WO2016143618A1 - コア／シェル構造の触媒粒子が担持された触媒の製造方法 - Google Patents

コア／シェル構造の触媒粒子が担持された触媒の製造方法 Download PDF

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WO2016143618A1
WO2016143618A1 PCT/JP2016/056353 JP2016056353W WO2016143618A1 WO 2016143618 A1 WO2016143618 A1 WO 2016143618A1 JP 2016056353 W JP2016056353 W JP 2016056353W WO 2016143618 A1 WO2016143618 A1 WO 2016143618A1
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platinum
catalyst
core
copper
particles
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French (fr)
Japanese (ja)
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耕一 松谷
武 海江田
朋弘 秋山
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Tanaka Kikinzoku Kogyo KK
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Tanaka Kikinzoku Kogyo KK
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Priority to KR1020177022787A priority Critical patent/KR101963068B1/ko
Priority to CN201680014687.1A priority patent/CN107405604B/zh
Priority to US15/548,193 priority patent/US10497942B2/en
Priority to EP16761588.9A priority patent/EP3269447B1/en
Publication of WO2016143618A1 publication Critical patent/WO2016143618A1/ja
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • 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
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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    • B01J35/396—Distribution of the active metal ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/04—Removal of gases or vapours ; Gas or pressure control
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • H—ELECTRICITY
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    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
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    • H01M4/88—Processes of manufacture
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    • H01M4/8853—Electrodeposition
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    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
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    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
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    • 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
    • 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
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    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for producing a catalyst in which catalyst particles having a core / shell structure composed of a shell layer made of platinum and core particles made of a metal other than platinum are supported on a carrier. More specifically, the present invention relates to a method for producing a catalyst that is useful as a catalyst for a polymer electrolyte fuel cell and has excellent production efficiency and good catalytic activity.
  • Fuel cells are highly expected as next-generation power generation systems. Solid polymer fuel cells that use solid polymers as electrolytes are particularly low in operating temperature and compact compared to phosphoric acid fuel cells. It is desired to be used as a power source for electric vehicles. In a polymer electrolyte fuel cell, a mixture of a catalyst and a solid polymer is used as an electrode for promoting an electrochemical reaction.
  • a catalyst for a fuel cell As a catalyst for a fuel cell, a catalyst in which platinum particles are supported as a catalyst component on a conductive substance such as carbon powder is generally known.
  • the activity of the catalyst is due to the presence of platinum, but platinum is particularly expensive among the noble metals, and the amount of use thereof determines the cost of the catalyst and hence the cost of the fuel cell. Therefore, there is a demand for the development of a catalyst that reduces the amount of platinum used.
  • Patent Document 1 describes a catalyst in which palladium or a palladium alloy is used as core particles, and a platinum layer is covered with a monoatomic or quasi-monoatomic level layer.
  • a copper underpotential deposition method (Cu Under Potential Deposition: hereinafter referred to as Cu-UPD method) is used.
  • Cu-UPD method Cu Under Potential Deposition: hereinafter referred to as Cu-UPD method
  • the surface of the core particles made of palladium or palladium alloy is coated with a monolayer of copper by a predetermined electrochemical treatment, and then the copper is replaced with platinum.
  • a platinum layer For example, a material in which core particles are supported on an appropriate carrier is subjected to electrolytic treatment in an electrolytic solution such as a copper sulfate solution under predetermined conditions to form a copper layer on the surface of the core particles, and this is contacted with a platinum compound solution.
  • a platinum shell layer is formed by replacing copper and platinum.
  • a platinum layer is directly deposited on the surface of the core particle, a thick platinum layer exceeding a monoatomic layer or a quasi-monoatomic layer is formed, This is because platinum deposition may occur in the solution without coating the core particles.
  • the Cu-UPD method has an advantage that a platinum shell having a suitable thickness of a monoatomic layer or a quasi-monoatomic layer can be formed, strict potential control is required when forming a copper layer on the core particles.
  • a platinum layer is formed based on a simple substitution reaction between platinum, which is a noble metal in terms of potential, and copper, which is a base metal. Therefore, it is necessary that the copper layer from which platinum is replaced is uniform at an extremely high level. Therefore, in the conventional method, it is necessary to perform an equal electrolytic treatment on all the core particles.
  • an ink composed of a carbon powder carrying core particles and an appropriate dispersion medium is manufactured, and this is uniformly applied to a disk electrode, dried, immersed in an electrolytic solution, and electrolyzed (See FIG. 2).
  • the core particles act as working electrodes, and copper is deposited on the core particle surfaces.
