WO2011115012A1 - Procédé de fabrication d'un catalyseur à noyau-enveloppe en platine, et ce catalyseur - Google Patents

Procédé de fabrication d'un catalyseur à noyau-enveloppe en platine, et ce catalyseur Download PDF

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WO2011115012A1
WO2011115012A1 PCT/JP2011/055780 JP2011055780W WO2011115012A1 WO 2011115012 A1 WO2011115012 A1 WO 2011115012A1 JP 2011055780 W JP2011055780 W JP 2011055780W WO 2011115012 A1 WO2011115012 A1 WO 2011115012A1
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platinum
gold
core
catalyst
shell catalyst
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Japanese (ja)
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稔 稲葉
裕明 辻
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学校法人同志社
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    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • 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
    • 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
    • H01M2008/1095—Fuel cells with polymeric 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 method for producing a platinum core-shell catalyst suitable for use as a catalyst for oxygen reduction reaction in a fuel cell, and a fuel cell using the catalyst.
  • a polymer electrolyte fuel cell is known as 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 platinum-supported carbon catalyst (Pt / C catalyst) in which platinum fine particles are supported in a highly dispersed manner on a carbon black carrier is generally used.
  • Pt / C catalysts have the advantages of high catalytic activity and high electrical conductivity, and because they are noble metals, they are less susceptible to corrosion and poisoning due to the state of the surrounding environment and substances present in the surrounding environment. Have However, there is a problem that platinum is expensive and has a small amount of resources, and a reduction in the amount of platinum is required.
  • a platinum core-shell catalyst in which platinum is coated on a dissimilar metal at an atomic level has attracted attention.
  • the platinum core-shell catalyst has a configuration in which different metal fine particles (core metal) coated with a platinum atomic layer (shell) are supported in a highly dispersed manner on a carrier (carbon black or the like). With such a configuration, the surface area can be increased while reducing the amount of platinum, so that the activity per mass of platinum can be improved and the amount of platinum can be reduced.
  • Gold is a noble metal and is as expensive as platinum, but it is less prone to ionization than platinum, is stable to oxidation, and is much more resource-rich than platinum, so it is expected as one of the core metals Has been.
  • a platinum core-shell catalyst Pt / Au / C catalyst
  • reducing agent such as hydrogen or sodium borohydride
  • depositing platinum on gold (core metal) Since a thick platinum (shell) layer is deposited on gold (core metal) or in a solution, it is difficult to efficiently produce a platinum core-shell catalyst.
  • Non-Patent Document 1 A method for producing a platinum core-shell catalyst using the UPD method is schematically shown in FIG.
  • the gold surface can be coated with a copper monoatomic layer, and then immersed in a hydrochloric acid solution containing chloroplatinate ions, For substitution, a monoatomic layer of platinum can be formed.
  • gold (core metal) can be theoretically coated with a monolayer, but it is synthesized because it requires a metal to be replaced such as copper or undergoes an electrochemical treatment. There was a problem that the method was complicated and mass synthesis was difficult.
  • an object of the present invention is to provide a method that can produce a platinum core-shell catalyst in a large amount at a low cost without using a reducing agent and having a simpler process than a method using an underpotential deposition method. .
  • the present inventors simply immersed the gold core particles in a solution containing divalent platinum ions or tetravalent platinum ions without using the underpotential precipitation method.
  • the platinum core-shell catalyst produced by this method is comparable to the platinum core-shell catalyst produced by the underpotential deposition method. It was confirmed that the catalyst had catalytic activity, and the present invention was completed.
  • the present invention is characterized in that platinum is directly deposited on the gold core particles by immersing the gold core particles in a solution containing divalent platinum ions or tetravalent platinum ions in the absence of a reducing agent. And a method for producing a platinum core-shell catalyst.
  • the gold core particles are preferably supported on the surface of an appropriate carrier (preferably carbon powder such as carbon black, or conductive oxide powder such as tin oxide or titanium oxide).
  • an appropriate carrier preferably carbon powder such as carbon black, or conductive oxide powder such as tin oxide or titanium oxide.
