the above-mentioned specification regarding the nitrogen adsorption amount. Therefore, according to the production method of this embodiment, the porous carbon material of this embodiment can be easily produced.

[0145] FIG. 1( a ) is a cross-sectional view schematically showing an example of a resin molded body, and FIG. 1( b ) is a cross-sectional view schematically showing an example of a porous carbon material.

[0146] 1(a) contains a resin material 11 and latex particles 12. The resin material 11 also contains micelles (not shown) of amphipathic molecules. When such a resin material 10 is baked, the micelles in the resin material 11 are burned away, forming micropores corresponding to the first pore group, and the latex particles 12 are burned away, creating voids and forming a branched higher-order structure.

[0147] 1(b) has a higher-order structure formed by the burning of latex particles 12, and micropores formed by the burning of micelles in the porous carbon material 20. Such a porous carbon material 20 has a pore size distribution with a first peak due to the micropores and a second peak due to the higher-order structure.

[0148] Each step of the manufacturing method of this embodiment will be described in detail below.

[0149] In the preparation step, a resin molded body containing a resin material serving as a carbon source, a first template, and a second template is prepared.

[0150] Examples of the resin material, the first template, and the second template may be the same as the resin material, the first template, and the second template described above regarding the porous carbon material that satisfies (A).

[0151] The amounts of the first template and the second template blended in the preparation step may be the same as the amounts blended in the description of the porous carbon material satisfying (A) above.

[0152] In a preferred embodiment (hereinafter referred to as the first embodiment), the preparation step may include a resin material formation step of forming a resin material in a dispersion containing micelles formed by amphipathic molecules, latex particles, and an aqueous solvent to obtain a precipitate containing the micelles, latex particles, and resin material, and a drying step of drying the precipitate to obtain a resin molded product containing the resin material, amphipathic molecules, and latex particles.

[0153] The resin material forming step and drying step of the first embodiment may be the same steps as the resin material forming step and drying step of the first embodiment in the description regarding the porous carbon material satisfying (A) above.

[0154] In another preferred embodiment (second embodiment), the preparation step may include an impregnation step of impregnating the latex particle aggregates with a dispersion containing micelles formed by amphiphilic molecules, a resin material (or a precursor thereof), and an aqueous solvent, and a drying step of removing the aqueous solvent.

[0155] The impregnation step and drying step of the second embodiment may be the same steps as the resin material formation step and drying step of the second embodiment in the description of the porous carbon material satisfying (A) above, respectively.

[0156] The firing step is a step of firing the resin molded body to obtain a porous carbon material.

[0157] The firing step includes firing at 1100°C or higher. The firing temperature may be 1300°C or higher, 1500°C or higher, 1700°C or higher, 1900°C or higher, or 2000°C or higher. The firing temperature may be, for example, 3000°C or lower, or 2700°C or lower. The firing may be performed in an inert gas atmosphere (for example, a nitrogen atmosphere, an argon atmosphere, etc.).

[0158] The firing step may include, for example, a first firing step in which firing is performed at a firing temperature of less than 1100°C, and a second firing step in which firing is performed at a firing temperature of 1100°C or higher.

[0159] The first firing step may be a step of firing the resin molded body to obtain a first fired body. The firing in the first firing step (hereinafter referred to as firing (i)) may be performed under conditions that allow the resin material in the resin molded body to form amorphous carbon, and the firing temperature may be less than 1100°C.

[0160] The firing temperature in firing (i) may be any temperature at which the resin material in the resin molded body can form amorphous carbon, and may be, for example, 400° C. or higher, 600° C. or higher, or 800° C. or higher. The firing temperature in firing (i) may be lower than 1100° C. and 1000° C. or lower.

[0161] The firing time of firing (i) (the time during which the target is maintained at the firing temperature) is not particularly limited and may be, for example, 30 minutes or more, 1 hour or more, 2 hours or more, or 2.5 hours or more. The firing time of firing (i) may be, for example, 7 hours or less, 6 hours or less, 5 hours or less, or 4 hours or less.

[0162] The calcination (i) may be calcination under an inert gas atmosphere (for example, under a nitrogen atmosphere, under an argon atmosphere, etc.).

[0163] The first fired body obtained in the first firing step may be a block-shaped porous carbon material, i.e., in the first fired body, amorphous carbon may be formed from the resin material, and the first template and the second template may be burned away.

[0164] The second firing step may be a step of firing the first fired body to obtain the porous carbon material of the present embodiment. The firing in the second firing step (hereinafter referred to as firing (ii)) may be performed at a firing temperature of 1100°C or higher.

[0165] The firing step may further include a pulverization step of pulverizing the first fired body, and in this case, the second firing step may be a step of firing the pulverized product of the first fired body to obtain the porous carbon material of this embodiment. The pulverization method is not particularly limited, and may be, for example, pulverization using a mortar. The degree of pulverization may be appropriately changed depending on the application of the porous carbon material, etc.

[0166] The firing temperature in the firing (ii) is 1100° C. or higher, and from the viewpoint of making it easier to obtain a porous carbon material that satisfies the above-mentioned properties, it may be 1300° C. or higher, 1500° C. or higher, 1700° C. or higher, 1900° C. or higher, or 2000° C. or higher. The firing temperature in the firing (ii) may be, for example, 3000° C. or lower, 2900° C. or lower, 2800° C. or lower, or 2700° C. or lower.

[0167] The calcination time of calcination (ii) (the time during which the target is maintained at the calcination temperature) is not particularly limited and may be, for example, 0.5 hours or more, 1 hour or more, 2 hours or more, or 3 hours or more. The calcination time of calcination (ii) may be, for example, 7 hours or less, 6 hours or less, 5 hours or less, or 4 hours or less.

[0168] The calcination (ii) may be performed under an inert gas atmosphere (e.g., under a nitrogen atmosphere, under an argon atmosphere, etc.), and particularly when the calcination temperature is 2000°C or higher, calcination may be performed under an argon atmosphere from the viewpoint of suppressing gas reactions.

