WO2023166755A1 - Catalyseur sur support métal et son procédé de fabrication ainsi qu'électrode et batterie - Google Patents

Catalyseur sur support métal et son procédé de fabrication ainsi qu'électrode et batterie Download PDF

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WO2023166755A1
WO2023166755A1 PCT/JP2022/023286 JP2022023286W WO2023166755A1 WO 2023166755 A1 WO2023166755 A1 WO 2023166755A1 JP 2022023286 W JP2022023286 W JP 2022023286W WO 2023166755 A1 WO2023166755 A1 WO 2023166755A1
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metal
catalyst
supported
carbon support
precursor
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PCT/JP2022/023286
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English (en)
Japanese (ja)
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卓也 石塚
鉄太郎 佐藤
武亮 岸本
義和 小林
規晟 片桐
亮ファクソン 市川
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日清紡ホールディングス株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a supported metal catalyst, a method for producing the same, an electrode and a battery.
  • Patent Document 1 discloses a catalyst for an air electrode of a polymer solid electrolyte fuel cell in which catalyst particles obtained by alloying platinum and one auxiliary metal are supported on a carbon powder carrier, wherein the auxiliary metal is , iron or cobalt, and the compounding ratio of platinum to the auxiliary metal is 6:1 to 3:2 (molar ratio). ing.
  • Patent Document 2 describes a fuel cell electrode catalyst containing a solid carbon support and an alloy of platinum and cobalt supported on the support.
  • Patent Document 3 discloses an electrode catalyst in which a catalyst metal is supported on a catalyst carrier, the catalyst metal contains platinum and a metal component other than platinum, and has mesopores with a radius of 1 nm or more.
  • the modal radius of the pore distribution of the mesopores is 1 nm or more and less than 2.5 nm, platinum and alloy fine particles of a metal component other than platinum are supported in the mesopores, and the alloy fine particles other than platinum are supported in the mesopores.
  • Electrocatalysts are described which contain platinum in a molar ratio of 1.0 to 10.0 to the metal component of the.
  • Patent Document 5 a first step of mixing a noble metal compound containing a noble metal element, a base metal compound containing a base metal element, a first solvent and a porous material to obtain a mixture, and the following formula "(in the mixture The noble metal compound and the base metal compound are separated from the porous material by removing the first solvent from the mixture until the volume of the first solvent ⁇ (pore volume of the porous material) x 5 is satisfied. and a third step of contacting the porous material with a reducing solution containing a reducing agent having an oxidation-reduction potential of ⁇ 1.20 V or less and a second solvent. , a method for producing an alloy catalyst, wherein the substance amount of the reducing agent in the reducing solution is at least five times the total substance amount of the noble metal elements.
  • the present invention has been made in view of the above problems, and provides a metal-supported catalyst having a large noble metal content and excellent durability and excellent catalytic function, a method for producing the same, an electrode and a battery.
  • One of its purposes is to provide
  • a metal-supported catalyst according to an embodiment of the present invention for solving the above problems is a metal-supported catalyst comprising a carbon support and catalyst metal particles containing a noble metal alloy supported on the carbon support, The ratio of the weight of the noble metal to the weight of the metal-supported catalyst is 35% by weight or more, and the following characteristics (a) and / or (b): (a) the alloy composition non-uniformity calculated by the following formula (I) is 0.55 or less; (In formula (I) above, the theoretical lattice constant and the measured lattice constant are the theoretical lattice constant and the measured lattice constant of the noble metal alloy, respectively.) (b) both the half-value asymmetry and the quarter-value asymmetry calculated by the following formulas (II) and (III) are 0.55 or less; (In the above formulas (II) and (III), D m is the maximum diffraction line in the range of the diffraction angle 2 ⁇ where the diffraction peak of the (111) plane of the
  • D Lh is the value of the smallest diffraction angle 2 ⁇ among the diffraction angles 2 ⁇ at which the diffraction line exhibits half the maximum intensity in the above range
  • D Hh is the diffraction angle 2 ⁇ in the above range
  • D Lq is the value of the largest diffraction angle 2 ⁇ among the diffraction angles 2 ⁇ at which the line shows half the maximum intensity
  • D Lq is the diffraction angle 2 ⁇ at which the diffraction line shows a quarter of the maximum intensity in the above range.
  • D Hq is the smallest value of the diffraction angle 2 ⁇
  • D Hq is the largest value of the diffraction angles 2 ⁇ among the diffraction angles 2 ⁇ at which the intensity of the diffraction line is 1/4 of the maximum intensity in the above range.
  • the metal-supported catalyst may have the property (a). Moreover, the metal-supported catalyst may have the property (b). In the metal-supported catalyst, the catalyst metal particles may have a number average particle size of 8.0 nm or less. In the metal-supported catalyst, the catalyst metal particles may have a volume-average particle size of 8.0 nm or less.
  • An electrode according to an embodiment of the present invention for solving the above problems includes any of the metal-supported catalysts described above. According to the present invention, electrodes having excellent properties are provided.
  • a battery according to one embodiment of the present invention for solving the above problems includes the electrode.
  • ADVANTAGE OF THE INVENTION According to this invention, the battery which has the outstanding characteristic is provided.
  • a method for producing a metal-supported catalyst according to one embodiment of the present invention for solving the above problems is a metal-supported catalyst containing a carbon support and catalytic metal particles containing a noble metal alloy supported on the carbon support.
  • a manufacturing method comprising: a first impregnation step of impregnating the carbon support with a precursor of a first metal that is one of a noble metal and a non-noble metal constituting the noble metal alloy; a first gas phase reduction step of subjecting the carbon support to a gas phase reduction treatment to obtain a first metal-supported catalyst supporting the first metal; a second impregnation step of impregnating a precursor of a second metal; and subjecting the first metal-supported catalyst impregnated with the precursor of the second metal to a vapor phase reduction treatment and then to an alloying treatment to obtain the and a second vapor phase reduction step of obtaining a metal-supported catalyst on which catalyst metal particles containing an alloy of the first metal and the second metal are supported.
  • the vapor phase reduction treatment may be a treatment of heating in a reducing atmosphere.
  • the first impregnation step includes maintaining a solution containing the precursor of the first metal and the carbon support under reduced pressure, and/or the second impregnation step comprises: and holding the solution containing the precursor of and the first metal-supported catalyst under reduced pressure.
  • the first impregnating step includes maintaining a solution containing the precursor of the first metal and the carbon support under pressure, and/or the second impregnating step comprises: and the first metal-supported catalyst under pressure.
  • the first impregnation step includes holding the solution comprising the precursor of the first metal and the carbon support first under reduced pressure and then under pressure, and/or The impregnation step may comprise first holding the solution comprising the second metal precursor and the first metal supported catalyst under reduced pressure and then under pressure. Further, the first impregnation step includes maintaining a solution containing the precursor of the first metal and the carbon support at a temperature of 5° C. or less, and/or the second impregnation step includes: It may comprise maintaining the solution comprising the second metal precursor and the first metal supported catalyst at a temperature of 5° C. or less.
  • a metal-supported catalyst, an electrode and a battery are provided that have both excellent durability and excellent catalytic function while having a large noble metal content.
  • FIG. 2 is an explanatory diagram showing an example of the results of analysis of Raman spectra obtained by Raman spectroscopy of metal-supported catalysts in Examples according to the present embodiment.
  • FIG. 2 is an explanatory diagram showing a typical X-ray diffraction pattern obtained by powder X-ray diffraction of a supported metal catalyst.
  • FIG. 2 is an explanatory diagram showing an example of the result of analysis of an X-ray diffraction pattern obtained by powder X-ray diffraction of a metal-supported catalyst in an example according to the present embodiment.
  • FIG. 2 is an explanatory diagram showing an example of the results of analysis of Raman spectra obtained by Raman spectroscopy of metal-supported catalysts in Examples according to the present embodiment.
  • FIG. 2 is an explanatory diagram showing a typical X-ray diffraction pattern obtained by powder X-ray diffraction of a supported metal catalyst.
  • FIG. 2 is an explanatory diagram showing an example of the result of analysis of an
  • FIG. 4 is an explanatory diagram showing another example of the result of analyzing an X-ray diffraction pattern obtained by powder X-ray diffraction of a metal-supported catalyst in an example according to the present embodiment.
  • FIG. 2 is an explanatory diagram showing an example of the result of analysis of an X-ray diffraction pattern obtained by powder X-ray diffraction of a metal-supported catalyst in an example according to the present embodiment.
  • FIG. 4 is an explanatory diagram showing another example of the result of analyzing an X-ray diffraction pattern obtained by powder X-ray diffraction of a metal-supported catalyst in an example according to the present embodiment.
  • FIG. 2 is an explanatory diagram showing an example of the result of analysis of an X-ray diffraction pattern obtained by powder X-ray diffraction of a metal-supported catalyst in an example according to the present embodiment.
  • FIG. 4 is an explanatory diagram showing another example of the result of analyzing an X-ray dif
  • FIG. 2 is an explanatory diagram showing an example of the result of analysis of an X-ray diffraction pattern obtained by powder X-ray diffraction of a metal-supported catalyst in an example according to the present embodiment.
  • FIG. 4 is an explanatory diagram showing another example of the result of analyzing an X-ray diffraction pattern obtained by powder X-ray diffraction of a metal-supported catalyst in an example according to the present embodiment.
  • FIG. 3 is an explanatory diagram showing still another example of the result of analysis of an X-ray diffraction pattern obtained by powder X-ray diffraction of a metal-supported catalyst in an example according to the present embodiment. It is explanatory drawing which expands and shows a part of X-ray diffraction pattern shown to FIG.
  • FIG. 3 is an explanatory diagram showing still another example of the result of analysis of an X-ray diffraction pattern obtained by powder X-ray diffraction of a metal-supported catalyst in an example according to the present embodiment. It is explanatory drawing which expands and shows a part of X-ray-diffraction pattern shown to FIG. 6A.
  • FIG. 3 is an explanatory diagram showing an example of the results of evaluation of ECSA sweep speed dependence of a metal-supported catalyst in an example according to the present embodiment. It is an explanatory view showing an equivalent circuit.
  • FIG. 3 is an explanatory diagram showing actual measurement values and fitting results of Nyquist plots obtained for metal-supported catalysts in Examples according to the present embodiment.
  • FIG. 3 is an explanatory diagram showing actual measurement values and fitting results of Nyquist plots obtained for metal-supported catalysts in Examples according to the present embodiment.
  • FIG. 2 is an explanatory diagram showing production conditions for supported metal catalysts and evaluation results of characteristics of fuel cells containing the supported metal catalysts in examples according to the present embodiment.
  • FIG. 4 is an explanatory diagram showing the results of evaluating the properties of metal-supported catalysts in examples according to the present embodiment.
  • a metal-supported catalyst according to the present embodiment (hereinafter referred to as "the present catalyst”) includes a carbon support and catalyst metal particles containing a noble metal alloy supported on the carbon support.
  • the carbon carrier contained in this catalyst is a carbon material mainly composed of carbon.
  • the carbon content of the carbon support may be, for example, 70% by weight or more, preferably 75% by weight or more, more preferably 80% by weight or more, and particularly 85% by weight or more. preferable.
  • the carbon content of the carbon support may be, for example, 100% by weight or less, 95% by weight or less, or 90% by weight or less.
  • the carbon content of the carbon support may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • the carbon content of the carbon support is obtained by elemental analysis (combustion method).
  • the carbon carrier is preferably a carbonized material.
  • a carbonized material is obtained by carbonizing a raw material containing an organic substance.
  • the organic substance content in the raw material for carbonization may be, for example, 5% by weight or more and 90% by weight or less, preferably 10% by weight or more and 80% by weight or less.
  • the organic matter contained in the raw material is not particularly limited as long as it can be carbonized.
  • the organic compounds contained in the organic matter may be polymers (eg, thermosetting resins and/or thermoplastic resins) and/or organic compounds with lower molecular weights.
  • the carbon carrier preferably contains nitrogen. That is, the carbon support preferably contains nitrogen atoms in its carbon structure.
  • the carbon support containing nitrogen is preferably a carbonized material containing nitrogen.
  • a nitrogen-containing carbonized material is obtained, for example, by carbonizing a raw material containing a nitrogen-containing organic substance.
  • the nitrogen-containing organic substance preferably contains a nitrogen-containing organic compound.
  • the nitrogen-containing organic compound is not particularly limited as long as it is an organic compound containing a nitrogen atom in its molecule. Nitrogen contained in the carbon support may be introduced by nitrogen doping.
  • the nitrogen content of the carbon support may be, for example, 0.10% by weight or more, preferably 0.15% by weight or more, more preferably 0.20% by weight or more, and 0.25% by weight or more. % by weight or more is more preferable, and 0.30% by weight or more is particularly preferable.
  • the nitrogen content of the carbon support may be, for example, 10.00% by weight or less.
  • the nitrogen content of the carbon support is obtained by elemental analysis (combustion method) of the carbon support.
  • the carbon carrier is preferably a carbonized material obtained by carbonizing raw materials containing organic substances and metals.
  • the carbon support may be a carbonized material subjected to metal removal treatment after carbonization.
  • the metal removal treatment is a treatment for reducing the amount of raw material-derived metal contained in the carbonized material.
  • the metal removal treatment is preferably acid cleaning treatment and/or electrolytic treatment, for example.
  • the carbon support When the carbon support is a carbonized material obtained by carbonizing a raw material containing an organic substance and a metal, the carbon support may contain a metal derived from the raw material for carbonization (hereinafter referred to as "raw metal"). good.
  • the carbon support contains the raw material metal inside the skeleton that constitutes its porous structure. Even if the carbon support is a carbonized material produced through the metal removal treatment as described above, the starting metal remains inside the skeleton of the carbon support.
  • the weight of the raw metal contained inside the skeleton of the carbon support may be greater than the weight of the raw metal contained on the surface of the skeleton of the carbon support.
  • the raw material metal inside the skeleton of the carbon support can be detected, for example, by subjecting the skeleton to surface etching treatment and analyzing the cross section exposed by the etching treatment. That is, in this case, when one particle of the carbon support is etched, the raw material metal is detected in the cross section of the particle exposed by the etching process.
  • the raw material metal contained in the carbon support can be detected, for example, by inductively coupled plasma emission spectroscopy of the carbon support.
  • the raw material metal content of the carbon support (the ratio of the weight of the raw material metal contained in the carbon support to the weight of the carbon support) may be, for example, 0.001% by weight or more, or 0.005% by weight or more. 0.01% by weight or more, or 0.02% by weight or more.
  • the raw material metal content of the carbon support may be, for example, 5% by weight or less, 4% by weight or less, 3% by weight or less, or 2% by weight or less. may be 1% by weight or less, 0.8% by weight or less, or 0.5% by weight or less.
  • the raw material metal content of the carbon support may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the raw material metal content of the carbon support can be obtained, for example, by inductively coupled plasma emission spectroscopy of the carbon support.
  • the raw material metal is preferably a transition metal. That is, the raw material metal is preferably a transition metal belonging to Groups 3 to 12 of the periodic table, and particularly preferably a transition metal belonging to Period 4 of Groups 3 to 12 of the periodic table.
  • the raw material metal may be a transition metal other than platinum.
  • the raw metal is a noble metal (e.g., ruthenium (Ru), palladium (Pd), rhodium (Rh), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au) ) may be transition metals other than
  • raw metals include, for example, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), Copper (Cu), Zinc (Zn), Yttrium (Y), Zirconium (Zr), Niobium (Nb), Molybdenum (Mo), Ruthenium (Ru), Rhodium (Rh), Palladium (Pd), Silver (Ag), It may be one or more selected from the group consisting of lanthanides (e.g., gadolinium (Gd)) and actinides, and one or more selected from the group consisting of Fe, Co, Ni, Cu, and Zn. and more preferably one or more selected from the group consisting of Fe, Co, Ni, and Zn, and one or more selected from the group consisting of Co, Ni, and Zn. is particularly preferred.
