WO2016143784A1 - Procédé de fabrication de catalyseur au platine et pile à combustible l'utilisant - Google Patents

Procédé de fabrication de catalyseur au platine et pile à combustible l'utilisant Download PDF

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WO2016143784A1
WO2016143784A1 PCT/JP2016/057170 JP2016057170W WO2016143784A1 WO 2016143784 A1 WO2016143784 A1 WO 2016143784A1 JP 2016057170 W JP2016057170 W JP 2016057170W WO 2016143784 A1 WO2016143784 A1 WO 2016143784A1
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platinum
catalyst
platinum catalyst
potential
gas
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PCT/JP2016/057170
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English (en)
Japanese (ja)
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稔 稲葉
大門　英夫
紘介 奥野
峻哉 樋口
祐貴 松井
直也 青木
井上　秀男
健仁 西川
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学校法人同志社
石福金属興業株式会社
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Priority claimed from JP2015198803A external-priority patent/JP6653875B2/ja
Application filed by 学校法人同志社, 石福金属興業株式会社 filed Critical 学校法人同志社
Priority to EP16761752.1A priority Critical patent/EP3269449A4/fr
Priority to US15/554,470 priority patent/US10749186B2/en
Publication of WO2016143784A1 publication Critical patent/WO2016143784A1/fr

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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
    • B01J23/38—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
    • B01J23/44—Palladium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • 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
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • 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 platinum catalyst suitable for use as a catalyst for an oxygen reduction reaction in a fuel cell, and a fuel cell using the catalyst.
  • a polymer electrolyte fuel cell is a clean energy device that produces only water by causing an oxidation reaction of hydrogen on the anode side and a reduction reaction of oxygen on the cathode side.
  • a catalyst on the cathode side Those using platinum (Pt) are known.
  • a catalyst using platinum which is a noble metal, has high catalytic activity and high electrical conductivity, and has an advantage that it is less susceptible to corrosion and poisoning due to the state of the surrounding environment and substances present in the surrounding environment.
  • platinum has a problem that its resource amount is small and its price is high, and various studies are being conducted to improve its utilization efficiency and durability and reduce the amount of use.
  • a platinum core-shell catalyst obtained by coating platinum on a different metal has attracted attention.
  • the platinum core-shell catalyst was devised by focusing on the fact that the platinum atoms exhibiting catalytic activity are only the platinum atoms exposed in the outermost layer of the catalyst particles.
  • the dissimilar metal fine particles covered with the platinum atomic layer (shell) The (core) is configured to be highly dispersed and supported on a carrier such as carbon.
  • Palladium (Pd) is known as one of the core metals of the platinum core-shell catalyst.
  • Non-Patent Document 1 and Non-Patent Document 2 disclose that when Pd is used as the core metal, the oxygen reduction reaction (Oxygen Reduction Reaction: ORR) activity in PEFC is enhanced. Since the lattice constant (0.38898 nm) of Pd is smaller than Pt (0.39231 nm), a slight compressive stress is generated in the Pt shell provided on the Pd core. It is thought that this compressive stress realizes a situation where the oxygen reduction reaction easily proceeds on the surface of the Pt shell and increases the ORR activity.
  • ORR Oxygen Reduction Reaction
  • Non-Patent Document 3 in a PEFC using a carbon-supported Pd core / Pt shell catalyst (hereinafter also referred to as a Pt / Pd / C catalyst) as a cathode, a part of the Pd core is oxidized and dissolved by power generation. It has been reported that metal Pd is reprecipitated in the solid polymer electrolyte membrane and a Pd band appears.
  • Patent Document 1 discloses that application of a voltage, which has been conventionally performed as a potential cycle durability test (Accelerated Durability Test, ADT) of a catalyst, results in improving the activity of a Pt / Pd / C catalyst. ing.
  • Patent Document 1 discloses that a Pt / Pd / C catalyst is repeatedly given a potential higher than the Pt oxide reduction start potential and a potential lower than the Pt oxide formation start potential, whereby Pt / Pd / C. It is also disclosed that the activity of the C catalyst is improved.
  • Patent Document 1 a platinum core-shell catalyst is dispersed in an acidic solution containing protons, and a metal having a redox potential lower than the oxide generation start potential of the platinum core-shell catalyst is allowed to coexist.
  • a method of stirring under oxygen supply This method is a completely new method and has obtained a certain effect, but further improvement of ORR activity has been expected.
  • Patent Document 2 discloses a platinum alloy catalyst and a method for producing the same.
  • a mixed solution prepared by adding a reducing agent after dispersing an organometallic complex of platinum and a metal chloride in an organic solvent is pressurized and heated to have a diameter of 2 nm or less.
  • the platinum alloy nanoparticles are synthesized, and the platinum alloy nanoparticles are heated (annealed) in a vacuum at a temperature of 300 ° C. or higher and 1000 ° C. or lower to have a diameter of 2 nm or more and 100 nm or less.
  • Patent Document 2 by synthesizing platinum alloy nanoparticles and then heating (annealing), the particle diameter of the alloy particles is adjusted to 2 nm or more and 100 nm or less to obtain platinum alloy particles having a specific crystal form. It is considered possible.
  • An object of the present invention is to provide a carbon-supported platinum catalyst having excellent ORR activity in a platinum catalyst using a combination of platinum and a metal other than platinum, and a production method for obtaining such a catalyst.
