WO2021020377A1 - 合金ナノ粒子、合金ナノ粒子の集合体、触媒および合金ナノ粒子の製造方法 - Google Patents

合金ナノ粒子、合金ナノ粒子の集合体、触媒および合金ナノ粒子の製造方法 Download PDF

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WO2021020377A1
WO2021020377A1 PCT/JP2020/028834 JP2020028834W WO2021020377A1 WO 2021020377 A1 WO2021020377 A1 WO 2021020377A1 JP 2020028834 W JP2020028834 W JP 2020028834W WO 2021020377 A1 WO2021020377 A1 WO 2021020377A1
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alloy nanoparticles
elements
alloy
catalyst
nanoparticles
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French (fr)
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北川　宏
康平 草田
冬霜 ▲呉▼
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Kyoto University NUC
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Kyoto University NUC
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Priority to US17/630,731 priority patent/US12325903B2/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/45—Nanoparticles
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
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    • B22F1/054—Nanosized particles
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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    • H01M4/90—Selection of catalytic material
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    • H01M4/00—Electrodes
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    • H01M4/90—Selection of catalytic material
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    • 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
    • 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
    • H01M4/928—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18—Non-metallic particles coated with metal

Definitions

  • the present invention relates to alloy nanoparticles, an aggregate of alloy nanoparticles, a catalyst, and a method for producing alloy nanoparticles.
  • High entropy alloy is a material with a short history of about 20 years since it was proposed, and it is used for various structural metal materials such as steel materials and aluminum alloys.
  • the name of the high entropy alloy is derived from the fact that the sum of thermodynamic entropy when multi-elements are mixed and alloyed shows a high value as compared with the conventional solid-state reinforced alloy.
  • High-entropy alloys are expected as materials that exhibit excellent mechanical properties and functionality, but their development is mainly focused on 3d alloys (Patent Document 1).
  • Non-Patent Document 1 discloses a method for producing high-entropy alloy nanoparticles in which a metal salt is supported on a carbon material, a large current is applied thereto, the mixture is rapidly heated to a high temperature of 2000 K or higher, and then rapidly cooled.
  • Patent Document 3 discloses a carbon monoxide-resistant catalyst material containing a binary alloy represented by PtX [X is rhodium or osmium] and a carrier material in which the PtX alloy is dispersed, but is ternary or higher. There is no description of the alloy, and this alloy is manufactured by the impregnation method and is not a solid solution.
  • Patent Document 4 discloses a method for producing a catalyst containing a ruthenium-containing catalyst layer formed on the surface of a structure, and a ruthenium (Ru) precursor-containing solution used for producing the catalyst layer includes platinum (Pt) and palladium. It may contain (Pd), rhodium (Rh), iridium (Ir), osmium (Os) or a mixed metal precursor thereof, but in the examples, a catalyst layer containing a noble metal other than ruthenium has not been produced.
  • ruthenium (Ru) precursor-containing solution used for producing the catalyst layer includes platinum (Pt) and palladium. It may contain (Pd), rhodium (Rh), iridium (Ir), osmium (Os) or a mixed metal precursor thereof, but in the examples, a catalyst layer containing a noble metal other than ruthenium has not been produced.
  • Patent Document 5 discloses a platinum alloy catalyst PtX and describes that X is one or more metals selected from the group consisting of precious metals, ruthenium, rhodium, palladium, iridium, osmium, gold, silver, and transition metals.
  • X is one or more metals selected from the group consisting of precious metals, ruthenium, rhodium, palladium, iridium, osmium, gold, silver, and transition metals.
  • X is one or more metals selected from the group consisting of precious metals, ruthenium, rhodium, palladium, iridium, osmium, gold, silver, and transition metals.
  • X is one or more metals selected from the group consisting of precious metals, ruthenium, rhodium, palladium, iridium, osmium, gold, silver, and transition metals.
  • Ru is disclosed, and an alloy catalyst having a ternary
  • Patent Document 6 discloses a catalyst for hydrogen purification containing (a) at least one of ruthenium, rhodium, and iridium, (b) platinum, and (c) osmium, but in Examples, Pt- A ternary or quaternary catalyst of Ru-Os, Pt-Rh-Os, and Pt-Ru-Os-Ir is produced, and there is no description of an alloy catalyst of 5 yuan or more, and no solid solution is disclosed.
  • Non-Patent Document 2 describes a production method of mechanically pulverizing a graphene carrier and a metal to form high-entropy alloy nanoparticles on the graphene carrier.
  • Fig. The elemental composition of the FeCrCoCuNi nanoparticles shown in 9 did not show a uniform mixture.
  • Non-Patent Document 3 describes a manufacturing method for obtaining nanoparticles by irradiating a target of a bulk high-entropy alloy of a 3d transition metal (4th period) with a laser.
  • Table 2 the composition of CoCrFeMnNi nanoparticles was described, but the uniformity of mixing was not shown.
  • Non-Patent Document 4 describes a production method for obtaining nanoparticles by solvent hydrothermal synthesis at about 200 ° C. using an organometallic salt of a platinum group element.
  • Fig. 5 contains scanning transmission electron microscope (STEM) -energy dispersive X-ray analysis (EDS, also referred to as EDX) images of PtRhRu and PtPdIrRhRu particles, but the uniformity of mixing at the atomic level from the images is described. I could't read it.
  • STEM scanning transmission electron microscope
  • EDS energy dispersive X-ray analysis
  • Patent Document 2 The effect of the invention described in Patent Document 2 is "By adding an additional element to the PdRu solid solution alloy that cannot be obtained in bulk, the solid solution state of Pd and Ru is stabilized, and under high temperature conditions and long-term reactions. To prevent catalyst deterioration in the above ”(see [0028]). That is, the problem to be solved in Patent Document 2 is to increase the catalytic efficiency of PdRu. It is unclear whether the catalytic efficiency of PdRu increases when the number of elements to be solid-dissolved is increased to obtain the idea of alloy nanoparticles of quintuple or more from the disclosure of Examples of quaternary solid solution fine particles of Patent Document 2. Therefore, it was difficult because the tasks were different.
  • Non-Patent Document 1 a conductive carbon fiber (carbon nanofiber) carrier is indispensable because the metal salt is reacted by a pulse voltage, and in Non-Patent Document 2, a graphene carrier is indispensable, and only these supported alloy nanoparticles can be obtained. There wasn't. Further, in Non-Patent Document 2, since it is mechanical milling, it is not possible to produce particles having a non-uniform particle size and uniform at several nm. In the lower left part of the sixth page of Non-Patent Document 4, it is described that the obtained nanoparticles are stable up to 700 K (427 ° C.). In particular, an XRD pattern corresponding to hcp appears from 800K, which suggests that a Ru-rich phase of hcp is emerging.