  • a highly active platinum core-shell catalyst can be produced in large quantities at a low cost. Since this catalyst can be used as a catalyst for a fuel cell, the cost of the fuel cell can be drastically reduced.
  • (a) is a figure explaining typically the manufacturing method of the conventional platinum core-shell catalyst using an underpotential method
  • (b) is a figure explaining the manufacturing method of the platinum core-shell catalyst of this invention typically.
  • (a) is a figure which shows typically the apparatus used for the method of this invention
  • (b) is a figure which shows typically the rotating ring disk electrode used for oxygen reduction activity evaluation.
  • (a) is a figure which shows the cyclic voltammogram of the Pt / Au / C catalyst created in Example 1 and Comparative Example 2 (UPD method),
  • (b) explains the peak of the voltammogram shown in (a). It is a figure to do.
  • (a) is a view showing a cyclic voltammogram of the Pt / Au / C catalyst prepared in Example 1 and Comparative Example 2 (UPD method) and a gold-supported carbon support (Au / C) not subjected to platinum coating treatment.
  • (B) is a partially enlarged view for explaining the voltammogram peak shown in (a). The figure which shows the convective voltammogram of the Pt / Au / C catalyst created in Example 1 (1.0mM), Example 2 (0.1mM), and Comparative Example 2 (UPD method), and a gold
  • the gold core particles used in the present invention preferably have a particle size of about 1 nm to 30 nm.
  • the gold core particle may be a particle whose surface is made of gold, and may contain a metal other than gold or platinum.
  • the gold core particles are dispersed on the surface of the carrier and the gold core particles It is preferable that it is supported in an amount that occupies 1% to 70% of the combined weight of the carrier and the carrier.
  • the specific surface area of the carrier is preferably 10 to 1000 m 2 / g, and the particle size of the carrier is preferably in the range of 10 nm to 1 mm.
  • the gold core particles are supported on the surface of the carrier, whereby the nanometer-scale gold core particles can be held in a highly dispersed state with high density.
  • the particle diameter of the gold core particle means an average crystallite diameter measured by an XRD method, and the particle diameter of a carrier means an average particle diameter of primary particles observed by an electron microscope.
  • a gold-supporting carrier in which gold fine particles having a particle size of 1 nm to 30 nm are supported in a highly dispersed state on the surface of a carbon black carrier.
  • a gold-supported carrier the same gold-supported carrier used in the conventional method for producing a platinum core-shell catalyst (method using the UPD method) can be used.
  • Examples of the solution containing divalent platinum ions or tetravalent platinum ions used in the present invention include, for example, an aqueous solution of tetrachloroplatinum (II) acid, an aqueous solution of potassium tetrachloroplatinate (II), and diaminemineplatinum platinum (II).
  • An aqueous solution an aqueous solution of diamminedinitroplatinum (II), an aqueous solution of tetraammineplatinum (II) chloride (monohydrate), an aqueous solution of hexachloroplatinum (IV) acid, an aqueous solution of potassium hexachloroplatinum (IV), and the like.
  • these platinum ions may exist in the solution in any state of an anion complex, a cation complex, and a nonionic complex.
  • immersing the gold core particles in a solution containing platinum ions means that the gold core particles only need to be immersed in the platinum ion-containing solution as a result. That is, the gold core particles may be immersed in a solution that already contains platinum ions, or the platinum complex may be added after the gold core particles are immersed in a solvent.
  • the amount of platinum ions contained in the solution may be appropriately adjusted according to the amount of gold core particles. That is, in order to cover the surface of the gold core particle with the shell of the platinum monoatomic layer, it is sufficient that sufficient platinum ions are included in the solution.
  • the solution is preferably prepared so that the amount of platinum ions is about 1 to 1000 times the amount covered by the platinum atoms in the monoatomic layer per surface area of the gold used. If the concentration of the solution is too thin, it takes time to coat, so the platinum ion concentration is preferably 0.05 mM or more. In general, an aqueous solution containing platinum ions of 0.1 mM to 100 mM may be used.
  • “in the absence of a reducing agent” means that a reducing agent (such as hydrogen or borohydride) is not intentionally added to the solution. That is, even if a substance having a reducing action is present in a small amount in the solution, it is included in “in the absence of a reducing agent” as long as platinum ions are not reduced.