  • ORR mass activity (ORR mass activity: MA) indicating activity per Pt mass is ORR area specific activity (ORR specific activity: SA) and electrochemical surface area (Electro-Chemical Surface Area: ECSA). Focusing on the fact that it is expressed by the product of the above, we thought that it is possible to further improve the ORR mass activity by increasing both SA and ECSA. Then, it was found that some of the particles of the platinum core-shell catalyst that had undergone the potential cycle durability test had agglomerated, and by suppressing the agglomeration, the decrease in ECSA was suppressed, thereby improving the ORR mass activity.
  • platinum catalysts include both platinum core-shell catalysts and platinum alloy catalysts.
  • the inventors have further studied, and the above-described method is to apply a constant potential alternately and continuously to the platinum catalyst, and as a method for applying the potential, a gas is fed in. It was found that the present invention is not limited to this, and the present invention was further completed.
  • a method other than the method of feeding gas specifically, an acidic solution in which a platinum catalyst is dispersed has an oxidation-reduction potential lower than the oxide reduction start potential of the platinum catalyst in the presence of an inert gas. A method of coexisting metals has been found.
  • the present invention [1] A method for producing a platinum catalyst for a fuel cell containing platinum and a metal other than platinum, wherein the platinum catalyst is dispersed in an acidic solution containing protons. (I) a step of causing a chemical species to give a potential higher than a platinum oxide formation start potential of the platinum catalyst; (II) a step of causing a chemical species to give a potential lower than the oxide reduction initiation potential of platinum of the platinum catalyst.
  • the present invention also provides [2] The method for producing a platinum catalyst according to [1], wherein the step (I) and the step (II) are alternately performed a plurality of times. [3] The method for producing a platinum catalyst according to [1] or [2], wherein the step (I) and the step (II) are each performed for a predetermined duration. [4] The method for producing a platinum catalyst according to [3], wherein the predetermined duration is any one of 1 minute to 30 minutes.
  • the present invention also provides [5] The platinum according to any one of [1] to [4], wherein the step (I) and the step (II) are steps in which a gas and / or a solid is present in the dispersion solution.
  • the present invention relates to a method for producing a catalyst.
  • the present invention also provides [6]
  • the step (I) is a step (A) of feeding a gas giving a higher potential than the platinum oxide formation start potential of the platinum catalyst. Any one of [1] to [4], wherein the step (II) is a step (B-1) of feeding a gas giving a potential lower than a platinum oxide reduction start potential of the platinum catalyst. It relates to the manufacturing method of the platinum catalyst as described in above.
  • the present invention also provides [7] The method for producing a platinum catalyst according to [6], wherein in the step (B-1), the gas that gives a potential lower than the oxide reduction start potential of platinum is hydrogen.
  • the present invention also provides [8]
  • the step (I) is a step (A) of feeding a gas giving a higher potential than the platinum oxide generation start potential of the platinum catalyst.
  • the step (II) is a step (B-2) of introducing an inert gas while a solid that gives a potential lower than the platinum oxide reduction start potential of the platinum catalyst is present in the dispersion. , [1] to [4].
  • the present invention also provides [9] The platinum according to [8], wherein in the step (B-2), the solid giving a potential lower than the oxide reduction start potential of platinum is copper, and the inert gas is nitrogen gas or argon gas
  • the present invention relates to a method for producing a catalyst.
  • the present invention provides [10] The platinum catalyst according to any one of [6] to [9], wherein in the step (A), the gas that gives a higher potential than the platinum oxide formation start potential is a gas containing oxygen. It relates to the manufacturing method. [11] The method for producing a platinum catalyst according to any one of [1] to [10], wherein the acidic solution containing protons is a sulfuric acid solution. [12] The method according to any one of [1] to [11], further including (III) a step of feeding an inert gas between the step (I) and the step (II). The present invention relates to a method for producing a platinum catalyst.
  • the present invention also provides [13] The platinum catalyst according to any one of [1] to [12], wherein the platinum catalyst is a platinum core-shell catalyst having palladium-containing core particles and a platinum shell formed on the surface of the core particles.
  • the present invention relates to a method for producing a platinum catalyst.
  • the present invention also provides [15]
  • the present invention relates to a platinum catalyst produced by the method according to any one of [1] to [14].
  • the present invention relates to a fuel cell that uses a platinum catalyst produced by the method according to any one of [1] to [14] as a catalyst for an oxygen reduction reaction.
  • the present invention provides [17] A method for improving the activity of a platinum catalyst for a fuel cell, wherein the platinum catalyst is dispersed in an acidic solution, (1) a step of feeding an inert gas into the platinum catalyst dispersion solution; (2) a step of feeding hydrogen into the platinum catalyst dispersion solution; (3) a step of feeding an inert gas into the platinum catalyst dispersion solution; (4) The present invention relates to a method in which the step of feeding oxygen into the platinum catalyst dispersion solution is repeated a plurality of times in order.
  • the present invention provides [18] A method for improving the activity of a platinum catalyst for a fuel cell, wherein the platinum catalyst is dispersed in an acidic solution, (101) a step of feeding an inert gas into the platinum catalyst dispersion solution; (102) a step of causing solid copper to exist while feeding an inert gas into the platinum catalyst dispersion solution; (103) removing the solid copper of the step (102) from the platinum catalyst dispersion solution; (104) It is related with the method of repeating oxygen supplying to a platinum catalyst dispersion solution, and repeating several times in order.