[0169] The use of the porous carbon material of this embodiment is not particularly limited, and it can be used for known uses of carbon materials without particular limitation.

[0170] The porous carbon material of this embodiment can allow the reaction sites to function effectively even when coated with a coating material, and therefore can be particularly suitably used in applications where the material is coated with a coating material.

[0171] For example, the porous carbon material of this embodiment can be suitably used as a cathode catalyst support for a polymer electrolyte fuel cell. A cathode catalyst is used by supporting an active metal (e.g., platinum) on the porous carbon material and coating it with an ionomer. According to the porous carbon material of this embodiment, the active metal supported inside the first group of pores can fully exhibit catalytic activity without being poisoned by the ionomer.

[0172] The porous carbon material of this embodiment can also be suitably used as an electrode material for capacitors, an electrode material for secondary batteries, a gas adsorption material, and the like.

[0173] The porous carbon material of this embodiment has excellent oxidation resistance. The oxidation resistance can be evaluated, for example, by the 5% weight loss temperature. The 5% weight loss temperature of the porous carbon material of this embodiment may be, for example, 500°C or higher, or may be 520°C or higher, 540°C or higher, 560°C or higher, 580°C or higher, or 600°C or higher.

[0174] In this specification, the 5% weight loss temperature of a porous carbon material is measured by the following method. <Measurement of 5% weight loss temperature> After weighing out about 5 mg of a porous carbon material, the sample is placed in a thermogravimetric / differential calorimeter (STA2500 manufactured by NETZSCH), and the weight loss is measured from 25°C to 1000°C under a heating rate of 10°C / min and an air flow of 20 mL / min. The weight at 25°C on the obtained weight curve is taken as 100%, and the temperature at which 5% weight loss occurs is taken as the 5% weight loss temperature.

[0175] [Porous carbon material satisfying (C)] The porous carbon material of this embodiment has, in a pore size distribution measured by mercury intrusion porosimetry, a first peak located in a pore size range of 3 nm or more and less than 10 nm, and a second peak located in a pore size range of 10 nm or more and 1 μm or less. １ ~A ２ "having a peak in the range of pore diameter A １ ~A ２ This means that a peak having a peak top in the range of

[0176] The porous carbon material of this embodiment can also be said to have a first group of pores forming a first peak and a second group of pores forming a second peak. The porous carbon material of this embodiment can also be said to have a microstructure formed by the first group of pores and a higher-order structure formed by the second group of pores.

[0177] The porous carbon material of this embodiment allows the reaction substrates to move efficiently through the wide pores of the higher-order structure, so that the reaction substrates can be efficiently transported to the reaction sites and the reaction products can be efficiently discharged. Furthermore, the porous carbon material of this embodiment has a first group of pores, which allows a high specific surface area and efficient support of the active metal. Furthermore, in this embodiment, by coating the higher-order structure with a coating material, the coating material can be provided on the porous carbon material without poisoning or burying the active metal supported within the microstructure. Thus, the porous carbon material of this embodiment allows the reaction substrates to easily reach the reaction sites, and the reaction sites can function effectively even when coated with a coating material. Therefore, the porous carbon material of this embodiment is suitable as a catalyst support.

[0178] The first peak is located in the pore diameter range of 3 nm or more and less than 10 nm, and preferably in the pore diameter range of 4 nm or more and 7 nm or less. The second peak is located in the pore diameter range of 10 nm or more and 1 μm or less, and preferably in the pore diameter range of 20 nm or more and 200 nm or less. This makes the above-mentioned effects more pronounced.

[0179] The first peak and the second peak may each have a peak value of 0.1 mL / g or more, preferably 0.5 mL / g or more, and may each have a peak value of 4 mL / g or less, or 2 mL / g or less.

[0180] The first peak and the second peak are preferably the peak with the highest peak value (Peak A) or the peak with the second highest peak value (Peak B) among the peaks located in the pore diameter range of 3 nm to 1 μm. That is, when the first peak is Peak A, the second peak is preferably Peak B, and when the first peak is Peak B, the second peak is preferably Peak A.

[0181] In this specification, the pore size distribution of the porous carbon material is measured by mercury intrusion porosimetry. More specifically, it is measured by the following method. The pore size distribution is represented by a pore size distribution curve with the horizontal axis representing the pore size (pore diameter) (logarithmic scale) and the vertical axis representing the log differential pore volume (linear scale). <Measurement of Pore Size Distribution> First, 40 to 80 mg of the porous carbon material is collected in a 5 cc measurement cell. Next, using an automatic mercury porosimeter (Shimadzu Corporation-Micromeritics Autopore V9620), the mercury pressure is increased from 1 psia to 60,000 psia, and the amount of mercury intrusion is measured. The pore size distribution is then determined from the obtained pressure vs. intrusion amount curve. The mercury contact angle is 130 degrees, and the mercury surface tension is 485 dynes / cm.

[0182] The porous carbon material of this embodiment has a surface oxygen concentration of 6 at % or less as measured by XPS.

[0183] A porous carbon material with a low surface oxygen concentration can be said to have a low amount of surface functional groups. When the surface oxygen concentration is low, the amount of surface functional groups in the porous carbon material is low, and the surface of the porous carbon material becomes more hydrophobic. As a result, when the porous carbon material is used as a catalyst support, reaction products are more likely to be discharged from the inside of the porous carbon material. Such a porous carbon material can be formed, for example, by the manufacturing method described below. Furthermore, while oxidation of carbon materials tends to occur from the surface, a porous carbon material with a low surface oxygen concentration measured by XPS can be said to have excellent oxidation resistance due to the low surface oxygen.

[0184] The surface oxygen concentration of the porous carbon material of this embodiment may be, for example, 6 at% or less, and from the viewpoint of more significantly achieving the above-mentioned effect, it may be 4.5 at% or less, 3 at% or less, 2 at% or less, 1 at% or less, or 0.5 at% or less. The lower limit of the surface oxygen concentration of the porous carbon material of this embodiment is not particularly limited, and may be 0 at%.