  • Non-Patent Document 4 the nanoparticles obtained in Non-Patent Document 4 are not uniformly mixed, and cannot be said to be alloy nanoparticles containing five or more kinds of elements mixed at the atomic level.
  • the sealed vial since the sealed vial is gradually heated, the metal that is easily decomposed and reduced gradually reacts, and the reduction rate differs depending on each metal, so that a uniform alloy can be obtained. It is considered difficult to do.
  • An object to be solved by the present invention is to provide novel alloy nanoparticles containing five or more kinds of elements which may be supported on a carrier other than a carbon fiber carrier and a graphene carrier.
  • alloy nanoparticles containing 5 or more kinds of elements are directly supported on the carbon material carrier, the case where the carbon material carrier is graphene or carbon fiber is excluded.
  • the elements constituting the alloy nanoparticles are platinum group (Ru, Rh, Pd, Os, Ir, Pt), Ag, Au, Cd, Hg, In, Tl, Sn, Pb, Sb, Bi, Mo, W, Tc, Re, 3d metals (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn), Ga, Ge, As, H, B, Al, C, Si, N, P,
  • the elements constituting the alloy nanoparticles include at least one of the group consisting of Ru, Rh, Pd, Os, Ir, Pt, Ag, Au, Cu, and Ni.
  • [8] The alloy nanoparticles according to any one of [1] to [7], which have an average particle size of 0.5 to 30 nm.
  • the catalyst according to [12], wherein any alloy nanoparticles contained in the catalyst contain all of five or more kinds of elements as constituent elements.
  • Alloy nanoparticles comprising a step of adding an aqueous solution containing salts of 5 or more kinds of elements to a liquid reducing agent heated to 200 ° C. to 300 ° C. and reacting them to obtain alloy nanoparticles containing 5 or more kinds of elements. Manufacturing method; However, when the alloy nanoparticles are directly supported on the carbon material carrier, the case where the carbon material carrier is graphene or carbon fiber is excluded.
  • one preferred aspect of the present invention is the following configuration.
  • Item 1. The alloy nanoparticles according to any one of [1] to [10] or a platinum group multidimensional solid solution containing 5 or more kinds of platinum group elements.
  • Item 2. Item 3. The platinum group multi-dimensional solid solution according to Item 1 or the alloy nano according to any one of [1] to [10], wherein the platinum group multi-dimensional solid solution is fine particles having an average particle size of 0.5 nm to 0.5 ⁇ m. particle.
  • Item 3. The platinum group multi-dimensional solid solution according to Item 1 or the alloy nanoparticles according to any one of [1] to [10], wherein the content of the platinum group element is 5 at% or more.
  • Item 5 The platinum group multi-dimensional solid solution according to any one of Items 1 to 4 or the alloy nanoparticles according to any one of [1] to [10], which is supported on a carrier.
  • the platinum group multi-dimensional solid solution according to any one of Items 1 to 5, or the alloy nanoparticles according to any one of [1] to [10].
  • Item 7. Item 6.
  • Item 8. Item 4. The platinum group multi-dimensional solid solution according to any one of Items 1 to 7, or the alloy nanoparticles according to any one of [1] to [10], wherein the crystal structure is fcc or hcp.
  • Item 9. A catalyst containing the platinum group multidimensional solid solution according to any one of Items 1 to 8 or the alloy nanoparticles according to any one of [1] to [10] as a component.
  • Hydrogenation reaction catalyst hydrogen oxidation reaction catalyst, oxygen reduction reaction (ORR) catalyst, oxygen generation reaction (OER) catalyst, nitrogen oxide (NOx) reduction reaction catalyst, carbon monoxide (CO) oxidation reaction Item 10.
  • the catalyst according to Item 10 which is a catalyst, a catalyst for dehydrogenation reaction, a catalyst for VVOC or VOC oxidation reaction, a catalyst for exhaust gas purification, a catalyst for water electrolysis reaction, or a catalyst for hydrogen fuel cell.
  • Item 12 A step of reacting by adding an aqueous solution containing 5 or 6 kinds selected from the group consisting of Ru salt, Rh salt, Pd salt, Os salt, Ir salt and Pt salt to a liquid reducing agent heated to 200 ° C. to 300 ° C.
  • a method for producing a platinum group multidimensional solid solution which comprises, and obtains a platinum group multidimensional solid solution containing 5 or more kinds of platinum group elements.
  • An aqueous solution containing 5 or 6 types selected from the group consisting of Ru salt, Rh salt, Pd salt, Os salt, Ir salt and Pt salt and a carrier are added to a liquid reducing agent heated to 200 ° C. to 300 ° C. and reacted.
  • a method for producing a supported catalyst which comprises a step and obtains a carrier on which a platinum group multidimensional solid solution containing 5 or more kinds of platinum group elements is supported.
  • novel alloy nanoparticles containing five or more kinds of elements which may be supported on a carrier other than the carbon fiber carrier and the graphene carrier.
  • a method for producing platinum group hex-based solid solution fine particles, which are alloy nanoparticles of Example 1 is shown.
  • Six kinds of platinum group elements (Ru, Rh, Pd, Os, Ir, Pt) were uniformly distributed in the fine particles, indicating that they were solid solutions.
  • Quantification of 6 kinds of platinum group elements by (a) powder X-ray diffraction (PXRD) pattern, (b) EDS ray analysis, and (c) fluorescent X-ray analysis of the platinum group hex-based solid solution fine particles obtained in Example 1. The result (at%) is shown.
  • FIG. 4 is an in situ XRD pattern of the alloy nanoparticles of Example 1. Application of the platinum group 6-element solid solution fine particles obtained in Example 1 to an ORR catalyst.
  • FIG. 6 is a graph relating to the comparison of the current density with the commercially available Pt / C catalyst when the ethylene glycol oxide electrode catalytic activity of the alloy nanoparticles obtained in Example 1 was measured.
  • FIG. 7A is a graph relating to the comparison of the current density with the elemental metal particles when the initial ethanol oxidation electrode catalytic activity of the alloy nanoparticles obtained in Example 1 was measured.
  • FIG. 4 is an in situ XRD pattern of the alloy nanoparticles of Example 1. Application of the platinum group 6-element solid solution fine particles obtained in Example 1 to an ORR catalyst.
  • FIG. 6 is a graph relating to the comparison of the current density with the commercially available Pt / C catalyst when the ethylene glycol oxide electrode catalytic activity of the alloy nanoparticles obtained in Example 1 was measured.