  • a reducing agent such as hydrogen or borohydride
  • the method according to the present invention is intended to coat the surface of the gold core particle with a platinum monoatomic layer by depositing platinum atoms on the gold core particle. Even if not, sufficient catalytic activity can be obtained. It is preferable to cover 60% or more, particularly 70% or more of the surface area of the gold core particle with platinum atoms.
  • the temperature of the solution is not particularly limited, and the reaction can proceed even at room temperature.
  • the method according to the present invention can be carried out, for example, as follows. First, a carrier on which gold fine particles (gold core particles) are highly dispersed and supported is prepared, added to water, and subjected to ultrasonic treatment for about 10 to 60 minutes to disperse the carrier in water. Add a sufficient amount of Pt complex (divalent or tetravalent) for coating, and stir for about 1 to 24 hours in an inert atmosphere such as Ar atmosphere. Thereafter, centrifugation and washing with ultrapure water are performed, and the obtained powder (platinum core-shell catalyst) is dried. In the powder thus obtained, 60 to 70% or more of the surface of the gold core particle on the support is coated with a platinum monoatomic layer, and has high catalytic activity.
  • Pt complex divalent or tetravalent
  • the platinum coverage of the gold core particles described above is the cyclic voltammogram obtained by performing cyclic voltammetry on the gold core particles (Au) before platinum coating and the gold core particles (Pt / Au) after platinum coating. It can obtain
  • Formula (1) Coverage (%) ⁇ [(Au peak area)-(Pt / Au peak area)] / (Au peak area) ⁇ ⁇ 100
  • the gold core particles can be directly coated with a monoatomic platinum shell (see FIG. 1b) and can be produced from powder with the simple equipment and steps described above. So mass production is possible.
  • platinum and gold gold is a noble metal (less ionization tendency), so from the common knowledge in the art, even if a gold core is immersed in a solution of platinum ions, the gold core is covered with platinum atoms. It cannot be predicted. Therefore, the underpotential deposition method has been used so far, and the phenomenon in the method of the present invention is an unexpected phenomenon found in the research process for improving the platinum core-shell catalyst.
  • Example 1 Production of platinum core-shell catalyst 0.1 g of gold-supported carbon support (Au / C, gold average particle diameter: 5 nm, carbon support: particle diameter of 50 nm, specific surface area of 800 m 2 / g ketjen black, gold support density 28.6 wt%) was ultrasonically dispersed in 1 liter of ultrapure water for 30 minutes, and then thoroughly degassed with argon gas, and potassium tetrachloroplatinate (II) (K 2 PtCl 4 ) was adjusted to 1.0 mM. ) Was added. The mixture was stirred at 30 ° C. for 24 hours while flowing argon gas, to obtain a Pt / Au / C suspension (see FIG. 2a). This suspension was centrifuged and washed with ultrapure water ( ⁇ 3 times), and then dried at room temperature to produce Pt / Au / C powder.
  • Au / C gold average particle diameter: 5 nm
  • carbon support particle diameter of 50 nm,
  • a 5% Nafion (registered trademark) solution manufactured by Aldrich
  • Example 2 Production of platinum core-shell catalyst Pt / Au / C powder was produced in the same manner as in Example 1 except that the concentration of potassium tetrachloroplatinate (II) (K 2 PtCl 4 ) was 0.1 mM. did. The obtained Pt / Au / C powder was uniformly dispersed and supported on the rotating disk electrode in the same manner as in Example 1 to produce a performance evaluation electrode.
  • II potassium tetrachloroplatinate
  • Example 3 Production of platinum core-shell catalyst Pt / Au / C powder was produced in the same manner as in Example 1 except that the reaction temperature was 60 ° C. The obtained Pt / Au / C powder was uniformly dispersed and supported on the rotating disk electrode in the same manner as in Example 1 to produce a performance evaluation electrode.