  • the platinum compound solution is brought into contact with the disk electrode, copper and platinum are substituted to form a platinum shell layer on the surface of the core particle.
  • applying a small amount of core particles to the disk electrode and performing the electrolytic treatment ensures that the potential is applied uniformly and uniformly to each core particle to form a uniform single-layer copper layer. Because.
  • the present invention has been made based on the above background, and a method for producing a catalyst by forming catalyst particles having a core / shell structure by the Cu-UPD method can be mass-produced with improved production efficiency.
  • a catalyst capable of producing a catalyst having good catalytic activity is provided.
  • the low manufacturing efficiency of the conventional Cu-UPD method is due to the electrolytic treatment process for forming the copper layer on the core particles.
  • a small amount of core particles is uniformly applied and adhered to an electrode to ensure the uniformity of potential control. This is because when a large amount of core particles are contacted with the electrode, the contact between the core particles and the electrode becomes non-uniform, resulting in variations in potential control between the core particles, and the thickness of the copper layer cannot be made uniform. .
  • the present inventors examined optimization of the platinum replacement process after forming the copper layer as an approach for solving the above problems. Even if a somewhat non-uniform copper layer is formed by relaxing the strictness of the potential control in the electrolytic treatment process, it can be used for the final purpose as long as the subsequent platinum replacement is effective. This is because the catalyst particles having a certain core / shell structure can be produced. And it was considered that the strictness of the electrolytic treatment process can lead to an increase in the amount of treatment and can improve the overall production efficiency. Therefore, the present inventors conducted further studies and found that an effective platinum layer can be formed by adding citric acid to the reaction system in the substitution reaction step for forming the platinum layer.
  • the present invention that solves the above-mentioned problems is a catalyst in which catalyst particles having a core / shell structure comprising a shell layer made of platinum and core particles made of a metal other than platinum covered with the shell layer are supported on a carrier.
  • An electrolytic treatment step of electrolyzing the carrier carrying the core particles in an electrolytic solution containing copper ions to deposit copper on the surface of the core particles; and the core particles having copper deposited thereon
  • the platinum compound solution is contacted to replace the copper on the surface of the core particles with platinum, and form a shell layer made of platinum.
  • the platinum compound solution in the substitution reaction step contains citric acid. Is a method for producing a catalyst.
  • the present invention is characterized in that the Cu-UPD method is improved with respect to the step of replacing platinum after forming a copper layer on the core particles.
  • This improvement has an effect of improving the coverage of platinum on the surface of the core particles by performing the treatment with citric acid added to the platinum compound solution.
  • citric acid added to the platinum compound solution.
  • the coverage of platinum is improved and optimized because citric acid mediates the substitution reaction between copper and platinum, and after copper and citric acid are substituted, citric acid and It has a reaction mechanism in which platinum substitutes.
  • the basic process of the method for producing a catalyst according to the present invention is based on the Cu-UPD method.
  • a core particle supported on a carrier is prepared, an electrolytic treatment process for coating the surface of the core particle with a copper layer, and copper and platinum on the surface of the core particle are replaced with platinum.
  • a substitution reaction step for forming a shell layer is provided.
  • the core particle is made of a metal other than platinum.
  • this metal palladium, iridium, rhodium, ruthenium, gold or an alloy of these metals can be applied, and preferably palladium or a palladium alloy is applied.
  • the reason why palladium is preferable as the core particle is that it has excellent chemical stability and can improve the activity of the catalyst.
  • the palladium alloy palladium-nickel alloy, palladium-copper alloy, palladium-cobalt alloy, palladium-gold alloy can be applied. These palladium alloys can further improve the activity of the catalyst.
  • the concentration of additive elements such as nickel and copper is preferably such that the molar ratio of additive element to palladium (added element / palladium) is 1/1 or more and 1/12 or less.
  • the average particle size of the core particles is preferably 2 nm or more and 50 nm or less.
  • the treatment is performed in a state where the core particles are supported on a carrier.
  • a carrier a conductive material made of conductive carbon powder, conductive ceramic powder or the like that is usually used as a catalyst carrier can be applied.
  • Formation of the core particles on the carrier is not particularly limited, and a known method is used.
  • fine core particles can be produced by impregnating a carrier into a metal compound solution of a metal constituting the core particles and subjecting the support to a reduction treatment.
  • the core particles are made of an alloy
  • the metal particles produced as described above are infiltrated into a metal compound solution as an alloy additive element and subjected to heat treatment after reduction.
  • an alloy can be formed by impregnating a carrier into a compound solution of two or more kinds of metals constituting the core particle and performing a heat treatment after the reduction.