  • FIG. 7B is a graph relating to the comparison of the current density with the commercially available catalyst when the initial ethanol oxidation electrode catalytic activity of the alloy nanoparticles obtained in Example 1 was measured.
  • FIG. 7 (c) relates to a comparison of current densities at 0.45 V (left side) and 0.60 V (right side) when the first ethanol oxidation electrode catalytic activity of the alloy nanoparticles obtained in Example 1 was measured. It is a graph.
  • FIG. 7D is a graph relating to the comparison of the current density with Au @ PtIr / C when the initial ethanol oxidation electrode catalytic activity of the alloy nanoparticles obtained in Example 1 was measured.
  • FIG. 7E is a graph relating to the comparison of the current densities when the first and 50th ethanol oxidation electrode catalytic activities of the alloy nanoparticles obtained in Example 1 were measured.
  • FIG. 8 is a graph relating to the comparison of current densities when the ethylene glycol oxidation electrode catalytic activity of the alloy nanoparticles obtained in Example 3 was measured.
  • FIG. 9A is a graph relating to the comparison of current densities when measuring the catalytic activity of the hydrogen generating electrode when the H 2 SO 4 aqueous solution of the alloy nanoparticles obtained in Example 3 is used.
  • FIG. 9 (b) shows the current density per area of the electrode (mA cm- 2 ) when the hydrogen generating electrode catalytic activity was measured when the H 2 SO 4 aqueous solution of the alloy nanoparticles obtained in Example 3 was used.
  • FIG. 9C is a graph relating to a comparison of current densities when measuring the catalytic activity of a hydrogen generating electrode when the KOH aqueous solution of the alloy nanoparticles obtained in Example 3 is used.
  • FIG. 9D is a graph relating to the comparison of the current density per electrode area when the hydrogen generating electrode catalytic activity when the KOH aqueous solution of the alloy nanoparticles obtained in Example 3 was used was measured.
  • FIG. 10 is a STEM-EDS map of the alloy nanoparticles obtained in Example 4.
  • the present invention will be described in detail below.
  • the description of the constituent elements described below may be based on typical embodiments or specific examples, but the present invention is not limited to such embodiments.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the alloy nanoparticles of the present invention are alloy nanoparticles containing five or more kinds of elements.
  • the alloy nanoparticles when the alloy nanoparticles are directly supported on the carbon material carrier, the case where the carbon material carrier is graphene or carbon fiber is excluded. With this configuration, it is possible to provide novel alloy nanoparticles containing five or more kinds of elements which may be supported on a carrier other than the carbon fiber carrier and the graphene carrier.
  • the alloy nanoparticles refer to alloy particles having an average particle size of 0.5 nm to 0.5 ⁇ m.
  • the alloy nanoparticles preferably have high material uniformity, and more preferably show a stable structure when heated and have high material uniformity.
  • the uniform solid solution phase becomes stable.
  • the alloy nanoparticles show a stable structure and have high material uniformity when heated to, for example, 500 K or more (preferably 700 K or more, more preferably 900 K or more).
  • the homogeneity of the substance can be confirmed by in situ XRD or STEM-EDS.
  • the constituent elements of the alloy nanoparticles are mixed at the atomic level.
  • the aggregate of the alloy nanoparticles contains 98% by number or more of the alloy nanoparticles of the present invention.
  • any alloy nanoparticles constituting the aggregate of alloy nanoparticles contain all five or more kinds of elements as constituent elements.
  • the alloy nanoparticles contained in the catalyst when used as a catalyst containing a large number of alloy nanoparticles, it is preferable that the alloy nanoparticles contained in the catalyst contain 98% by number or more of the alloy nanoparticles of the present invention. Alternatively, it is preferable that any alloy nanoparticles contained in the catalyst contain all of five or more kinds of elements as constituent elements.
  • the alloy nanoparticles of the present invention are preferably novel high entropy alloy nanoparticles.
  • the alloy nanoparticles of the present invention are composed of 5 or more kinds of elements, preferably composed of 5 to 50 kinds of elements, more preferably composed of 5 to 25 kinds of elements, and 5 to 10 kinds. It is particularly preferable that it is composed of the above elements, and it is more preferable that it is composed of 5 or 6 kinds of elements.
  • the types of elements constituting the alloy nanoparticles of the present invention are not particularly limited. However, it is preferable that the alloy nanoparticles are not a combination of elements that serve as an insulator (including an insulator oxide).
  • the elements constituting the alloy nanoparticles may contain a combination of elements that do not dissolve in the phase equilibrium diagram, and may not include a combination of elements that do not dissolve in the phase equilibrium diagram. That is, the alloy nanoparticles may be a combination of elements that cannot easily form a solid solution, or may be a combination of elements that can easily form a solid solution.
  • the phase equilibrium diagram is also referred to as a phase diagram, a phase diagram, an alloy phase diagram, or the like, and all similar diagrams can be used as the phase equilibrium diagram in the present specification.
  • the phase equilibrium diagram may be a phase equilibrium diagram of two elements or a phase equilibrium diagram of three or more elements.
  • the elements constituting the alloy nanoparticles include a combination of elements that do not dissolve in the phase equilibrium diagram.
  • the combination of elements that do not dissolve in solid solution means a combination having an immiscible region of 30 atomic% or more when the pressure is 1 atm (normal pressure) at 1000 ° C.
  • the elements constituting the alloy contain a combination of elements that do not dissolve in the binary phase equilibrium diagram or the ternary phase equilibrium diagram, and the binary phase equilibrium diagram and the ternary phase equilibrium state.
  • the combinations of elements that do not dissolve in at least one set of binary phase equilibrium diagrams include PdRu, AuIr, AgRh, AuRh, AuRu, CuRu, and CuIr. , AgCu, FeCu, AgIr, AgRu, MoRu, RhC, RuN, RuSn, PdOs, CuOs, AgOs, AuOs, CuRh, IrRh, IrPd, AgPt, AuPt, and other combinations of precious metals with most metals other than precious metals. Can be mentioned.
  • alloy nanoparticles containing a combination of two elements that do not dissolve in the binary phase equilibrium diagram include a combination of PdRuRhOsIr and Pt, and a combination of RuRhPdIr and Pt. , AuRuRhIrPt and the like.
  • the combinations of elements that do not dissolve in at least one set of ternary phase equilibrium diagrams include PdRuB, AuRuIr, RuRhAu, PtIrRu, FeRuRh, AuIrRh, and AgIrRh. And so on.