  • Example 4 Production of platinum core-shell catalyst Pt / Au / C powder was produced in the same manner as in Example 1 except that the platinum source used was potassium hexachloroplatinate (IV) (K 2 PtCl 6 ). The obtained Pt / Au / C powder was uniformly dispersed and supported on the rotating disk electrode in the same manner as in Example 1 to produce a performance evaluation electrode.
  • the platinum source used was potassium hexachloroplatinate (IV) (K 2 PtCl 6 ).
  • the obtained Pt / Au / C powder was uniformly dispersed and supported on the rotating disk electrode in the same manner as in Example 1 to produce a performance evaluation electrode.
  • a commercially available platinum-supported carbon catalyst (Pt / C, platinum average particle size: 2.8 nm, carbon support: Ketjen black with a particle size of 50 nm, platinum support density: 50% by weight) is composed of a glassy carbon disk with a diameter of 6 mm.
  • rotating disk electrode (geometric area: 0.283cm 2) was uniformly dispersed and supported so as to 14.1 ⁇ g (Pt) cm -2 on.
  • a 5% Nafion (registered trademark) solution manufactured by Aldrich
  • This electrode was quickly washed with water and immersed in a 5 mM aqueous potassium tetrachloroplatinate (II) solution that had been degassed with argon gas for 10 minutes to replace the copper atoms with platinum atoms, resulting in a platinum monolayer core-shell catalyst (Pt / Au / C) was obtained. Further, a 5% Nafion (registered trademark) solution (manufactured by Aldrich) as a binder was cast to a film thickness of 0.1 mm and dried to prepare a performance evaluation electrode.
  • II aqueous potassium tetrachloroplatinate
  • Example 5 Performance evaluation of catalyst
  • the electrodes obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were subjected to electrochemical evaluation as follows, and compared with the electrodes obtained in Comparative Examples 1 and 2. Oxygen reduction activity was evaluated.
  • the structure of the rotating ring disk electrode used in this example is shown in FIG.
  • the catalyst was supported on the disk portion and the working electrode was rotated to generate a constant convection in the electrolyte solution to control mass transfer.
  • RHE reversible hydrogen electrode
  • FIG. 3A shows a cyclic voltammogram of the Pt / Au / C catalyst prepared in Example 1 and Comparative Example 2 (UPD method).
  • the horizontal axis represents the potential, and the vertical axis represents the current value.
  • FIG. 3B is a diagram for explaining the peak of the voltammogram shown in FIG.
  • Both Pt / Au / C prepared in Example 1 and Comparative Example 2 exhibited Pt-specific hydrogen adsorption / desorption and platinum oxide coating generation / reduction peaks.
  • Pt / Au / C prepared in Examples 2 to 4 showed the same peak.
  • FIG. 4A shows cyclic voltammograms of the Pt / Au / C catalyst prepared in Example 1 and Comparative Example 2 (UPD method) and an untreated gold-supported carbon support (Au / C).
  • the horizontal axis represents the potential, and the vertical axis represents the current value.
  • FIG. 4B is an enlarged view of the reduction peak portion of the voltammogram shown in FIG. As can be seen from FIG.
  • FIG. 5 shows convective voltammograms of the Pt / Au / C catalyst prepared in Example 1 (1.0 mM), Example 2 (0.1 mM) and Comparative Example 2 (UPD method), and a gold-supported carbon support (Au / C). Indicates.
  • the horizontal axis represents the potential, and the vertical axis represents the current value.
  • the core-shell catalyst produced by the method of the present invention exhibited an oxygen reduction reaction behavior similar to that of the core-shell catalyst produced by the UPD method, with the oxygen reduction current rising from around 1.0 V. The same behavior was also observed with Pt / Au / C prepared in Examples 3-4. Than the current I in 0.9V, using a limiting current I L in 0.4V, it was calculated activity dominant current I K in 0.9V according the following equation (2).
  • I K (I ⁇ I L ) / (I L ⁇ I)
  • the platinum core-shell catalyst (Pt / Au / C: Examples 1 to 4) prepared according to the method of the present invention was compared with a commercially available platinum-supported carbon catalyst (Pt / C: Comparative Example 1).
  • both have high surface area specific activity and mass activity.