[0185] The porous carbon material of this embodiment may have a surface carbon concentration of 94 at % or more as measured by XPS.

[0186] A porous carbon material with a high surface carbon concentration can be said to have a small amount of surface functional groups. When the surface carbon concentration is high, the amount of surface functional groups in the porous carbon material is small, and the surface of the porous carbon material becomes more hydrophobic. As a result, when the porous carbon material is used as a catalyst support, reaction products are more likely to be discharged from the inside of the porous carbon material. Such a porous carbon material can be formed, for example, by a calcination step including calcination at 1100°C or higher, as shown in the manufacturing method described below.

[0187] The surface carbon concentration of the porous carbon material of this embodiment may be, for example, 94 at% or more, and from the viewpoint of more significantly achieving the above-mentioned effect, it may be 95.5 at% or more, 97 at% or more, 98 at% or more, 99 at% or more, or 99.5 at% or more. The upper limit of the surface carbon concentration of the porous carbon material of this embodiment is not particularly limited, and may be 100 at%.

[0188] In the porous carbon material of this embodiment, the sum of the surface oxygen concentration and the surface carbon concentration is 100 at %, and for example, when the surface oxygen concentration is 2 at %, the surface carbon concentration is 98 at %.

[0189] In this specification, the surface oxygen concentration and surface carbon concentration of a porous carbon material are measured by the following method. <Measurement of Surface Oxygen Concentration and Surface Carbon Concentration> The surface oxygen concentration and surface carbon concentration are determined by XPS measurement using an X-ray photoelectron spectrometer (K-Alpha type X-ray photoelectron spectrometer manufactured by Thermo Instruments). Specifically, the porous carbon material is filled into a recess (φ3 mm × 1 mm thick) of a powder sample holder, and the sample surface is flattened and crushed for measurement. The excitation source used for the measurement is an Al-Kα with a monochromator, the X-ray irradiation area is 400 × 200 μm (elliptical in shape), the detection angle is 90° (perpendicular to the sample surface), the pass energy is 50 eV, and the number of scans is 5. The elements to be detected are oxygen (O) and carbon (C), and their narrow spectra are measured. The surface oxygen concentration and the surface carbon concentration are calculated by integrating O in the O1s range (approximately 540 to 527 eV) and C in the C1s range (approximately 293 to 280 eV). Charge correction is performed using the C1s peak (284.8 eV) as the reference peak, and the background is specified by Shirley. The surface oxygen concentration and the surface carbon concentration are normalized so that the sum of them is 100 at%.

[0190] The porous carbon material of this embodiment may have, in an X-ray diffraction pattern, a peak (i) having a half-width of 0.6° or less and a peak top within the range of 2θ=25° to 27°.

[0191] It can be said that a porous carbon material having the above peak (i) has a highly crystalline region formed in part. The porous carbon material having a highly crystalline region realizes better oxidation resistance. Such a porous carbon material can be formed, for example, by a firing step including firing at 1100°C or higher, as shown in the manufacturing method described below.

[0192] The half width of peak (i) may be, for example, 0.6° or less, 0.5° or less, 0.4° or less, or 0.3° or less. The half width of peak (i) may be, for example, 0.1° or more, 0.2° or more, or 0.3° or more. The crystallite diameter of peak (i) may be, for example, 60 nm or less, 55 nm or less, 50 nm or less, or 45 nm or less. The crystallite diameter of peak (i) may be, for example, 20 nm or more.

[0193] The porous carbon material of this embodiment may further have a peak (ii) in its X-ray diffraction pattern, which has a half-width of 9° or less and partially overlaps with the peak (i). In other words, the peak (i) can be said to be a peak that exists at a position overlapping with the peak (ii).

[0194] The half width of peak (ii) may be, for example, 8.5° or less. The half width of peak (ii) may be, for example, 1.0° or more, 4.0° or more, or 7.0° or more. The peak height ratio of peak (i) to peak (ii) may be, for example, 0.1 or more, 0.2 or more, or 0.3 or more. The peak height ratio of peak (i) to peak (ii) may be, for example, 5.0 or less, 3.0 or less, or 1.5 or less.

[0195] In this specification, the X-ray diffraction pattern of a porous carbon material is measured by the following method. <Measurement of X-ray diffraction pattern> A porous carbon material is placed on a Si anti-reflective sample holder (filled portion: 20 mm × 18 mm × 0.2 mmt), and a measurement sample is obtained by spreading it with a glass plate so that the sample surface (the height of the portion filled with the sample) coincides with the reference plane of the sample holder. The obtained measurement sample is placed in an X-ray diffractometer (Rigaku Corporation, X-ray diffractometer Ultima IV), and the X-ray diffraction pattern is measured at room temperature using a Cu-Kα X-ray source, a standard sample stage, a focusing optical system, a semiconductor detector (D / teX Ultra), and an anti-scatter tube (slit width 4 mm, length approximately 9 cm) with a measurement angle range of 2θ = 10° to 70°, a sampling width of 0.02°, and a scan rate of 5° / min.