  • phase equilibrium diagram shows. It is included in the combination of elements that do not dissolve in solid solution.
  • Oxidation-resistant metals are precious metals, Ni, etc. that maintain a metallic state (metal structure such as fcc, bcc, hcp, etc.) with a particle size of 50 nm or less.
  • the alloy nanoparticles of the present invention include platinum group (Ru, Rh, Pd, Os, Ir, Pt), Ag, Au, Cd, Hg, In, Tl, Sn, Pb, Sb, Bi, Mo, W, Tc, Re, 3d metals (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn), Ga, Ge, As, H, B, Al, C, Si, N, P, Y, Zr, It preferably contains at least 5 of the group consisting of Nb, lanthanoids, Hf and Ta.
  • the elements constituting the alloy nanoparticles are platinum group (Ru, Rh, Pd, Os, Ir, Pt), Ag, Au, Cd, Hg, In, Tl, Sn, Pb, Sb. , Bi, Mo, W, Tc, Re, 3d metals (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn), Ga, Ge, As, B, Al, C, Si, N , P, and lanthanoids, more preferably at least 5 of the group.
  • the elements constituting the alloy nanoparticles are platinum group (Ru, Rh, Pd, Os, Ir, Pt), Ag, Au, In, Tl, Sn, Bi, Mo, W, Re, and 3d metals ( It is particularly preferable to include at least 5 types in the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn), Ga, B, C, N and lanthanoids. It is more preferable that the elements constituting the alloy nanoparticles contain at least 5 kinds from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, Ag, Au, Cu and Ni.
  • the elements constituting the alloy nanoparticles contain at least 5 kinds from the group consisting of the platinum group (Ru, Rh, Pd, Os, Ir, Pt).
  • the elements constituting the alloy nanoparticles are Rh, Ru, Os, Ir, Pt, Au, Ag, Mo, W, Re. , Fe, Co, Ni, Cu, C, N, B, or an embodiment containing at least 5 types, or Rh, Pd, Os, Ir, Pt, Au, Ag, Mo, W, Re, Fe, Even more particularly preferred is an embodiment comprising at least 5 of the group consisting of Co, Ni, Cu, C, N and B.
  • the element constituting the alloy nanoparticles preferably contains at least one of the group consisting of platinum group (Ru, Rh, Pd, Os, Ir, Pt), Ag, Au, and Ni, and preferably contains two types. Is more preferable. Further, it is particularly preferable to include at least one of the group consisting of the platinum group (Ru, Rh, Pd, Os, Ir, Pt), and it is more preferable to include two types.
  • the proportion of platinum group elements is preferably 5 atomic% or more, 10 atomic% or more, 15 atomic% or more, 20 atomic% or more, 25 atomic% or more, 30 atomic% or more, 35 atomic% or more, 40 atomic% or more, 45 atomic% or more, 50 atomic% or more, 55 atomic% or more, 60 atomic% or more, 65 atomic% or more, 70 atomic% or more, 75 atomic% or more, It is 80 atomic% or more, 85 atomic% or more, 90 atomic% or more, 95 atomic% or more, 98 atomic% or more, or 100 atomic% or more.
  • a stable high-entropy solid solution (PGM-HEA) containing a platinum group element can be obtained.
  • the alloy nanoparticles of the present invention it has 5 or 6 kinds of platinum group elements, and it is possible to control the adsorption energy with respect to the catalytic substrate in a wide energy range, so that the desired reaction can be achieved.
  • Os which has been difficult to handle in the past.
  • the crystal structure of the alloy nanoparticles is not particularly limited.
  • the alloy may have a crystal structure such as fcc (face-centered cubic lattice), hcp (closest packed hexagonal lattice), or bcc (body-centered cubic lattice), depending on the composition of the alloy nanoparticles and the total average number of valence electrons.
  • the alloy nanoparticles of one preferred embodiment of the present invention are solid solutions of fcc or hcp structure. However, when the alloy nanoparticles become a regular alloy (that is, when they have a regular phase), when forming an amorphous structure or when forming an intermetallic compound, a structure other than the above can be maintained.
  • an intermetallic compound When elements having significantly different atomic radii or electronegativity are mixed, an intermetallic compound may be formed.
  • the atomic arrangement is not random, but a regular alloy.
  • at least one set is part of the combination of RhC, PdB, precious metal and transition metal, part of the combination of precious metal such as RuSn and main group element.
  • the atomic sites in the regular alloy may be randomly composed of a plurality of specific elements.
  • an element having a large atomic radius may be randomly arranged at an atomic site of an element having a large atomic radius
  • an element having a small atomic radius may be randomly arranged at an atomic site of an element having a small atomic radius.
  • fcc face-centered cubic lattice
  • Rh Rh
  • Pd Rh
  • Ir Ir
  • Pt hcp
  • Os and Ru two types of Os and Ru.
  • the alloy nanoparticles of one preferred embodiment of the present invention are solid solutions having an fcc structure containing elements of the platinum group.
  • the alloy nanoparticles of another preferred embodiment of the present invention are solid solutions having an hcp structure containing elements of the platinum group. Even when the six elements of the platinum group are used, the proportion of the fcc structure may be high as in the original proportion, or the proportion of the hcp structure may be high.
  • the alloy nanoparticles of the present invention have high solid solution uniformity, it is preferable that five or more kinds of elements are uniformly distributed and solid solution.
  • uniform distribution means that the distribution of five or more kinds of elements is not biased, and it can be confirmed by the energy dispersive X-ray analysis map that the distribution of each element (atom) is not biased.
  • a single fcc or hcp pattern can be confirmed from powder X-ray diffraction (XRD). Even if fcc and hcp coexist, if the interatomic distances of both structures are equal, it is considered that the constituent elements are uniformly distributed in each structure. At that time, since the metal compositions of both the fcc and hcp structures are the same, the interatomic distances are the same.
  • the ratio of each element constituting the alloy nanoparticles in the alloy nanoparticles is not particularly limited. That is, the average composition of the alloy nanoparticles of the present invention is not particularly limited.
  • the upper limit of the proportion of the most abundant elements when the total alloy nanoparticles are 100 atomic% or less is 80 atomic% or less, 70 atomic% or less, 60 atomic% or less, 50 atomic% or less. , 45 atomic% or less, 40 atomic% or less, or 35 atomic% or less.
  • the lower limit of the proportion of the smallest element when the total alloy nanoparticles are 100 atomic% or more is 1 atomic% or more, 5 atomic% or more, 9 atomic% or more, 10 atoms or more. Alternatively, it is 15 atomic% or more.
