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WO2018159644A1 - NANOPARTICULES DE SOLUTION SOLIDE DE Pd-Ru, LEUR PROCÉDÉ DE PRODUCTION ET CATALYSEUR ASSOCIÉ, PROCÉDÉ DE RÉGULATION DE LA STRUCTURE CRISTALLINE DE NANOPARTICULES DE SOLUTION SOLIDE DE Pt-Ru, NANOPARTICULES DE SOLUTION SOLIDE Au-Ru, ET LEUR PROCÉDÉ DE FABRICATION - Google Patents

NANOPARTICULES DE SOLUTION SOLIDE DE Pd-Ru, LEUR PROCÉDÉ DE PRODUCTION ET CATALYSEUR ASSOCIÉ, PROCÉDÉ DE RÉGULATION DE LA STRUCTURE CRISTALLINE DE NANOPARTICULES DE SOLUTION SOLIDE DE Pt-Ru, NANOPARTICULES DE SOLUTION SOLIDE Au-Ru, ET LEUR PROCÉDÉ DE FABRICATION Download PDF

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WO2018159644A1
WO2018159644A1 PCT/JP2018/007370 JP2018007370W WO2018159644A1 WO 2018159644 A1 WO2018159644 A1 WO 2018159644A1 JP 2018007370 W JP2018007370 W JP 2018007370W WO 2018159644 A1 WO2018159644 A1 WO 2018159644A1
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solid solution
catalyst
hcp
nanoparticles
reaction
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PCT/JP2018/007370
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English (en)
Japanese (ja)
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北川　宏
康平 草田
冬霜 ▲呉▼
権 張
徹也 池渕
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国立大学法人京都大学
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Priority to JP2019503039A priority Critical patent/JP7157456B2/ja
Publication of WO2018159644A1 publication Critical patent/WO2018159644A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • B01J37/08—Heat treatment
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C22C5/02—Alloys based on gold
    • 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
    • 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 PdRu solid solution nanoparticle, its production method and catalyst, a method for controlling the crystal structure of the PtRu solid solution nanoparticle, and AuRu solid solution nanoparticle and its production method.
  • Palladium (Pd) is one of the rare metals, and its fine particles are industrially used for various reactions such as automobile exhaust gas purification catalysts (three-way catalysts) and electrode catalysts for household fuel cell energy farms. It is used as. However, the palladium fine particles used as these catalysts are poisoned by CO (carbon monoxide) produced in the course of various chemical reactions, and it is difficult to use them at high output for a long time. Therefore, techniques for suppressing such deterioration due to poisoning have been actively studied. On the other hand, ruthenium (Ru), one of the platinum group, has a catalytic activity to oxidize CO to CO 2 (carbon dioxide), and therefore has durability against CO poisoning.
  • Ru ruthenium
  • ruthenium is actually used as an alloy with platinum or the like in order to suppress CO poisoning on the electrode of the fuel cell.
  • palladium and ruthenium are separated and cannot be mixed (solid solution) at the atomic level in an equilibrium state.
  • Patent Document 1 discloses a binary alloy of Pd and Ru, but does not disclose a solid solution alloy containing gold.
  • Patent Document 2 describes a solid solution of at least two kinds of Pt, Ir, Pd, Rh, Ru, Au, and Ag, but in the examples, only a solid solution of Ir and Pt is described. Other solid solutions are not manufactured.
  • Patent Document 3 discloses a ruthenium fine particle group having a substantially face-centered cubic structure, but does not disclose information on the alloy.
  • Patent Document 4 discloses fine particles of an alloy of platinum and ruthenium supported on carbon powder, but there is no description that the crystal structure is controlled by reaction conditions as in the present invention.
  • Patent Documents 5 and 6 disclose PtRu alloys in Examples, but Ru has a core and platinum has a shell structure, and is not a solid solution alloy.
  • the object of the present invention is to further improve the catalytic activity and durability in a solid solution of Pd and Ru.
  • the present invention also aims to control the crystal structure in a PtRu solid solution.
  • an object of the present invention is to provide an AuRu solid solution having a desired crystal structure and a method for producing the same.
  • the present invention provides the following PdRu solid solution nanoparticles, a production method and catalyst thereof, a method for controlling the crystal structure of PtRu solid solution nanoparticles, and AuRu solid solution nanoparticles and a production method thereof.
  • Item 1 PdRu solid solution nanoparticles represented by the formula Pd x Ru 1-x (0.1 ⁇ x ⁇ 0.8), wherein Pd and Ru are in solid solution at the atomic level, and the main structure is a hexagonal close-packed structure (hcp).
  • Item 2. The nanoparticle according to Item 1, wherein 0.4 ⁇ x ⁇ 0.6.
  • Item 3. Item 3.
  • Item 5. A catalyst obtained by supporting the nanoparticles according to any one of Items 1 to 4 on a carrier.