  • a copper layer is electrolytically deposited on the surface in an electrolytic treatment process.
  • the electrolytic treatment is a treatment in which core particles are arranged on the working electrode side and copper is deposited from the electrolytic solution by applying a certain potential.
  • the platinum layer formation in the subsequent substitution reaction step is optimized, so that strict and uniform potential control is performed on individual core particles as in the conventional method. This is not required. In the present invention, it is not necessary to apply and adhere a small amount of core particles to an electrode as in the conventional method, and the throughput can be increased.
  • a state in which core particles (a carrier carrying core particles) are stacked on an electrode (working electrode) may be used. Even if the core particles are not in close contact as in the conventional application / dry state, the core particles can be electrolyzed via the carrier. At this time, although there is some nonuniformity in the potential of the individual core particles, in the case of the present invention, catalyst particles having a core / shell structure can be finally formed.
  • electrolytic deposition is performed in an electrolytic cell that contains an electrolytic solution.
  • the bottom of the electrolytic cell is made of a conductive material, which is used as a working electrode, and core particles are laminated thereon. Large quantities of core particles can be processed.
  • the present invention can be effectively processed even if a carrier carrying core particles of 1 mg / cm 2 or more and 800 mg / cm 2 or less is stacked on the working electrode.
  • capacitance of an electrolytic cell can also be increased and the catalyst manufacture in the electrolytic cell in consideration of the industrial manufacture of 1L or more and 50L or less is possible.
  • the electrolytic solution in the electrolytic treatment is a copper compound solution, but is not particularly limited as long as it is a solution that can be generally used for Cu-UPD.
  • Specific examples of preferable copper compounds to be used include copper sulfate, copper nitrate, copper chloride, copper chlorite, copper perchlorate, and copper oxalate.
  • the potential control conditions for electrolytic deposition are adjusted according to the type of core particle metal. For example, when palladium or palladium alloy is used as the core particle and copper is coated, the potential is fixed at 0.35 V or more and 0.40 V or less (vs. RHE), and the potential fixing time is 1 hour or more and 10 hours or less. Is preferable.
  • the dissolved oxygen content of the electrolytic solution is 1 ppm or less. This is because when there is a large amount of dissolved oxygen, the deposited copper may be oxidized and dissolved, which may cause a subsequent inhibition reaction with platinum. In addition, it is difficult for the amount of dissolved oxygen in the electrolytic solution to be 1 ppm or less by bubbling with a general inert gas (such as nitrogen). As a preferable pretreatment for reducing the amount of dissolved oxygen, an inert gas is bubbled for 4 hours to 48 hours in a closed space (preferably 0 ppm) with a reduced oxygen concentration. By doing in this way, the dissolved oxygen of electrolyte solution can be 1 ppm or less.
  • a general inert gas such as nitrogen
  • the core particle in which the copper layer is formed is formed by the above electrolytic treatment process, and the platinum compound solution is brought into contact with the core particle to form a platinum shell layer.
  • This replacement treatment can be continuously performed from the electrolytic deposition step by adding a platinum compound solution to the electrolytic cell. Further, the core particles may be taken out from the electrolytic cell and immersed in a platinum compound solution.
  • the platinum compound solution is not particularly limited, but a solution of chloroplatinic acid, potassium chloroplatinate, tetraammineplatinum chloride, diammine dinitroplatinum nitrate is preferable, and a solution of potassium chloroplatinate is particularly preferable.
  • the amount of the platinum compound in the solution is preferably equal to or more than 4 times the molar number of the required platinum compound calculated from Cu-UPD. In addition, also about this platinum compound solution, it is preferable that the amount of dissolved oxygen shall be 1 ppm or less.
  • citric acid it is necessary to add citric acid to the platinum compound solution in order to optimize the substitution reaction between copper and platinum.
  • the citric acid may be added by adding citric acid to the platinum compound solution in advance and bringing it into contact with the core particles.
  • the platinum compound may be added after bringing citric acid into contact with the core particles.
  • the amount of citric acid added (number of moles) is preferably 10 to 40 times the number of moles of the platinum compound. This is because when the amount of citric acid is small, the coverage of the platinum shell decreases. If it exceeds 40 times, citric acid is not preferable in that it covers the platinum shell and reduces the catalytic activity.
  • the processing temperature does not require any special control and can be processed at room temperature.