  • the element having the highest atomic ratio is preferably 1 to 500 times, more preferably 1 to 5 times, still more preferably 1 to 3 times, particularly preferably 1 to 2 times, most preferably the element having the lowest atomic ratio. Is 1 to 1.5 times.
  • the atomic ratios of five or more elements are preferably as close as possible, and in particular, the atomic ratios of the five or six platinum group elements are more preferably as close as possible.
  • the alloy nanoparticles of the invention contain Os.
  • Os is easily oxidized among platinum group elements and can be a toxic oxide such as OsO 4 , but by forming a solid solution alloy together with other 4 or 5 platinum group elements, it is like OsO 4 . The formation of toxic oxides can be suppressed.
  • the shape of the alloy nanoparticles of the present invention includes various shapes such as spherical, ellipsoidal, square cylinder, cylindrical, cubic, rectangular parallelepiped, and scaly, and is preferably spherical or ellipsoidal.
  • the average particle size of the alloy nanoparticles is preferably 0.5 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1.0 to 20 nm.
  • the average particle size of the particles can be calculated as an arithmetic mean, for example, by direct observation with a transmission electron microscope (TEM).
  • the average particle size of the above particles is the average particle size of the alloy nanoparticles, and when supported on a carrier, it is the average particle size of the alloy nanoparticles other than the carrier.
  • the particle size distribution of the particles is preferably an average particle size of ⁇ 0.1 to 15 nm, more preferably ⁇ 0.3 to 15 nm, and particularly preferably ⁇ 0.5 to 10 nm.
  • the alloy nanoparticles of the present invention may have a shape that is an aggregate of alloy nanoparticles, or may have a shape that is supported on a carrier.
  • An aggregate of alloy nanoparticles is a powder in which a large number of alloy nanoparticles are gathered.
  • the aggregate of alloy nanoparticles preferably contains substantially no carrier or the like, or is preferably not supported on a carrier.
  • the aggregate of alloy nanoparticles may contain a protective agent such as a polymer.
  • the aggregate of alloy nanoparticles may have an oxide film or the like on the surface of each alloy nanoparticle.
  • the aggregate of alloy nanoparticles may contain impurity particles in addition to the alloy nanoparticles of the present invention.
  • the aggregate of alloy nanoparticles preferably contains 90% by number or more of the alloy nanoparticles of the present invention, more preferably 98% by number or more, particularly preferably 99% by number or more, and contains 100% by number. Is more particularly preferred.
  • the aggregate of alloy nanoparticles is one of the five elements contained in the compound used in the production, in addition to the alloy nanoparticles in which all five elements contained in the compound used in the production are solid-solved. It may contain alloy nanoparticles in which only the part is solid-solved. However, it is preferable that the proportion of alloy nanoparticles in which the same type of element is solid-solved is high.
  • alloy nanoparticles constituting the aggregate of alloy nanoparticles it is preferable to contain alloy nanoparticles containing all of 5 or more kinds of elements as constituent elements in an amount of 90% by number or more, and more preferably 98% by number or more. It is particularly preferable to contain 99% by number or more, and more preferably 100% by number.
  • the ratio of each particle contained in the aggregate of alloy nanoparticles is determined within the range of the field of view in which a part of the aggregate of alloy nanoparticles is observed. For example, within a certain field of view in which a part of an aggregate of alloy nanoparticles is observed, alloy nanoparticles containing all five or more kinds of elements among the alloy nanoparticles constituting the aggregate of alloy nanoparticles.
  • the particles are contained in the above range. However, it is more preferable that the ratio of each particle contained in the aggregate of alloy nanoparticles is obtained as an average within a range of a plurality of fields of view in which a part of the aggregate of alloy nanoparticles is observed.
  • the carrier excludes cases where the carbon material carrier is graphene or carbon fiber when the alloy nanoparticles are directly supported on the carbon material carrier.
  • Specific examples of the carrier used include oxides, nitrides, carbides, simple carbon (excluding graphene or carbon fiber), and single metal.
  • the oxides used for the carrier include oxides such as silica, alumina, ceria, titania, zirconia and niobia, and composite oxides such as silica-alumina, titania-zirconia, ceria-zirconia and strontium titanate. .
  • Examples of elemental carbon include activated carbon, carbon black, graphite, carbon nanotubes and the like.
  • nitrides examples include boron nitride, silicon nitride, gallium nitride, indium nitride, aluminum nitride, zirconium nitride, vanadium nitride, tungsten nitride, molybdenum nitride, titanium nitride, and niobium nitride.
  • carbides include silicon carbide, gallium carbide, indium carbide, aluminum carbide, zirconium carbide, vanadium carbide, tungsten carbide, molybdenum carbide, titanium carbide, niobium carbide, and boron carbide.
  • the carrier is preferably a non-carbon fiber carrier (a material that is not a material composed of a single carbon) or a particulate carbon carrier, and a non-carbon material carrier is considered from the viewpoint that the carrier does not burn in a high temperature oxidizing atmosphere. It is preferably an oxide carrier, and particularly preferably an oxide carrier. Activated carbon or the like can be used as the particulate carbon carrier.
  • the alloy nanoparticles of the present invention may be coated with a protective agent (preferably a surface protective agent).
  • a protective agent preferably a surface protective agent.
  • the protective agent include polymers such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG), amines such as oleylamine, and carboxylic acids such as oleic acid.
  • the method for producing alloy nanoparticles of the present invention includes a step of adding an aqueous solution containing salts of five or more kinds of elements to a liquid reducing agent heated to 200 ° C. to 300 ° C. and reacting them, and an alloy containing five or more kinds of elements. Obtain nanoparticles. However, when the alloy nanoparticles are directly supported on the carbon material carrier, the case where the carbon material carrier is graphene or carbon fiber is excluded.
  • an aqueous solution containing 5 or 6 types selected from the group consisting of Ru salt, Rh salt, Pd salt, Os salt, Ir salt and Pt salt is heated to 200 ° C.
  • a method for producing a platinum group multidimensional solid solution which comprises a step of reacting with the liquid reducing agent to obtain a platinum group multidimensional solid solution containing five or more kinds of platinum group elements.
  • a method for producing alloy nanoparticles which comprises a step of reacting with the liquid reducing agent to obtain a platinum group multidimensional solid solution containing five or more kinds of platinum group elements.
  • the method for producing alloy nanoparticles preferably includes a step of preparing a solution (raw material solution) of a compound containing each element constituting the alloy nanoparticles.
  • Each element constituting the alloy nanoparticles is dissolved in a solvent.