  • Item 6. Catalyst for hydrogenation reaction, catalyst for hydrogen oxidation reaction, catalyst for oxygen reduction reaction, catalyst for oxygen generation reaction (OER), catalyst for hydrogen generation reaction (HER), catalyst for nitrogen oxide (NOx) reduction reaction, carbon monoxide
  • Item 7. Item 7.
  • Item 8 Formula Pd x Ru characterized in that the PdRu solid solution nanoparticles of formula PdRu, whose face-centered cubic lattice structure (fcc) is the main structure, are heated in a hydrogen atmosphere to convert part or all of the fcc crystal structure into an hcp crystal structure A method for producing solid solution nanoparticles represented by 1-x (0.1 ⁇ x ⁇ 0.8), wherein Pd and Ru are in solid solution at the atomic level and the main structure is a hexagonal close-packed structure (hcp).
  • Item 9 Formula Pd x Ru characterized in that the PdRu solid solution nanoparticles of formula PdRu, whose face-centered cubic lattice structure (fcc) is the main structure, are heated in a hydrogen atmosphere to convert part or all of the fcc crystal structure into an hcp crystal structure A method for producing solid solution nanoparticles represented by 1-x (0.1 ⁇
  • fcc becomes the main structure, and is represented by the formula Pt y Ru 1-y (0.05 ⁇ y ⁇ 0.3)
  • hcp hexagonal close-packed structure
  • fcc face-centered cubic lattice
  • Item 14 A method for producing AuRu solid solution nanoparticles whose main structure is a hexagonal close-packed structure (hcp), including a step of adding a solution containing an Au compound and a Ru compound to a heated solution containing CTAB (Cetyl trimethyl ammonium bromide) and a liquid reducing agent .
  • CTAB Cetyl trimethyl ammonium bromide
  • the nanoparticle according to item 11 or 12, which is supported on a carrier comprising a hydrogenation reaction catalyst, a hydrogen oxidation reaction catalyst, an oxygen reduction reaction catalyst, an oxygen generation reaction (OER) catalyst, a hydrogen generation reaction (HER).
  • a hydrogenation reaction catalyst a hydrogen oxidation reaction catalyst, an oxygen reduction reaction catalyst, an oxygen generation reaction (OER) catalyst, a hydrogen generation reaction (HER).
  • 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 or A catalyst which is a catalyst for a hydrogen fuel cell.
  • Metal fine particles containing Pd and Ru are useful catalysts used in various reactions, and according to the present invention, a catalyst having high activity and durability that has never been achieved can be developed.
  • the crystal structure of the catalyst containing Pt and Ru was almost determined by the composition, but according to the present invention, the ratio of hcp and fcc in the crystal structure can be freely controlled by controlling the production temperature of the PtRu solid solution nanoparticles. I can do it now.
  • Au and Ru are alloy systems that do not inherently dissolve. According to the present invention, by producing an AuRu solid solution having a main structure of fcc or hcp, which did not exist conventionally, it becomes possible to create a crystal surface as a new electronic state and reaction field, and such an AuRu solid solution. Is considered to have a catalytic activity different from Au alone, Ru alone, and non-solid solution.
  • the present invention relates to a PdRu solid solution nanoparticle having a main structure of hexagonal close-packed structure (hcp), a method for producing the same, a catalyst (first invention), a method for controlling the crystal structure of the PtRu solid solution nanoparticle (second invention),
  • the present invention also relates to AuRu solid solution nanoparticles whose main structure is a hexagonal close-packed structure (hcp) or a face-centered cubic lattice structure (fcc), a method for producing the same, and a catalyst (third invention).
  • the “main structure” of the solid solution nanoparticles is hcp or fcc, and the ratio of hcp or fcc is 50% or higher, preferably 55% or more when the total of hcp and fcc is 100% , 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 100%.
  • FIG. 17A shows XRD patterns of Ru NPs, hcp-AuR 3 , fcc-AuR 3 , and Au NPs
  • FIG. 17C shows Topas (Bruker) for the XRD pattern of fcc-AuR 3.
  • Rietveld analysis using AXS is calculated to be fcc (78.5%) and hcp (21.5%), demonstrating that fcc is the main structure.
  • Result of Rietveld analysis using Topas (Bruker AXS, Inc.) for XRD patterns of hcp-Aur 3 is shown in FIG. 17 (d). Therefore, whether the main structure of the PdRu, PtRu or AuRu solid solution nanoparticles of the present invention is hcp or fcc can be confirmed by analysis of the XRD pattern.
  • Pd has an fcc structure
  • Ru has an hcp structure.
  • the crystal structure of the solid solution composed of Pd and Ru is a mixture of fcc and hcp.
  • the proportion of fcc increases as the proportion of Pd increases
  • the proportion of hcp increases as the proportion of Ru increases.