  • lanthanides e.g., gadolinium (Gd)
  • Carbonization in the production of carbonized materials is performed by heating the raw materials at a temperature at which the organic substances contained in the raw materials are carbonized.
  • the carbonization temperature is not particularly limited as long as it is a temperature at which the raw material is carbonized. 1500° C. or higher is particularly preferred.
  • the carbonization temperature may be, for example, 3000°C or lower, preferably 2500°C or lower, and particularly preferably 2000°C or lower.
  • the carbonization temperature may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the rate of temperature increase to the carbonization temperature is not particularly limited, and may be, for example, 0.5° C./min or more and 300° C./min or less. Carbonization is preferably carried out in an inert atmosphere such as a nitrogen atmosphere.
  • Carbonization may be carried out under normal pressure (atmospheric pressure), but is preferably carried out under pressure (under pressure higher than atmospheric pressure).
  • the pressure of the atmosphere in which the carbonization is performed may be, for example, 0.05 MPa or more in gauge pressure, preferably 0.15 MPa or more in gauge pressure, and 0.20 MPa. It is more preferably 0.40 MPa or more, and particularly preferably 0.50 MPa or more.
  • the upper limit of the pressure of the carbonization atmosphere is not particularly limited, the pressure may be, for example, 10 MPa or less in gauge pressure.
  • the carbon carrier is preferably a carbonized material that has been graphitized after carbonization. That is, the carbon support is preferably, for example, a carbonized material obtained by subjecting a carbonized material obtained by carbonizing a raw material containing an organic matter to a graphitization treatment.
  • Graphitization is performed by heating the carbonized material at a temperature at which graphitization proceeds.
  • the heating temperature for heating the carbonized material in the graphitization treatment is not particularly limited as long as it is a temperature at which graphitization proceeds in the carbonized material, but it is a temperature higher than the carbonization temperature for obtaining the carbonized material. is preferred.
  • the heating temperature in the graphitization treatment may be, for example, 1300° C. or higher, preferably 1400° C. or higher, more preferably 1500° C. or higher, and further preferably 1600° C. or higher. It is preferably 1,700° C. or higher, more preferably 1,750° C. or higher, and particularly preferably 1,800° C. or higher.
  • the heating temperature in the graphitization treatment may be, for example, 3000° C. or lower, preferably 2500° C. or lower, more preferably 2400° C. or lower, and even more preferably 2300° C. or lower, It is more preferably 2250° C. or lower, more preferably 2200° C. or lower, even more preferably 2150° C. or lower, and particularly preferably 2100° C. or lower.
  • the heating temperature in the graphitization treatment may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the rate of temperature increase to the heating temperature in the graphitization treatment is not particularly limited, and may be, for example, 0.5° C./min or more and 300° C./min or less.
  • the graphitization treatment is preferably performed in an inert atmosphere such as a nitrogen atmosphere.
  • the carbon support is a carbonized material that has undergone graphitization after carbonization
  • the graphitized carbonized material is not subjected to pulverization. That is, in the production of a carbon support, for example, a carbonized material obtained by carbonizing a raw material is subjected to a pulverization treatment to adjust the median diameter, and then the pulverized carbonized material is subjected to a graphitization treatment. It is preferable that the carbonized material after the graphitization treatment is not subjected to the pulverization treatment.
  • the carbon carrier is preferably a carbon material that exhibits catalytic activity. That is, in this case, the carbon support is a carbon catalyst that exhibits catalytic activity by itself.
  • the carbon support, which is a carbon catalyst is preferably a carbonized material obtained by carbonizing a raw material containing an organic substance and a metal as described above.
  • the catalytic activity exhibited by the carbon support is, for example, preferably reduction activity and/or oxidation activity, more preferably oxygen reduction activity and/or hydrogen oxidation activity, and particularly preferably at least oxygen reduction activity.
  • the catalytic metal particles supported on the carbon support contain precious metal alloys.
  • Noble metal alloys are alloys of noble metals and metals other than noble metals (hereinafter referred to as "non-noble metals"). That is, a noble metal alloy includes one or more noble metals and one or more non-noble metals.
  • the catalyst metal particles may further contain a noble metal that does not form an alloy (hereinafter sometimes referred to as "pure noble metal").
  • Noble metals are selected from the group consisting of, for example, ruthenium (Ru), palladium (Pd), rhodium (Rh), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt) and gold (Au). more preferably one or more selected from the group consisting of Ru, Pd, Rh, Ir and Pt, particularly preferably Pt.
  • the catalytic metal particles preferably contain a platinum alloy.
  • Platinum alloys are alloys of platinum and non-noble metals. That is, platinum alloys include platinum and one or more non-noble metals.
  • the platinum alloy may further contain one or more other precious metals, or may contain no other precious metals.
  • the catalyst metal particles may further contain platinum that does not form an alloy (hereinafter sometimes referred to as “pure platinum”).
  • non-precious metals that make up the noble metal alloy are not particularly limited as long as they are metals other than noble metals that form alloys with noble metals, but are preferably transition metals other than noble metals.
  • non-noble metals contained in noble metal alloys include, for example, titanium (Ti), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium (Nb) and It is preferably one or more selected from the group consisting of cerium (Ce), more preferably one or more selected from the group consisting of Fe, Co and Ni, and selected from the group consisting of Co and Ni. It is particularly preferred that one or more of the
  • the catalyst metal particles supported on the carbon support may contain the same metal as the raw material metal, or may contain the same metal as the raw material metal. It is good also as not containing a kind of metal.
  • the catalytic activity of the catalytic metal particles is not particularly limited as long as the effects of the present invention can be obtained. It is more preferable to exhibit oxidation activity, and particularly preferably to exhibit at least oxygen reduction activity.
  • the present catalyst has a peak top near the Raman shift of 1600 cm -1 (specifically, for example, within the range of 1550 cm -1 or more and 1700 cm -1 or less).
  • Raman shift 2680 cm ⁇ 1 (specifically, for example, within the range of 2600 cm ⁇ 1 or more and 2800 cm ⁇ 1 or less) of the intensity ratio of the 2D band (hereinafter referred to as “Raman 2D/G ratio”).
  • Raman shift 2680 cm ⁇ 1 specifically, for example, within the range of 2600 cm ⁇ 1 or more and 2800 cm ⁇ 1 or less
  • Raman 2D/G ratio the intensity ratio of the 2D band
  • the Raman 2D/G ratio of the present catalyst is, for example, more preferably 0.25 or more, still more preferably 0.30 or more, still more preferably 0.35 or more, and 0.40 or more. It is more preferably 0.45 or more, more preferably 0.50 or more, and particularly preferably 0.55 or more.
  • the Raman 2D/G ratio of the present catalyst is, for example, preferably 0.95 or less, more preferably 0.90 or less, further preferably 0.85 or less, and 0.80 or less. is more preferably 0.75 or less, more preferably 0.70 or less, even more preferably 0.65 or less, particularly preferably 0.60 or less .
  • the Raman 2D/G ratio of the present catalyst may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • a carbon structure exhibiting a Raman 2D/G ratio that is too small that is, a carbon structure with too many layers of graphene laminates, has an excessively large amount relative to the basal plane of the edge portion, which is the starting point of oxidation deterioration, and is therefore inferior in durability.
  • a carbon structure exhibiting a Raman 2D/G ratio equal to or higher than the above-mentioned lower limit is a small-layer graphene (Few Layer Graphene), and the relative amount of the edge portion to the exposed basal surface is controlled within an appropriate range, contributing to improved durability.
  • the edge portion also functions as a supporting site for catalytic metal particles.
  • a carbon structure exhibiting a too large Raman 2D/G ratio is less suitable for supporting catalytic metal particles because the amount of edge portions relative to the basal surface is too small.
  • a carbon structure exhibiting a Raman 2D/G ratio equal to or lower than the above-described upper limit contains an appropriate amount of edge portions with respect to the basal plane, and is therefore excellent in suitability for supporting catalytic metal particles. , contributes to improving the durability and/or the catalytic function of the metal-supported catalyst.
  • the present catalyst has a peak top near Raman shift 1340 cm ⁇ 1 (specifically, in the range of 1320 cm ⁇ 1 or more and 1360 cm ⁇ 1 or less) in the Raman spectrum obtained by Raman spectroscopy. (hereinafter referred to as “Raman D half width at half maximum”) preferably has a carbon structure exhibiting 41.0 cm ⁇ 1 or less.
  • the Raman D half width at half maximum of the present catalyst is, for example, more preferably 40.0 cm ⁇ 1 or less, more preferably 38.0 cm ⁇ 1 or less, even more preferably 36.0 cm ⁇ 1 or less, It is more preferably 34.0 cm ⁇ 1 or less, further preferably 32.0 cm ⁇ 1 or less, further preferably 30.0 cm ⁇ 1 or less, further preferably 28.0 cm ⁇ 1 or less. It is preferably 27.0 cm ⁇ 1 or less, further preferably 26.5 cm ⁇ 1 or less, and particularly preferably 26.0 cm ⁇ 1 or less.
  • the Raman D half width at half maximum of the present catalyst may be, for example, 20.0 cm ⁇ 1 or more, preferably 21.0 cm ⁇ 1 or more, more preferably 22.0 cm ⁇ 1 or more, It is more preferably 22.5 cm ⁇ 1 or more, further preferably 23.0 cm ⁇ 1 or more, further preferably 23.5 cm ⁇ 1 or more, further preferably 24.0 cm ⁇ 1 or more. 24.5 cm ⁇ 1 or more is particularly preferable.
  • the Raman D half width at half maximum of the present catalyst may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the D band is close to the disordered lattice such as the edge part of the graphene layer It is a component derived from carbon atoms.
  • the half width at half maximum of the D band indicates the crystallinity of carbon around the edge. That is, as the crystallinity of the carbon around the edge portion of the carbon structure increases, the Raman D half maximum width of the carbon structure decreases. Therefore, the carbon structure exhibiting a Raman D half-width at half maximum equal to or less than the above-described upper limit contains carbon with high crystallinity around the edge portion, which contributes to the improvement of durability.
  • a carbon structure exhibiting a too small Raman D half-maximum width has too high crystallinity of carbon around the edge portion, and is therefore inferior in suitability for supporting catalytic metal particles.
  • a carbon structure exhibiting a Raman D half-width at or above the lower limit described above contains moderately crystalline carbon around the edge portion, and is therefore excellent in suitability for supporting catalytic metal particles. It contributes to improving the durability and/or the catalytic function of the supported catalyst.
  • the catalyst preferably has a BET specific surface area of 350 (m 2 /g-carbon support) or more.
  • the numerical unit "/g-carbon support” indicates a value per 1 g of the carbon support contained in the present catalyst.
  • the numerical unit "/g” indicates a value per 1 g of the present catalyst.
  • the BET specific surface area of the present catalyst is, for example, more preferably 400 (m 2 /g-carbon support) or more, further preferably 450 (m 2 /g-carbon support) or more, and more preferably 500 (m 2 /g-carbon support) or more, more preferably 550 ( m /g-carbon support) or more, more preferably 600 (m / g-carbon support) or more, It is more preferably 650 (m 2 /g-carbon support) or more, further preferably 700 (m 2 /g-carbon support) or more, and 750 (m 2 /g-carbon support) or more.
  • ⁇ is more preferably 800 (m 2 /g-carbon support) or more, more preferably 850 (m 2 /g-carbon support) or more, 900 (m 2 /g-carbon support) It is more preferably 950 (m 2 /g-carbon carrier) or more, and particularly preferably 950 (m 2 /g-carbon carrier) or more.
  • the BET specific surface area of the present catalyst may be, for example, 3000 (m 2 /g-carbon support) or less, 2500 (m 2 /g-carbon support) or less, or 2000 (m 2 / g-carbon support) or less, may be 1800 ( m /g-carbon support) or less, may be 1600 ( m /g-carbon support) or less, may be 1400 (m 2 / g-carbon support) may be less.
  • the BET specific surface area of the present catalyst may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the BET specific surface area (m 2 /g-carbon support) of the present catalyst is obtained by the BET method from the nitrogen adsorption isotherm at a temperature of 77 K, and the BET specific surface area (m 2 /g) of the present catalyst obtained by the BET method, It is calculated from the weight ratio of the carbon support contained in the present catalyst obtained by
  • the present catalyst preferably has an average pore size of 8.0 nm or less.
  • the average pore diameter of the present catalyst is, for example, more preferably 7.0 nm or less, more preferably 6.0 nm or less, even more preferably 5.0 nm or less, and 4.5 nm or less. is more preferably 4.0 nm or less, more preferably 3.5 nm or less, and most preferably 3.0 nm or less.
  • the average pore size of the present catalyst may be, for example, 1.0 nm or more, preferably 1.5 nm or more, and particularly preferably 2.0 nm or more.
  • the average pore diameter of the present catalyst may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the average pore diameter of this catalyst is obtained by the BJH method from the nitrogen adsorption isotherm at a temperature of 77K.
  • the average pore diameter of the metal-supported catalyst is too large, for example, when the metal-supported catalyst is used as an electrode catalyst for a fuel cell, the ionomer tends to enter the pores of the metal-supported catalyst, and as a result, the pores The catalyst metal particles carried inside are coated with the ionomer, and the catalytic activity tends to decrease.
  • a porous structure having an average pore diameter equal to or less than the above-mentioned upper limit value contributes to improvement in durability and/or catalytic function, since the ionomer is less likely to enter the pores.
  • the average pore diameter of the metal-supported catalyst is too small, the catalyst metal particles are more likely to be supported on the outer surface of the carbon support than in the pores, resulting in low durability.
  • a porous structure having an average pore diameter equal to or larger than the above-mentioned lower limit value contributes to improvement in durability because catalyst metal particles are effectively supported in the pores.
  • the present catalyst has a ratio of the weight of the noble metal contained in the present catalyst (more specifically, the noble metal contained in the catalyst metal particles) to the weight of the present catalyst (hereinafter referred to as "precious metal content"). is preferably 35% by weight or more.
  • the noble metal content of the present catalyst is, for example, more preferably 37% by weight or more, more preferably 40% by weight or more, still more preferably 42% by weight or more, and 45% by weight or more. is more preferable, and 47% by weight or more is particularly preferable.
  • the noble metal content of the present catalyst may be, for example, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less. good.
  • the noble metal content of the present catalyst may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • the noble metal content of the catalyst is obtained by inductively coupled plasma emission spectroscopy.
  • the catalyst preferably has a molar ratio of the noble metal contained in the catalyst to the non-noble metal contained in the catalyst (hereinafter referred to as "noble metal/non-noble metal molar ratio") of 1.0 or more.
  • the noble metal/non-noble metal molar ratio of the present catalyst is, for example, more preferably 1.5 or more, more preferably 2.0 or more, further preferably 2.5 or more, and 3.0 or more. is particularly preferred.
  • the noble metal/non-noble metal molar ratio of the present catalyst may be, for example, 20.0 or less, preferably 15.0 or less, more preferably 14.0 or less, and 13.0 or less. is more preferably 12.0 or less, more preferably 11.0 or less, and particularly preferably 10.5 or less.
  • the noble metal/non-noble metal molar ratio of the present catalyst may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • the noble metal/non-noble metal molar ratio of the present catalyst is calculated from the respective molar fractions of noble metals and non-noble metals contained in the present catalyst obtained by inductively coupled plasma emission spectroscopy.
  • the present catalyst preferably has an alloy composition non-uniformity of 0.55 or less calculated by the following formula (I).