  • a platinum catalyst having a high oxygen reduction activity per mass of platinum (ORR mass activity: MA) can be obtained by treating the platinum catalyst by a method capable of mass production on an industrial scale. Since the platinum catalyst of the present invention has a high activity per mass of platinum, the amount of platinum used can be suppressed, which is advantageous in terms of cost and environment.
  • Example 2 is a TEM image showing forms of platinum core-shell catalysts of Example 1, Comparative Example 1, and Reference Example 1.
  • the ORR mass activity of the platinum core-shell catalyst of Example 1, Comparative Example 1, and Reference Example 1 is shown.
  • the ORR mass activity of the PtPd / C alloy catalyst of Example 2, Comparative Example 2, and Reference Example 2 is shown.
  • the ORR mass activity of the PtCo / C alloy catalyst of Example 3 and Comparative Example 3 is shown.
  • the copper sheet is immersed in an acidic solution in an argon atmosphere, and then the potential change of the copper sheet when copper sulfate is added is shown.
  • the ORR mass activity of the Pt / Pd / C core-shell catalyst of Example 4, Comparative Example 4, and Reference Example 4 is shown.
  • the ORR mass activity of the PtPd / C alloy catalyst of Example 5, Comparative Example 5, and Reference Example 5 is shown.
  • the ORR mass activity of the PtCo / C alloy catalyst of Example 6, Comparative Example 6, and Reference Example 6 is
  • the present invention first relates to a method for producing a platinum catalyst.
  • the production method of the present invention includes a step of repeatedly applying a predetermined potential to the platinum catalyst by repeatedly feeding a plurality of types of chemical species into the acidic solution in which the platinum catalyst is dispersed with a constant duration. It is characterized by that.
  • the said process is a post-processing process in manufacture of a platinum catalyst, and is a catalyst activity improvement processing process for improving the activity of a catalyst.
  • a part of different metals palladium, cobalt, nickel, iron, copper, etc.
  • a redox potential lower than that of platinum are oxidized and eluted, and the rearrangement of platinum atoms occurs on the surface of the catalyst particles. Aggregation of the catalyst particles is suppressed.
  • it is considered that a catalyst having a high ORR mass activity can be obtained by increasing the ORR area specific activity of the catalyst and maintaining the electrochemical surface area.
  • the cause of the improved ORR activity was considered as follows. That is, the platinum shell of the Pt / Pd / C catalyst before ADT is not perfect, and there are many defects. When a high potential and a low potential are repeatedly applied in ADT, the Pd core whose oxidation-reduction potential is lower than that of Pt is selectively oxidized and eluted through this defect site, and at the same time, the Pt shell atoms are rearranged to form a thick film. Turn into. In this process, it was thought that the ORR activity was improved by reducing the number of low-coordination Pt atoms present in the Pt shell before ADT and changing to a smooth Pt shell with few defects ([Fig. 1]). reference).
  • the ECSA of Pd / C (calculated from the hydrogen adsorption / desorption wave appearing in the CV potential range of 0.05V-0.4V) is reduced to the same extent, and the oxidation elution of the Pd core is the number of potential cycles. It was confirmed that it does not depend greatly on On the other hand, looking at the change in Pt / C, it was confirmed that the ECSA of Pt decreased as the number of potential cycles increased (see [FIG. 4]). That is, by increasing the potential holding time per cycle and reducing the number of potential cycles, it is possible to suppress the aggregation of catalyst particles and suppress the decrease in ECSA without stopping the oxidation elution of the Pd core. It was confirmed that the ORR mass activity of the Pt / Pd / C catalyst could be increased by treatment under such conditions.
  • test results are results obtained by applying a catalyst on a 6 mm diameter GC electrode (Glassy Carbon Electrode) and performing precise potential control using a potentiostat. Requires a separate method.
  • the inventors have already been able to repeatedly apply a high potential and a low potential by simulating a potential cycle test, and as an industrially feasible method, the platinum core-shell catalyst is dispersed in an acidic solution containing protons and oxidized.
  • a method of stirring under the supply of oxygen while coexisting a metal (for example, copper) whose reduction potential is lower than the oxide generation start potential of the platinum core-shell catalyst has been developed (Patent Document 1).
  • Patent Document 1 A method of stirring under the supply of oxygen while coexisting a metal (for example, copper) whose reduction potential is lower than the oxide generation start potential of the platinum core-shell catalyst has been developed (Patent Document 1).
  • a low potential is applied at the moment when the catalyst particles dispersed in the acidic solution collide with a metal disposed in the solution, and a high potential is applied at the moment when the catalyst particles collide with oxygen molecules. That is, the time during which the high potential and the low potential are maintained is extremely short, and it is impossible to control the collision
  • the platinum catalyst is dispersed in an acidic aqueous solution containing protons.
  • this solution it is devised that chemical species for applying a high potential and a low potential are alternately present in the solution.
  • a platinum catalyst is dispersed in an acidic solution containing protons, and (I) a chemical species that gives a potential higher than the platinum oxide formation start potential of the platinum catalyst is present in the dispersion solution. And (II) a step of causing the presence of a chemical species that provides a potential lower than a platinum oxide reduction initiation potential of the platinum catalyst.
  • Step (I) is typically a step of (A) feeding a gas that gives a higher potential than the platinum oxide formation start potential of the platinum catalyst.
  • Step (II) typically includes (B-1) a step of feeding a gas that gives a potential lower than the platinum oxide reduction start potential of platinum of the platinum catalyst, or (B-2) of the platinum catalyst.