[0196] <Calculation of Half-Width, Crystallite Diameter, and Peak Height Ratio> The powder X-ray diffraction pattern comprehensive analysis software Jade 9 was used to calculate the half-width and crystallite diameter. Peaks (i) and (ii) are assumed to exist in the range of 2θ = 10° to 40° in the X-ray diffraction pattern, and peak separation is performed to calculate the half-width (β measured), peak position 2θ (°), and peak height of peaks (i) and (ii) derived from the Cu-Kα1 line. However, when a sharp peak (i) is not observed in the X-ray diffraction pattern, peak separation is performed assuming that only peak (ii) exists. In this case, the peak shape is a pseudo-Voigt function, and the background shape is a Cubic Spline (fixed). The background is drawn by manually specifying six points as binding points (for example, in Figure 3, 2θ = 10°, 11°, 12.3°, 15°, 35°, and 40°). When calculating the half width and crystallite diameter, the half width derived from the instrument is corrected using the following method. Specifically, the same measurement as in the above <X-ray diffraction pattern measurement> is performed on Si powder (NIST SRM 640c), and full pattern fitting (WPPF) is performed on the measurement results using Jade 9 to obtain the half width curve of Si. Using the obtained half width curve of Si, the half width of Si at the peak position 2θ of peak (i) in the porous carbon material is calculated, and this is taken as the half width derived from the instrument corresponding to peak (i) (β instrument). This value is substituted into the following formula for correction, and the half width derived from the sample of peak (i) (β sample) is calculated. Similarly, in the case of peak (ii), the half width of Si at the peak position 2θ of peak (ii) is calculated, and this is taken as the half width derived from the instrument corresponding to peak (ii) (β instrument). This value is substituted into the following formula for correction, and the half width derived from the sample of peak (ii) (β sample) is calculated. (β sample) ２ = [(β measured) ２ - (β device) ２] Next, the half width of peak (i) (β sample) is substituted into the following Scherrer formula to calculate the crystallite size. At this time, the Scherrer constant K is 1, the measurement X-ray wavelength λ is 0.154 nm, and the peak position of peak (i) obtained by peak separation in Jade 9 is used as the value of the diffraction angle 2θ (°). Crystallite size = (K × λ) / (β × cos θ) The peak height ratio is calculated by substituting the peak height of peak (i) and the peak height of peak (ii) obtained by the above peak separation into the following formula. (Peak height ratio) = (peak height of peak (i)) / (peak height of peak (ii))

[0197] The porous carbon material of this embodiment has a relative pressure (P / P ０ ) is 0.2, the amount of nitrogen adsorption is, for example, 10 to 250 cm ３ / g.

[0198] Relative pressure (P / P ０ When the nitrogen adsorption amount is 250 cm or less, the porous carbon material having a low nitrogen adsorption amount can be said to have a small number of micropores. ３ / g or less, there are fewer fine pores that are likely to be the starting points for deterioration, and therefore the porous carbon material tends to have better oxidation resistance. ３ A porous carbon material having a porosity of 1 / g or more tends to be more suitable as a catalyst support because the presence of fine pores makes it easier to support a catalyst. Such a porous carbon material can be formed, for example, by a calcination step including calcination at 1100°C or higher, as shown in the production method described below.

[0199] Relative pressure (P / P ０ ) is 0.2, the amount of nitrogen adsorption is, for example, 250 cm ３ / g or less, and from the viewpoint of more significantly exhibiting the above-mentioned effect, it is preferable that the ３ / g or less, 180cm ３ / g or less, 170cm ３ / g or less, 160cm ３ / g or less, 150cm ３ / g or less, 140cm ３ / g or less, 130cm ３ / g or less or 120 cm３ / g or less.

[0200] Relative pressure (P / P ０ When the nitrogen adsorption rate is 0.2, the nitrogen adsorption rate is 10 cm ３ / g or more, and from the viewpoint of exhibiting the above effect more significantly, 20 cm ３ / g or more, 30cm ３ / g or more, 40cm ３ / g or more or 50 cm ３ / g or more.

[0201] In the porous carbon material of this embodiment, the relative pressure (P / P ０ ) is 0.8, the nitrogen adsorption amount (N ０ ) relative pressure (P / P ０ The nitrogen adsorption amount (N １ ) ratio (N １ / N ０ ) may be, for example, 0.6 or less, and from the viewpoint of more significantly achieving the above-mentioned effects, it may be 0.5 or less or 0.4 or less.

[0202] In this specification, the nitrogen adsorption amount of a porous carbon material is measured by the following method. <Measurement of nitrogen adsorption amount> A porous carbon material is dried under vacuum at 300°C for 3 hours using a pretreatment device (BELPREP-VAC II manufactured by Microtrac-Bell). Next, a nitrogen adsorption isotherm is measured using a high-precision gas / vapor adsorption amount measuring device (BELSORP MAX II manufactured by Microtrac-Bell). The nitrogen adsorption amount at a predetermined relative pressure is then calculated from the obtained nitrogen adsorption isotherm.

[0203] The specific surface area of ​​the porous carbon material of this embodiment is, for example, 200 m ２ / g or more, and ２ / g or more, 300m ２ / g or more or 350m ２ / g or more. This improves the dispersibility of the active metal on the porous carbon material when the active metal is supported, and reaction sites tend to be formed more efficiently. The specific surface area of ​​the porous carbon material of this embodiment may be, for example, 1800 m ２ / g or less, and ２ / g or less, 1000m ２ / g or less, 700m ２ / g or less or 500m ２ / g or less. This tends to further improve the strength of the porous structure of the porous carbon material and make the porous structure more stable.

[0204] In this specification, the specific surface area of ​​a porous carbon material refers to a value measured by a nitrogen adsorption method. More specifically, it is measured by the following method in accordance with JIS Z8830. <Measurement of specific surface area> A porous carbon material is dried under vacuum at 300°C for 3 hours using a pretreatment device (BELPREP-VAC II, manufactured by Microtrac-Bel). Next, a nitrogen adsorption isotherm is measured using an automatic specific surface area measuring device (BELSORP MAX II, manufactured by Microtrac-Bel). The specific surface area is then calculated from the obtained nitrogen adsorption isotherm using the BET method.

[0205] The porous carbon material of the present embodiment may include, for example, a fired product of a resin material. The porous carbon material of the present embodiment may also be, for example, a fired product of a resin molded product containing a resin material.

[0206] The resin material may be any material that can form amorphous carbon by firing. Examples of the resin material include the same resin materials as those described above regarding the porous carbon material that satisfies (A).

[0207] The fired resin material may be any material that has been fired under conditions that allow amorphous carbon to be formed. By appropriately changing the firing conditions as described below, a porous carbon material having the above-described properties can be obtained.

[0208] The porous carbon material of this embodiment can be produced, for example, by the following production method.

[0209] (Method for Producing Porous Carbon Material) The method for producing a porous carbon material of the present embodiment includes a preparation step of preparing a resin molded body containing a resin material serving as a carbon source, a first template, and a second template, and a firing step of firing the resin molded body to obtain a porous carbon material.