  • Polar solvents include water, alcohols (methanol, ethanol, isopropanol, etc.), polyols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, etc.), polyethers (polyethylene glycol, etc.), acetonitrile, acetone, etc. Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and the like can be used. Of these, water and alcohol are preferable.
  • non-polar solvent hexane, benzene, toluene, diethyl ether, chloroform, ethyl acetate, THF and the like can be used.
  • the raw material solution it is preferable to use an aqueous solution containing a water-soluble salt of a metal element or a water-soluble salt of an element other than a metal, but in the case of a combination of non-polar metal salts, a non-polar metal salt containing a non-polar metal salt is used.
  • a solvent may be used.
  • Examples of the salt of the water-soluble element include the following platinum group (Ru, Rh, Pd, Os, Ir, Pt), Ag, Au, Cd, Hg, In, Tl, Sn, Pb, Sb, Bi. , Mo, W, Tc, Re, 3d metals (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn), Ga, Ge, As, B, Al, C, Si, N, P , Y, Zr, Nb, lanthanoids, Hf and Ta known water-soluble salts (eg, sulfates, nitrates, acetates, chlorides, bromides, iodides, potassium cyanate, sodium cyanate, hydroxides, Carbonate etc.).
  • Ru Ruthenium halides such as RuCl 3 , RuCl 3 ⁇ nH 2 O, RuBr 3 , K 2 RuCl 5 (NO), ruthenium nitrate, Ru 3 (CO) 12 , Ru (NO) (NO 3 ) a (OH) b , Ru (acac) 3, etc.
  • Rh rhodium acetate, rhodium nitrate, rhodium chloride (RhCl 3), such as RhCl 3 ⁇ 3H 2 O.
  • Pd K 2 PdCl 4 , Na 2 PdCl 4 , K 2 PdBr 4 , Na 2 PdBr 4 , palladium nitrate, etc.
  • Os Halogenated osmium such as OsCl 3 and OsBr 3 .
  • Ir Iridium chloride, iridium acetylacetonate (acac; acac system is preferably dissolved in a nonpolar solvent), potassium iridium cyanate, potassium iridium acid, such as H 2 IrCl 6.
  • Pt K 2 PtCl 4 , (NH 4 ) 2 K 2 PtCl 4 , (NH 4 ) 2 PtCl 6 , Na 2 PtCl 6 , H 2 PtCl 6 , Pt (acac) 2, etc.
  • Au AuCl 3 , HAuCl 4 , K [AuCl 4 ], Na [AuCl 4 ], K [Au (CN) 2 ], K [Au (CN) 4 ], AuBr 3 , HAuBr 4, etc.
  • Ag AgNO 3 , Ag (CH 3 COO), etc.
  • Sn SnCl 3 ⁇ 2H 2 O , Sn (ethyhex) 2 and the like.
  • Mo Mo (CO) 6, etc.
  • Cu Cu (NO 3 ) 2 , CuSO 4 , Cu (CH 3 COO) 2 , CuCO 3 , CuCl, CuCl 2, etc.
  • Fe FeCl 3 ⁇ 6H 2 O , etc. FeCl 2 ⁇ 4H 2 O, Fe (NO 3) 3.
  • Co CoCl 2 ⁇ 6H 2 O and so on.
  • Ni NiCl 2 ⁇ 6H 2 O and so on.
  • B BH 3, etc.
  • N Ru (NO) (NO 3 ) a (OH) b , ammonia, nitric acid, hydrazine, etc.
  • the method for producing alloy nanoparticles preferably includes a step of preparing a reducing agent.
  • the reducing agent is preferably a liquid reducing agent.
  • Liquid reducing agents include, for example, polyhydric alcohols such as ethylene glycol, glycerin, diethylene glycol, triethylene glycol; or lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol under high pressure; or Hydrous alcohols such as hydrous ethanol under high pressure; THF solution of BH 3 (THF complex); or hydrazine, NaBH 4 solution, sodium naphthalenide solution and the like can be mentioned.
  • each element constituting the alloy nanoparticles may be used as a reducing agent.
  • a THF solution (THF complex) of BH 3 may be used as a reducing agent to form alloy nanoparticles containing element B.
  • a reducing agent having a low boiling point can be preferably used.
  • the boiling point of the lower alcohol, which is a preferable reducing agent is about 130 ° C. from room temperature, more preferably about 40 to 120 ° C., and even more preferably about 60 to 100 ° C.
  • alloy nanoparticles composed of metals that do not dissolve in the phase equilibrium diagram are obtained by reducing compounds (metal compounds, etc.) containing each element that constitutes alloy nanoparticles. Difficult to form. By reacting under pressure at a high temperature, reducing property is obtained, and in the phase equilibrium diagram, it can function as a reducing agent for obtaining alloy nanoparticles composed of metals that do not dissolve in solid solution.
  • the reducing agent is used in an amount of 1 equivalent or more, preferably an excess amount, for the reduction of a compound (preferably a water-soluble salt) containing each element constituting the alloy nanoparticles.
  • the method for producing alloy nanoparticles preferably includes a step of mixing raw material solutions into a mixed solution. It is preferable to mix the reducing agent with the raw material solution before or when heating the mixed solution.
  • the method for producing alloy nanoparticles preferably includes a step of heating and reacting the mixed solution.
  • the reaction time during heating can be about 1 minute to 12 hours.
  • the heating is preferably performed under stirring.
  • the reaction temperature during heating is preferably about 170 to 300 ° C, more preferably about 180 to 250 ° C.
  • a reducing agent such as NaBH 4
  • the method of mixing or heating is not particularly limited, and for example, one or both of the reducing agent and the mixed solution may be heated and then mixed.
  • the method for producing alloy nanoparticles preferably includes a step of heating the reducing agent, and it is preferable to mix the raw material solution with the reducing agent heated by this step and cause a heating reaction.
  • the reducing agent may be heated and the mixed solution may be dropped by a pump (syringe pump) or sprayed by a spray device to mix the mixture.
  • the sonicated raw material solution and the reducing agent solution may be supplied to the reaction vessel and mixed and heated using a flow device (flow reactor) that heats and reacts under pressure.
  • the pressures of the raw material solution and the reducing agent solution are preferably about 0.1 to 20 MPa, more preferably about 0.2 to 10 MPa, and particularly preferably about 0.2 to 9 MPa. is there.
  • the pressure in the reaction vessel is preferably about 0.1 to 20 MPa, more preferably about 0.2 to 10 MPa, and particularly preferably about 0.2 to 9 MPa.
  • the pressure in the reaction vessel is about the same as the back pressure of the back pressure valve provided downstream of the reaction vessel, and the back pressure valve can be adjusted and controlled.
