WO2021132335A1 - Nanoparticules solides en solution, procédé pour les produire, liquide de dispersion de nanoparticules solides en solution, et catalyseur - Google Patents

Nanoparticules solides en solution, procédé pour les produire, liquide de dispersion de nanoparticules solides en solution, et catalyseur Download PDF

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WO2021132335A1
WO2021132335A1 PCT/JP2020/048169 JP2020048169W WO2021132335A1 WO 2021132335 A1 WO2021132335 A1 WO 2021132335A1 JP 2020048169 W JP2020048169 W JP 2020048169W WO 2021132335 A1 WO2021132335 A1 WO 2021132335A1
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nanoparticles
salt
solid solution
catalyst
solution
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Japanese (ja)
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北川　宏
康平 草田
羽田　政明
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国立大学法人京都大学
国立大学法人 名古屋工業大学
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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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • 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
    • B01J37/16—Reducing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust

Definitions

  • the present invention relates to solid solution nanoparticles, a method for producing the same, a dispersion of solid solution nanoparticles, and a catalyst.
  • Precious metal nanoparticles such as Pt nanoparticles are known to exhibit different optical, electrical, and chemical properties than bulk nanoparticles, and are known to exhibit electronic, magnetic, catalytic, pharmaceutical, cosmetic, or cosmetic materials. It is used in various fields as a food material.
  • catalysts are one of the most well-known uses of precious metal nanoparticles.
  • Patent Document 5 describes that noble metal nanoparticles are used as an antioxidant.
  • Patent Document 6 describes that noble metal nanoparticles are used as a material for a contrast medium.
  • Pt nanoparticles are highly useful because they exert various effects. It is conceivable to alloy a noble metal other than Pt with Pt in order to improve the desired effect.
  • PtIr forms a total solid solution at high temperatures, but is immiscible over a wide composition range of 1370 ° C. or lower.
  • PtRu and IrRu also have an immiscible composition range of about 15 atom% in the entire temperature range. Therefore, even if noble metal nanoparticles are synthesized by a conventional reduction method using a solution containing a plurality of noble metal salts, only a mixture of simple noble metal nanoparticles can be obtained.
  • An object of the present invention is to provide a novel solid solution nanoparticles, a method for producing the same, a dispersion liquid of the solid solution nanoparticles, and a catalyst using the solid solution nanoparticles.
  • the present invention It has a composition represented by the formula Pt x M1 y M2 1-xy (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, x + y ⁇ 1).
  • M1 is Ru or Ir and
  • M2 is at least one selected from the group consisting of Ir, Rh, Ag, Cu and Au.
  • M1 is Ir
  • M2 is at least one selected from the group consisting of Rh, Pd, Ag, Cu and Au.
  • Pt, M1 and M2 form a solid solution, Provided are solid solution nanoparticles.
  • the present invention Provided is a catalyst containing the solid solution nanoparticles of the present invention.
  • the present invention With solvent With the solid solution nanoparticles of the present invention dispersed in the solvent, Provided is a dispersion liquid of solid solution nanoparticles provided with.
  • the present invention A method for producing solid solution nanoparticles having a composition represented by the formula Pt x M1 y M2 1-xy (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, x + y ⁇ 1). It involves adding a solution containing a Pt salt, a salt of M1 and a salt of M2 to a liquid reducing agent heated to a temperature in the range of 150 ° C. or higher and 250 ° C. or lower for reaction.
  • the salt of M1 is a Ru salt or an Ir salt.
  • the salt of M2 contains at least one selected from the group consisting of Ir salt, Rh salt, Ag salt, Cu salt and Au salt.
  • the salt of M1 is an Ir salt
  • the salt of M2 contains at least one selected from the group consisting of Rh salt, Pd salt, Ag salt, Cu salt and Au salt.
  • a method for producing solid solution nanoparticles is provided.
  • FIG. 1 is a TEM image of PtRuIr solid solution nanoparticles supported on ZrO 2 of Example 1.
  • FIG. 2A is a HAADF-STEM image of PtRuIr solid solution nanoparticles supported on ZrO 2 of Example 1.