  • the theoretical lattice constant and the measured lattice constant are the theoretical lattice constant and the measured lattice constant of the noble metal alloy contained in the present catalyst, respectively.
  • the theoretical lattice constant of the noble metal alloy contained in the present catalyst is calculated using the respective molar fractions of noble metals and non-noble metals obtained by inductively coupled plasma emission spectroscopy of the present catalyst.
  • the measured lattice constant of the noble metal alloy contained in the present catalyst is the peak top position (diffraction angle 2 ⁇ ).
  • the peak top position of the diffraction peak corresponding to the (111) plane of the platinum alloy in the X-ray diffraction pattern of the present catalyst is at a diffraction angle 2 ⁇ of 35° to It is within the range of 44°.
  • the alloy composition non-uniformity of the present catalyst is, for example, more preferably 0.50 or less, more preferably 0.48 or less, further preferably 0.45 or less, and 0.42 or less. It is more preferably 0.40 or less, and particularly preferably 0.38 or less. Also, the alloy composition non-uniformity of the present catalyst may be, for example, 0.01 or more, or may be 0.05 or more.
  • the alloy composition heterogeneity of the present catalyst may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • the alloy composition non-uniformity equal to or lower than the above upper limit indicates high uniformity of the composition of the noble metal alloy contained in the metal-supported catalyst, and contributes to improvement of durability and/or catalytic function.
  • the present catalyst preferably has half-value asymmetry and quarter-value asymmetry calculated by the following formulas (II) and (III), respectively, of 0.55 or less.
  • D m is the range of diffraction angles 2 ⁇ in which the diffraction peak of the (111) plane of the noble metal alloy appears in the X-ray diffraction pattern obtained by powder X-ray diffraction of the present catalyst (for example, When the noble metal alloy is a platinum alloy, the value of the diffraction angle 2 ⁇ at which the diffraction peak of the (111) plane of the platinum alloy appears and the diffraction angle 2 ⁇ is in the range of 35 ° to 44 °) at which the diffraction line exhibits the maximum intensity.
  • D Lh is the value of the smallest diffraction angle 2 ⁇ among the diffraction angles 2 ⁇ at which the diffraction line exhibits half the maximum intensity in the range
  • D Hh indicates half the maximum intensity of the diffraction line in the range.
  • D Lq is the smallest value of the diffraction angle 2 ⁇ among the diffraction angles 2 ⁇ at which the diffraction line exhibits a quarter of the maximum intensity in the range
  • D Hq is the value of the largest diffraction angle 2 ⁇ among the diffraction angles 2 ⁇ at which the diffraction line shows a quarter of the maximum intensity in the range.
  • Both the half-value asymmetry and the quarter-value asymmetry of the present catalyst are, for example, more preferably 0.53 or less, more preferably 0.50 or less, and further preferably 0.48 or less. It is preferably 0.45 or less, and particularly preferably 0.43 or less. Both the half-value asymmetry and the quarter-value asymmetry of the present catalyst may be, for example, 0.01 or more, or may be 0.05 or more.
  • the half-value asymmetry and the quarter-value asymmetry of the present catalyst may each be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the half-value asymmetry and quarter-value asymmetry below the upper limit value described above exhibit high uniformity in the composition of the noble metal alloy contained in the metal-supported catalyst, and contribute to improvement in durability and/or catalytic function.
  • the number average particle diameter of the catalyst metal particles contained in the present catalyst is preferably 8.0 nm or less.
  • the number average particle diameter of the catalyst metal particles is, for example, preferably 7.5 nm or less, more preferably 7.0 nm or less, even more preferably 6.5 nm or less, and 6.0 nm or less. is more preferably 5.5 nm or less, more preferably 5.0 nm or less, even more preferably 4.5 nm or less, even more preferably 4.0 nm or less, and 3 0.5 nm or less is particularly preferred.
  • the number average particle diameter of the catalyst metal particles may be, for example, 1.0 nm or more, 1.5 nm or more, or 2.0 nm or more.
  • the number average particle diameter of the catalytic metal particles contained in the present catalyst may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the number average particle diameter of the catalytic metal particles contained in the present catalyst is obtained by powder X-ray diffraction of the present catalyst.
  • Catalytic metal particles having a number average particle size equal to or less than the above upper limit contribute to improvement in durability and/or catalytic function. If the number average particle diameter of the catalytic metal particles is too large, the output characteristics may deteriorate because the metal surface area per unit metal mass of the catalytic metal particles is too small.
  • a number average particle diameter equal to or less than the above-mentioned upper limit increases the metal surface area per unit metal mass of the catalyst metal particles, contributing to the improvement of the output characteristics.
  • the volume average particle size of the catalyst metal particles contained in the present catalyst is preferably 8.0 nm or less.
  • the volume average particle diameter of the catalyst metal particles is, for example, preferably 7.5 nm or less, more preferably 7.0 nm or less, even more preferably 6.5 nm or less, and 6.0 nm or less. is more preferably 5.5 nm or less, more preferably 5.0 nm or less, even more preferably 4.5 nm or less, and particularly preferably 4.2 nm or less.
  • the volume average particle diameter of the catalyst metal particles may be, for example, 1.0 nm or more, 1.5 nm or more, or 2.0 nm or more.
  • the volume-average particle size of the catalyst metal particles contained in the present catalyst may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the volume average particle diameter of the catalytic metal particles contained in the present catalyst is obtained by powder X-ray diffraction of the present catalyst. If the volume average particle size of the catalyst metal particles is too large, the output characteristics may deteriorate because the metal surface area per unit metal mass of the catalyst metal particles is too small. The metal forming the surface of the catalyst metal particles is likely to dissolve as metal ions.
  • the volume average particle diameter equal to or less than the above upper limit increases the metal surface area per unit metal mass of the catalyst metal particles, contributes to the improvement of the output characteristics, suppresses the dissolution of the catalyst metal particles, Contributes to improvement of durability and/or catalytic function.
  • the present catalyst has a sweep speed dependence of the electrochemical effective specific surface area (ECSA) of the noble metal contained in the present catalyst (hereinafter referred to as "ECSA sweep speed dependence") calculated by the following formula (IV) is 60. % or more.
  • the numerical unit "/g-noble metal” indicates the value per 1 g of the noble metal contained in the present catalyst. That is, for example, the numerical unit “/g-Pt” indicates a value per 1 g of platinum contained in the present catalyst.
  • the ECSA sweep rate dependence of the present catalyst is, for example, more preferably 65% or more, more preferably 70% or more, even more preferably 75% or more, and particularly preferably 80% or more. preferable. Further, the ECSA sweep rate dependence of the present catalyst may be, for example, less than 100%, may be 95% or less, or may be 90% or less. The ECSA sweep rate dependence of the present catalyst may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • the ECSA sweep rate dependence (%) of platinum contained in the present catalyst is expressed in the above formula (IV) as follows: cyclic voltammetry with a potential sweep at a sweep rate of 1000 mV/sec and a sweep rate of 10 mV/sec using a rotating ring-disk electrode device having a working electrode on which the present catalyst is supported as ECSA @ 1000 mV and "ECSA @ 10 mV".
  • ECSA (m 2 /g-Pt) per gram of platinum contained in the present catalyst obtained by potential sweeping cyclic voltammetry (i.e., “ECSA @ 1000 mV (m 2 /g-Pt)” and “ECSA @ 10 mV (m 2 /g-Pt)”).
  • the catalytic metal particles supported inside the pores of the carbon support are less likely to agglomerate than the catalytic metal particles supported on the outer surface of the carbon support, thus contributing to catalytic activity and/or durability.
  • the metal-supported catalyst when most of the catalytic metal particles are supported on the outer surface of the carbon support, the decrease in ECSA due to the increase in potential sweep speed in the cyclic voltammetry described above is small.
  • the proportion of catalytic metal particles supported inside the pores of the carbon support is large, the amount of decrease in ECSA due to the increase in the potential sweep speed in the above-described cyclic voltammetry is large.
  • the magnitude of the dependence of the metal-supported catalyst on the ECSA sweep rate is greater than that of the catalyst supported inside the pores of the carbon support relative to the catalyst metal particles supported on the outer surface of the carbon support of the metal-supported catalyst. It reflects the size of the relative amount of metal particles.
  • a method for producing a metal-supported catalyst according to the present embodiment is a method for producing a metal-supported catalyst containing a carbon support and catalytic metal particles containing a noble metal alloy supported on the carbon support.
  • a method comprising: a first impregnation step of impregnating the carbon support with a precursor of one of a noble metal and a non-noble metal (hereinafter referred to as "first metal") constituting the noble metal alloy; and a precursor of the first metal.
  • a first gas phase reduction step of subjecting the carbon support impregnated with the body to a gas phase reduction treatment to obtain a first metal-supported catalyst supporting the first metal;
  • the carbon support which has not yet been impregnated with any of the precursors of the noble metals and non-precious metals that constitute the noble metal alloy contained in the catalyst metal particles, is impregnated with the precursor of the first metal.
  • the first metal may be either a noble metal or a non-noble metal that should constitute the noble metal alloy contained in the catalyst metal particles. Since the non-noble metal, which is the first metal, is ionized when impregnated with the noble metal, which is the second metal, the noble metal having a lower ionization tendency is preferable.
  • the first impregnation step includes, for example, first impregnating the carbon support with one of the two or more first metal precursors. and then impregnating the carbon support with another first metal precursor, or simultaneously impregnating the carbon support with two or more first metal precursors. It's okay.
  • the method of impregnating the carbon support with the precursor of the first metal is not particularly limited as long as the effects of the present invention can be obtained.
  • the carbon support can be impregnated with a solution containing the precursor of the first metal.
  • the first impregnation step includes, for example, first adding carbon to a solution containing one of the two or more first metal precursors. impregnating the support and then impregnating the carbon support with a solution containing one other precursor of the first metal; or a solution containing two or more precursors of the first metal. may include impregnating the carbon support with.
  • the pressure (atmospheric pressure) of the atmosphere in which the first impregnation step is performed is not particularly limited as long as the effects of the present invention can be obtained, and may be normal pressure (atmospheric pressure). It preferably includes maintaining the solution comprising the metal precursor and the carbon support under reduced pressure. By holding the solution containing the precursor of the first metal and the carbon support under reduced pressure, the inside of the pores of the carbon support is effectively degassed, and the precursor is effectively trapped inside the pores. impregnated with
  • the pressure of the reduced atmosphere holding the solution containing the precursor of the first metal and the carbon support is not particularly limited as long as the effects of the present invention can be obtained. .02 MPa) or less, preferably ⁇ 0.04 MPa or less, more preferably ⁇ 0.06 MPa or less, further preferably ⁇ 0.08 MPa or less, and ⁇ 0.10 MPa or less is particularly preferred. Also, the pressure of the reduced atmosphere holding the solution containing the first metal precursor and the carbon support may be, for example, ⁇ 0.1013 MPa or more in gauge pressure. The pressure of the reduced atmosphere holding the solution containing the precursor of the first metal and the carbon support may be specified by any combination of the above lower limit and any of the above upper limits.
  • the time for which the solution containing the precursor of the first metal and the carbon support is held under reduced pressure is not particularly limited as long as the effects of the present invention can be obtained. well, preferably 20 minutes or more, more preferably 30 minutes or more, even more preferably 40 minutes or more, even more preferably 50 minutes or more, particularly 55 minutes or more preferable.
  • the time for which the solution containing the precursor of the first metal and the carbon support is held under reduced pressure may be, for example, 24 hours or less, 5 hours or less, or 3 hours or less. good too.
  • the time for which the solution containing the precursor of the first metal and the carbon support is held under reduced pressure may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • the first impregnation step preferably includes holding the solution containing the precursor of the first metal and the carbon support under pressure. Maintaining the solution containing the precursor of the first metal and the carbon support under pressure effectively impregnates the precursor within the pores of the carbon support.
  • the pressure of the pressurized atmosphere that holds the solution containing the precursor of the first metal and the carbon support is not particularly limited as long as the effects of the present invention can be obtained. It is preferably 0.06 MPa or more, more preferably 0.09 MPa or more, still more preferably 0.12 MPa or more, and particularly preferably 0.15 MPa or more. Further, the pressure of the pressurized atmosphere holding the solution containing the precursor of the first metal and the carbon support may be, for example, 10 MPa or less in gauge pressure, or 5 MPa or less. The pressure of the pressurized atmosphere holding the solution comprising the precursor of the first metal and the carbon support may be specified in any combination of any of the above lower limits and any of the above upper limits. .
  • the time for holding the solution containing the precursor of the first metal and the carbon support under pressure is not particularly limited as long as the effects of the present invention can be obtained. well, preferably 20 minutes or more, more preferably 30 minutes or more, even more preferably 40 minutes or more, even more preferably 50 minutes or more, particularly 55 minutes or more preferable.
  • the time for holding the solution containing the precursor of the first metal and the carbon support under pressure may be, for example, 24 hours or less, 5 hours or less, or 3 hours or less. good too.
  • the time for which the solution containing the precursor of the first metal and the carbon support is held under pressure may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • the first impregnation step preferably includes holding the solution containing the precursor of the first metal and the carbon support first under reduced pressure and then under pressure.
  • the interior of the pores of the carbon support is very effectively impregnated with the precursor of the first metal.
  • the first impregnation step includes holding the solution containing the precursor of the first metal and the carbon support under reduced pressure and/or holding the solution containing the precursor of the first metal and the carbon support under pressure. prior to mixing with agitation a solution comprising the precursor of the first metal and the carbon support. By mixing the solution containing the precursor of the first metal and the carbon support with stirring before holding under reduced pressure and/or before holding under pressure, the precursor is effective inside the pores of the carbon support. effectively impregnated.
  • the solution containing the precursor of the first metal and the carbon support is kept under reduced pressure, and/or the solution containing the precursor of the first metal and the carbon support is kept under pressure. After holding, it preferably includes mixing with agitation the solution comprising the precursor of the first metal and the carbon support. After being held under reduced pressure and/or after being held under pressure, the solution containing the precursor of the first metal and the carbon support is mixed with stirring, so that the precursor is effectively inside the pores of the carbon support. impregnated with
  • the time for mixing the solution containing the precursor of the first metal and the carbon support while stirring is not particularly limited as long as the effects of the present invention can be obtained. preferably 5 hours or longer, more preferably 1 hour or longer, even more preferably 5 hours or longer, still more preferably 10 hours or longer, further preferably 18 hours or longer; It is more preferably 24 hours or longer, more preferably 35 hours or longer, even more preferably 50 hours or longer, and particularly preferably 65 hours or longer. Further, the stirring and mixing time may be, for example, 120 hours or less, 96 hours or less, or 72 hours or less. The time for stirring and mixing the solution containing the precursor of the first metal and the carbon support may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • the temperature (air temperature) of the atmosphere in which the first impregnation step is performed is not particularly limited as long as the effects of the present invention can be obtained, and may be normal temperature (for example, about 25 ° C.). It preferably includes maintaining the solution comprising the precursor of the first metal and the carbon support at a low temperature. By maintaining the solution containing the precursor of the first metal and the carbon support at a low temperature, adsorption is promoted by equilibrium shift and/or dissolution of gas molecules is promoted, and the inside of the pores of the carbon support is effectively impregnated with the precursor.
  • the first impregnation step preferably includes holding the solution containing the precursor of the first metal and the carbon support at a low temperature under reduced pressure. Also, the first impregnation step preferably includes maintaining the solution containing the precursor of the first metal and the carbon support under pressure at a low temperature. In the first impregnation step, before holding the solution containing the precursor of the first metal and the carbon support under reduced pressure, and/or holding the solution containing the precursor of the first metal and the carbon support under pressure, Preferably, prior to holding, it includes mixing with agitation the solution comprising the precursor of the first metal and the carbon support at the low temperature.