  • the temperature (reaction temperature) of the reaction vessel when pressurized is about 100 to 400 ° C., preferably about 150 to 300 ° C., and more preferably about 180 to 240 ° C.
  • the method for producing alloy nanoparticles preferably includes a step of separating a precipitate from the solution after the heating reaction. By this step, alloy nanoparticles containing 5 or more kinds of metals in a solid solution state can be obtained. Examples of the method for separating the precipitate include vacuum drying, centrifugation, filtration, sedimentation, reprecipitation, separation by a powder separator (cyclone), and the like.
  • the solution after the reaction is preferably allowed to cool or quench before the precipitate is separated.
  • Particles (preferably nanoparticles) in which aggregation is suppressed can be obtained by adding a protective agent to a mixed solution, a reducing agent, or a reaction solution in which these are mixed.
  • the protective agent is preferably 0.01 to 100 times, more preferably, a mass ratio of the total amount of the metal compound in the reaction solution formed by mixing the mixed solution of the raw material solution and the reducing agent. It is contained in a concentration of 0.5 to 50 times, more preferably 1 to 10 times.
  • the protective agent may be contained in the raw material solution, may be contained in the reducing agent, or may be contained in both the raw material solution and the reducing agent.
  • a supported catalyst in which alloy nanoparticles are supported on the carrier can be obtained.
  • a supported catalyst in which the multidimensional solid solution is supported on the carrier can be obtained.
  • a supported catalyst in which aggregation of the fine particles is suppressed can be obtained by adding a protective agent at the same time as the carrier to the reaction solution for producing the multidimensional solid solution fine particles.
  • alloy nanoparticles which are an aggregate of alloy nanoparticles
  • the alloy nanoparticles were supported on the carrier by molding the alloy nanoparticles and the carrier, which are aggregates of the alloy nanoparticles, in a solution or by mixing the powders with each other in a non-catalyst system or a catalyst system.
  • a supported catalyst can be obtained.
  • a solvent it may be dried after filtration if necessary.
  • the alloy nanoparticles of the present invention can be used as a catalyst exhibiting excellent performance. There is no particular limitation on the morphology of the alloy nanoparticles when used as a catalyst. It may be used as a supported catalyst supported on a carrier.
  • the catalytic reaction in which the alloy nanoparticles of the present invention exhibit excellent performance as a catalyst is not particularly limited, and examples thereof include reactions known to be generally used with a catalyst containing a platinum group element. Specific examples thereof include reduction reactions including hydrogenation reactions, dehydrogenation reactions, oxidation reactions including combustion, and chemical reactions such as coupling reactions. Further, by utilizing these catalytic performances, it can be suitably used for various processes, devices and the like.
  • the applications that can be preferably used are not particularly limited, and for example, a catalyst for hydrogen generation reaction (HER), a catalyst for hydrogenation reaction, a catalyst for hydrogen oxidation reaction, a catalyst for oxygen reduction reaction (ORR), and an oxygen generation reaction (OER).
  • Catalyst nitrogen oxide (NOx) reduction reaction catalyst, carbon monoxide (CO) oxidation reaction catalyst, dehydrogenation reaction catalyst, VVOC or VOC oxidation reaction catalyst, exhaust gas purification catalyst, water electrolysis reaction catalyst, Examples include catalysts for hydrogen fuel cells.
  • Example 1 Production of platinum group 6-element solid solution fine particles ⁇ Preparation of alloy nanoparticles> Triethylene glycol (TEG) 300 ml was heated and stirred at 230 °C, K 2 PdCl 4 ( 0.167mmol) to the solution, RuCl 3 ⁇ nH 2 O ( 0.167mmol), RhCl 3 ⁇ 3H 2 O (0.167mmol ), the metal ion mixed solution is OsCl 3 ⁇ 3H 2 O (0.167mmol ), IrCl 4 ⁇ xH 2 O (0.167mmol), K 2 [PtCl 4] (0.167mmol ion exchange aqueous solution) (40 ml) was sprayed and added, maintained at 230 ° C.
  • TOG Triethylene glycol
  • FIG. 1 EDS map (Fig. 2), powder X-ray diffraction (PXRD) pattern (Fig. 2) for a part of the separated platinum group hex-based solid solution fine particles (alloy nanoparticles of Example 1; also referred to as PGM-HEA) in a solid solution state. 3 (a)) and EDS line analysis (FIG. 3 (b)).
  • XRF analysis of fine particles was performed to calculate the metal composition of six platinum group elements (FIG. 3 (c)). From FIG. 2, as far as the STEM image was observed, it was confirmed that all the elements were solid-solved in each alloy nanoparticles.
  • the aggregate of alloy nanoparticles is 100 alloy nanoparticles in which all five types of elements contained in the compound used for production as constituent elements are solid-solved. It can be seen that the number% is included. Further, it can be seen that in the alloy nanoparticles of the present invention, any alloy nanoparticles constituting the aggregate contain all five kinds of elements contained in the compound used for production as a constituent element. From FIGS. 3 (a), 3 (b) and 3 (c), it was confirmed that all the elements were solid-solved in each alloy nanoparticles with substantially the same composition. The crystal structure of the alloy nanoparticles was a single fcc.
  • STEM-EDS analysis of the alloy nanoparticles of Example 1 is performed. Elemental analysis by line analysis using a plurality of fields of scanning transmission electron microscope is performed, and the metal composition of six kinds of elements is calculated. Find the average composition.
  • Example 2 Production of platinum group pentogenic solid solution fine particles ⁇ Preparation of alloy nanoparticles> Triethylene glycol (TEG) 300 ml was heated and stirred at 230 ° C., this solution K 2 PdCl 4 (0.3mmol), RuCl 3 ⁇ nH 2 O (0.3mmol), RhCl 3 ⁇ 3H 2 O (0.2mmol ), IrCl 4 ⁇ xH 2 O (0.1 mmol), K 2 [PtCl 4 ] (0.1 mmol) sprayed with a metal ion mixed solution (40 ml), and maintained at 230 ° C. for 5 minutes.
  • TOG Triethylene glycol
  • RuRhPdIrPt Platinum group pentogenic solid solution fine particles, which are the alloy nanoparticles of Example 2, separated by centrifugation. 28.9: 19.6: 32.0: 10.2: 9.30) was obtained.