  • the PdRu solid solution nanoparticles are heated in a reducing hydrogen atmosphere, or heated in a vacuum or an inert gas atmosphere, the percentage of hcp increases, and if heating is continued, the crystal structure is converted to hcp at a rate of almost 100%. And the catalyst activity and durability improved as the hcp ratio increased.
  • the heating of the PdRu solid solution nanoparticles can be performed at a temperature of preferably about 200 to 600 ° C., more preferably about 300 to 500 ° C.
  • the reaction time is about 5 minutes to 12 hours, preferably about 10 minutes to 5 hours, more preferably about 20 minutes to 3 hours. The reaction time tends to be longer as the reaction temperature is lower.
  • a hydrogen atmosphere is particularly preferable as the reaction atmosphere for increasing the crystal structure ratio of hcp.
  • the hydrogen concentration in the hydrogen atmosphere is about 5 to 100% by volume.
  • PdRu solid solution nanoparticles are represented by the formula Pd x Ru 1-x (0.1 ⁇ x ⁇ 0.8).
  • a preferable range of x is 0.12 ⁇ x ⁇ 0.75, more preferably 0.15 ⁇ x ⁇ 0.7, still more preferably 0.17 ⁇ x ⁇ 0.65, and particularly 0.2 ⁇ x ⁇ 0.6.
  • the ratio of the hcp crystal structure in the PdRu solid solution nanoparticles is 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, or 100%.
  • the average particle size of the PdRu solid solution nanoparticles of the present invention is about 1 to 20 nm, preferably about 1 to 15 nm, more preferably about 1 to 10 nm, and further preferably about 1 to 6 nm. A small average particle size is preferable because the catalyst performance is high.
  • the average particle diameter of the solid solution nanoparticles can be confirmed by a micrograph such as TEM.
  • the shape of the solid solution nanoparticles is not particularly limited, and may be any shape such as a spherical shape, an ellipsoidal shape, a rod shape, a column shape, or a flake shape.
  • the PdRu solid solution nanoparticles of the present invention may be supported on a carrier.
  • the carrier is not particularly limited, and specific examples include oxides, nitrides, carbides, simple carbon, simple metal, etc. Among them, oxides and simple carbon are preferable, and oxides are particularly preferable.
  • Preferred carrier. Examples of oxides include oxides such as silica, alumina, ceria, titania, zirconia, and niobium, and composite oxides such as silica-alumina, titania-zirconia, ceria-zirconia, and strontium titanate.
  • Examples of the simple carbon include activated carbon, carbon black, graphite, carbon nanotube, and activated carbon fiber.
  • nitrides 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 single metal include pure metals such as iron, copper, and aluminum, and alloys such as stainless steel.
  • the PdRu solid solution nanoparticles of the present invention may be coated with a surface protective agent.
  • the surface protecting agent include polymers such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG), amines such as oleylamine, and carboxylic acids such as oleic acid.
  • PdRu solid solution nanoparticles of the present invention include hydrogenation reaction catalyst, hydrogen oxidation reaction catalyst, oxygen reduction reaction (ORR) catalyst, oxygen generation reaction (OER) catalyst, hydrogen generation reaction (HER) catalyst, nitrogen oxidation (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, hydrogen fuel cell catalyst It is excellent as a catalyst for oxidation reaction of hydrocarbons and is preferably used as an exhaust gas purification catalyst such as a catalyst for water electrolysis reaction and a three-way catalyst. In the case of a three-way catalyst, for example, NOx is reduced to nitrogen, CO is oxidized to carbon dioxide, and hydrocarbon (CH) is oxidized to water and carbon dioxide.
  • ORR oxygen reduction reaction
  • OER oxygen generation reaction
  • HER hydrogen generation reaction
  • NOx nitrogen oxidation
  • CO carbon monoxide
  • the PdRu solid solution nanoparticles before enriching the hcp structure of the present invention are known and can be produced according to conventional methods. For example, a mixed aqueous solution containing a Pd compound and a Ru compound and a liquid reducing agent are prepared, and a mixed aqueous solution containing a Pd compound and a Ru compound is added to the liquid reducing agent and heated (for example, about 150 to 250 ° C.) for 1 minute to 12 minutes. PdRu solid solution nanoparticles containing a large amount of the fcc structure can be obtained by reacting with stirring for about an hour, then allowing to cool, and centrifuging.
  • the reaction between the liquid reducing agent, the Pd compound, and the Ru compound is performed in the presence of a carrier, PdRu solid solution nanoparticles supported on the carrier and containing a large amount of fcc structure can be obtained.
  • the reduction reaction may be performed under pressure.
  • Liquid reducing agents include lower alcohols such as methanol, ethanol and isopropanol, alkylene glycols such as ethylene glycol and propylene glycol, dialkylene glycols such as diethylene glycol and dipropylene glycol, and trialkylenes such as triethylene glycol and tripropylene glycol.
  • alkylene glycols such as ethylene glycol and propylene glycol
  • dialkylene glycols such as diethylene glycol and dipropylene glycol
  • trialkylenes such as triethylene glycol and tripropylene glycol.