  • a step of feeding an inert gas while a solid that provides a potential lower than the oxide reduction initiation potential of platinum is present in the dispersion solution is referred to as “gas-gas method”, and the method including the step (A) and step (B-2) is referred to as “solid-gas method”. May be referred to as “respectively”.
  • the platinum catalyst used in the present invention may be a catalyst having a core-shell structure (platinum core-shell catalyst) in which the shell is platinum and the core is a metal other than platinum such as palladium, and includes an alloy of platinum and a metal other than platinum.
  • a platinum alloy catalyst may also be used.
  • catalysts using platinum as a substance having catalytic activity are collectively referred to as a platinum catalyst.
  • Platinum catalysts include both platinum core-shell catalysts and platinum alloy catalysts.
  • Examples of the acidic solution containing protons include nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, and the like.
  • sulfuric acid is used.
  • the concentration can be, for example, 10 ⁇ m to 3 ⁇ M, and is not particularly limited, but can be about 20 ⁇ m to 2.5 ⁇ M from the viewpoint of reaction rate and potential control.
  • the acidic solution is usually an aqueous solution, but may contain other solvents and additives as necessary.
  • the platinum catalyst As the gas used in the step of feeding the gas that gives a potential higher than the platinum oxide formation start potential of the platinum catalyst (A), since the platinum oxide formation start potential is about 0.7 V, the platinum catalyst Any gas that can apply a voltage higher than 0.7V is not limited. Specifically, oxygen is mentioned. As oxygen, pure oxygen gas may be used, a gas containing oxygen such as air, or a mixed gas of oxygen and inert gas may be used. When oxygen is fed into the solution, a reaction of the following formula (1) occurs in the solution, and a potential of 1.23 V is continuously applied to the platinum catalyst. Note that the actual measured potential may be lower than 1.23V due to overvoltage.
  • the temperature and the amount of gas fed may be appropriately adjusted according to the reaction rate, the amount of platinum catalyst particles, the partial pressure of oxygen in the gas to be fed, etc., and are not particularly limited. °C ⁇ 95 °C, the gas feed rate can be 10 ml / min. ⁇ 1,000 ml / min. With respect to 1 ⁇ L of solution.
  • (B-1) As a gas used in the step of feeding a gas that gives a potential lower than the platinum oxide reduction start potential of the platinum catalyst, since the platinum oxide reduction start potential of platinum is about 0.9 V, The gas is not limited as long as it can apply a voltage lower than 0.9 V to the platinum catalyst.
  • An example of such a gas is hydrogen.
  • the hydrogen gas pure hydrogen gas may be used, or a mixed gas of hydrogen and inert gas may be used.
  • a reaction of the following formula (2) occurs in the solution, and a potential of 0.00 V is continuously applied to the platinum catalyst. Note that the actual measured potential may be higher than 0.00V due to overvoltage.
  • the temperature, the gas feed amount and the feed time may be appropriately adjusted according to the reaction rate, the amount of platinum catalyst particles, the hydrogen partial pressure in the gas to be fed, etc., and are not particularly limited.
  • the temperature can be 10 to 95 ° C.
  • the amount of gas fed can be 10 to 1,000 ml / min.
  • the solid used in the step of feeding an inert gas while the solid that gives a potential lower than the platinum oxide reduction starting potential of the platinum catalyst is present in the dispersion is platinum oxide. Since the reduction starting potential is about 0.9 V, there is no limitation as long as it is a solid that can apply a voltage lower than 0.9 V to the platinum catalyst. Furthermore, it can be seen from the CV shown in FIG. 4 that the reduction of the Pt oxide is almost completed in the vicinity of 0.4 V and the reduction adsorption of hydrogen has not started. For this reason, it is considered more preferable to apply about 0.4 V on the low potential side. Examples of the solid that provides such a potential include metallic copper (sometimes simply referred to as “copper”).
  • the metal copper to be added may be any of a plate shape, a sheet shape, a net shape, a granular shape, and the like, but a shape that has a large surface area and can be quickly pulled up from the platinum catalyst dispersion (for example, Sheet-like) is preferable.
  • the inert gas is preferably nitrogen gas or argon gas.
  • Cu 2+ ions are contained in the acidic solution in which the platinum catalyst is dispersed.
  • Substances that give Cu 2+ ions include copper sulfate (CuSO 4 ), copper chloride (CuCl 2 ), copper acetate (Cu (CH 3 COO) 2 ), and copper nitrate (Cu (NO 3 ) 2 ).
  • CuSO 4 copper sulfate
  • CuCl 2 copper chloride
  • Cu nitrate Cu (NO 3 ) 2 .
  • the Cu 2+ ion concentration is not particularly limited, but can be, for example, 1 mM to 1000 mM, and may be about 10 mM to 500 mM from the viewpoint of the reaction rate and the stability of the reaction solution. preferable.
  • the step (A) and the step (B-1) or (B-2) are preferably performed with stirring.
  • the stirring method is not particularly limited and can be performed by a conventionally known method.
  • the duration of each of the step (A) and the step (B-1) or (B-2) is performed with a predetermined duration.
  • a predetermined duration For example, it can be 30 seconds to 100 minutes, preferably 1 minute to 60 minutes, and more preferably 2 minutes to 30 minutes.
  • the step (A) and the step (B-1) or (B-2) are preferably performed by alternately repeating the step (A) and the step (B-1) or (B-2) a plurality of times.