  • Example 2 ⁇ Elemental analysis by STEM-EDS> STEM-EDS analysis of some of all the alloy nanoparticles obtained in Example 2 is performed in the same manner as in Example 1. Find the average composition. As far as it was observed in the STEM image, it was confirmed that all the elements of the alloy nanoparticles of the present invention were solid-solved in each alloy nanoparticles. That is, within the range of the field of view confirmed in this example, the aggregate of alloy nanoparticles is 100 alloy nanoparticles in which all five types of elements contained in the compound used for production as constituent elements are solid-solved. It can be seen that the number% is included. Further, it can be seen that in the alloy nanoparticles of the present invention, any alloy nanoparticles constituting the aggregate contain all five kinds of elements contained in the compound used for production as a constituent element.
  • a catalyst ink was prepared.
  • a catalyst electrode was prepared by applying an appropriate amount of this ink to a working electrode such as a rotating ring disk electrode or a glassy carbon electrode.
  • the ethanol oxidation electrode catalytic activity was evaluated 50 times. The results of the initial ethanol oxidation electrode catalytic activity are shown in FIGS. 7 (a) to 7 (d). From FIGS. 7 (a), 7 (b) and 7 (c), it was found that the alloy nanoparticles (PGM-HEA) of Example 1 exhibited higher activity than Pd. From FIG. 7D, the alloy nanoparticles (PGM-HEA) of Example 1 are the previously reported highest active catalyst Au @ PtIr / C (J. Am. Chem. Soc. 2019, 141, 24, 9629-9636). It was found to show higher activity. Initiation of the reaction at low potential was found to suggest a 12-electron reaction.
  • FIG. 7 (e) the result of comparing the ethanol oxidation electrode catalytic activity for the first time and the ethanol oxidation electrode catalytic activity after 50 times is shown in FIG. 7 (e). From FIG. 7 (e), it was found that the alloy nanoparticles (PGM-HEA) of Example 1 had high durability. The durability was also high when compared with Pd particles (not shown).
  • Example 3 Production of platinum group quintuple solid solution fine particles (2) ⁇ Preparation of alloy nanoparticles> Triethylene glycol (TEG) 300 ml was heated and stirred at 230 ° C., this solution K 2 PdCl 4 (0.2mmol), RuCl 3 ⁇ nH 2 O (0.2mmol), RhCl 3 ⁇ nH 2 O (0.2mmol ), H 2 IrCl 6 (0.2 mmol), K 2 [PtCl 4 ] (0.2 mmol) by spraying a metal ion mixed solution which is an ultrapure aqueous solution (50 ml), and maintaining at 230 ° C. for 10 minutes. The mixture was allowed to cool to room temperature, and the resulting precipitate was separated by centrifugation to obtain the alloy nanoparticles of Example 3.
  • TOG Triethylene glycol
  • Example 3 ⁇ Elemental analysis by STEM-EDS> STEM-EDS analysis of all some alloy nanoparticles obtained in Example 3 is performed in the same manner as in Example 1. Find the average composition. As far as it was observed in the STEM image, it was confirmed that all the elements of the alloy nanoparticles of the present invention were solid-solved in each alloy nanoparticles. That is, within the range of the field of view confirmed in this example, the aggregate of alloy nanoparticles is 100 alloy nanoparticles in which all five types of elements contained in the compound used for production as constituent elements are solid-solved. It can be seen that the number% is included. Further, it can be seen that in the alloy nanoparticles of the present invention, any alloy nanoparticles constituting the aggregate contain all five kinds of elements contained in the compound used for production as a constituent element.
  • Example 4 Production of 9-element FeCoNiCuRuRhPdIrPt solid solution fine particles by a flow reactor ⁇ Preparation of alloy nanoparticles> 0.14 ml of HCl was added to 50 ml of ion-exchanged water to prepare an aqueous hydrochloric acid solution.
  • K 2 PdCl 4 (0.05mmol), RuCl 3 ⁇ nH 2 O (0.05mmol), IrCl 4 ⁇ nH 2 O (0.05mmol), K 2 PtCl 4 (0.05mmol), RhCl 3 ⁇ 3H 2 O (0.05mmol), FeCl 2 ⁇ 4H 2 O (0.05mmol), CoCl 2 ⁇ 6H 2 O (0.05mmol), CuCl 2 ⁇ 2H 2 O (0.05mmol), NiCl 2 ⁇ 6H 2 O (0 .05 mmol) was dissolved in 2 ml of each hydrochloric acid aqueous solution and mixed to prepare 9 kinds of metal salt solutions having a pH of 1.60.
  • Polyvinylpyrrolidone (PVP) K30 (5 mmol; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 20 ml of an aqueous hydrochloric acid solution to prepare a PVP solution.
  • PVP solution Nine kinds of metal salt solutions were mixed with the PVP solution to prepare a raw material solution (metal ion mixed solution).
  • the obtained raw material solution was stored in a raw material solution container.
  • a 10.5 mM reducing agent solution was prepared by adding a 15.75 mol / L KOH aqueous solution to a 25% by volume ethanol aqueous solution, and stored in a reducing agent solution tank.
  • the reducing agent solution was sent from the reducing agent solution tank through the pump A at a set flow rate of 30 mL / min, and heated by a heater having a set temperature of 375 ° C.
  • the metal ion mixed solution was sent from the precursor solution container through the pump B at 3.0 mL / min, and the two kinds of solutions were mixed in the reaction container.
  • the mixed solution was cooled in the cooling section, and the back pressure of the back pressure valve provided downstream of the cooling section was set to 9.9 to 10.1 MPa, and the product containing the alloy nanoparticles was collected.
  • the solution temperature during the collection of the alloy nanoparticles was 285 ° C.
  • the solution recovered as a product was concentrated on an evaporator and centrifuged to recover alloy nanoparticles.
  • Example 4 ⁇ Elemental analysis by STEM-EDS> STEM-EDS analysis of some of the alloy nanoparticles obtained in Example 4 was performed in the same manner as in Example 1. The obtained results are shown in FIG. From FIG. 10, as far as the STEM image was observed, it was confirmed that all the elements were solid-solved in each alloy nanoparticles. That is, within the range of the field of view confirmed in this example, the aggregate of alloy nanoparticles is 100 alloy nanoparticles in which all nine kinds of elements contained in the compound used for production as constituent elements are solid-solved. It can be seen that the number% is included. Further, it can be seen that in the alloy nanoparticles of the present invention, any alloy nanoparticles constituting the aggregate include all nine kinds of elements contained in the compound used for production as a constituent element.

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CN118600298A (zh) * 2024-05-28 2024-09-06 上海工程技术大学 一种石墨烯纳米片增强高熵合金复合材料及其制备方法
CN120838428A (zh) * 2025-09-18 2025-10-28 西南石油大学 一种天然气脱碳制高值产物用NiCu基合金催化剂及其应用

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