  • a catalyst having a core / shell structure having a platinum shell layer is formed by the above platinum replacement step. Further, if the above steps are performed in a state where the core particles are supported on a carrier, a catalyst in which catalyst particles having a core / shell structure are supported on the carrier can be obtained. In addition, it is preferable to perform washing
  • the present invention aims at optimizing the platinum substitution process for the Cu-UPD method for producing a catalyst including the electrolysis process and the platinum substitution process. Strict processing conditions are relaxed and an increase in throughput is achieved. According to the present invention, catalyst particles having a core / shell structure can be efficiently produced. Further, the catalyst produced according to the present invention has a good activity, and is excellent in the balance between the cost reduction effect due to the reduction of the amount of platinum used and the improvement of the catalyst performance.
  • First Embodiment a catalyst on which catalyst particles having a core / shell structure with palladium as core particles was supported was manufactured, and its activity was evaluated.
  • carbon powder trade name: Ketjen Black EC, specific surface area: 800 g / m 3
  • Pd amount 15 g (0.028 mol)
  • the electrolysis apparatus used in this embodiment is shown in FIG.
  • a counter electrode having a platinum mesh as a counter electrode and a reference electrode are inserted into an electrolytic cell in which an electrolytic solution is accommodated.
  • the bottom of the electrolytic cell is composed of a carbon block, and this carbon block acts as a working electrode.
  • the counter electrode, the reference electrode, and the working electrode are connected to the potential control device.
  • Electrolysis conditions are as follows. Note that nitrogen blowing into the glove box and nitrogen bubbling into the electrolyte continue during the electrolytic treatment. Electrolysis conditions / potential: Fixed at 0.39V (vs. RHE). ⁇ Potential fixation time: 3 hours
  • the catalyst obtained in the above manufacturing process is 10 g.
  • This production amount is 100000 times or more of the production amount ( ⁇ g order) by the conventional Cu-UPD method, and the catalyst can be produced in one step.
  • Comparative Examples 1 and 2 For comparison with a catalyst supporting catalyst particles having a core / shell structure, commercially available catalysts supporting platinum particles and platinum alloy particles were prepared.
  • the prepared catalysts are a platinum catalyst (trade name: TEC10E50E) and a platinum-cobalt catalyst (trade name: TEC36E52).
  • FIG. 1 This evaluation method examines oxygen reduction activity by rotating a rotating disk electrode coated with 8 ⁇ g of catalyst in an electrolytic solution. Oxygen reduction current flowing from 0.1 V to 1.0 V at a sweep speed of 5 mV / s in a steady rotation (1000 rpm, 1250 rpm, 1500 rpm, 1750 rpm, 2000 rpm, 2250 rpm, 2500 rpm) of this electrode in an electrolyte saturated with oxygen was measured. After the measurement, the current value at 0.9 V at each rotation speed was approximated by the Koutecky-Levic equation, and the mass activity of platinum was calculated from the activity-dominated current. The results are shown in Table 1.
  • the catalyst produced according to this embodiment exhibits extremely high oxygen reduction activity with respect to the platinum catalyst and platinum-cobalt catalyst which are comparative examples. It can be confirmed that the production method of the present embodiment is favorable also from the characteristics of the produced catalyst.
  • the catalyst was manufactured by changing the amount of citric acid added in the substitution reaction step after the electrolytic treatment step.
  • the core particle was a palladium-nickel alloy.
  • carbon powder serving as a carrier is immersed in a solution of palladium nitrate (Pd amount 53 g (0.50 mol)) and nickel nitrate (Ni amount 176 g (3.0 mol)) and neutralized with sodium hydroxide. did. Thereafter, heat treatment was performed to form particles made of a palladium-nickel alloy on the carbon powder.
  • the carrier was immersed in 0.5 M sulfuric acid (80 ° C.) to remove nickel. The formation of the palladium-nickel alloy particles and the removal of nickel are for forming pores by elution of nickel on the surface of the alloy particles and improving the surface area and activity.
  • a preferable addition amount of citric acid is 10 times or more and 40 times or less.
  • the present invention achieves an increase in catalyst production by optimizing the platinum substitution process in a catalyst production method based on the Cu-UPD method. According to the present invention, a suitably active catalyst having a core / shell structure can be efficiently produced, and a cost reduction effect due to a reduction in the amount of platinum used can be expected.

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PCT/JP2016/056353 2015-03-09 2016-03-02 コア／シェル構造の触媒粒子が担持された触媒の製造方法 Ceased WO2016143618A1 (ja)

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US15/548,193 US10497942B2 (en) 2015-03-09 2016-03-02 Method for manufacturing catalyst having supported catalyst particles of core/shell structure
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US20180034062A1 (en) 2018-02-01
KR20170105570A (ko) 2017-09-19
EP3269447B1 (en) 2020-01-08
US10497942B2 (en) 2019-12-03
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