  • the number of repetitions is not particularly limited, but can be, for example, 10 to 10,000. If the number of repetitions is excessive, the aggregation of platinum catalyst particles may occur, ECSA may decrease, and ORR mass activity may decrease. From the viewpoint of suppressing aggregation of the catalyst particles and performing a sufficient reaction, the number of repetitions is preferably 20 to 500 times. Note that the repetition of the step (A) and the step (B-1) or (B-2) may be started from either the step (A) or the step (B).
  • the step (A) of supplying a gas that gives a higher potential than the platinum oxide formation start potential of the platinum catalyst it is preferable to end.
  • the manufacturing method including the step (A) and the step (B-1) further includes (C) a step of feeding an inert gas between the step (A) and the step (B-1). Is preferred. Further, before starting the repetition of the step (A) and the step (B-1), it is preferable to feed an inert gas in order to replace the gas in the reaction system. In particular, when the repetition is started from the step (B-1), an inert gas is introduced before the first step (B-1), and oxygen present in the air in the reaction system is discharged. It is preferable to do.
  • the inert gas is not particularly limited, and examples thereof include argon gas and nitrogen gas. What is necessary is just to select the flow volume etc.
  • the duration of the inert gas delivery is not particularly limited, but it is preferable that the gas used in the step (A) and the step (B-1) is sufficiently replaced with the inert gas.
  • the manufacturing method including the step (A) and the step (B-2) may further include (C) a step of introducing an inert gas between the step (A) and the step (B-2). preferable.
  • solid copper is removed from the platinum catalyst dispersion solution except when the step (B-2) is performed.
  • solid copper should not be present in the platinum catalyst dispersion solution.
  • step (A) and the step (B-2) a step of feeding an inert gas into the platinum catalyst dispersion solution; (102) a step of causing solid copper to exist while feeding an inert gas into the platinum catalyst dispersion solution; (103) removing the solid copper of step (102) from the platinum catalyst dispersion solution; (104) It is preferable to repeat the step of feeding oxygen into the platinum catalyst dispersion solution.
  • an inert gas is introduced before the first step (B-2), and oxygen present in the air in the reaction system is discharged. It is preferable to do.
  • limit especially as an inert gas, Argon gas, nitrogen gas, etc. are mentioned similarly to the above. What is necessary is just to select the flow volume etc. of an inert gas suitably, and it does not restrict
  • the inert gas delivery duration is not particularly limited as long as the oxygen in the system is sufficiently replaced with the inert gas.
  • a conventionally known platinum catalyst can be used as the platinum catalyst for use in the above-described steps, and a platinum core-shell catalyst or a platinum alloy catalyst is preferable.
  • the method for producing the core and / or shell is not particularly limited.
  • the platinum core-shell catalyst to be subjected to the above-described process may be manufactured immediately before being subjected to the above-described process, or the above-described process may be performed as a finishing process or a post-treatment process for a previously manufactured platinum core-shell catalyst. Good.
  • the platinum core-shell catalyst used in the production process of the present invention is not particularly limited, but can be produced, for example, by the following production method. That is, the Pd core particles supported on the carbonaceous carrier can be synthesized by a known synthesis method. Examples include palladium chloride (PdCl 2 ), palladium nitrate (Pd (NO 3 ) 2 ), palladium acetate (Pd (CH 3 COO) 2 ), palladium (II) chloride sodium trihydrate (Na 2 [PdCl 4 ] ⁇ 3H 2 O), dinitrodiamminepalladium (II) ([Pd (NH 3 ) 2 (NO 2 ) 2 ]), etc. There is a method for reducing carbon to obtain a carbon-supported Pd nanoparticle core.
  • an improved Cu-UPD method that does not require precise potential control using an external power source and a counter electrode or a reference electrode.
  • a Pd / C core is put into an acidic aqueous solution containing Cu 2+ ions in which a solid made of Cu is immersed, and stirred in an inert gas atmosphere such as argon or nitrogen.
  • an inert gas atmosphere such as argon or nitrogen.
  • a Cu monoatomic film is not necessarily a uniform film composed of a monoatomic film on the entire surface, but includes a partly defective or partly overlapping two or more atoms.
  • the solid made of Cu used in the improved Cu-UPD method is not limited as long as it is an object that at least has a surface composed of Cu and ionizes to produce Cu 2+ ions when contacted with Pd nanoparticles. Examples thereof include Cu mesh, Cu wire, Cu grain, Cu plate, and Cu lump.
  • Cu 2+ ions used in acidic aqueous solutions containing Cu ions include copper sulfate (CuSO 4 ), copper chloride (CuCl 2 ), copper acetate (Cu (CH 3 COO) 2 ), copper nitrate (Cu (NO 3 ) 2 ) and the like, and Cu 2+ ions are dissociated by making these Cu salts into aqueous solutions.
  • the Cu 2+ ion concentration is not particularly limited, but may be, for example, 0.1 mM to 100 mM, and may be about 1 mM to 50 mM from the viewpoint of the reaction rate and the stability of the reaction solution. preferable.
  • the acid that gives the acidic solution is not particularly limited as long as it can dissolve Cu, and examples thereof include nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, and the like, and the concentration can be set to 10 ⁇ m to 1 ⁇ M. From the viewpoint of controlling the speed and the potential of the Cu solid, it can be set to about 20 mm to 0.5 mm.
  • Pd / C core is put into the acidic solution containing the above Cu ions soaked with the above Cu solid, and for example, Pd / C core is stirred by flowing an inert gas at 5 to 30 ° C. for 1 to 50 hours. A Cu monoatomic film is formed on the surface of the core particle.