  • the platinum coverage is low, but the surface area specific activity and mass activity are It was confirmed that it would be higher. For this reason, it was found that the platinum core-shell catalyst produced by the method of the present invention exhibits a catalytic activity comparable to that of the platinum core-shell catalyst produced by the UPD method in the oxygen reduction reaction.
  • the concentration is not particularly limited as long as sufficient platinum ions are present in the solution to cover the surfaces of the gold core particles with the platinum monoatomic layer.
  • Example 1 and Example 3 it was found that even if the temperature of the solution was increased, no significant change was observed in the coverage ratio or the catalytic activity. Therefore, in the method of the present invention, it was found that a platinum core-shell catalyst having excellent catalytic activity could be produced even if it was carried out at room temperature, without having to manipulate the temperature.
  • Example 1 and Example 2 the experiment was carried out while keeping the temperature at 30 ° C. in order to make the production conditions completely the same. It has been confirmed that can be manufactured.
  • Example 1 From the results of Example 1 and Example 4, it was found that when the immersion time was the same, the coverage decreased when the valence of the platinum complex was increased. Therefore, there is a possibility that the deposition rate of platinum is slower for tetravalent platinum ions than for divalent platinum ions.
  • the cyclic voltammogram showed a peak peculiar to platinum regardless of whether it was divalent or tetravalent, and showed the same behavior of oxygen reduction current.
  • Example 6 Measurement of UV spectrum of supernatant liquid Based on the same procedure as in Example 1, the gold-supported carbon support was stirred in an aqueous solution of potassium tetrachloroplatinate (II) (K 2 PtCl 4 ) for 24 hours. Then, it was allowed to stand, the supernatant was collected, and the UV spectrum was measured. This UV spectrum was compared with the UV spectrum of an aqueous solution of potassium tetrachloroplatinate (II) immediately after preparation (no gold-supported carbon support). The same experiment was also conducted on an aqueous solution of potassium hexachloroplatinate (IV) (K 2 PtCl 6 ). The measurement results are shown in FIG.
  • II potassium tetrachloroplatinate
  • (a) is a UV spectrum of an aqueous solution of potassium tetrachloroplatinate (II), and (b) is an aqueous solution of potassium hexachloroplatinate (IV).
  • the peak due to the Pt-Cl charge transfer transition near 215 nm and the peak due to zero-valent Pt near 300 nm were almost the same regardless of whether or not the catalyst was prepared. . Therefore, it is considered that a part of the platinum complex in the solution is selectively reduced on the gold core particle to form a platinum core-shell catalyst, and the remaining platinum complex is not reduced but remains in the supernatant.
  • the catalyst produced by the method of the present invention has a reduced reduction peak of the gold oxide film as compared with the untreated gold-supported support (Au / C). Furthermore, a hydrogen adsorption / desorption peak and a formation and reduction peak of a platinum oxide film are observed.
  • the reduction of the reduction peak of the gold oxide film is based on the fact that the gold surface was coated with platinum, and the hydrogen adsorption / desorption peak and the generation and reduction peak of the platinum oxide film are considered to be based on platinum deposited on the gold surface. From the cyclic voltammogram, it can be seen that gold was coated with platinum.
  • the catalyst produced by the method according to the present invention has a core-shell structure in which gold particles are coated with platinum, like the catalyst produced by the UPD method.
  • Example 7 Production of platinum core-shell catalyst A gold-supported carbon support (Au / C, gold average particle size: 5 nm, carbon support: particle size 50 nm, specific surface area 800 m 2) in a different production lot from that used in Example 1 Pt / Au / C powder was produced in the same manner as in Example 1, using Ketjen black / g, gold loading density: 29.5 wt%. The obtained Pt / Au / C powder was uniformly dispersed and supported on the rotating disk electrode in the same manner as in Example 1 to produce a performance evaluation electrode.
  • Example 8 Observation with a transmission electron microscope and calculation of particle size distribution and average particle diameter
  • the Au / C carrier used in Example 7 and the Pt / Au / C powder obtained in Example 7 were measured with a transmission electron microscope (TEM). ) And the diameters of 500 noble metal fine particles in the obtained TEM image were measured to obtain a particle size distribution. Further, the average particle size of the noble metal fine particles was calculated from the particle size distribution.