  • polyhydric alcohols such as glycols and glycerin.
  • Pd compound and Ru compound examples include the following: Pd: K 2 PdCl 4 , Na 2 PdCl 4 , K 2 PdBr 4 , Na 2 PdBr 4 , palladium nitrate, etc. Ru: ruthenium halides such as RuCl 3 and RuBr 3 and ruthenium nitrate.
  • the raw PdRu solid solution nanoparticles containing a lot of fcc structure can convert fcc into hcp by heating in hydrogen atmosphere, inert atmosphere or vacuum.
  • the reaction for converting fcc to hcp is preferably carried out in a hydrogen atmosphere.
  • the reaction may be performed in an atmosphere containing hydrogen and an inert gas.
  • the inert gas used in the inert atmosphere include nitrogen, argon, helium, and neon, and nitrogen or argon is preferable.
  • the reaction pressure in a hydrogen atmosphere or an inert atmosphere is about 100 to 1000000 Pa, more preferably about 1000 to 1000000 Pa.
  • the reaction temperature is preferably about 200 to 600 ° C, more preferably about 250 to 550 ° C, and further preferably about 300 to 500 ° C.
  • the reaction time is about 5 minutes or more, preferably about 30 minutes to 3 hours.
  • the present invention relates to a method for controlling the ratio of the hexagonal close-packed structure (hcp) and the face-centered cubic lattice (fcc) in the crystal structure of the PtRu solid solution nanoparticles.
  • the ratio of hcp and fcc can be controlled by controlling the reaction temperature.
  • PtRu solid solution nanoparticles in which the ratio of the hexagonal close-packed structure (hcp) and the face-centered cubic lattice (fcc) is controlled can be obtained by cooling after completion of the reaction and centrifuging.
  • Pt compound and the Ru compound examples include the following: Pt: K 2 PtCl 4 , (NH 4 ) 2 K 2 PtCl 4 , (NH 4 ) 2 PtCl 6 , Na 2 PtCl 6 etc., bisacetylacetonatoplatinum (II), Ru: ruthenium halides such as RuCl 3 and RuBr 3 and ruthenium nitrate.
  • the reduction temperatures of the Pt compound and the Ru compound are shown in the following table.
  • the reaction temperature is preferably about 150 to 300 ° C, more preferably about 170 to 270 ° C, and further preferably about 200 to 250 ° C.
  • the reaction time is about 5 minutes or more, preferably about 10 minutes to 2 hours.
  • the reduction temperature of the Pt compound is 5 ° C. or more higher than the reduction temperature of the Ru compound, more preferably the reduction temperature of the Pt compound is 10 ° C. higher than the reduction temperature of the Ru compound, and more preferably Pt.
  • the reduction temperature of the compound is 15 ° C. higher than the reduction temperature of the Ru compound.
  • the second invention it is preferable to gradually add a solution containing a Pt compound and a Ru compound to the liquid reducing agent solution so that the heating temperature of the liquid reducing agent is maintained.
  • the addition method include spraying, dropping, and liquid feeding by a pump.
  • the heating temperature of the liquid reducing agent is almost equal to the reaction temperature.
  • the reaction temperature (that is, the temperature of the reducing agent solution) is from the reduction temperature of the Pt compound to the above-mentioned reduction.
  • the temperature is preferably + 15 ° C, more preferably the higher reduction temperature of the Pt compound and the Ru compound to the reduction temperature + 10 ° C, and still more preferably the higher reduction temperature of the Pt compound and the Ru compound to the reduction temperature. + 5 ° C.
  • the reaction temperature is the same as or slightly higher than the reduction temperature of the Pt compound, but is sufficiently higher than the reduction temperature of the Ru compound, so the timing of the reduction of the Ru compound is a little earlier, resulting in an hcp rich crystal structure. Although the timing of the reduction of the Ru compound is a little earlier, since the reduction of the Pt compound also occurs at the same time, a solid solution can be obtained. A solid solution is not formed when the timing of the reduction of the Ru compound is much earlier. In order to obtain solid solution and hcp-rich PtRu solid solution nanoparticles, delicate temperature control is required.
  • the reaction temperature (that is, the temperature of the reducing agent solution) is more preferable than the reduction temperature of the Pt compound. Is higher than 15 ° C, more preferably higher than 20 ° C, more preferably higher than 25 ° C. If the reaction temperature is sufficiently higher than the reduction temperature of the Pt compound, the timing of the reduction of the Pt compound will be a little earlier, resulting in an fcc rich crystal structure. If the reduction timing of the Pt compound is much earlier, no solid solution is formed. In order to obtain solid solution and hcp-rich PtRu solid solution nanoparticles, delicate temperature control is required.
  • Preferred Pt compounds are Pt (acac) 2 and C 10 H 8 Cl 2 N 2 Pt, and a preferred Ru compound is RuCl 3 .