  • Pt ions include platinum salts (K 2 PtCl 4 , K 2 PtBr 4 ), tetraammineplatinum (II) nitrate (Pt (NH 3 ) 4 (NO 3 ) 2 ), tetraammineplatinum (II) hydroxide (Pt (NH 3 ) 4 (OH) 2 ), tetraammineplatinum (II) chloride (Pt (NH 3 ) 4 Cl 2 ), bis (ethylenediamine) platinum (II) chloride ([Pt (NH 2 CH 2 CH 2 NH 2 ) 2 ] Cl 2 ), dinitrodiammineplatinum (II) (Pt (NH 3 ) 2 (NO 2 ) 2 ) and the like.
  • the step of substituting the monoatomic film made of Cu with Pt is performed by removing the Cu solid from the above-described acidic solution containing Cu ions immersed in the Cu solid, and then adding the compound containing Pt to the aqueous solution. This can be done by stirring.
  • the addition of the Pt compound is preferably performed with as little time as possible after removing the Cu solid.
  • oxygen in the atmosphere enters the solution during the operation, the Cu monoatomic film formed on the Pd core is oxidized and dissolved. Therefore, it is preferable to add the platinum compound immediately after removing the Cu solid.
  • the reaction time and temperature can be appropriately selected. For example, the reaction time is 5 minutes to 30 degrees C. for 1 minute to 50 hours, more preferably 1 minute to 1 hour. preferable.
  • the platinum core-shell catalyst obtained by the above method is washed, dried, etc. by a known method as necessary.
  • separation, purification, washing steps and the like can be included as necessary.
  • the obtained catalyst is subjected to the above-described step (catalytic activity improving treatment step) which is a feature of the present invention to obtain the platinum core-shell catalyst of the present invention.
  • the Pd core particles of the platinum core-shell catalyst obtained by the production method of the present invention may contain other elements other than Pd, for example, metals such as silver, copper and nickel. Further, it may contain other substances as long as it does not affect the effects of the present invention, and it contains residues or a part of additives (reducing agents, microparticulating agents, etc.) used in the production process. Also good.
  • the particle size of the Pd core particles of the platinum core-shell catalyst obtained by the production method of the present invention is suitably 3.0 to 7.0 nm.
  • Pd core particles having a particle size of less than 3.0 nm are used, there is a problem that the particle size of the platinum core-shell catalyst becomes small and aggregation due to potential fluctuation is likely to occur.
  • the particle diameter exceeds 7.0 nm the particle diameter of the platinum core-shell catalyst becomes large, the catalyst particles become porous due to potential fluctuations, and there is a problem that the ORR activity does not increase.
  • the particle diameter of the Pd core particle means an average particle diameter obtained from a TEM image or a value calculated by applying the Scherrer equation to the X-ray diffraction peak of the (220) plane of Pd.
  • the average thickness of the Pt shell of the platinum core-shell catalyst obtained by the production method of the present invention is preferably from a monoatomic layer (equivalent to 1 ML) to a triatomic layer (equivalent to 3 ML), that is, about 0.3 to 0.9 nm. .
  • Pt atoms that exhibit activity as an oxygen reduction catalyst are only Pt atoms located in the outermost layer (outermost surface) of the shell, but a Pt monoatomic layer is considered insufficient from the viewpoint of corrosion resistance.
  • the Pt shell in the platinum core-shell catalyst may consist of Pt alone, Pd and Pt may be mixed, or a Pt—Pd alloy shell. Further, it may be an alloy shell with a different metal other than Pd.
  • a metal having a lower redox potential than platinum is preferable, and examples thereof include silver (Ag), copper (Cu), nickel (Ni), and cobalt (Co).
  • Pd of the core of the platinum core-shell catalyst is oxidized and eluted, and the Pt atoms of the shell are rearranged while repeating redox. Therefore, it is considered that the Pt / Pd / C catalyst before being subjected to the process of the present invention may have some defects in the Pt shell.
  • the dissimilar metal used in combination with platinum preferably includes palladium, cobalt, nickel, iron, copper, etc., specifically, carbon Examples thereof include a supported platinum / palladium alloy catalyst (hereinafter sometimes referred to as PtPd / C catalyst), a carbon-supported platinum / cobalt alloy catalyst (hereinafter sometimes referred to as PtCo / C catalyst), and the like.
  • PtPd / C catalyst a supported platinum / palladium alloy catalyst
  • PtCo / C catalyst carbon-supported platinum / cobalt alloy catalyst
  • a method for producing a platinum alloy catalyst for example, there is a method in which a salt or complex of platinum and a salt or complex of a metal other than platinum (for example, palladium, cobalt, etc.) are dissolved in a solvent and heated and reduced in a liquid with a reducing agent.
  • the production method is not particularly limited, and a known method can be used.
  • the platinum alloy catalyst to be used in the present invention may be produced immediately before being subjected to the catalyst activity improving treatment step, or the above-described steps are carried out as a finishing step or a post-treatment step for a previously produced platinum alloy catalyst. You may do it.
  • the platinum catalyst of the present invention is preferably dispersed and supported on the surface of a carrier made of a carbonaceous material.
  • the carbonaceous material as a carrier include carbon black, ketjen black, acetylene black, and carbon nanotube.
  • a metal oxide support such as tin oxide (SnOx) or titanium oxide (TiOx) having high oxidation resistance may be used. May be used in combination.
  • the support preferably has a specific surface area of about 10 to 1000 m 2 / g.