  • the obtained TEM image is shown in FIG. (a) shows an image of Au / C support, and (b) shows an image of Pt / Au / C powder. It can be seen that the noble metal fine particles on the Au / C support and the Pt / Au / C powder are both supported on the carbon support with good dispersion.
  • FIG. 8 shows the particle size distribution of the noble metal fine particles obtained from the TEM image.
  • (a) shows the particle size distribution of the noble metal fine particles on the Au / C support
  • (b) shows the particle size distribution of the noble metal fine particles on the Pt / Au / C powder.
  • the particle size distribution of the noble metal fine particles is shifted to the large particle size as a whole, but there is no significant change in the distribution state, and in particular, there is a phenomenon that particles with a small particle size increase. Therefore, it can be seen that the overall particle size was increased by depositing on the gold fine particles without platinum being deposited on the carbon.
  • the average particle size calculated from the particle size distribution was 4.4 nm for gold particles on the Au / C support and 5.1 nm for noble metal particles on the Pt / Au / C powder. This average particle size difference of 0.7 nm is close to 0.54 nm, which is twice the atomic diameter of platinum of 0.27 nm, indicating that platinum is deposited in a monoatomic layer on the gold core particles.
  • Example 9 Production of platinum core-shell catalyst Pt / Au / C powder was produced in the same manner as in Example 7 except that the reaction time was 1 hour. The obtained Pt / Au / C powder was uniformly dispersed and supported on the rotating disk electrode in the same manner as in Example 1 to produce a performance evaluation electrode.
  • Example 10 Production of platinum core-shell catalyst Pt / Au / C powder was produced in the same manner as in Example 7 except that the reaction time was 3 hours. The obtained Pt / Au / C powder was uniformly dispersed and supported on the rotating disk electrode in the same manner as in Example 1 to produce a performance evaluation electrode.
  • Example 11 Production of platinum core-shell catalyst Pt / Au / C powder was produced in the same manner as in Example 7 except that the reaction time was 6 hours. The obtained Pt / Au / C powder was uniformly dispersed and supported on the rotating disk electrode in the same manner as in Example 1 to produce a performance evaluation electrode.
  • Example 12 Production of platinum core-shell catalyst Pt / Au / C powder was produced in the same manner as in Example 7 except that the reaction time was 48 hours. The obtained Pt / Au / C powder was uniformly dispersed and supported on the rotating disk electrode in the same manner as in Example 1 to produce a performance evaluation electrode.
  • Example 13 Measurement of platinum coverage The platinum coverage (%) of the electrodes obtained in Examples 7 and 9 to 12 was determined in the same manner as described in Example 5.
  • Example 14 Measurement of platinum, gold content and platinum / gold atomic ratio A small amount of the Pt / Au / C powder obtained in Examples 7 and 9 to 12 was taken, and aqua regia (hydrochloric acid and nitric acid in a volume ratio of 3: 1). The concentration of platinum and gold in the solution was determined using inductively coupled high-frequency plasma emission (ICP) analysis. From the obtained results, the platinum and gold contents (% by weight) and platinum / gold (atomic ratio) in the noble metal of the Pt / Au / C powder were calculated.
  • ICP inductively coupled high-frequency plasma emission

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Abstract

Procédé permettant de fabriquer, de manière simple, un volume important de catalyseur à noyau-enveloppe en platine convenant en tant que tel pour des réactions de réduction d'oxygène dans une pile à combustible. Ce procédé est caractérisé en ce que des particules de noyau métalliques sont immergées, en présence d'un agent réducteur, dans une solution contenant des ions platine bivalents ou des ions platine tétravalents, faisant que le platine est déposé directement sur les particules de noyau métallique. Il est préférable que les particules de noyau métallique reposent sur la surface d'un élément porteur et que la solution soit une solution aqueuse contenant des ions platine à une concentration de 0,1-10 mM.
PCT/JP2011/055780 2010-03-19 2011-03-11 Procédé de fabrication d'un catalyseur à noyau-enveloppe en platine, et ce catalyseur WO2011115012A1 (fr)

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