  • the solution containing the precursor of the first metal and the carbon support is kept under reduced pressure, and/or the solution containing the precursor of the first metal and the carbon support is kept under pressure.
  • it preferably comprises mixing with agitation the solution comprising the precursor of the first metal and the carbon support at the low temperature.
  • the low temperature for holding the solution containing the precursor of the first metal and the carbon support is not particularly limited as long as the effects of the present invention can be obtained, but for example, it is preferably 20° C. or less, It is more preferably 15° C. or lower, still more preferably 10° C. or lower, and particularly preferably 5° C. or lower. Also, the low temperature at which the solution containing the precursor of the first metal and the carbon support is maintained may be, for example, above 0° C. or 1° C. or above. The low temperature at which the solution containing the precursor of the first metal and the carbon support is maintained may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • first gas phase reduction treatment the carbon support impregnated with the precursor of the first metal in the first impregnation step is subjected to a gas phase reduction treatment (hereinafter referred to as “first gas phase reduction treatment”) to obtain the A first metal-supported catalyst containing a carbon support and the first metal supported on the carbon support is obtained.
  • the temperature for drying the solution containing the carbon support impregnated with the precursor of the first metal is not particularly limited as long as the effects of the present invention can be obtained.
  • the drying temperature may be, for example, 200° C. or lower, preferably 190° C. or lower, more preferably 180° C. or lower, further preferably 170° C. or lower, and 160° C. or lower. is particularly preferred.
  • the temperature for drying the solution containing the carbon support impregnated with the precursor of the first metal may be specified by any combination of any of the above lower limits and any of the above upper limits. If the temperature for drying the solution containing the carbon support impregnated with the precursor of the first metal is too low, it will take a long time to sufficiently remove the solvent, resulting in the precursor of the first metal adsorbed on the carbon support. The body may detach. Further, if the temperature for drying the solution containing the carbon support impregnated with the precursor of the first metal is too high, oxidation of the carbon support and/or bumping of the solution may cause uniform deposition of the first metal on the carbon support. proper carrying may be hindered. Therefore, as the temperature for drying the solution containing the carbon support impregnated with the precursor of the first metal, it is preferable to adopt a temperature within the above-described range.
  • the first vapor-phase reduction treatment is performed by heating the carbon support impregnated with the precursor of the first metal in a reducing atmosphere.
  • the reducing atmosphere in which the first gas-phase reduction treatment is performed is not particularly limited as long as the effects of the present invention can be obtained. An atmosphere containing gas is preferred.
  • the concentration of the reducing gas in the reducing atmosphere is not particularly limited as long as the effect of the present invention can be obtained, but for example, it is preferably 50% by volume or more, more preferably 60% by volume or more, and 70% by volume. % or more, more preferably 80% by volume or more, more preferably 90% by volume or more, even more preferably 95% by volume or more, particularly 100% by volume. preferable.
  • the temperature at which the carbon support impregnated with the precursor of the first metal is heated in the first vapor-phase reduction treatment is not particularly limited as long as the effects of the present invention can be obtained. However, for example, it is preferably 100° C. or higher, more preferably 150° C. or higher, still more preferably 200° C. or higher, further preferably 250° C. or higher, and 300° C. or higher. Especially preferred. Also, the first reduction heating temperature may be, for example, 550° C. or lower, preferably 500° C. or lower, more preferably 450° C. or lower, and particularly preferably 400° C. or lower.
  • the first reduction heating temperature may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. By adopting a temperature within the range described above as the first reduction heating temperature, it is possible to efficiently reduce the precursor of the first metal while preventing excessive aggregation of the first metal particles.
  • the time for heating at the first reduction heating temperature in the first gas-phase reduction treatment (hereinafter referred to as "first reduction heating time") is not particularly limited as long as the effects of the present invention can be obtained, but is, for example, 10 minutes or more. is preferably 30 minutes or longer, more preferably 60 minutes or longer, even more preferably 90 minutes or longer, and particularly preferably 100 minutes or longer.
  • the first reduction heating time may be, for example, 24 hours or less, preferably 12 hours or less, more preferably 6 hours or less, and particularly preferably 3 hours or less.
  • the first reduction heating time may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the first metal-supported catalyst obtained in the first gas phase reduction step is impregnated with a second metal precursor.
  • the second metal is a non-noble metal if the first metal is a noble metal and a noble metal if the first metal is a non-noble metal.
  • the second impregnation step is a step of impregnating the carbon support with the non-noble metal precursor only after the first impregnation step. is preferred.
  • the second impregnation step is a step of impregnating the carbon support with the noble metal precursor only after the first impregnation step. is preferred.
  • the method forms a noble metal alloy comprising two or more noble metals and/or two or more non-noble metals
  • only one noble metal precursor is used as the precursor of the second metal.
  • only one non-noble metal precursor may be impregnated with the first metal supported catalyst, or two or more noble metal precursors or two or more non-noble metal precursors may be impregnated with the first metal supported catalyst. may be impregnated with.
  • the second impregnation step includes, for example, first impregnating one of the two or more second metal precursors with the first impregnating the supported metal catalyst and then impregnating the supported first metal catalyst with another precursor of the second metal, or two or more precursors of the second metal It may also include simultaneously impregnating the first metal supported catalyst.
  • the method of impregnating the first metal-supported catalyst with the second metal precursor is not particularly limited as long as the effects of the present invention can be obtained. Impregnation with a catalyst is preferred.
  • the second impregnation step first includes one of the two or more second metal precursors. impregnating the first metal supported catalyst in a solution and then impregnating the first metal supported catalyst in a solution containing another second metal precursor; or It may comprise impregnating the first metal supported catalyst with a solution comprising a precursor of the second metal.
  • the pressure (atmospheric pressure) of the atmosphere in which the second impregnation step is performed is not particularly limited as long as the effects of the present invention can be obtained, and may be normal pressure (atmospheric pressure). It preferably includes maintaining the solution comprising the precursor of the metal and the supported first metal catalyst under reduced pressure. By holding the solution containing the second metal precursor and the first metal-supported catalyst under reduced pressure, the inside of the pores of the first metal-supported catalyst is effectively degassed, and the inside of the pores The precursor is effectively impregnated.
  • the pressure of the decompressed atmosphere holding the solution containing the second metal precursor and the first metal-supported catalyst is not particularly limited as long as the effects of the present invention can be obtained. (Minus 0.02 MPa) or less, preferably -0.04 MkPa or less, more preferably -0.06 MkPa or less, more preferably -0.08 MPa or less, -0 0.10 MPa or less is particularly preferred. Further, the pressure of the reduced atmosphere holding the solution containing the second metal precursor and the first metal-supported catalyst may be, for example, ⁇ 0.1013 MPa or more in gauge pressure. The pressure of the reduced atmosphere holding the solution containing the second metal precursor and the first metal-supported catalyst may be specified by any combination of the above lower limit and any of the above upper limits. .
  • the time for which the solution containing the second metal precursor and the first metal-supported catalyst is held under reduced pressure is not particularly limited as long as the effects of the present invention can be obtained. For example, it is 10 minutes or longer. It is preferably 20 minutes or longer, more preferably 30 minutes or longer, even more preferably 40 minutes or longer, even more preferably 50 minutes or longer, and 55 minutes or longer. is particularly preferred.
  • the time for which the solution containing the second metal precursor and the first metal-supported catalyst is held under reduced pressure may be, for example, 24 hours or less, 5 hours or less, or 3 hours or less. may be
  • the time for holding the solution containing the second metal precursor and the first metal-supported catalyst under reduced pressure may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. .
  • the second impregnation step preferably includes holding the solution containing the second metal precursor and the first metal-supported catalyst under pressure. Maintaining a solution containing the second metal precursor and the first metal supported catalyst under pressure effectively impregnates the precursor within the pores of the carbon support.
  • the pressure of the pressurized atmosphere that holds the solution containing the second metal precursor and the first metal-supported catalyst is not particularly limited as long as the effects of the present invention can be obtained. It may be 0.06 MPa or more, more preferably 0.09 MPa or more, still more preferably 0.12 MPa or more, and particularly preferably 0.15 MPa or more. In addition, the pressure of the pressurized atmosphere holding the solution containing the second metal precursor and the first metal-supported catalyst may be, for example, 10 MPa or less in gauge pressure, or 5 MPa or less. . The pressure of the pressurized atmosphere holding the solution containing the second metal precursor and the first metal supported catalyst is specified by any combination of any of the above lower limits and any of the above upper limits. may
  • the time for holding the solution containing the second metal precursor and the first metal-supported catalyst under pressure is not particularly limited as long as the effects of the present invention can be obtained, but for example, 10 minutes or more. It is preferably 20 minutes or longer, more preferably 30 minutes or longer, even more preferably 40 minutes or longer, even more preferably 50 minutes or longer, and 55 minutes or longer. is particularly preferred.
  • the time for holding the solution containing the second metal precursor and the first metal-supported catalyst under pressure may be, for example, 24 hours or less, 5 hours or less, or 3 hours or less. may be
  • the time for holding the solution containing the second metal precursor and the first metal-supported catalyst under pressure may be specified by any combination of any of the above lower limits and any of the above upper limits. .
  • the second impregnation step preferably includes holding the solution containing the second metal precursor and the first metal-supported catalyst first under reduced pressure and then under pressure.
  • the interior of the pores of the first metal-supported catalyst is very effectively impregnated with the precursor of the second metal.
  • the second impregnation step is performed before the solution containing the second metal precursor and the first metal-supported catalyst is held under reduced pressure and/or after the solution containing the second metal precursor and the first metal-supported catalyst is is mixed under pressure with stirring the solution comprising the precursor of the second metal and the supported first metal catalyst.
  • the solution containing the precursor of the second metal and the first metal-supported catalyst is stirred and mixed to remove the inside of the pores of the first metal-supported catalyst. is effectively impregnated with the precursor.
  • the second impregnation step after the solution containing the second metal precursor and the first metal-supported catalyst is held under reduced pressure and/or the second metal precursor and the first metal-supported catalyst are It preferably comprises mixing with stirring the solution containing the precursor of the second metal and the supported first metal catalyst after holding the solution containing under pressure. After being held under reduced pressure and/or after being held under pressure, the solution containing the precursor of the second metal and the first metal-supported catalyst is stirred and mixed to obtain the inside of the pores of the first metal-supported catalyst. The precursor is effectively impregnated.
  • the time for mixing the solution containing the second metal precursor and the first metal-supported catalyst while stirring is not particularly limited as long as the effects of the present invention can be obtained. It is preferably 0.5 hours or longer, more preferably 1 hour or longer, even more preferably 5 hours or longer, even more preferably 10 hours or longer, and preferably 18 hours or longer. It is more preferably 24 hours or longer, more preferably 35 hours or longer, even more preferably 50 hours or longer, and particularly preferably 65 hours or longer. Further, the stirring and mixing time may be, for example, 120 hours or less, 96 hours or less, or 72 hours or less. The time for mixing while stirring the solution containing the second metal precursor and the first metal-supported catalyst may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. .
  • the temperature (air temperature) of the atmosphere in which the second impregnation step is performed is not particularly limited as long as the effects of the present invention can be obtained, and may be normal temperature (for example, about 25 ° C.). It preferably includes maintaining the solution comprising the precursor of the second metal and the supported first metal catalyst at a low temperature. By maintaining the solution containing the precursor of the second metal and the first metal-supported catalyst at a low temperature, adsorption is promoted by equilibrium shift and/or dissolution of gas molecules is promoted to support the first metal. The precursor is effectively impregnated inside the pores of the catalyst.
  • the second impregnation step preferably includes holding the solution containing the second metal precursor and the first metal-supported catalyst under reduced pressure at a low temperature. Also, the second impregnation step preferably includes maintaining the solution containing the second metal precursor and the first metal-supported catalyst under pressure at a low temperature. In the second impregnation step, before the solution containing the second metal precursor and the first metal-supported catalyst is held under reduced pressure, and/or the second metal precursor and the first metal-supported catalyst are It preferably includes mixing with agitation the solution comprising the precursor of the second metal and the supported first metal catalyst at a low temperature prior to holding the solution comprising under pressure.
  • the second impregnation step after the solution containing the second metal precursor and the first metal-supported catalyst is held under reduced pressure and/or the second metal precursor and the first metal-supported catalyst are It preferably comprises mixing with stirring the solution containing the precursor of the second metal and the supported first metal catalyst at a low temperature after holding the solution containing under pressure.
  • the low temperature for holding the solution containing the second metal precursor and the first metal-supported catalyst is not particularly limited as long as the effects of the present invention can be obtained, but for example, it should be 20°C or less. is preferably 15° C. or lower, more preferably 10° C. or lower, and particularly preferably 5° C. or lower. Also, the low temperature for holding the solution containing the second metal precursor and the first metal-supported catalyst may be, for example, above 0° C. or 1° C. or higher. The low temperature at which the solution containing the second metal precursor and the first metal-supported catalyst is maintained may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • the first metal supported catalyst impregnated with the second metal precursor in the second impregnation step is subjected to a gas phase reduction treatment (hereinafter referred to as “second gas phase reduction treatment”).
  • a gas phase reduction treatment hereinafter referred to as “second gas phase reduction treatment”.
  • an alloying treatment is performed to obtain a supported metal catalyst in which catalytic metal particles containing an alloy of a first metal and a second metal (that is, a noble metal alloy that is an alloy of a noble metal and a non-noble metal) are carried.
  • the temperature for drying the solution containing the first metal-supported catalyst impregnated with the second metal precursor is not particularly limited as long as the effects of the present invention can be obtained.
  • the temperature is preferably 60° C. or higher, more preferably 80° C. or higher, and particularly preferably 100° C. or higher.
  • the temperature for drying the solution containing the first metal-supported catalyst impregnated with the second metal precursor may be, for example, 200° C. or lower, preferably 180° C. or lower, and 160° C. or lower. It is more preferably 140° C.
  • the temperature for drying the solution containing the first metal-supported catalyst impregnated with the second metal precursor may be specified by any combination of any of the above lower limits and any of the above upper limits. If the temperature for drying the solution containing the first metal-supported catalyst impregnated with the second metal precursor is too low, it will take a long time to sufficiently remove the solvent, resulting in adsorption on the first metal-supported catalyst. The precursor of the second metal may be desorbed. Further, if the temperature for drying the solution containing the first metal-supported catalyst impregnated with the second metal precursor is too high, for example, oxidation of the carbon support and/or bumping of the solution may cause Uniform loading of the second metal may be hindered. Therefore, as the temperature for drying the solution containing the first metal-supported catalyst impregnated with the second metal precursor, it is preferable to adopt a temperature within the above-described range.
  • the second gas-phase reduction treatment is performed by heating the first metal-supported catalyst impregnated with the second metal precursor in a reducing atmosphere.
  • the reducing atmosphere in which the second gas-phase reduction treatment is performed is not particularly limited as long as the effects of the present invention can be obtained. It is preferable that the atmosphere contains a chemical gas.
  • the concentration of the reducing gas in the reducing atmosphere is not particularly limited as long as the effect of the present invention can be obtained, but for example, it is preferably 50% by volume or more, more preferably 60% by volume or more, and 70% by volume. % or more, more preferably 80% by volume or more, more preferably 90% by volume or more, even more preferably 95% by volume or more, particularly 100% by volume. preferable.
  • the temperature for heating the first metal-supported catalyst impregnated with the second metal precursor in the second gas phase reduction treatment is particularly although not limited, for example, the temperature is preferably 500° C. or higher, more preferably 550° C. or higher, even more preferably 600° C. or higher, and particularly preferably 650° C. or higher.