  • Liquid reducing agents include lower alcohols such as methanol, ethanol and isopropanol, alkylene glycols such as ethylene glycol and propylene glycol, dialkylene glycols such as diethylene glycol and dipropylene glycol, and trialkylenes such as triethylene glycol and tripropylene glycol.
  • alkylene glycols such as ethylene glycol and propylene glycol
  • dialkylene glycols such as diethylene glycol and dipropylene glycol
  • trialkylenes such as triethylene glycol and tripropylene glycol.
  • polyhydric alcohols such as glycols and glycerin.
  • the carrier is not particularly limited, but specific examples include oxides, nitrides, carbides, carbon, and simple metals, among which oxides and carbon are preferable.
  • oxides include oxides such as silica, alumina, ceria, titania, zirconia, and niobium, and composite oxides such as silica-alumina, titania-zirconia, ceria-zirconia, and strontium titanate.
  • Examples of carbon include activated carbon, carbon black, graphite, carbon nanotube, and activated carbon fiber.
  • nitrides 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 single metal include pure metals such as iron, copper, and aluminum, and alloys such as stainless steel.
  • the PtRu solid solution nanoparticles of the present invention may be coated with a surface protective agent.
  • the surface protecting agent include polymers such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG), amines such as oleylamine, and carboxylic acids such as oleic acid.
  • the PtRu solid solution nanoparticles of the present invention include a methanol oxidation catalyst, a hydrogenation reaction catalyst, a hydrogen oxidation reaction catalyst, an oxygen reduction reaction (ORR) catalyst, an oxygen generation reaction (OER) catalyst, a hydrogen generation reaction (HER).
  • NOx nitrogen oxide
  • CO carbon monoxide
  • the solid solution nanoparticles obtained by the third invention are represented by the formula Au z Ru 1-z (0.05 ⁇ z ⁇ 0.4), and Au and Ru are in solid solution at the atomic level, and the main structure is a hexagonal close-packed structure ( hRp) or AuRu solid solution nanoparticles with a face-centered cubic lattice structure (fcc).
  • AuRu solid solution nanoparticles in which the ratio of Au and Ru is the same and the main structure of the crystal structure is hcp or fcc are obtained.
  • Au and Ru solid solution nanoparticle means that Au and Ru exist uniformly in the nanoparticle, and the distribution of each metal atom is not biased.
  • z is 0.05 ⁇ z ⁇ 0.4, preferably 0.1 ⁇ z ⁇ 0.35, more preferably 0.15 ⁇ z ⁇ 0.25.
  • the average particle size of the AuRu solid solution nanoparticles of the present invention is about 1 to 100 nm, preferably about 1 to 50 nm, more preferably about 1 to 10 nm, and still more preferably about 1 to 6 nm. A small average particle size is preferable because the catalyst performance is high.
  • the average particle diameter of the solid solution nanoparticles can be confirmed by a micrograph such as TEM.
  • the shape of the solid solution nanoparticles is not particularly limited, and may be any shape such as a spherical shape, an ellipsoidal shape, a rod shape, a column shape, or a flake shape.
  • the method for producing solid solution nanoparticles of the present invention comprises preparing a solvent solution of an Au compound and a Ru compound, a solvent solution of a reducing agent and a surface protecting agent, and then reducing the solvent solution of the Au compound and Ru compound to a reducing agent and a surface protecting agent (optional It can be obtained by adding to the solvent solution of component) little by little by spraying, dropping, liquid feeding by a pump or the like.
  • the AuRu solid solution nanoparticles of the present invention are prepared, for example, by preparing a solvent solution containing a Au compound and a Ru compound and a liquid reducing agent, adding the solvent solution containing the Au compound and the Ru compound to the liquid reducing agent, and heating (for example, 150 to AuRu solid solution nanoparticles having a main structure of fcc can be obtained by reacting with stirring at about 300 ° C. for about 1 minute to 12 hours, followed by cooling and centrifugation.
  • the reaction between the liquid reducing agent, the Au compound, and the Ru compound is performed in the presence of a carrier, AuRu solid solution nanoparticles supported on the carrier and containing a large amount of the fcc structure can be obtained.
  • the concentration of CTAB in the reaction system is preferably about 1/10 to 100 times, more preferably about 1 to 30 times the metal salt concentration.
  • solvent water, alcohol (methanol, ethanol, isopropanol, etc.), polyols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, etc.), polyethers (polyethylene glycol, etc.), etc. can be used.
  • One species can be used alone, or two or more species can be used in combination.
  • solvent water, alcohol or hydrous alcohol is preferable.
  • the reaction temperature is preferably about 150 to 300 ° C, more preferably about 170 to 270 ° C, and further preferably about 200 to 250 ° C.
  • the reaction time is about 5 minutes or more, preferably about 10 minutes to 2 hours.
  • the Au compound and the Ru compound are preferably water-soluble, and more preferably a salt.