[0210] In this embodiment, the first template includes amphiphilic molecules, the second template includes latex particles, and the calcination step includes calcination at 1100° C. or higher.

[0211] According to the production method of this embodiment, a first group of pores is formed by the first template, and a second group of pores is formed by the second template. Furthermore, according to the production method of this embodiment, the firing step includes firing at 1100°C or higher, which makes it easier to obtain a porous carbon material that satisfies the above-mentioned requirements. Therefore, according to the production method of this embodiment, the porous carbon material of this embodiment can be easily produced.

[0212] FIG. 1( a ) is a cross-sectional view schematically showing an example of a resin molded body, and FIG. 1( b ) is a cross-sectional view schematically showing an example of a porous carbon material.

[0213] 1(a) contains a resin material 11 and latex particles 12. The resin material 11 also contains micelles (not shown) of amphipathic molecules. When such a resin material 10 is baked, the micelles in the resin material 11 are burned away, forming micropores corresponding to the first pore group, and the latex particles 12 are burned away, creating voids and forming a branched higher-order structure.

[0214] 1(b) has a higher-order structure formed by the burning of latex particles 12, and micropores formed by the burning of micelles in the porous carbon material 20. Such a porous carbon material 20 has a pore size distribution with a first peak due to the micropores and a second peak due to the higher-order structure.

[0215] Each step of the manufacturing method of this embodiment will be described in detail below.

[0216] In the preparation step, a resin molded body containing a resin material serving as a carbon source, a first template, and a second template is prepared.

[0217] Examples of the resin material, the first template, and the second template may be the same as the resin material, the first template, and the second template described above regarding the porous carbon material that satisfies (A).

[0218] The amounts of the first template and the second template blended in the preparation step may be the same as the amounts blended in the description of the porous carbon material satisfying (A) above.

[0219] In a preferred embodiment (hereinafter referred to as the first embodiment), the preparation step may include a resin material formation step of forming a resin material in a dispersion containing micelles formed by amphipathic molecules, latex particles, and an aqueous solvent to obtain a precipitate containing the micelles, latex particles, and resin material, and a drying step of drying the precipitate to obtain a resin molded product containing the resin material, amphipathic molecules, and latex particles.

[0220] The resin material forming step and drying step of the first embodiment may be the same steps as the resin material forming step and drying step of the first embodiment in the description regarding the porous carbon material satisfying (A) above.

[0221] In another preferred embodiment (second embodiment), the preparation step may include an impregnation step of impregnating the latex particle aggregates with a dispersion containing micelles formed by amphiphilic molecules, a resin material (or a precursor thereof), and an aqueous solvent, and a drying step of removing the aqueous solvent.

[0222] The impregnation step and drying step of the second embodiment may be the same steps as the resin material formation step and drying step of the second embodiment in the description of the porous carbon material satisfying (A) above, respectively.

[0223] The firing step is a step of firing the resin molded body to obtain a porous carbon material.

[0224] The firing step may be the same step as the firing step described above regarding the porous carbon material that satisfies (B).

[0225] The use of the porous carbon material of this embodiment is not particularly limited, and it can be used for known uses of carbon materials without particular limitation.

[0226] The porous carbon material of this embodiment can allow the reaction sites to function effectively even when coated with a coating material, and therefore can be particularly suitably used in applications where the material is coated with a coating material.

[0227] For example, the porous carbon material of this embodiment can be suitably used as a cathode catalyst support for a polymer electrolyte fuel cell. A cathode catalyst is used by supporting an active metal (e.g., platinum) on the porous carbon material and coating it with an ionomer. According to the porous carbon material of this embodiment, the active metal supported inside the first group of pores can fully exhibit catalytic activity without being poisoned by the ionomer.

[0228] The porous carbon material of this embodiment can also be suitably used as an electrode material for capacitors, an electrode material for secondary batteries, a gas adsorption material, and the like.

[0229] The porous carbon material of this embodiment has excellent oxidation resistance. The oxidation resistance can be evaluated, for example, by the 5% weight loss temperature. The 5% weight loss temperature of the porous carbon material of this embodiment may be, for example, 500°C or higher, or may be 520°C or higher, 540°C or higher, 560°C or higher, 580°C or higher, 600°C or higher, or 620°C or higher.

[0230] In this specification, the 5% weight loss temperature of a porous carbon material is measured by the following method. <Measurement of 5% weight loss temperature> After weighing out about 5 mg of a porous carbon material, the sample is placed in a thermogravimetric / differential calorimeter (STA2500 manufactured by NETZSCH), and the weight loss is measured from 25°C to 1000°C under a heating rate of 10°C / min and an air flow of 20 mL / min. The weight at 25°C on the obtained weight curve is taken as 100%, and the temperature at which 5% weight loss occurs is taken as the 5% weight loss temperature.

[0231] Although the preferred embodiments of the present disclosure have been described above, the present disclosure is not limited to the above embodiments.