  • the second reduction heating temperature may be, for example, 1300° C. or lower, preferably 1100° C. or lower, more preferably 1000° C. or lower, and particularly preferably 900° C. or lower.
  • the second reduction heating temperature may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the time for heating at the second reduction heating temperature in the second gas phase reduction treatment (hereinafter referred to as "second reduction heating time") is not particularly limited as long as the effects of the present invention can be obtained, but for example, 5 minutes or more. is preferably 10 minutes or longer, more preferably 30 minutes or longer, even more preferably 40 minutes or longer, and particularly preferably 50 minutes or longer.
  • the second reduction heating time may be, for example, 24 hours or less, preferably 12 hours or less, more preferably 6 hours or less, and particularly preferably 3 hours or less.
  • the second reduction heating time may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the metal-supported catalyst supporting the first metal and the second metal is heated to a temperature at which an alloy of the first metal and the second metal is formed (hereinafter referred to as “alloy (referred to as “heating temperature for curing”).
  • the alloying heating temperature is not particularly limited as long as the effect of the present invention can be obtained, but for example, it is preferably 500° C. or higher, more preferably 550° C. or higher, and further preferably 600° C. or higher. , 650° C. or higher is particularly preferred.
  • the alloying heating temperature may be, for example, 1300° C. or lower, preferably 1100° C. or lower, more preferably 1000° C. or lower, and particularly preferably 900° C. or lower.
  • the alloying heating temperature may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. By adopting a temperature within the range described above as the alloying heating temperature, it is possible to prevent excessive agglomeration of the alloy particles and advance the alloying.
  • the time for heating at the alloying heating temperature in the alloying treatment (hereinafter referred to as "alloying heating time") is not particularly limited as long as the effects of the present invention can be obtained, but for example, it is preferably 5 minutes or more. , more preferably 10 minutes or more, more preferably 30 minutes or more, even more preferably 40 minutes or more, and particularly preferably 50 minutes or more.
  • the alloying heating time may be, for example, 24 hours or less, preferably 12 hours or less, more preferably 6 hours or less, and particularly preferably 3 hours or less.
  • the alloying heating time may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. By adopting a time within the above-described range as the alloying heating time, it is possible to effectively prevent excessive agglomeration of the alloy particles while sufficiently progressing the alloying.
  • the atmosphere in which the alloying treatment is performed is not particularly limited as long as the effects of the present invention can be obtained, but it is preferably in an inert gas atmosphere or in a vacuum.
  • the inert gas atmosphere in which the alloying treatment is performed is not particularly limited as long as the effects of the present invention can be obtained, but includes, for example, one or more inert gases selected from the group consisting of nitrogen gas, argon gas and helium gas. Atmosphere is preferred.
  • the concentration of the inert gas in the inert gas atmosphere is not particularly limited as long as the effects of the present invention can be obtained, but for example, it is preferably 50% by volume or more, more preferably 60% by volume or more, and 70% by volume or more. It is more preferably vol% or more, more preferably 80 vol% or more, further preferably 90 vol% or more, further preferably 95 vol% or more, and 100 vol%. Especially preferred.
  • the second reduction heating temperature and the alloying heating temperature may be determined independently, but for example, the second reduction heating temperature is the temperature at which the reduction of the second metal proceeds. Moreover, it is preferable that the temperature be a temperature at which the alloying of the second metal and the first metal also progresses.
  • the first metal-supported catalyst impregnated with the second metal precursor is placed in a reducing atmosphere for the second reduction in which the alloying of the first metal and the second metal proceeds. Heating at the heating temperature is preferred.
  • the reduction of the precursor of the second metal and the alloying of the second metal and the first metal can proceed in parallel. The time and cost required for manufacturing are effectively reduced.
  • the time from reduction of the precursor to alloying is shortened. As a result, agglomeration of metal particles in a non-alloyed state is effectively suppressed, and as a result, support of alloy particles having a uniform alloy composition is achieved.
  • the second reduction heating temperature at which alloying proceeds is, for example, preferably 500° C. or higher, more preferably 550° C. or higher, even more preferably 600° C. or higher, and 650° C. or higher. Especially preferred. Further, the second reduction heating temperature at which alloying proceeds may be, for example, 1300° C. or lower, preferably 1100° C. or lower, more preferably 1000° C. or lower, and more preferably 900° C. or lower. Especially preferred. The second reduction heating temperature at which alloying proceeds may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the second vapor phase reduction treatment is performed in a reducing atmosphere at a second reduction heating temperature at which alloying proceeds to reduce the second metal, and then the second metal is further reduced with an inert gas.
  • the timing of performing the alloying treatment is not particularly limited as long as it is after the second vapor phase reduction treatment, but the second vapor phase reduction treatment and the alloying treatment can be performed in one container. Continuous operation is preferred. That is, in the second gas phase reduction step, for example, first, the second gas phase reduction treatment is performed in a reducing atmosphere in a container, then the reducing atmosphere in the container is exchanged with an inert gas atmosphere, and then the It is preferable to carry out the alloying treatment in an inert gas atmosphere inside the container.
  • the second gas phase reduction treatment is performed at the second reduction heating temperature in the reducing atmosphere in the container, and then the temperature in the container is changed to the second reduction temperature.
  • difference is 200° C. or less, preferably 150° C. or less, more preferably 100° C. or less, more preferably 70° C. or less, particularly preferably 50° C. or less, while maintaining the reducing atmosphere in the vessel with an inert gas. It is preferable to exchange for atmosphere.
  • the difference from the second reducing heating temperature in the inert gas atmosphere in the container is 200 ° C. or less, preferably 150 ° C. or less, more preferably is preferably 100° C. or lower, more preferably 50° C. or lower, more preferably 30° C. or lower, particularly preferably 10° C. or lower.
  • the method may further include a post-treatment step after the second gas phase reduction step.
  • the metal-supported catalyst obtained in the second gas phase reduction step is subjected to a treatment for removing excess metals and/or a treatment for removing noble metal oxides.
  • the treatment for removing excess metal is not particularly limited as long as the effects of the present invention can be obtained, but for example, cleaning treatment using an acid such as nitric acid is preferable.
  • the treatment for removing the noble metal oxide is not particularly limited as long as the effects of the present invention can be obtained, but for example, heat treatment in an inert gas atmosphere such as a nitrogen atmosphere is preferable.
  • heat treatment of the metal-supported catalyst in an inert gas atmosphere removes oxides on the metal surface generated in the treatment for removing excess metal and / or reduces the surface roughness of the metal. and contributes to the improvement of durability and/or catalytic function.
  • the temperature at which the metal-supported catalyst is heated in an inert gas atmosphere in the post-treatment step is not particularly limited as long as the effects of the present invention can be obtained. is preferably 550° C. or higher, more preferably 600° C. or higher, and particularly preferably 650° C. or higher.
  • the post-treatment heating temperature may be, for example, 1300° C. or lower, preferably 1100° C. or lower, more preferably 1000° C. or lower, and particularly preferably 900° C. or lower.
  • the post-treatment heating temperature may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the method may include an additional impregnation step and/or gas phase reduction step. That is, in the present method, for example, after the second gas phase reduction step described above, a precursor of a first metal, a second metal, or a third metal different from the first metal and the second metal is further impregnated. It may further include a third impregnation step and a third vapor phase reduction step in which vapor phase reduction treatment and alloying treatment are further performed after the third impregnation step.
  • the third impregnation step is not particularly limited as long as the effect of the present invention can be obtained, but it is preferably performed in the same manner as the above-described first impregnation step or second impregnation step, for example.
  • the third gas phase reduction step is not particularly limited as long as the effect of the present invention can be obtained, but for example, it is preferably performed in the same manner as the first gas phase reduction step or the second gas phase reduction step described above.
  • a metal-supported catalyst is produced that has both excellent durability and excellent catalytic function while having a large noble metal content. That is, the present catalyst described above is preferably produced by the present method.
  • the electrode according to the present embodiment contains the present catalyst. That is, the present electrode is, for example, a battery electrode including an electrode base material and the present catalyst supported on the electrode base material. This electrode is preferably a battery electrode. That is, the present electrode is, for example, an electrode of a fuel cell (e.g., polymer electrolyte fuel cell), air battery, water electrolyzer (e.g., polymer electrolyte water electrolyzer), redox flow battery, or halogen battery. is preferred.
  • a fuel cell e.g., polymer electrolyte fuel cell
  • air battery e.g., water electrolyzer (e.g., polymer electrolyte water electrolyzer), redox flow battery, or halogen battery.
  • water electrolyzer e.g., polymer electrolyte water electrolyzer
  • redox flow battery e.g., redox flow battery
  • halogen battery e.g., halogen battery.
  • the present electrode may be a cathode or an anode, but is preferably a cathode. That is, the electrode is a cathode or anode, preferably a cathode, of a fuel cell, air battery, water electrolyser, redox flow battery, or halogen battery.
  • the battery according to this embodiment (hereinafter referred to as "this battery”) includes this electrode.
  • the present battery is preferably a fuel cell (for example, polymer electrolyte fuel cell), an air battery, a redox flow battery, or a halogen battery including the present electrode.
  • the battery preferably has a membrane/electrode assembly (MEA) comprising the electrode.
  • MEA membrane/electrode assembly
  • the present battery is a battery having the present electrode as a cathode or an anode, preferably a battery having the present electrode as a cathode. That is, the present battery is a fuel cell, air battery, redox flow battery or halogen battery having the present electrode as a cathode or anode, preferably a fuel cell, air battery, redox flow battery or halogen battery having the present electrode as a cathode Battery.
  • the infusible mixture was carbonized by heating at 1500°C under a gauge pressure of 0.90 MPa in a nitrogen atmosphere.
  • Dilute hydrochloric acid was added to the carbonized material obtained by carbonization, and the mixture was stirred. Thereafter, the suspension containing the carbonized material was filtered using a filtration membrane, and the carbonized material was washed with distilled water until the filtrate became neutral. In this way, a metal removal treatment was performed by acid cleaning.
  • the carbonized material after the metal removal treatment was pulverized with a pulverizer until the median particle size was 0.4 ⁇ m or less.
  • the pulverized carbonized material was vacuum-dried to remove moisture. After that, the carbonized material was subjected to heat treatment at 300° C. in a nitrogen atmosphere. Furthermore, graphitization treatment was performed by heating the carbonized material thus obtained at 2000° C. under normal pressure in a nitrogen atmosphere. The carbonized material thus obtained was used as a carbon support.
  • the catalytic metal particles were supported on the carbon carrier by the following vapor phase reduction method.
  • a first impregnation step was performed. That is, 1 g of the carbon support and 22.2 g of an aqueous solution containing chloroplatinic acid (H 2 PtCl 6 ), which is a platinum precursor, in an amount to give a platinum concentration of 5% by weight (platinum content of 1.11 g) were stirred for 1 hour. and mixed.
  • the mixed solution is first held under a reduced pressure of ⁇ 0.10 MPa or less in gauge pressure (specifically, ⁇ 0.10 MPa to ⁇ 0.1013 MPa in gauge pressure) for 1 hour, and then 0.15 MPa in gauge pressure.
  • the above pressure (specifically, 0.15 MPa to 0.20 MPa in gauge pressure) was maintained for 1 hour, and then stirred and mixed for 66 hours.
  • This first impregnation step was performed while maintaining the temperature of the mixed solution at 5° C. or less (specifically, 0° C. to 5° C.).
  • the first gas phase reduction step was performed. That is, the mixed solution obtained in the first impregnation step was dried at 100° C. under vacuum and further held at 150° C. in a nitrogen atmosphere to volatilize the solvent component. The obtained solid matter was subjected to a heat treatment (first gas phase reduction treatment) at 350° C. for 120 minutes in a hydrogen atmosphere (100% by volume of hydrogen gas) to obtain a supported platinum catalyst.
  • a second impregnation step was then performed. That is, 2.1 g of the platinum-supported catalyst obtained in the first gas phase reduction step and cobalt chloride (CoCl 2 ) was stirred for 1 hour and mixed.
  • the mixed solution is first held under a reduced pressure of ⁇ 0.10 MPa or less in gauge pressure (specifically, ⁇ 0.10 MPa to ⁇ 0.1013 MPa in gauge pressure) for 1 hour, and then 0.15 MPa in gauge pressure.
  • the above pressure specifically, 0.15 MPa to 0.20 MPa in gauge pressure
  • This second impregnation step was performed while maintaining the temperature of the mixed solution at 5° C. or less (specifically, 0° C. to 5° C.).
  • the second vapor phase reduction process was carried out. That is, the mixed solution obtained in the second impregnation step was dried at 100°C under vacuum. The obtained solid is subjected to heat treatment (second gas phase reduction treatment) at 700 ° C. for 60 minutes in a hydrogen atmosphere (100% by volume of hydrogen gas), and then the temperature of the atmosphere is adjusted to within the range of 650 to 750 ° C. While maintaining the hydrogen atmosphere, the hydrogen atmosphere was replaced with a nitrogen atmosphere (nitrogen gas 100% by volume), and heat treatment (alloying treatment) was performed in the nitrogen atmosphere at 700° C. for 120 minutes to obtain a supported platinum alloy catalyst.
  • second gas phase reduction treatment a hydrogen atmosphere (100% by volume of hydrogen gas)
  • the post-processing process was carried out. That is, in order to remove excess metal from the platinum alloy-supported catalyst obtained in the second gas phase reduction step, the platinum alloy-supported catalyst and a 10% nitric acid solution were mixed for 2 hours. Thereafter, the platinum alloy-supported catalyst was separated from the acid solution by filtration, and the platinum alloy-supported catalyst was washed with distilled water until the filtrate became neutral. The washed platinum alloy-supported catalyst was dried in vacuum at 60° C. to remove moisture.
  • the platinum alloy supported catalyst was heat-treated at 300°C in nitrogen. Furthermore, in order to reduce and remove the platinum oxide, the platinum alloy-supported catalyst was subjected to heat treatment at 700° C. in nitrogen. Thus, a metal-supported catalyst containing a carbon support and platinum-cobalt alloy particles supported on the carbon support was obtained.
  • Example 2 in the second impregnation step, 20 g of an aqueous solution containing cobalt chloride in an amount to give a cobalt concentration of 0.32% by weight (cobalt content of 0.064 g) was used. In the same manner as in , a metal-supported catalyst containing a carbon support and platinum and cobalt alloy particles supported on the carbon support was obtained.
  • Example 3 the carbon support and the carbon support were prepared in the same manner as in Example 1 above, except that the first impregnation step and the second impregnation step were performed while the temperature of the mixed solution was kept at 25 ° C.
  • a metal-supported catalyst comprising supported platinum and cobalt alloy particles was obtained.
  • Example 4 after holding the mixed solution under reduced pressure and under increased pressure for 1 hour each, the mixed solution was stirred for 18 hours instead of 66 hours, and mixed as in Example 1 and the like described above. Thus, a metal-supported catalyst containing a carbon support and platinum-cobalt alloy particles supported on the carbon support was obtained.
  • Example 5 was the same as Example 1 above, except that in the second impregnation step, 20 g of an aqueous solution containing cobalt chloride in an amount to give a cobalt concentration of 0.23% by weight (cobalt content of 0.045 g) was used. In the same manner as in , a metal-supported catalyst containing a carbon support and platinum and cobalt alloy particles supported on the carbon support was obtained.
  • Example 6 instead of the aqueous solution containing cobalt chloride in the second impregnation step, an amount of nickel chloride hexahydrate (NiCl 2.6H A metal-supported catalyst containing a carbon support and platinum and nickel alloy particles supported on the carbon support was obtained in the same manner as in Example 1, etc., except that 20 g of an aqueous solution containing 2 O) was used. Ta.