  • Preferred Au compounds and Ru compounds include sulfates, nitrates, acetates and other organic acid salts, carbonates, halides (fluorides, chlorides, bromides, iodides), halides, acetates, etc. Organic acid salts and nitrates can be preferably used.
  • Au may be bivalent, trivalent, or tetravalent.
  • Ru may be monovalent, divalent, trivalent, or tetravalent.
  • Au compounds and Ru compounds include the following: Au: HAuCl 4 , HAuBr 4 , K 2 AuCl 6 , Na 2 AuCl 6 , gold acetate, etc.
  • Ru ruthenium halides such as RuCl 3 and RuBr 3 and ruthenium nitrate.
  • the concentration of the Au compound and the Ru compound in the solvent solution is about 0.01 to 1000 mmol / L, preferably about 0.05 to 100 mmol / L, more preferably about 0.1 to 50 mmol / L. If the concentration of the Au compound and the Ru compound is too high, the uniformity may be lowered at the atomic level of Au and Ru.
  • the reduction reaction may be performed under pressure.
  • liquid reducing agents examples include lower alcohols such as methanol, ethanol, and isopropanol, glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, and polyglycerins such as glycerin, diglycerin, triglycerin, and decaglycerin.
  • lower alcohols such as methanol, ethanol, and isopropanol
  • glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol
  • polyglycerins such as glycerin, diglycerin, triglycerin, and decaglycerin.
  • Ethylene glycol monomethyl ether Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, alkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, amines such as butylamine, dodecylamine, oleylamine, oleic acid, linoleic acid, linolenic acid, etc.
  • Saturated fatty acids, unsaturated hydrocarbons such as dodecene, tetradecene, octadecene, N aBH4, LiBH4, NaCNBH3, LiAlH4, etc. can be used.
  • polymers such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG), amines such as oleylamine, and carboxylic acids such as oleic acid can be used.
  • PVP polyvinylpyrrolidone
  • PEG polyethylene glycol
  • amines such as oleylamine
  • carboxylic acids such as oleic acid
  • the carrier is not particularly limited, and specific examples include oxides, nitrides, carbides, simple carbon, simple metal, etc. Among them, oxides and simple carbon are preferable, and oxides Is a particularly preferred carrier.
  • oxides include oxides such as silica, alumina, ceria, titania, zirconia, and niobium, and composite oxides such as silica-alumina, titania-zirconia, ceria-zirconia, and strontium titanate.
  • Examples of the simple carbon include activated carbon, carbon black, graphite, carbon nanotube, and activated carbon fiber.
  • nitrides 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 single metal include pure metals such as iron, copper, and aluminum, and alloys such as stainless steel.
  • the AuRu solid solution nanoparticles of the present invention include hydrogenation reaction catalysts, hydrogen oxidation reaction catalysts, oxygen reduction reaction (ORR) catalysts, oxygen generation reaction (OER) catalysts, hydrogen generation reaction (HER) catalysts, nitrogen oxidation. (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, hydrogen fuel cell catalyst It is excellent as a catalyst for oxidation reaction of hydrocarbons and is preferably used as an exhaust gas purification catalyst such as a catalyst for water electrolysis reaction and a three-way catalyst. In the case of a three-way catalyst, for example, NOx is reduced to nitrogen, CO is oxidized to carbon dioxide, and hydrocarbon (CH) is oxidized to water and carbon dioxide.
  • NOx is reduced to nitrogen
  • CO is oxidized to carbon dioxide
  • CH hydrocarbon
  • Example 1 Pd 0.4 Ru 0.6 solid solution nanoparticles (average particle size 13.2 nm) obtained in Reference Example 1 were heated at 573 K (300 ° C.) for 35 minutes, 41 minutes, 47 minutes or 53 minutes under a hydrogen atmosphere of 1 atm. went. The results are shown in FIG. 1 (53 minutes) and FIG. FIG. 1 shows the reaction in vacuum instead of the hydrogen atmosphere (Vac-treated), the Pd bulk, and the Pd 0.4 Ru 0.6 solid solution nanoparticles (As-synthesized) obtained in Reference Example 1.
  • Example 2 The Pd 0.5 Ru 0.5 solid solution nanoparticles (average particle size 10.5 nm) obtained in Reference Example 2 were 373 K (100 ° C.), 473 K (200 ° C.), 573 K (300 ° C.), 623 K (350 K) under a hydrogen atmosphere of 1 atm. ) And 673 K (400 ° C.) for 5 minutes each to perform PXRD. The results are shown in FIG. Furthermore, a TEM image of Pd 0.5 Ru 0.5 solid solution nanoparticles (treated with 573K) was obtained (FIG. 7).
  • Test example 1 A PdRu solid solution rotating ring disk electrode (PdRu / C: metal content 20 wt%) in which Pd 0.4 Ru 0.6 solid solution nanoparticles having a hcp structure of Example 1 (treated at 300 ° C. for 53 minutes) were supported on carbon particles was produced.