[0232] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0233] Example A-1: ​​5.9 parts by mass of resorcinol, 0.8 parts by mass of 5 mol / L hydrochloric acid, 9.3 parts by mass of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (Pluronic F127 manufactured by Sigma-Aldrich), 44.1 parts by mass of polystyrene latex particles, and 29.7 parts by mass of ethanol were mixed, and then 10.1 parts by mass of formaldehyde liquid (formaldehyde content 37% by mass) was added to prepare a dispersion. This dispersion was stirred at 25°C for 72 hours to obtain a precipitate. This precipitate was dried at 70°C for 48 hours to obtain a resin molded product. This resin molded product was heated to 900°C at 1.5°C / min under a nitrogen atmosphere and then maintained at 900°C for 3 hours. Thereafter, the temperature was raised to 2100°C at 10°C / min under an argon atmosphere and then maintained at 2100°C for 1 hour to obtain a block-shaped porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0234] (Example A-2) A resin molded body was obtained in the same manner as in Example A-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere and then held at 900°C for 3 hours. Thereafter, the temperature was raised to 2000°C at a rate of 10°C / min in an argon atmosphere and then held at 2000°C for 1 hour to obtain a block-shaped porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0235] Example A-3 A resin molded body was obtained in the same manner as in Example A-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere and then held at 900°C for 3 hours. Thereafter, the temperature was raised to 1800°C at a rate of 10°C / min in a nitrogen atmosphere and then held at 1800°C for 1 hour to obtain a block-shaped porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0236] (Reference Example A-1) A resin molded body was obtained in the same manner as in Example A-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere, and then held at 900°C for 3 hours. Thereafter, the temperature was raised to 1400°C at a rate of 10°C / min in a nitrogen atmosphere, and then held at 1400°C for 1 hour to obtain a porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0237] (Reference Example A-2) A resin molded body was obtained in the same manner as in Example A-1. The obtained resin molded body was heated to 1200°C at a rate of 1.5°C / min in a nitrogen atmosphere and then held at 1200°C for 3 hours to obtain a porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0238] (Reference Example A-3) A resin molded body was obtained in the same manner as in Example A-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere and then held at 900°C for 3 hours to obtain a porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0239] Comparative Example A-1 A resin molded body was obtained in the same manner as in Example A-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere and then held at 900°C for 3 hours. Next, it was pulverized in a mortar to obtain a powder, and the temperature was raised to 460°C at a rate of 1.5°C / min in an air atmosphere and then held at 460°C for 1 hour to obtain a powdered porous carbon material.

[0240] The porous carbon materials obtained in Examples A-1 to A-3, Reference Examples A-1 to A-3, and Comparative Example A-1 were subjected to the following measurements.

[0241] <Measurement of pore size distribution by mercury intrusion porosimetry> 40 to 80 mg of porous carbon material was collected in a 5 cc measurement cell. Next, using an automatic mercury porosimeter (Shimadzu Corporation-Micromeritics, Autopore V9620), the mercury pressure was increased from 1 psia to 60,000 psia, and the amount of mercury intrusion was measured. The pore size distribution was then determined from the obtained curve of pressure and intrusion amount. The mercury contact angle was 130 degrees, and the mercury surface tension was 485 dynes / cm. The positions of the first and second peaks in the obtained pore size distribution were determined and are listed in Tables 1 and 2. Note that FIG. 2 shows the pore size distribution curve of the porous carbon material obtained in Example A-1.

[0242] <Measurement of X-ray diffraction pattern> The porous carbon material was placed on a Si anti-reflective sample holder (filled portion: 20 mm x 18 mm x 0.2 mmt) and spread with a glass plate so that the sample surface (the height of the portion filled with the sample) coincided with the reference plane of the sample holder to obtain a measurement sample. The obtained measurement sample was placed in an X-ray diffractometer (Rigaku Corporation, X-ray diffractometer Ultima IV), and the X-ray diffraction pattern was measured at room temperature, with a measurement angle range of 2θ = 10 ° to 70 °, a sampling width of 0.02 °, and a scan rate of 5 ° / min, using a Cu-Kα X-ray source, a standard sample stage, a focusing optical system, a semiconductor detector (D / teX Ultra), and an anti-scattering tube (slit width 4 mm, length approximately 9 cm). <Calculation of half-width, crystallite diameter, and peak height ratio> The powder X-ray diffraction pattern comprehensive analysis software Jade 9 was used to calculate the half-width and crystallite diameter. Peak (i) and peak (ii) were assumed to exist in the range of 2θ = 10 ° to 40 ° in the X-ray diffraction pattern, and peak separation was performed to calculate the half-width (hereinafter, β measured), peak position 2θ (°), and peak height derived from the Cu-Kα1 ray of peak (i) and peak (ii). However, when a sharp peak (i) was not observed in the X-ray diffraction pattern, peak separation was performed assuming that only peak (ii) existed. In this case, the peak shape was a pseudo-Voigt function, and the background shape was a Cubic Spline (fixed). Note that the background was subtracted by manually specifying six points as bonding points (for example, in Figure 3, 2θ = 10 °, 11 °, 12.3 °, 15 °, 35 °, and 40 °). Note that when calculating the half-width and crystallite size, the half-width derived from the instrument was corrected using the following method. Specifically, the same measurement as in the above <X-ray diffraction pattern measurement> was performed on Si powder (NIST SRM 640c), and the measurement results were subjected to full pattern fitting (WPPF) using Jade 9 to obtain a Si half-width curve. Using the obtained Si half-width curve, the Si half-width at the peak position 2θ of peak (i) in the porous carbon material was determined, and this was designated as the instrument-derived half-width (β instrument) corresponding to peak (i). This value was substituted into the following formula for correction, and the sample-derived half-width (β sample) of peak (i) was calculated.Similarly, for peak (ii), the half-width of Si at the peak position 2θ of peak (ii) was determined, and this was designated as the instrument-derived half-width (β instrument) corresponding to peak (ii). This value was substituted into the following equation for correction, and the sample-derived half-width (β sample) of peak (ii) was calculated. (β sample). ２ = [(β measured) ２ - (β device) ２ ] Next, the half width of peak (i) (β sample) was substituted into the following Scherrer formula to calculate the crystallite size. In this case, the Scherrer constant K was 1, the measurement X-ray wavelength λ was 0.154 nm, and the peak position of peak (i) obtained by peak separation with Jade 9 was used as the value of the diffraction angle 2θ (°). Crystallite size = (K × λ) / (β × cos θ) The peak height ratio was calculated by substituting the peak height of peak (i) and the peak height of peak (ii) obtained by the above peak separation into the following formula. (Peak height ratio) = (peak height of peak (i)) / (peak height of peak (ii)) The presence or absence of peak (i), and the half widths and peak height ratios of peak (i) and peak (ii) are shown in Tables 1 and 2. Note that FIG. 3 shows the X-ray diffraction pattern of the porous carbon material obtained in Example A-1.