  • Example 7 the aqueous solution containing cobalt chloride was replaced in the second impregnation step with a nickel concentration of 0.278 wt.% (nickel content of 0.056 g) and a manganese concentration of 260 wt. 052 g) of nickel chloride hexahydrate (NiCl 2 .6H 2 O) and manganese chloride tetrahydrate (MnCl 2 .4H 2 O) in an amount of 20 g of an aqueous solution such as Example 1 above.
  • a metal-supported catalyst containing a carbon support and alloy particles of platinum, nickel and manganese supported on the carbon support was obtained in the same manner as in the case of .
  • Example 8 the procedure was the same as in Example 1 and the like above, except that 17.8 g of an aqueous solution containing chloroplatinic acid was used in an amount that gave a platinum concentration of 5% by weight (platinum content: 0.89 g). , a first impregnation step was performed. Thereafter, the first gas phase reduction step, the second impregnation step and the second gas phase reduction step were carried out in the same manner as in Example 1 and the like.
  • the third impregnation step was performed. That is, 1.99 g of the platinum alloy-supported catalyst obtained in the second gas phase reduction step and 22.2 g of an aqueous solution containing chloroplatinic acid in an amount that makes the platinum concentration 1% by weight (platinum content 0.22 g) Stir for 1 hour and mix.
  • the mixed solution is first held at a reduced pressure of ⁇ 0.10 MPa or less in gauge pressure (specifically, ⁇ 0.10 MPa to ⁇ 0.1013 MPa in gauge pressure) for 1 hour, and then 0.15 MPa or more in gauge pressure. (Specifically, 0.15 MPa to 0.20 MPa in terms of gauge pressure) was maintained for 1 hour, and then stirred and mixed for 66 hours.
  • This third impregnation step was performed while maintaining the temperature of the mixed solution at 5° C. or lower.
  • the third vapor phase reduction step was performed. That is, the mixed liquid obtained in the third impregnation step was dried at 100° C. in vacuum and further held at 150° C. in nitrogen to volatilize the solvent component.
  • the obtained solid was subjected to heat treatment (gas phase reduction treatment) at 700° C. for 60 minutes in a hydrogen atmosphere (100% by volume of hydrogen gas), followed by maintaining the temperature of the atmosphere within the range of 650 to 750° C. Meanwhile, the hydrogen atmosphere was replaced with a nitrogen atmosphere (nitrogen gas 100% by volume), and heat treatment (alloying treatment) was performed in the nitrogen atmosphere at 700° C. for 120 minutes. Thereafter, a post-treatment step was carried out in the same manner as in Example 1 and the like described above to obtain a metal-supported catalyst containing a carbon support and platinum-cobalt alloy particles supported on the carbon support.
  • Example 9 instead of holding the mixed solution under reduced pressure for 1 hour and under increased pressure for 1 hour in the first impregnation step and the second impregnation step, the mixed solution was held under atmospheric pressure for 2 hours.
  • a metal-supported catalyst containing a carbon support and platinum-cobalt alloy particles supported on the carbon support was obtained in the same manner as in Example 1, etc. above.
  • Example 10 carbon A supported metal catalyst containing a support and platinum and cobalt alloy particles supported on the carbon support was obtained.
  • Example C1 as in Example 1 above, except that in the first impregnation step, 9.0 g of an aqueous solution containing chloroplatinic acid in an amount to give a platinum concentration of 5% by weight (platinum content of 0.45 g) was used. In the same manner as in , a metal-supported catalyst containing a carbon support and platinum and cobalt alloy particles supported on the carbon support was obtained.
  • Example C2 in the first impregnation step, instead of the aqueous solution containing chloroplatinic acid, the platinum concentration was 5% by weight (platinum content 1.1 g) and the cobalt concentration was 0.56% by weight (cobalt content 0.112 g) of an aqueous solution containing chloroplatinic acid and cobalt chloride in an amount of 42.2 g), and in the first impregnation step and the second impregnation step, the mixed solution was heated under reduced pressure for 1 hour and under pressure for 1 hour. Instead of holding, the mixed solution was held under atmospheric pressure for 2 hours, and the second impregnation step and the second gas phase reduction step were not performed. Thus, a metal-supported catalyst containing a carbon support and platinum-cobalt alloy particles supported on the carbon support was obtained.
  • Example C3 the heating temperature in the hydrogen atmosphere and the nitrogen atmosphere in the second gas phase reduction step was set to 500°C instead of 700°C, in the same manner as in Example 1, etc.
  • Example C4 catalyst metal particles were supported on a carbon carrier by the following liquid phase reduction method.
  • a first impregnation step was performed. That is, 1 g of the carbon carrier and 22.2 g of an aqueous solution containing chloroplatinic acid in an amount to give a platinum concentration of 5% by weight (platinum content of 1.11 g) were stirred and mixed for 1 hour.
  • the mixed solution is first held under a reduced pressure of ⁇ 0.10 MPa or less in gauge pressure (specifically, ⁇ 0.10 MPa to ⁇ 0.1013 MPa in gauge pressure) for 1 hour, and then 0.15 MPa in gauge pressure.
  • the above pressure (specifically, 0.15 MPa to 0.20 MPa in gauge pressure) was maintained for 1 hour, and then stirred and mixed for 66 hours.
  • This first impregnation step was performed while maintaining the temperature of the mixed solution at 5° C. or less (specifically, 0° C. to 5° C.).
  • the first liquid phase reduction step was performed. That is, ethylene glycol was added as a reducing agent to the mixed solution obtained in the first impregnation step, and the mixed solution was maintained at 80° C. in the air for 4 hours to perform a liquid phase reduction treatment, thereby obtaining a supported platinum catalyst.
  • the second impregnation step was carried out. That is, the mixed liquid obtained in the first liquid phase reduction step was dried at 100° C. in vacuum and further held at 150° C. in nitrogen to volatilize the solvent component. 2.0 g of the obtained platinum-supported catalyst and 20 g of an aqueous solution containing cobalt chloride in an amount to give a cobalt concentration of 0.56% by weight (cobalt content of 0.112 g) were stirred for 1 hour and mixed.
  • the mixed solution is held under reduced pressure of ⁇ 0.10 MPa or less at gauge pressure (specifically, ⁇ 0.10 MPa to ⁇ 0.1013 MPa at gauge pressure) for 1 hour, and then 0.15 MPa or more at gauge pressure ( Specifically, the mixture was held under a pressure of 0.15 MPa to 0.20 MPa (gage pressure) for 1 hour, and then stirred for 18 hours for mixing.
  • This second impregnation step was performed while maintaining the temperature of the mixed solution at 5° C. or less (specifically, 0° C. to 5° C.).
  • the second liquid phase reduction process was carried out. Specifically, ethylene glycol was added as a reducing agent to the liquid mixture obtained in the second impregnation step, and the mixture was maintained in the air at 80° C. for 4 hours to perform a liquid phase reduction treatment.
  • the alloying process was carried out. That is, the mixed liquid obtained in the second liquid phase reduction step was dried at 100° C. in vacuum. The obtained solid is subjected to heat treatment (alloying treatment) at 700° C. for 60 minutes in a hydrogen atmosphere (100% by volume of hydrogen gas), and then while maintaining the temperature of the atmosphere within the range of 650 to 750° C. , the hydrogen atmosphere was replaced with a nitrogen atmosphere (nitrogen gas 100% by volume), and heat treatment was performed in the nitrogen atmosphere at 700° C. for 120 minutes to obtain a platinum alloy-supported catalyst.
  • heat treatment alloying treatment
  • the post-processing process was carried out. That is, in order to remove excess metal from the platinum alloy-supported catalyst obtained in the alloying step, the platinum alloy-supported catalyst and a 10% nitric acid solution were mixed for 2 hours. Thereafter, the platinum alloy-supported catalyst was separated from the acid solution by filtration, and the platinum alloy-supported catalyst was washed with distilled water until the filtrate became neutral. The washed platinum alloy-supported catalyst was dried in vacuum at 60° C. to remove moisture.
  • the platinum alloy supported catalyst was heat-treated at 300°C in nitrogen. Furthermore, in order to reduce and remove the platinum oxide, the platinum alloy-supported catalyst was subjected to heat treatment at 700° C. in nitrogen. Thus, a metal-supported catalyst containing a carbon support and platinum-cobalt alloy particles supported on the carbon support was obtained.
  • Raman spectroscopy Metal-supported catalysts were analyzed by Raman spectroscopy.
  • the Raman spectrum was measured using a HORIBA microlaser Raman spectrometer (LabRAM, HORIBA Jobin Yvon).
  • the laser used for the measurement had an excitation wavelength of 532 nm, an output of 50 mW, and a Raman spectrum was obtained by measuring under the conditions of 90 seconds of exposure and 2 times of integration via a neutral density filter D3.
  • a baseline correction was applied to the obtained Raman spectrum. That is, a straight line connecting the scattering intensity near 600 cm ⁇ 1 with a Raman shift (cm ⁇ 1 ) and the scattering intensity near 2000 cm ⁇ 1 is determined as the baseline, and the baseline is subtracted from each intensity of the scattering spectrum. Baseline correction was performed.
  • a 2D band having a peak top at 2800 cm ⁇ 1 or less was identified.
  • FIG. 1 shows the result of analyzing the Raman spectrum obtained by Raman spectroscopy of the metal-supported catalyst of Example 1 as an example of the Raman spectrum.
  • the horizontal axis indicates the Raman shift (cm ⁇ 1 )
  • the vertical axis indicates the scattering intensity after baseline correction
  • Ad indicates the Raman shift (cm ⁇ 1 ) corresponding to the peak top of the D band.
  • B d indicates the Raman shift (cm ⁇ 1 ) corresponding to the Raman spectrum showing half the intensity of the D band intensity I d (the height of the peak top of the D band) on the lower wavenumber side than A d .
  • FIG. 1 also shows the intensity I g of the G band (the height of the peak top of the G band) and the intensity I 2d of the 2D band (the height of the peak top of the 2D band), respectively.
  • ICP-OES inductively coupled plasma-optical emission spectroscopy
  • the metal-supported catalyst was immersed in 5 mL of aqua regia and heated at 50°C for 1 hour to dissolve the metal contained in the metal-supported catalyst. Further, distilled water was added to dilute the volume to 50 mL to obtain a metal solution. Thereafter, the platinum concentration and non-platinum metal concentration of the obtained metal solution were measured using a sequential type plasma emission spectrometer (ICPS-8100, manufactured by Shimadzu Corporation).
  • ICPS-8100 sequential type plasma emission spectrometer
  • Specific surface area and average pore diameter The specific surface area and average pore size of the metal-supported catalyst by the nitrogen adsorption method were measured using a specific surface area/pore size distribution measuring device (TriStar II 3020, manufactured by Shimadzu Corporation) and the attached analysis software (TriStar II 3020). .
  • the metal-supported catalyst was held at 100° C. and 6.7 ⁇ 10 ⁇ 2 Pa for 3 hours to remove moisture adsorbed on the metal-supported catalyst.
  • the nitrogen adsorption isotherm at a temperature of 77K was obtained by measuring the change in the amount of nitrogen adsorbed on the metal-supported catalyst accompanying the change in the pressure of the nitrogen gas.
  • the BET specific surface area (m 2 /g) of the metal-supported catalyst was calculated.
  • the total pore volume (cm 3 /g) of the metal-supported catalyst was obtained from the adsorption amount at the point where the relative pressure P/P 0 was 0.98 on the nitrogen adsorption isotherm at a temperature of 77K.
  • Average pore diameter (nm) 4 ⁇ ⁇ whole fine Pore volume (cm 3 /g) ⁇ 10 21 ⁇ / ⁇ specific surface area (m 2 /g) ⁇ 10 18 ⁇ .
  • the measured lattice constant of the platinum alloy contained in the metal-supported catalyst which is obtained by powder X-ray diffraction (XRD) of the metal-supported catalyst, and the platinum contained in the metal-supported catalyst, which is obtained by ICP-OES of the metal-supported catalyst.
  • the alloy composition nonuniformity was calculated by the following formula (I) using the theoretical lattice constant of the alloy. That is, the alloy composition non-uniformity was calculated by subtracting the value obtained by dividing the theoretical lattice constant by the actually measured lattice constant from 1 and multiplying by 100.
  • the measured lattice constant of the platinum alloy contained in the metal-supported catalyst was obtained using Bragg's equation from the XRD pattern obtained by powder X-ray diffraction of the metal-supported catalyst.
  • XRD measurement was performed using an X-ray diffractometer (Rigaku RINT2100/PC, Rigaku Corporation).
  • the voltage and current applied to the X-ray tube were 50 kV and 300 mA, respectively.
  • the sampling interval was 0.1°
  • the scanning speed was 1°/min
  • the measurement angle range (2 ⁇ ) was 5 to 90°.
  • CuK ⁇ was used as incident X-rays.
  • the sample thickness was 0.5 mm, and the divergence slit width ⁇ was 2/3°.
  • d is the lattice spacing
  • ⁇ is the X-ray incidence angle
  • ⁇ is the X-ray incidence wavelength
  • n is an integer.
  • d is the lattice spacing
  • a is the lattice constant (actually measured lattice constant)
  • h, k and l are the plane indices.
  • the theoretical lattice constant of the platinum alloy contained in the metal-supported catalyst was calculated from Vegard's law by determining the molar fractions of platinum and non-platinum metals by ICP-OES measurement.
  • Vegard's law is an empirical rule showing the relationship between the composition of an alloy and its lattice constant, and the lattice constant (theoretical lattice constant) a of an alloy is calculated by the following formula (V).
  • a on the left side is the lattice constant (theoretical lattice constant) of the alloy
  • N is the mole fraction of each metal
  • N A , N B and N c are metal A, metal B and the molar fraction of metal C
  • a on the right side is the lattice constant of each metal alone
  • a A , a B and ac are the lattice constants of metal A, metal B and metal C alone.
  • the molar fraction of each metal was obtained by measuring the metal content of the supported metal catalyst using ICP-OES. That is, by dividing the platinum content (% by weight) and the content (% by weight) of one or more non-platinum metals obtained by ICP-OES as described above by the atomic weight of each metal species, platinum, and the molar amount of each of the one or more non-platinum metals was calculated. Then, by dividing the molar amount of each metal species by the total molar amount of all metal species, the molar fraction of each metal species was calculated. The theoretical lattice constant of the platinum alloy was obtained by substituting the molar fraction obtained in this manner into the Vegard's law equation.
  • Formulas (II) and (III) above are explained with reference to a typical XRD pattern shown in FIG.
  • Dm is diffracted in the diffraction angle 2 ⁇ range of 35° to 44° in the XRD pattern of the metal-supported catalyst (the diffraction angle 2 ⁇ range in which the diffraction peak of the (111) plane of the platinum alloy appears).
  • the line is the value of the diffraction angle 2 ⁇ (the position of the peak top) showing the maximum intensity IM
  • D Lh is the intensity at which the diffraction line is half the maximum intensity IM when the diffraction angle 2 ⁇ is in the range of 35° to 44°.
  • D Hh is the value of the smallest diffraction angle 2 ⁇ among the diffraction angles 2 ⁇ indicating I h
  • D Hh is the value of half the maximum intensity I M of the diffraction line when the diffraction angle 2 ⁇ is in the range of 35° to 44°
  • D Lq is the value of the largest diffraction angle 2 ⁇ among the diffraction angles 2 ⁇ shown.
  • D Hq is the value of the smallest diffraction angle 2 ⁇ among the diffraction angles 2 ⁇ shown. It is the value of the largest diffraction angle 2 ⁇ among the diffraction angles 2 ⁇ shown.