  • the diameter of the rotating ring disk electrode (RDE) was 5 mm.
  • Test example 2 Instead of the hcp Pd 0.4 Ru 0.6 solid solution nanoparticles (53 minutes at 300 ° C.) of Example 1 and using the hcp Pd 0.5 Ru 0.5 solid solution nanoparticles (400 ° C. treatment) of Example 2, the same procedure as in Test Example 1 was performed. The OER catalytic activity was measured. The results are shown in FIG.
  • Test example 3 Using the hcp Pd 0.4 Ru 0.6 solid solution nanoparticles of Example 1 (treated at 300 ° C. for 53 minutes) and the fcc Pd 0.4 Ru 0.6 solid solution nanoparticles of Reference Example 1, an accelerated durability test (ADT) was conducted. A TEM image was obtained for the sample. The results are shown in FIG.
  • FIG. 13 shows the XPS measurement results of the hcp Pd 0.4 Ru 0.6 solid solution nanoparticles of Example 1 (treated at 300 ° C. for 53 minutes) and the fcc Pd 0.4 Ru 0.6 solid solution nanoparticles of Reference Example 1.
  • Examples 3 and 4 A mixture of 100 ml of triethylene glycol (TEG, reducing agent) and 1.0 mmol PVP (polyvinylpyrrolidone, protective agent) was heated and stirred at 220 ° C. (Example 3) or 250 ° C. (Example 4), and Pt ( Acac) 2 (0.04 mmol) and RuCl 3 (0.16 mmol) dissolved in 10 ml of ethanol were added dropwise, maintained at 220 ° C. or 250 ° C. for 1 hour, allowed to cool, and the resulting precipitate was separated by centrifugation. . XRD patterns and TEM images were obtained for the separated PtRu solid solution nanoparticles (Fig. 14). It was revealed that PtRu solid solution nanoparticles having an hcp structure were obtained in Example 3, and PtRu solid solution nanoparticles having an fcc structure were obtained in Example 4.
  • TOG triethylene glycol
  • PVP polyvinylpyrrolidone,
  • Examples 5 and 6 A mixture of 100 ml of triethylene glycol (TEG, reducing agent) and 1.0 mmol PVP (polyvinylpyrrolidone, protective agent) was heated and stirred at 220 ° C. (Example 5) or 250 ° C. (Example 6), and Pt ( Acac) 2 (0.02 mmol) and RuCl 3 (0.18 mmol) dissolved in 10 ml of ethanol were added dropwise, maintained at 220 ° C. or 250 ° C. for 1 hour, allowed to cool, and the resulting precipitate was separated by centrifugation. . XRD patterns and TEM images were obtained for the separated PtRu solid solution nanoparticles (Fig. 15). It was revealed that PtRu solid solution nanoparticles having an hcp structure were obtained in Example 5, and PtRu solid solution nanoparticles having an fcc structure were obtained in Example 6.
  • TOG triethylene glycol
  • PVP polyvinylpyrrolidone,
  • Comparative Example 1 A mixture of 100 ml of triethylene glycol (TEG, reducing agent) and 1.0 mmol PVP (polyvinylpyrrolidone, protective agent) is heated and stirred at 220 ° C., and H 2 PtCl 6 (0.04 mmol) and RuCl 3 (0.16 mmol) are added to this solution. Was added dropwise in 10 ml of ethanol, maintained at 220 ° C. for 1 hour, allowed to cool, and the resulting precipitate was separated by centrifugation. An XRD pattern and a TEM image were obtained for the separated PtRu solid solution nanoparticles (FIG. 16). In Comparative Example 1, it was revealed that PtRu solid solution nanoparticles with fcc structure were obtained.
  • TOG triethylene glycol
  • PVP polyvinylpyrrolidone, protective agent
  • Example 7 HAuBr 4 (0.03 mmol) and RuCl 3 (0.07 mmol) were dissolved in 30 ml of diethylene glycol (DEG, reducing agent) (hereinafter referred to as “precursor solution”).
  • DEG diethylene glycol
  • Example 8 HAuBr 4 (0.03 mmol) and RuCl 3 (0.07 mmol) were dissolved in 10 ml of diethylene glycol (DEG, reducing agent) (hereinafter referred to as “precursor solution”).
  • DEG diethylene glycol
  • PVP 4 mmol
  • the precursor solution was pumped at a rate of 1.5 ml / min while maintaining the temperature of this solution at 195 ° C. The temperature was further maintained at 195 ° C. for 10 minutes and cooled to room temperature.
  • Au 0.3 Ru 0.7 solid solution nanoparticles were collected as a precipitate by centrifugation and dried under vacuum.