  • the platinum catalyst is thought to be supported on the surface of the support mainly by electrostatic interaction. However, in order to reduce the amount of catalyst falling off from the support surface by supporting it more firmly, the platinum catalyst and the support A chemical bond can be formed between and supported.
  • the Cu mesh is removed from the aqueous solution, and K 2 PtCl 4 aqueous solution in which dissolved oxygen is removed in advance by bubbling with Ar is immediately added to a concentration of 2 mM, and the Cu shell layer is replaced with a Pt shell layer to obtain Pt / Pd A / C core-shell catalyst was obtained.
  • the produced Pt / Pd / C core-shell catalyst was filtered off, redispersed in 300 ml of pure water, stirred for 30 minutes, and then filtered off. This operation was repeated 3 times to wash the Pt / Pd / C core-shell catalyst. Thereafter, it was dried in an oven at 60 ° C. for 6 hours in the atmosphere.
  • the PtPd / C catalyst was filtered off, redispersed in 300 ml of ultrapure water, and stirred for 30 minutes. This operation was repeated three times to wash the PtPd / C catalyst. Thereafter, the PtPd / C catalyst was dried in an oven at 60 ° C. in the atmosphere.
  • the PtPd / C catalyst obtained above was taken as Example 2.
  • PtCo / C alloy catalyst (i) Production of PtCo / C alloy catalyst Pt (acac) 2 and Co (acac) 2 were dissolved in 30 ml of oleylamine (OAm) in an amount of 0.5 ⁇ 10 ⁇ 3 mol, respectively. And degassing for 30 minutes in an N 2 atmosphere. Thereafter, the temperature was raised to 300 ° C. with a mantle heater, and the mixture was stirred for 1 hour to reduce metal ions to obtain PtCo nanoparticles. The produced PtCo nanoparticles were washed with ethanol and hexane three times and finally redispersed in hexane.
  • OAm oleylamine
  • the PtCo / C catalyst was filtered off, redispersed in 300 ml of ultrapure water, and stirred for 30 minutes. This operation was repeated 3 times to wash the PtCo / C catalyst. Thereafter, the PtCo / C catalyst was dried in an oven at 60 ° C. in the atmosphere.
  • the PtCo / C catalyst obtained above was taken as Example 3.
  • Reference Example 1 A Pt / Pd / C catalyst to which a potential was applied under the following conditions was used as Reference Example 1 instead of the catalyst activity improving treatment step. That is, a suspension was prepared by ultrasonically dispersing a Pt / Pd / C catalyst (no catalyst activity improving treatment) in n-hexanol. Then, it was apply
  • the prepared electrode was immersed in a 0.1 M HClO 4 aqueous solution saturated with argon gas at 80 ° C, and a rectangular wave of 0.05 V (300 s)-1.0 V (300 s) was applied to the reversible hydrogen electrode (RHE). Applied to cycle Pt / Pd / C catalyst.
  • Reference Example 2 A PtPd / C catalyst to which a potential was applied under the following conditions was used as Reference Example 2 instead of the catalyst activity improving treatment step. That is, a suspension was prepared by ultrasonically dispersing a PtPd / C catalyst (no catalyst activity improvement treatment) in n-hexanol. Then, it was apply
  • the prepared electrode was immersed in a 0.1 M HClO 4 aqueous solution saturated with argon gas at 80 ° C, and a rectangular wave of 0.05 V (300 s)-1.0 V (300 s) was applied to the reversible hydrogen electrode (RHE). Applied to cycle PtPd / C catalyst.
  • a cyclic voltammogram (CV) was measured at a potential sweep rate of 50 mV / s. From the hydrogen desorption wave of the obtained CV, the electrochemical surface area (Electro-Chemical Surface Area: ECSA) of each catalyst was calculated. Thereafter, the gas was replaced with oxygen gas, and the polarization curve was measured at a potential width of 0.05 V to 1.0 V and a potential sweep rate of 10 mV / s while rotating the GC electrode at 1,600 rpm. From the obtained polarization curve, the activation dominant current (ik) was determined from the oxygen reduction current value of 0.9 V and the limiting current value at 0.4 V.
  • ECSA Electro-Chemical Surface Area
  • the obtained ik was divided by ECSA and Pt weights to calculate ORR area specific activity (Specific Activity: SA) and ORR mass activity (Mass Activity: MA).
  • SA Specific Activity
  • MA ORR mass activity
  • FIG. 7 shows a comparison graph of ORR mass activity.
  • the Pt / Pd / C catalyst of Example 1 improved the ORR mass activity by about 1.5 times compared with the catalyst of Comparative Example 1. Further, the Pt / Pd / C catalyst of Example 1 showed an ORR mass activity equivalent to that of the catalyst of Reference Example 1.
  • the above evaluation results indicate that the phenomenon of improving the catalytic activity generated in the Pt / Pd / C catalyst by applying a potential using a GC electrode can be reproduced by the method of the present invention.
  • FIG. 8 A comparison graph of ORR mass activity is shown in FIG. As shown in FIG. 8, the PtPd / C catalyst of Example 2 improved the ORR mass activity by about 1.9 times compared with the catalyst of Comparative Example 2. Further, the PtPd / C catalyst of Example 2 showed an ORR mass activity equivalent to that of the catalyst of Reference Example 2.
  • the above evaluation results show that the phenomenon of improving the catalytic activity generated in the PtPd / C catalyst by applying a potential using a GC electrode can be reproduced by the method of the present invention.