  • Figures 3A and 3B show the XRD patterns obtained for the metal-supported catalysts of Examples 1 and 5, respectively.
  • Figures 4A and 4B also show the XRD patterns obtained for the supported metal catalysts of Examples C2 and C4, respectively.
  • Platinum/non-platinum metal molar ratio The ratio of the molar amount of platinum to the molar amount of non-platinum metals constituting the platinum alloy particles supported on the metal-supported catalyst (Pt/M molar ratio) is the ratio of the platinum obtained by ICP-OES as described above. The mole fraction was calculated by dividing by the mole fraction of the non-platinum metal.
  • the number average particle size (nm) and volume average particle size (nm) of the catalyst metal particles supported on the carbon support in the metal supported catalyst were measured by a powder X-ray diffraction (XRD) method. That is, first, a powdery metal-supported catalyst sample is placed in a concave portion (2 cm x 2 cm x 0.5 mm thick) of a glass sample plate and pressed with a slide glass so that the surface of the sample is aligned with the reference surface. The recess was uniformly filled in such a manner as to Then, the glass sample plate was fixed on a wide-angle X-ray diffraction sample stage so that the filled sample would not lose its shape.
  • XRD powder X-ray diffraction
  • powder X-ray diffraction measurement was performed using an X-ray diffractometer (Rigaku RINT2100/PC, Rigaku Corporation).
  • the voltage and current applied to the X-ray tube were 50 kV and 300 mA, respectively.
  • the sampling interval was 0.1°
  • the scanning speed was 1°/min
  • the measurement angle range (2 ⁇ ) was 5 to 90°.
  • CuK ⁇ was used as incident X-rays.
  • the sample thickness was 0.5 mm, and the divergence slit width ⁇ was 2/3°.
  • the obtained XRD pattern was subjected to peak separation using a Gaussian function as described later, and the crystallite size corresponding to each peak obtained by the peak separation was determined using Scherrer's formula.
  • the number average particle size of the catalyst metal particles was calculated by weighted averaging using the obtained crystallite size and the number, that is, "peak area ratio/crystallite size 3 " as a weight.
  • the volume average particle size of the catalyst metal particles was calculated by weighted averaging using the obtained crystallite size as a weight, that is, the volume, that is, the “peak area ratio”.
  • the method for obtaining the number average particle size (nm) and the volume average particle size (nm) will be explained more specifically.
  • the XRD pattern obtained by powder X-ray diffraction using CuK ⁇ rays shows that the diffraction angle (2 ⁇ ) is around 40° (for example, 35° to 44°
  • the (111) diffraction line of the platinum alloy appears at the position of (within the range of ).
  • This diffraction line includes a diffraction line derived from pure platinum, a diffraction line derived from a platinum alloy, and a diffraction line derived from the carbon structure of the carbon support.
  • a diffraction line derived from pure platinum is defined as a diffraction line having a peak top at a diffraction angle (2 ⁇ ) of 39.6° or more and less than 39.8°.
  • a diffraction line derived from a platinum alloy is defined as a diffraction line having a peak top at a diffraction angle (2 ⁇ ) of 39.9° or more and less than 43.0°.
  • a diffraction line derived from the carbon structure of the carbon support is defined as a diffraction line having a peak top at a diffraction angle (2 ⁇ ) of 43.3° or more and less than 43.7°.
  • the metal-supported catalyst contains multiple types of platinum alloys with different compositions and/or crystal structures, multiple diffraction lines derived from the platinum alloys appear.
  • the diffraction angle at which the peak top of the diffraction line originating from the platinum alloy is located is determined by its composition and crystal structure.
  • a diffraction line derived from a platinum-cobalt alloy represented by the composition PtCo is defined as a diffraction line having a peak top at a diffraction angle of 41.4° or more and less than 41.8°.
  • a diffraction line derived from a platinum-cobalt alloy represented by the composition Pt 3 Co is defined as a diffraction line having a peak top at a diffraction angle of 40.3° or more and less than 41.2°.
  • the diffraction line derived from the platinum-cobalt alloy represented by the composition Pt 7 Co is defined as a diffraction line having a peak top at a diffraction angle of 39.9° or more and less than 40.3°.
  • a diffraction line derived from a platinum-nickel alloy represented by the composition PtNi is defined as a diffraction line having a peak top at a diffraction angle of 41.6° or more and less than 42.0°.
  • a diffraction line derived from a platinum-nickel alloy represented by the composition Pt 3 Ni is defined as a diffraction line having a peak top at a diffraction angle of 40.4° or more and less than 41.2°.
  • a diffraction line derived from a platinum-nickel alloy represented by the composition Pt 7 Ni is defined as a diffraction line having a peak top at a diffraction angle of 39.9° or more and less than 40.3°.
  • a diffraction line derived from a platinum-nickel-manganese alloy represented by the composition Pt 6 Ni 1 Mn 1 is defined as a diffraction line having a peak top at a diffraction angle of 40.1° or more and less than 40.8°.
  • the metal-supported catalyst contains a plurality of types of platinum particles having the same composition and crystal structure but different crystallite diameters, a plurality of diffraction patterns having peak tops at substantially the same diffraction angle positions and different full widths at half maximum A line appears.
  • the (111) diffraction line of the platinum alloy appeared at a position where the diffraction angle (2 ⁇ ) was around 40°. Therefore, baseline correction was performed first. That is, a straight line connecting the diffraction intensity at a diffraction angle (2 ⁇ ) of 35° to 37° and the diffraction intensity at 50° to 52° is determined as a baseline, and the baseline is subtracted from each intensity of the diffraction line. Baseline correction was performed.
  • the diffraction line after baseline correction was separated into one or more pure platinum-derived peaks and/or one or more platinum alloy-derived peaks, and a carbon-derived peak. Separation of the diffraction line is assumed that each of the plurality of peaks obtained by the separation is represented by a Gaussian function, and the sum of the intensity of the diffraction line and the intensity of each of the plurality of peaks at each diffraction angle of the XRD pattern The intensity of the Gaussian function of each of the plurality of peaks, the diffraction angle of the peak top, and by optimizing the full width at half maximum.
  • the diffraction angle (2 ⁇ ) has a peak top at a position near 40° (within the range of 39° to 44°). Peak separation of the (111) diffraction line of a platinum-cobalt alloy will be described.
  • the diffraction line having the peak top at the diffraction angle (2 ⁇ ) of 40.6 ° is divided into the first peak derived from Pt 3 Co and the second peak derived from Pt 3 Co. It was separated into three components consisting of a peak due to carbon and a peak derived from carbon.
  • the diffraction line “after baseline correction” indicates the diffraction line obtained by performing baseline correction on the diffraction line obtained by XRD measurement
  • the peak of “Pt 3 Co (1)”, “ Pt 3 Co (2)” peak and “carbon” peak are respectively the first Pt 3 Co-derived peak and the second Pt 3 Co peak obtained by peak separation of the diffraction line “after baseline correction”.
  • a peak derived from Pt 3 Co and a peak derived from carbon are indicated.
  • the diffraction line after the baseline correction is adjusted so that the spread of the tail when the diffraction angle (2 ⁇ ) is around 35° to around 39° matches the intensity up to the eighth point of the peak.
  • the sharp angle of the peak top around 40.6° could not be reproduced.
  • the diffraction line derived from the platinum-cobalt alloy represented by Pt 3 Co has a peak top at a diffraction angle of 40.3 ° or more and less than 41.2 °, so 40.6 It was considered that the diffraction line of the third Pt 3 Co having a peak top at a position near 10° was mixed.
  • the diffraction line having the peak top at the diffraction angle (2 ⁇ ) of 40.6 ° is divided into the first peak derived from Pt 3 Co and the second peak derived from Pt 3 Co. It was separated into four components consisting of a peak derived from Pt 3 Co, a third peak derived from Pt 3 Co, and a peak derived from carbon.
  • FIG. 5C shows the results of this peak separation into four components.
  • FIG. 5D shows an enlarged part of FIG. 5C.
  • the diffraction line “after baseline correction” indicates the diffraction line obtained by performing baseline correction on the diffraction line obtained by XRD measurement, and is the diffraction line of “Pt 3 Co (1)”.
  • the peak, the “Pt 3 Co(2)” peak, the “Pt 3 Co(3)” peak, and the “carbon” peak, respectively, were obtained by peak separation of the diffraction lines after the “baseline correction”. , a first Pt 3 Co peak, a second Pt 3 Co peak, a third Pt 3 Co peak, and a carbon peak.
  • the metal-supported catalyst of Example 2 supported the first Pt 3 Co particles, the second Pt 3 Co particles, and the third Pt 3 Co particles as the platinum-cobalt alloy particles. .
  • crystallite size (nm) K ⁇ / ⁇ cos ⁇ .
  • K is the Scherrer constant (0.94)
  • ⁇ is the wavelength of CuK ⁇ rays (0.15418 nm)
  • ⁇ is the full width at half maximum (radian)
  • ⁇ is Diffraction angle (radian).
  • the crystallite size of the first Pt 3 Co particles is obtained by substituting the diffraction angle and full width at half maximum of the separation peak of “Pt 3 Co (1)” in the XRD pattern shown in FIG. 5C into the above Scherrer formula. Calculated by As a result, the crystallite size of the first Pt 3 Co particles was calculated to be 2.9 nm, the crystallite size of the second Pt 3 Co particles was calculated to be 3.4 nm, and the crystallite size of the third Pt 3 Co particles was calculated to be 3.4 nm. The child diameter was calculated to be 10.7 nm.
  • the area of each of the three Pt 3 Co separation peaks obtained in the above peak separation (that is, the peak area of "Pt 3 Co (1)", the peak area of "Pt 3 Co (2)", and the “ Pt 3 Co (3)” peak area) is divided by the sum of the areas of the three Pt 3 Co separated peaks and multiplied by 100 to obtain the peak area ratio (%) of each of the Pt 3 Co separated peaks was calculated.
  • the peak area ratio of the first Pt 3 Co particles was calculated to be 55.2%
  • the peak area ratio of the second Pt 3 Co particles was calculated to be 35.0%
  • the third Pt 3 Co particles was calculated to be 9.8%.
  • FIG. 6A shows the results of peak separation in the XRD pattern obtained for the metal-supported catalyst of Example C2.
  • FIG. 6B shows an enlarged part of the XRD pattern shown in FIG. 6A.
  • the diffraction lines after baseline correction were separated into one pure platinum-derived peak, one platinum-cobalt alloy-derived peak, and a carbon-derived peak.
  • the three diffraction lines of the third Pt which has a different crystallite diameter and a smaller full width at half maximum than the first and second Pt, were considered to overlap.
  • the diffraction line of the first Pt 3 Co having a relatively large full width at half maximum at the peak at 41.0 °
  • the diffraction line of the second Pt 3 Co having a different crystallite diameter and a smaller full width at half maximum from the first PtCo It was considered that three diffraction lines overlapped with the diffraction line of the third Pt 3 Co, which has a different crystallite diameter from the first and second Pt 3 Co and a smaller full width at half maximum.
  • the metal-supported catalyst contains a carbon support, it was thought that the diffraction line (2 ⁇ ) would have a carbon-derived diffraction line near 43.5°.
  • a diffraction line having a peak top at a diffraction angle (2 ⁇ ) of 39.7° and a diffraction line having a diffraction angle (2 ⁇ ) of 40.1° The diffraction lines having peak tops at the positions are divided into a first Pt-derived peak, a second Pt-derived peak, a third Pt-derived peak, and a first Pt 3 Co-derived peak. , a second Pt 3 Co-derived peak, a third Pt 3 Co-derived peak, and a carbon-derived peak.
  • the diffraction line “after baseline correction” indicates the diffraction line obtained by performing baseline correction on the diffraction line obtained by XRD measurement
  • the peak of “Pt (1)”, “Pt(2)” peak, “Pt(3)” peak, “ Pt3Co (1)” peak, “ Pt3Co (2)” peak, “ Pt3Co (3)” peak , and the “carbon” peaks are the first Pt-derived peak, the second Pt-derived peak, and the third Pt-derived peak, respectively, obtained by peak separation of the diffraction line “after baseline correction”
  • a peak derived from a first Pt 3 Co, a peak derived from a second Pt 3 Co, a peak derived from a third Pt 3 Co and a peak derived from carbon are shown.
  • the diameter was calculated by the Scherrer formula above. That is, for example, the crystallite size of the first Pt particles is obtained by substituting the diffraction angle and full width at half maximum of the separation peak of "Pt (1)" in the XRD patterns shown in FIGS. 6A and 6B into the above Scherrer formula.
  • the crystallite size of the first Pt particles was calculated to be 3.7 nm
  • the crystallite size of the second Pt particles was calculated to be 8.1 nm
  • the crystallite size of the third Pt particles was calculated to be 18.7 nm.
  • the crystallite size of the first Pt 3 Co particles was calculated to be 5.7 nm
  • the crystallite size of the second Pt 3 Co particles was calculated to be 18.6 nm
  • the crystallite size of the third Pt 3 Co particles was calculated as The child diameter was calculated to be 29.5 nm.
  • the areas of each of the three Pt and three Pt 3 Co particle separation peaks obtained by the above peak separation that is, the peak area of "Pt (1)”, the peak area of "Pt (2)”, and the peak area of “Pt (3)”, the peak area of “Pt 3 Co (1)”, the peak area of “Pt 3 Co (2)”, and the peak area of “Pt 3 Co (3)”
  • the peak area ratio (%) of each of the Pt and Pt 3 Co was calculated by dividing by the total area of the separated peaks of the three Pt and three Pt 3 Co and multiplying by 100.
  • the peak area ratio of the first Pt particles was calculated to be 17.3%
  • the peak area ratio of the second Pt particles was calculated to be 44.4%
  • the peak area ratio of the third Pt particles was calculated to be 17.
  • the peak area percentage of the first Pt 3 Co particles was calculated to be 8.7%
  • the peak area percentage of the second Pt 3 Co particles was calculated to be 5.8%
  • the third Pt The peak area percentage of 3Co particles was calculated to be 6.1%.
  • volume average particle size of the catalyst metal particles was calculated by weighted average using these peak area ratios as weights.
  • ECSA Sweep Speed Dependence The electrochemical effective specific surface area (ECSA) (m 2 /g-Pt) of platinum contained in the supported metal catalyst was measured using a rotating ring disk electrode device (RRDE-3A rotating ring disk electrode device ver.1.2, BA). ⁇ S Co., Ltd.) and a dual electrochemical analyzer (CHI700C, manufactured by ALS Co., Ltd.).
  • a three-electrode rotating ring-disk electrode device having a working electrode containing a metal-supported catalyst was fabricated. Specifically, 5 mg of a metal-supported catalyst, 50 ⁇ L of 5% Nafion (registered trademark) (manufactured by Sigma-Aldrich, Nafion perfluorinated ion exchange resin, 5% solution (product number: 510211)), 400 ⁇ L of water, and isopropyl alcohol A slurry was prepared by mixing 100 ⁇ L. The slurry was then subjected to ultrasonic treatment for 10 minutes, followed by homogenizer treatment for 2 minutes.
  • Nafion registered trademark
  • 5% solution product number: 510211
  • the obtained slurry was applied to the working electrode (ring disk electrode for RRDE-3A, platinum ring-gold disk electrode, disk diameter 4 mm, BA) so that the coating amount of the metal-supported catalyst was 0.1 mg/cm 2 . (manufactured by S Co., Ltd.) and dried to prepare a working electrode on which the metal-supported catalyst was supported.
  • a platinum electrode (Pt counter electrode 23 cm, manufactured by BAS Co., Ltd.) is used as the counter electrode, and a reversible hydrogen electrode (RHE) (storage-type reversible hydrogen electrode, manufactured by EC Frontier Co., Ltd.) is used as the reference electrode. used.