  • FIG. 2B shows the result of elemental mapping of Pt in Example 1.
  • FIG. 2C shows the result of elemental mapping of Ir in Example 1.
  • FIG. 2D shows the result of elemental mapping of Ru in Example 1.
  • FIG. 3A is a STEM image of PtRuIr solid solution nanoparticles subjected to EDX ray analysis.
  • FIG. 3B is a graph showing the results of EDX ray analysis.
  • FIG. 4 is a TEM image of Pt nanoparticles supported on ZrO 2 of Reference Example 1.
  • FIG. 5 is a TEM image of Ru nanoparticles supported on ZrO 2 of Reference Example 2.
  • FIG. 6 is a TEM image of Ir nanoparticles supported on ZrO 2 of Reference Example 3.
  • FIG. 7 is a TEM image of Pd nanoparticles supported on ZrO 2 of Reference Example 4.
  • FIG. 8 is a graph showing the evaluation of the methane oxidation activity of the catalysts of Examples, Reference Examples and Comparative Examples.
  • FIG. 9 is a graph showing the evaluation of the methane oxidation activity of the catalysts of Examples 1 to 6.
  • FIG. 10 is a triangular graph showing the relationship between the methane conversion rate at 400 ° C. and the composition of the solid solution nanoparticles.
  • FIG. 10 is a triangular graph showing the relationship between the methane conversion rate at 400 ° C. and the composition of the solid solution nanoparticles.
  • FIG. 11A is a graph showing the time course of methane oxidation activity at 400 ° C.
  • FIG. 11B is a graph showing the time course of methane oxidation activity at 400 ° C.
  • FIG. 12 is a graph showing the time course of the methane oxidation activity of the catalysts of Examples 3, 5 and 7 at 400 ° C.
  • FIG. 13A is a graph showing the measurement results of NH 3-TPD.
  • FIG. 13B is a graph showing the measurement results of CO 2-TPD.
  • FIG. 14 is a TEM image of PtIrPd solid solution nanoparticles of Example 8.
  • FIG. 15 is an X-ray diffraction pattern of the PtIrPd solid solution nanoparticles of Example 8.
  • FIG. 16 is a TEM image of PtIrPdRh solid solution nanoparticles of Example 9.
  • FIG. 17 is an X-ray diffraction pattern of the PtIrPdRh solid solution nanoparticles
  • Patent Documents 1 to 4 disclose catalysts using a plurality of precious metals. These catalysts are produced by impregnating a carrier with an aqueous solution containing a plurality of noble metal salts, and then calcining the carrier in air at 550 to 600 ° C. for 3 to 6 hours. This method is called the impregnation method. According to the impregnation method, it is presumed that the plurality of noble metals constituting the catalyst exist in the state of simple noble metal particles without alloying, or form noble metal particles having a variable and non-uniform composition. Therefore, the catalyst produced by the impregnation method cannot sufficiently exert the effect of alloying.
  • methane when the main component of hydrocarbons in exhaust gas is methane, such as combustion exhaust gas of natural gas, methane has high chemical stability, so oxidative decomposition of hydrocarbons (removal of methane) proceeds sufficiently. It's not easy to get it done. Further, there is also a problem that the activity of the catalyst decreases with time due to the precipitation of a reaction inhibitor such as sulfur oxide (SOx) derived from the sulfur compound contained in the fuel on the surface of the catalyst.
  • SOx sulfur oxide
  • the present inventors have found that solid solution nanoparticles in which metals that normally do not dissolve in solid solution are solid-solved can be produced, and that the solid solution nanoparticles can be used as a novel catalyst.
  • the present invention is based on this new finding.
  • the present invention reveals that by mixing and alloying Pt with various metals, it is possible to adjust the catalytic activity of Pt on a nanoscale, which was difficult in the past.
  • This demonstrates the new industrial applicability of Pt as a catalyst.
  • the following embodiments show one aspect of Pt in which such catalytic activity is adjusted at the nano level.
  • the solid solution nanoparticles of the present embodiment have a composition represented by the following formula (1).
  • M1 is Ru or Ir.