  • the ORR mass activity of the PtCo / C alloy catalyst of Example 3 was improved by about 1.3 times compared to Comparative Example 3 in which the catalytic activity improvement treatment was not performed.
  • a comparison graph of ORR mass activity is shown in FIG.
  • the PtCo / C catalyst of Example 3 improved the ORR mass activity by about 1.3 times compared to the catalyst of Comparative Example 3.
  • 0.2 g of the Pt / Pd / C catalyst prepared above was ultrasonically dispersed in a separable flask containing 800 ml of an aqueous solution containing 2 M sulfuric acid and 0.1 M copper sulfate for 5 minutes.
  • a thermostatic bath and kept at 80 ° C.
  • argon gas was first allowed to flow as an inert gas at a flow rate of 500 ml / min for 20 minutes.
  • the copper sheet was immersed in the solution while flowing argon gas at a flow rate of 500 ml / min., And held for 5 minutes while stirring. After 5 minutes, the copper sheet was pulled up and the argon gas was stopped.
  • PtPd / C alloy catalyst (i) Preparation of PtPd / C alloy catalyst A PtPd / C alloy catalyst was obtained in the same manner as in Example 2 except for the activity enhancement treatment. (Ii) Activity enhancement treatment (solid-gas method) The produced PtPd / C alloy catalyst was subjected to catalytic activity improvement treatment (solid-gas method). That is, 0.2 g of the PtPd / C alloy catalyst prepared above was ultrasonically dispersed in a separable flask containing 800 ml of an aqueous solution containing 2 M sulfuric acid and 0.1 M copper sulfate for 5 minutes. It moved to the thermostat and hold
  • argon gas was first allowed to flow as an inert gas at a flow rate of 500 ml / min for 20 minutes.
  • the copper sheet was immersed in the solution while flowing argon gas at a flow rate of 500 ml / min., And held for 5 minutes while stirring. After 5 minutes, the copper sheet was pulled up and the argon gas was stopped. Subsequently, oxygen gas was allowed to flow at 200 ml / min for 6 minutes. After repeating this cycle 30 times, the PtPd / C alloy catalyst was separated by filtration, redispersed in 300 ml of ultrapure water, and stirred for 30 minutes.
  • PtCo / C alloy catalyst (i) Preparation of PtCo / C alloy catalyst A PtCo / C alloy catalyst was obtained in the same manner as in Example 3 except for the activity enhancement treatment. (Ii) Activity enhancement treatment (solid-gas method) The produced PtCo / C alloy catalyst was subjected to catalytic activity improvement treatment (solid-gas method). That is, 0.2 g of the PtCo / C alloy catalyst prepared above was ultrasonically dispersed in a separable flask containing 800 ml of an aqueous solution containing 2 M sulfuric acid and 0.1 M copper sulfate for 5 minutes. It moved to the thermostat and hold
  • Reference Example 4 instead of the catalyst activity improving treatment of Example 4, a Pt / Pd / C catalyst to which a potential was applied under the following conditions was used as Reference Example 4. That is, a suspension was prepared by ultrasonically dispersing a Pt / Pd / C catalyst (no catalyst activity improving treatment) in n-hexanol. Then, it was apply
  • the prepared electrode was immersed in a 0.1 M HClO 4 aqueous solution saturated with argon gas at 80 ° C, and a rectangular wave of 0.4 V (300 s)-1.0 V (300 s) was applied to the reversible hydrogen electrode (RHE). Applied to cycle Pt / Pd / C catalyst.
  • Reference Example 5 instead of the catalyst activity improving treatment of Example 5, a PtPd / C alloy catalyst to which a potential was applied under the same conditions as in Reference Example 4 was used as Reference Example 5.
  • the catalysts of Examples 4 to 6 were improved in ORR mass activity by about 1.5 to 2.2 times compared to Comparative Examples 4 to 6. Further, the catalysts of Examples 4 to 6 showed ORR mass activity comparable to or superior to that of Reference Examples 4 to 6. This indicates that the phenomenon of improving the catalytic activity caused by applying a potential using a GC electrode can be reproduced by the method of the present invention.

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Abstract

La présente invention a pour but de fournir un procédé de fabrication d'un catalyseur de type noyau-coquille en platine qui utilise du palladium (Pd) en tant que métal de noyau, ou un catalyseur au platine contenant du platine et un métal autre que le platine, le catalyseur au platine étant supporté sur du carbone et présentant une excellente activité de réduction de l'oxygène ; un procédé de fabrication par lequel il est possible de fabriquer le catalyseur industriellement à grande échelle. Ce procédé de fabrication d'un catalyseur au platine pour une pile à combustible, contenant du platine et un métal autre que le platine, comprend (I) une étape consistant à provoquer la présence d'une espèce chimique qui confère un potentiel supérieur au potentiel de formation initiale d'oxyde du platine du catalyseur au platine, et (II) une étape consistant à provoquer la présence d'une espèce chimique qui confère un potentiel inférieur à celui du potentiel de formation initiale d'oxyde du platine du catalyseur au platine, les étapes étant effectuées dans une solution de dispersion du catalyseur au platine dispersé dans une solution acide contenant des protons.
PCT/JP2016/057170 2015-03-10 2016-03-08 Procédé de fabrication de catalyseur au platine et pile à combustible l'utilisant WO2016143784A1 (fr)

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CN114068966B (zh) * 2020-07-31 2024-01-09 广州市香港科大***研究院 一种核壳催化剂后处理方法和***

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