  • RHE reversible hydrogen electrode
  • a rotating ring-disk electrode device having a working electrode containing a metal-supported catalyst, a platinum electrode as a counter electrode, and a reversible hydrogen electrode (RHE) as a reference electrode was obtained.
  • a 0.1 M perchloric acid aqueous solution was used as the electrolytic solution.
  • ECSA was measured using the rotating ring-disk electrode device. That is, cyclic voltammetry (CV) was performed in a nitrogen atmosphere using a three-electrode rotating ring-disk electrode apparatus with a working electrode containing a supported metal catalyst.
  • CV cyclic voltammetry
  • the ECSA@10 mV (m 2 /g-Pt) was obtained from the cyclic voltammogram thus obtained.
  • the hydrogen adsorption charge (Q Hupd ) (mC/cm 2 ) at 0.0 V (vs. NHE) to 0.4 V (vs. NHE) during negative scanning ECSA was calculated by the following formula (VI) using the area-converted electric charge (210 ⁇ C/cm 2 ) and the platinum coating amount (L Pt ) (mg-Pt/cm 2 ).
  • ECSA@1000 mV (m 2 /g-Pt) at a sweep rate of 1000 mV/sec was calculated.
  • ECSA @ 10 mV and ECSA @ 1000 mV thus obtained were used to calculate the ECSA sweep speed dependence (%) of the metal-supported catalyst according to the following formula (IV). That is, the value obtained by dividing ECSA @ 1000 mV by ECSA @ 10 mV was subtracted from 1, and the resulting value was multiplied by 100 to obtain the ECSA sweep rate dependency (%).
  • FIG. 7 shows the results of evaluating ECSA sweep speed dependence using the metal-supported catalyst of Example 1 and the metal-supported catalyst of Example C4.
  • the horizontal axis is the sweep speed (mV/sec) and the vertical axis is the ECSA retention rate (%).
  • ECSA retention was calculated by dividing ECSA at each sweep rate by ECSA@10 mV and multiplying by 100. That is, a value obtained by subtracting the ECSA retention rate (%) at a sweep rate of 1000 mV/sec on the horizontal axis from 100 corresponds to the above ECSA sweep rate dependency (%).
  • EW Equivalent Weight
  • the obtained slurry composition for catalyst layer is applied to a gas diffusion layer ("29BC", manufactured by SGL Carbon) (2.3 cm ⁇ 2.3 cm) on a 5 cm area per unit area of the battery electrode.
  • a catalyst layer was formed on the gas diffusion layer by coating and drying such that the platinum content was 0.2 (mg-Pt/cm 2 ).
  • a battery electrode having a catalyst layer containing a supported metal catalyst was obtained.
  • a fuel cell including a cell electrode with a catalyst layer containing a metal-supported catalyst was manufactured. That is, as the positive electrode, a battery electrode including the catalyst layer (positive electrode catalyst layer) manufactured as described above was used.
  • the negative electrode was produced as follows. 0.5 g of a commercially available platinum-supported catalyst (Pt/C) (UNPC40-II, manufactured by Ishifuku Metal Industry Co., Ltd.) containing platinum particles supported on a carbon support, 10 g of 5% Nafion (registered trademark), and distilled water 2 g and 25 g of balls were put into a pot and mixed with a ball mill at 200 rpm for 50 minutes to prepare a slurry Pt/C composition. The above positive electrode except that the slurry Pt/C composition was placed on the gas diffusion layer (5 cm 2 ) so that the platinum content per unit area was 0.1 (mg-Pt/cm 2 ). A negative electrode including a catalyst layer (negative electrode catalyst layer) formed from the Pt/C composition was produced in the same manner as in .
  • Pt/C platinum-supported catalyst
  • a solid polymer electrolyte membrane (manufactured by Dupont, "NAFION (registered trademark) 211") is placed between the positive electrode catalyst layer and the negative electrode catalyst layer, and these are heated at 150°C and 1 MPa for 3 hours.
  • a MEA was fabricated by pressing for minutes. A pair of gaskets was attached to this MEA, and the MEA was sandwiched between a pair of separators to produce a single fuel cell. After that, the single cell produced as described above was installed in a fuel cell automatic evaluation system (manufactured by Toyo Technica Co., Ltd.), and first a power generation test was conducted, and then a durability test was conducted.
  • the single cell was supplied with saturated humidified air (oxygen) at 2.5 L/min at a back pressure of 150 kPa to the positive electrode side (relative humidity 100%), and saturated humidified hydrogen at 1.0 L/min on the negative electrode side.
  • saturated humidified air oxygen
  • saturated humidified hydrogen at 1.0 L/min on the negative electrode side.
  • the cell temperature was set at 75° C. and the open circuit voltage was measured for 5 minutes. After that, the cell voltage was measured by maintaining the cell current density from 4.0 A/cm 2 to 0 A/cm 2 for 3 minutes at each current density.
  • a startup/shutdown test was conducted. That is, the cell temperature was set to 80 ° C., saturated humidified nitrogen was supplied to both sides of the single cell at a back pressure of 35 kPa at 1.0 L / min (relative humidity 100%), and saturated humidified hydrogen was supplied to the anode side at 1.0 mL. /min (100% relative humidity), with a sweep rate of 500 mV/sec, a start-stop test was performed by repeating a triangular wave cycle that scans the potential from 1.0 V to 1.5 V.
  • the power generation test was performed again, and the voltage (mV) at 1.0 A/cm 2 after the start-stop test was recorded. Then, the voltage (mV) at 1.0 A/cm 2 measured as the initial performance in the power generation test before the start/stop test was changed to the voltage (mV) at 1.0 A/cm 2 measured in the power generation test after the start/stop test ( mV) (voltage (mV) after 1000 cycles) was subtracted to obtain a voltage loss (mV), which was used as an index of durability in the first start-stop test.
  • a load variation test was also conducted. That is, as in the start-stop test described above, the voltage (mV) at a current density of 1.0 A/cm 2 was recorded as the voltage at the start of the load variation test. After that, the cell temperature was set to 75° C., saturated humidified nitrogen was supplied to both sides of the single cell at a back pressure of 150 kPa at 0.5 L/min (relative humidity of 100%), and saturated humidified hydrogen was supplied to the anode side at 0.5 mL. /min (100% relative humidity) and a load change test was performed by repeating a square wave cycle in which the potential was first held at 0.6 V for 10 seconds and then held at 0.95 V for 10 seconds.
  • the power generation test was performed again, and the voltage (mV) at the current density of 1.0 A/cm 2 after the load variation test was recorded. Then, the voltage (mV) at 1.0 A/cm 2 measured as the initial performance in the power generation test before the load change test was changed to the voltage (mV) at 1.0 A/cm 2 measured in the power generation test after the load change test ( mV) (voltage (mV) after 10000 cycles) was subtracted to obtain a voltage loss (mV), which was used as an index of durability in the load variation test.
  • Impedance measurement was carried out by setting the cell temperature to 80° C., supplying saturated humidified nitrogen at 0.5 L/min at a back pressure of 35 kPa to both sides of the single cell (relative humidity of 100%), and saturated humidified hydrogen to 0 on the anode side. 0.5 mL/min (100% relative humidity) and the open circuit voltage was measured for 10 minutes. Then, using an electrochemical measurement system (VSP-300, manufactured by BioLogic), measurement was performed with an applied voltage of 450 mV, a measurement frequency of 20 kHz to 50 mHz, and an amplitude voltage of ⁇ 10 mV.
  • VSP-300 electrochemical measurement system
  • the ionic resistance R i was obtained by fitting the Nyquist plot of the measured values obtained by the measurement using ZView equivalent circuit analysis software (Scribner Associates).
  • the state of the electrodes under the above measurement conditions can be modeled by an equivalent circuit shown in FIG. 8A.
  • L is the inductance derived from wiring, etc.
  • Rc is the resistance of the electrolyte membrane and electrode members
  • Rsh is the short-circuit resistance
  • W DeLevie is the Warburg impedance.
  • the Warburg impedance Zw is represented by the following formula (VII).
  • T is a time constant defined as the product of R i and C dl .
  • R i is the ionic resistance (m ⁇ cm 2 ) and C dl is the electric double layer capacitance (F).
  • ⁇ is the frequency (Hz).
  • j is the imaginary unit.
  • R i was calculated by fitting the Nyquist plot of the measured values using the equivalent circuit shown in FIG. 8A (Reference: Journal of The Electrochemical Society, 157 (3) B425-B436 (2010)).
  • R i is mainly derived from the ionic resistance of the catalyst layer, and the ionic resistance is considered to be affected by the thickness of the catalyst layer, the hydrophilicity of the catalyst layer, and the degree of deterioration of the ionomer.
  • FIG. 8B shows the measured values and fitting results of the Nyquist plot obtained for Example 1.
  • FIG. 9A shows the production conditions for the supported metal catalysts of Examples 1 to 10 and C1 to C4, and the results of evaluating the properties of fuel cells containing the supported metal catalysts.
  • the durability test was conducted at a relatively high potential of 1.0V to 1.5V.
  • a relatively high potential of 1.0V to 1.5V for example, deterioration due to oxidation of the carbon support is likely to proceed. Therefore, the smaller the voltage loss in the start-stop test, the higher the durability of the supported metal catalyst.
  • the durability of the metal-supported catalysts of Examples 1 to 10 is superior to that of Examples C3 and C4 and comparable to that of Examples C1 and C2. Ta.
  • durability of the supported metal catalysts of Examples 1, 2 and 4 to 10 was superior to that of Example 3 in the load fluctuation test.
  • the output characteristics of the supported metal catalysts of Examples 1-10 were comparable to those of Examples C1-C4, but the output characteristics of Examples 1-3 and 5-8 were lower than those of Example 4. , 9 and 10, and the output characteristics of Examples 1, 2 and 5-8 were superior to that of Example 3.
  • the overvoltage of fuel cells is classified into activation overvoltage, resistance overvoltage, and diffusion overvoltage. Suitable for
  • the catalytic activity of the supported metal catalysts of Examples 1-10 was comparable to that of Examples C1-C4, whereas the catalytic activities of Examples 1, 2 and 6-8 were lower than that of Example 3. -5, 9 and 10 were better than that.
  • a catalyst layer containing a supported metal catalyst preferably has a low ionic resistance.
  • the ionic resistance of the supported metal catalysts of Examples 1-10 was smaller than that of Examples C1-C4.
  • FIG. 9B shows the results of evaluating the characteristics of the metal-supported catalysts of each example.
  • the supported metal catalysts of Examples 1-10 had similar Raman 2D/G ratios, Raman D half widths, average pore sizes, and BET specific surface areas to Examples C1-C4.
  • the metal-supported catalysts of Examples 1-10 had a platinum content greater than that of Example C1 and similar to that of Examples C2-C4.
  • the supported metal catalysts of Examples 1-10 had similar platinum/non-platinum metal molar ratios to those of Examples C1-C4.
  • the supported metal catalysts of Examples 1-10 have less alloy heterogeneity than that of Examples C2-C4, and the supported metal catalysts of Examples 1-3 and 5-10 have less alloy heterogeneity than that of Example 4. had an alloy heterogeneity smaller than that of
  • the metal-supported catalysts of Examples 1-10 have a half-value asymmetry less than that of Example C4, and the metal-supported catalysts of Examples 1-3 and 5-10 have an alloy dissymmetry less than that of Example 4.
  • the supported metal catalysts of Examples 1, 2, 5-8 and 10 had less alloy heterogeneity than that of Examples 3 and 9.
  • the supported metal catalysts of Examples 1-10 have a lower quarter-value asymmetry than that of Examples C2-C4, and the supported metal catalysts of Examples 1, 3, 5 and 7-10. has a quarter-value asymmetry smaller than that of Examples 2, 4 and 6, and the supported metal catalysts of Examples 1, 5, 7, 8 and 10 have a quarter-value asymmetry smaller than that of Examples 3 and 9. had asymmetry.
  • the supported metal catalysts of Examples 1 to 10 had similar number average particle sizes to those of Examples C1 to C4, but the supported metal catalysts of Examples 1 to 8 had:
  • the metal-supported catalysts of Examples 1, 2 and 5-8 had smaller number average particle sizes than those of Examples 3 and 4.
  • the supported metal catalysts of Examples 1 to 10 had a volume average particle size similar to that of Examples C1 to C3 and smaller than that of Example C4, and the volume average particle size of Examples 1 to 8.
  • the supported metal catalysts have smaller number average particle sizes than those of Examples 9 and 10, and the supported metal catalysts of Examples 1, 2 and 5-8 have smaller number average particle sizes than those of Examples 3 and 4.
  • the metal-supported catalysts of Examples 1-10 had ECSA sweep rate dependence similar to that of Examples C1-C4, whereas the metal-supported catalysts of Examples 1-9 had ECSA sweep rate dependence similar to that of Examples C1-C4.
  • the metal-supported catalysts of Examples 1, 2 and 5-8 had ECSA sweep rate dependencies greater than that of Examples 3, 4 and 9.

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Abstract

L'invention concerne un catalyseur sur support métal présentant à la fois une excellente durabilité et une excellente fonction catalytique malgré une grande teneur en métal noble et son procédé de fabrication ainsi qu'une électrode et une batterie. Le catalyseur sur support métal comprend un support de carbone et des particules métalliques catalytiques supportées par le support de carbone et contenant un alliage de métal précieux, le rapport du poids du métal noble au poids du catalyseur supporté par un métal étant de 35 % en poids ou plus ; et présente une caractéristique (a) et/ou une caractéristique (b) donnée ci-dessous, à savoir, (a) une non-uniformité dans la composition d'alliage est de 0,55 ou moins, et (b) à la fois une asymétrie de demi-valeur et une asymétrie de quart de valeur sont de 0,55 ou moins.
PCT/JP2022/023286 2022-03-04 2022-06-09 Catalyseur sur support métal et son procédé de fabrication ainsi qu'électrode et batterie WO2023166755A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015134352A (ja) * 2013-07-12 2015-07-27 昭和電工株式会社 酸素還元触媒の起動停止耐久性を向上させる方法および酸素還元触媒の検査方法
WO2021024658A1 (fr) * 2019-08-02 2021-02-11 日清紡ホールディングス株式会社 Catalyseur sur support métal, électrode de batterie et batterie
WO2021024657A1 (fr) * 2019-08-02 2021-02-11 日清紡ホールディングス株式会社 Catalyseur à métal supporté, électrode de batterie et batterie
WO2021024656A1 (fr) * 2019-08-02 2021-02-11 日清紡ホールディングス株式会社 Catalyseur au métal, électrode de batterie et batterie
WO2021044983A1 (fr) * 2019-09-06 2021-03-11 Ａｇｃ株式会社 Procédé de production d'hydrofluorooléfine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015134352A (ja) * 2013-07-12 2015-07-27 昭和電工株式会社 酸素還元触媒の起動停止耐久性を向上させる方法および酸素還元触媒の検査方法
WO2021024658A1 (fr) * 2019-08-02 2021-02-11 日清紡ホールディングス株式会社 Catalyseur sur support métal, électrode de batterie et batterie
WO2021024657A1 (fr) * 2019-08-02 2021-02-11 日清紡ホールディングス株式会社 Catalyseur à métal supporté, électrode de batterie et batterie
WO2021024656A1 (fr) * 2019-08-02 2021-02-11 日清紡ホールディングス株式会社 Catalyseur au métal, électrode de batterie et batterie
WO2021044983A1 (fr) * 2019-09-06 2021-03-11 Ａｇｃ株式会社 Procédé de production d'hydrofluorooléfine

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