[0243] <Measurement of nitrogen adsorption amount> The porous carbon material was dried under vacuum at 300°C for 3 hours using a pretreatment device (BELPREP-VAC II manufactured by Microtrac-Bell). Next, a nitrogen adsorption isotherm was measured using a high-precision gas / vapor adsorption amount measuring device (BELSORP MAX II manufactured by Microtrac-Bell). From the measurement results, the relative pressure (P / P ０ The amount of nitrogen adsorption when the relative pressure (P / P) is 0.2 ０ ) is 0.8, the nitrogen adsorption amount (N ０ ) relative pressure (P / P ０ The nitrogen adsorption amount (N １ ) ratio (N １ / N ０ ) were calculated and are shown in Tables 1 and 2.

[0244] <Measurement of Surface Oxygen Concentration and Surface Carbon Concentration by XPS> The surface oxygen concentration and surface carbon concentration were determined by XPS measurement using an X-ray photoelectron spectrometer (Thermo K-Alpha X-ray photoelectron spectrometer). Specifically, the porous carbon material was filled into a recess (φ3 mm × 1 mm thick) of a powder sample holder, and the sample surface was flattened and subjected to measurement. The excitation source used for the measurement was an Al-Kα with a monochromator, the X-ray irradiation area was 400 × 200 μm (elliptical in shape), the detection angle was 90° (perpendicular to the sample surface), the pass energy was 50 eV, and the number of scans was 5. The elements to be detected were oxygen (O) and carbon (C), and their narrow spectra were measured. Integration was performed for O in the O1s range (approximately 540 to 527 eV) and for C in the C1s range (approximately 293 to 280 eV), and the surface oxygen concentration and surface carbon concentration were calculated. Charge correction was performed using the C1s peak (284.8 eV) as the reference peak, and the background was specified by Shirley. The surface oxygen concentration and surface carbon concentration were normalized so that the sum of them was 100 at%. The measured surface oxygen concentration and surface carbon concentration are shown in Tables 1 and 2.

[0245] <Measurement of specific surface area> The porous carbon material was dried under vacuum at 300°C for 3 hours using a pretreatment device (BELPREP-VAC II manufactured by Microtrac-Bell). Next, a nitrogen adsorption isotherm was measured using a high-precision gas / vapor adsorption measurement device (BELSORP MAX II manufactured by Microtrac-Bell). The specific surface area was then calculated from the obtained nitrogen adsorption isotherm using the BET method. The calculated specific surface areas are shown in Tables 1 and 2.

[0246] <Evaluation of Oxidation Resistance> The oxidation resistance of the porous carbon material was evaluated by measuring the 5% weight loss temperature. The higher the 5% weight loss temperature, the better the oxidation resistance. The 5% weight loss temperature was measured using the following method. The results are shown in Tables 1 and 2. <Measurement of 5% Weight Loss Temperature> Approximately 5 mg of the porous carbon material was weighed out, and the sample was placed in a thermogravimetric / differential calorimeter (STA2500, manufactured by NETZSCH). The weight loss was measured from 25°C to 1000°C at a heating rate of 10°C / min and an air flow of 20 mL / min. The weight at 25°C in the obtained weight curve was taken as 100%, and the temperature at which 5% weight loss occurred was taken as the 5% weight loss temperature.

[0247]

[0248]

[0249] (Example B-1) A resin molded body was obtained in the same manner as in Example A-1. Further, a block-shaped porous carbon material was obtained in the same manner as in Example A-1. The obtained porous carbon material was pulverized in a mortar to obtain a powdery porous carbon material.

[0250] Example B-2 A resin molded body was obtained in the same manner as in Example B-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere and then held at 900°C for 3 hours. Thereafter, the temperature was raised to 1400°C at a rate of 10°C / min and then held at 1400°C for 1 hour to obtain a block-shaped porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0251] (Example B-3) A resin molded body was obtained in the same manner as in Example B-1. The obtained resin molded body was heated to 1200°C at a rate of 1.5°C / min in a nitrogen atmosphere, and then held at 1200°C for 3 hours to obtain a block-shaped porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0252] (Example B-4) A resin molded body was obtained in the same manner as in Example B-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere and then held at 900°C for 3 hours to obtain a block-shaped porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0253] Comparative Example B-1 A resin molded body was obtained in the same manner as in Example B-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere, and then held at 900°C for 3 hours to obtain a block-shaped material. The obtained block-shaped material was pulverized in a mortar to obtain a powder, and the temperature was raised to 460°C at a rate of 1.5°C / min in an air atmosphere, and then held at 460°C for 1 hour to obtain a powder-shaped porous carbon material.

[0254] Comparative Example B-2 A resin molded body was obtained in the same manner as in Example B-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere, and then held at 900°C for 3 hours to obtain a block-shaped material. The obtained block-shaped material was pulverized in a mortar to obtain a powder, and the temperature was raised to 520°C at a rate of 1.5°C / min in an air atmosphere, and then held at 520°C for 1 hour to obtain a powder-shaped porous carbon material.

[0255] The porous carbon materials obtained in Examples B-1 to B-4 and Comparative Examples B-1 and B-2 were subjected to the same measurements as above, and the results are shown in Tables 3 and 4.

[0256]

[0257]

[0258] Example C-1 A resin molded body was obtained in the same manner as in Example A-1, and a block-shaped porous carbon material was obtained in the same manner as in Example A-1.

[0259] Example C-2 A resin molded body was obtained in the same manner as in Example C-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere and then held at 900°C for 3 hours. Thereafter, the temperature was raised to 1800°C at a rate of 10°C / min and then held at 1800°C for 1 hour to obtain a block-shaped porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0260] (Example C-3) A resin molded body was obtained in the same manner as in Example C-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere and then held at 900°C for 3 hours. Thereafter, the temperature was raised to 1400°C at a rate of 10°C / min and then held at 1400°C for 1 hour to obtain a block-shaped porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0261] (Example C-4) A resin molded body was obtained in the same manner as in Example C-1. The obtained resin molded body was heated to 1200°C at a rate of 1.5°C / min in a nitrogen atmosphere, and then held at 1200°C for 3 hours to obtain a block-shaped porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0262] (Example C-5) A resin molded body was obtained in the same manner as in Example C-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere and then held at 900°C for 3 hours to obtain a block-shaped porous carbon material. The obtained porous carbon material was pulverized in a mortar to obtain a powdered porous carbon material.