  • Test example 4 [Manufacture of electrodes] Pd 0.4 Ru 0.6 solid solution nanoparticles or Pd 0.4 Ru 0.6 solid solution nanoparticles (53 min 300 ° C. treatment) were supported on carbon particles fcc or PdRu solid solution rotational ring hcp the hcp structure of the first embodiment of the fcc structure of Reference Example 1 A disk electrode (PdRu / C: metal content 20 wt%) was produced. The diameter of the rotating ring disk electrode (RDE) was 5 mm. The loading amount of Pd 0.4 Ru 0.6 solid solution nanoparticles on the electrode was 0.051 mg / cm 2 .
  • the HER catalytic activity was measured in the same manner using Ru nanoparticles (Ru NPs) and Pd nanoparticles (Pd NPs) instead of PdRu solid solution nanoparticles.
  • Ru NPs Ru nanoparticles
  • Pd NPs Pd nanoparticles
  • FIG. 21 fccPdRu has lower activity than Pd, whereas hcpPdRu shows higher activity than Pd.
  • the current value I was measured when the potential E was swept at 5 mV / s.
  • the OER catalytic activity was measured in the same manner using Au nanoparticles (Au NPs) and Ru nanoparticles (Ru NPs) instead of Au 0.3 Ru 0.7 solid solution nanoparticles.
  • Au NPs Au nanoparticles
  • Ru NPs Ru nanoparticles
  • FIG. After about 1.5V, a decrease in activity accompanying the elution of the catalyst is observed for Ru. However, in the case of fcc solid solution, the activity gradually decreases after 1.6V, and the activity decreases with the number of measurements. On the other hand, no decrease in activity is observed in the hcp solid solution, and the activity is maintained even after 5000 measurements. Improvement of catalytic properties by controlling the crystal structure of Au 0.3 Ru 0.7 solid solution nanoparticles was observed.

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Abstract

La présente invention concerne les trois aspects suivants. Premièrement, l'invention concerne des nanoparticules de solution solide de Pd-Ru représentées par la formule Pd x Ru 1-x (0,1 ≤ x ≤ 0,8 ), dans laquelle Pd et Ru forment une solution solide au niveau atomique, et une structure hexagonale très compacte (hcp) constitue la structure principale de celles-ci. Deuxièmement, l'invention concerne un procédé de régulation de la structure cristalline d'un corps de solution solide Pt-Ru par régulation de la température de chauffe d'un agent réducteur destiné au corps de solution solide Pt-Ru. Troisièmement, l'invention concerne des nanoparticules de solution solide Au-Ru exprimées par la formule Au z Ru 1-z (0,05 ≤ z ≤ 0,4 ), dans laquelle Au et Ru forment une solution solide au niveau atomique, et une structure hexagonale très compacte (hcp) ou une structure cubique à faces centrées (fcc) constitue la structure principale de celles-ci.
PCT/JP2018/007370 2017-03-01 2018-02-27 NANOPARTICULES DE SOLUTION SOLIDE DE Pd-Ru, LEUR PROCÉDÉ DE PRODUCTION ET CATALYSEUR ASSOCIÉ, PROCÉDÉ DE RÉGULATION DE LA STRUCTURE CRISTALLINE DE NANOPARTICULES DE SOLUTION SOLIDE DE Pt-Ru, NANOPARTICULES DE SOLUTION SOLIDE Au-Ru, ET LEUR PROCÉDÉ DE FABRICATION WO2018159644A1 (fr)

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JP2020081918A (ja) * 2018-11-16 2020-06-04 フタムラ化学株式会社 金属担持活性炭及びその製法
CN113458409A (zh) * 2021-06-17 2021-10-01 西南大学 一种室温合成纳米合金催化剂的方法
WO2022009871A1 (fr) * 2020-07-06 2022-01-13 国立大学法人京都大学 Alliage, agrégat de nanoparticules d'alliage, et catalyseur
CN115165978A (zh) * 2022-07-11 2022-10-11 吉林大学 一种基于双金属PdRu纳米颗粒修饰SnO2的高选择性三乙胺气体传感器及其制备方法
JP7547480B2 (ja) 2019-12-30 2024-09-09 ハー．ツェー．スタルク タングステン ゲゼルシャフト ミット ベシュレンクテル ハフツング タングステン金属粉末の製造プロセス及びそれを実行するための装置

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JP7547480B2 (ja) 2019-12-30 2024-09-09 ハー．ツェー．スタルク タングステン ゲゼルシャフト ミット ベシュレンクテル ハフツング タングステン金属粉末の製造プロセス及びそれを実行するための装置
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CN113458409A (zh) * 2021-06-17 2021-10-01 西南大学 一种室温合成纳米合金催化剂的方法
CN115165978A (zh) * 2022-07-11 2022-10-11 吉林大学 一种基于双金属PdRu纳米颗粒修饰SnO2的高选择性三乙胺气体传感器及其制备方法
CN115165978B (zh) * 2022-07-11 2023-11-10 吉林大学 一种基于双金属PdRu纳米颗粒修饰SnO2的高选择性三乙胺气体传感器及其制备方法

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