[0263] Comparative Example C-1 A resin molded body was obtained in the same manner as in Example C-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere, and then held at 900°C for 3 hours to obtain a block-shaped material. The obtained block-shaped material was pulverized in a mortar to obtain a powder, and the temperature was raised to 430°C at a rate of 1.5°C / min in an air atmosphere, and then held at 430°C for 1.5 hours to obtain a powder-shaped porous carbon material.

[0264] Comparative Example C-2 A resin molded body was obtained in the same manner as in Example C-1. The obtained resin molded body was heated to 900°C at a rate of 1.5°C / min in a nitrogen atmosphere, and then held at 900°C for 3 hours to obtain a block-shaped material. The obtained block-shaped material was pulverized in a mortar to obtain a powder, and the temperature was raised to 460°C at a rate of 1.5°C / min in an air atmosphere, and then held at 460°C for 1 hour to obtain a powder-shaped porous carbon material.

[0265] The porous carbon materials obtained in Examples C-1 to C-5 and Comparative Examples C-1 and C-2 were subjected to the same measurements as above, and the results are shown in Tables 5 and 6. The following measurements were carried out.

[0266]

[0267]

[0268] 10...resin molded body, 11...resin material, 12...latex particles, 20...porous carbon material

Claims

1. A porous carbon material having a first peak located in a pore diameter range of 3 nm or more and less than 10 nm and a second peak located in a pore diameter range of 10 nm or more and 1 μm or less in a pore diameter distribution measured by mercury intrusion porosimetry, and satisfying at least one of the following (A), (B), and (C): (A) In an X-ray diffraction pattern, the material has a peak (i) having a half-width of 0.6° or less and a peak top in the range of 2θ = 25° to 27°; (B) In a nitrogen adsorption measurement, the amount of nitrogen adsorption at a relative pressure of 0.2 is 10 cm ３ / g or more 250cm ３ / g or less. (C) The surface oxygen concentration measured by XPS is 6 at % or less.

2. The porous carbon material according to claim 1, which satisfies (A).

3. The porous carbon material according to claim 2, further comprising a peak (ii) having a half-width of 9° or less and partially overlapping with said peak (i) in an X-ray diffraction pattern.

4. The porous carbon material according to claim 1, which satisfies (B).

5. The nitrogen adsorption volume is 10 cm ３ / g or more 200cm ３ The porous carbon material according to claim 4, wherein the molecular weight is 1 / g or less.

6. The porous carbon material according to claim 1, which satisfies (C).

7. The porous carbon material according to claim 6, which has a surface oxygen concentration measured by XPS of 2 at % or less and a surface carbon concentration measured by XPS of 98 at % or more.

8. The specific surface area is 200 m ２ / g or more 1800m ２ The porous carbon material according to any one of claims 1 to 7, wherein the molecular weight is 1 / g or less.

9. The porous carbon material according to any one of claims 1 to 7, wherein the first peak is located in a pore diameter range of 4 nm or more and 7 nm or less.

10. A porous carbon material according to any one of claims 1 to 7, wherein the second peak is located in a pore diameter range of 20 nm or more and 700 nm or less.

11. A method for producing a porous carbon material, comprising: a preparation step of preparing a resin molded body containing a resin material as a carbon source, a first template, and a second template; and a calcination step of calcining the resin molded body to obtain the porous carbon material according to claim 2 or 3, wherein the calcination step includes calcination at 1200°C or higher, the first template contains amphipathic molecules, and the second template contains latex particles.

12. A method for producing a porous carbon material as described in claim 11, wherein the sintering step includes: a first sintering step of sintering the resin molded body at a sintering temperature of less than 1200°C to obtain a first sintered body; and a second sintering step of sintering the first sintered body at a sintering temperature of 1500°C or higher.

13. A method for producing a porous carbon material as described in claim 11, wherein the sintering step includes: a first sintering step of sintering the resin molded body at a sintering temperature of less than 1200°C to obtain a first sintered body; a crushing step of crushing the first sintered body; and a second sintering step of sintering the first sintered body crushed in the crushing step at a sintering temperature of 1500°C or higher.

14. The method for producing a porous carbon material according to claim 11, wherein the calcination step includes calcination at 2000° C. or higher.

15. The method for producing a porous carbon material according to claim 11, wherein the firing at 1500° C. or higher in the firing step is carried out in an argon atmosphere.

16. A method for producing a porous carbon material, comprising: a preparation step of preparing a resin molded body containing a resin material as a carbon source, a first template, and a second template; and a calcination step of calcining the resin molded body to obtain the porous carbon material according to any one of claims 4 to 7, wherein the calcination step includes calcination at 1100°C or higher, the first template contains amphipathic molecules, and the second template contains latex particles.

17. A method for producing a porous carbon material as described in claim 16, wherein the sintering step includes: a first sintering step of sintering the resin molded body at a sintering temperature of less than 1100°C to obtain a first sintered body; and a second sintering step of sintering the first sintered body at a sintering temperature of 1100°C or higher.

18. A method for producing a porous carbon material as described in claim 16, wherein the sintering step includes: a first sintering step of sintering the resin molded body at a sintering temperature of less than 1100°C to obtain a first sintered body; a crushing step of crushing the first sintered body; and a second sintering step of sintering the first sintered body crushed in the crushing step at a sintering temperature of 1100°C or higher.

19. The method for producing a porous carbon material according to claim 16, wherein the calcination step includes calcination at 2000° C. or higher.

20. The method for producing a porous carbon material according to claim 16, wherein the firing at 1,100° C. or higher in the firing step is carried out in an argon atmosphere.

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