  • M2 is at least one selected from the group consisting of Ir, Rh, Ag, Cu and Au.
  • M1 is Ir, M2 is at least one selected from the group consisting of Rh, Pd, Ag, Cu and Au.
  • Pt, M1 and M2 form a solid solution. In other words, Pt, M1 and M2 are in solid solution with each other at the atomic level. In the solid solution nanoparticles, a region in which each element is uniformly distributed is included. It is preferable that each element is uniformly distributed throughout the solid solution nanoparticles.
  • a solid solution is one form included in the concept of alloy, and means a state in which constituent elements are mixed at the atomic level.
  • alloy means an alloy in a broad sense that includes not only solid solutions but also non-solid solutions.
  • the local alloy composition is uniform in a solid solution, whereas it is not uniform in a non-solid solution system.
  • the physical characteristics of alloys generally differ depending on whether a plurality of metal elements are mixed as a solid solution alloy as a whole at the atomic level or simply form a non-solid solution type alloy.
  • the solid solution nanoparticles of this embodiment can be precious metal nanoparticles.
  • Cu is not classified as a noble metal, but is treated as a noble metal in the present specification.
  • the noble metal nanoparticles are a solid solution
  • element mapping by energy dispersive X-ray analysis (EDX) using a scanning transmission electron microscope (STEM), EDX ray analysis, and X-ray diffraction (XRD) are performed.
  • Structural analysis and the like can be mentioned.
  • the average particle size of the solid solution nanoparticles of the present embodiment may be in the range of 0.5 nm or more and 100 nm or less, or may be in the range of 1 nm or more and 10 nm or less. When the average particle size is small enough, the solid solution nanoparticles can exhibit high activity.
  • the average particle size can be calculated from the electron microscope image of the solid solution nanoparticles. In the electron microscope image, the particle size (major axis) of a plurality of solid solution nanoparticles (for example, 100) is measured. The average value of the measured particle sizes represents the average particle size of the solid solution nanoparticles.
  • x representing the content ratio of Pt satisfies, for example, 0.01 ⁇ x ⁇ 0.98.
  • y representing the content ratio of M1 satisfies, for example, 0.01 ⁇ y ⁇ 0.98.
  • (1-xy) representing the content ratio of M2 satisfies 0.01 ⁇ (1-xy) ⁇ 0.98.
  • the respective content ratios of Pt, M1 and M2 are in the range of, for example, 1 mol% or more and 98 mol% or less based on the solid solution nanoparticles (100 mol%).
  • the respective content ratios of Pt, M1 and M2 may be in the range of 5 mol% or more and 90 mol% or less, or may be in the range of 10 mol% or more and 80 mol% or less.
  • the solid solution nanoparticles of this embodiment contain Pt as an essential component.
  • Pt nanoparticles can be used in various applications such as electronic materials, magnetic materials, catalytic materials, pharmaceutical materials, cosmetic materials, food materials and the like.
  • Pt is expensive. Therefore, if the function and activity equal to or higher than those of the Pt nanoparticles can be achieved while lowering the Pt content ratio, the solid solution nanoparticles having excellent economic efficiency can be provided.
  • the solid solution nanoparticles of the present embodiment exhibit catalytic activity exceeding that of Pt nanoparticles.
  • catalytic activity is only one function of solid solution nanoparticles.
  • M1 can be Ru. Ru is cheaper than Pt and is suitable as a substitute element for Pt in solid solution nanoparticles.
  • M1 may be Ir.
  • Ir is an expensive precious metal like Pt, it often exhibits higher activity than Ru, and is suitable as a material for the solid solution nanoparticles of the present embodiment. By including Ir, the solid solution nanoparticles can exhibit higher activity.
  • M1 may be Ru and M2 may be Ir.
  • M1 may be Ru and M2 may be Ir.
  • M2 may consist of 1 type, 2 types, 3 types, 4 types or 5 types of metal elements.
  • the solid solution nanoparticles of the present embodiment are ternary solid solution nanoparticles. That is, in the formula (1), when M1 is Ru, M2 is Ir, Rh, Ag, Cu or Au. When M1 is Ir, M2 is Rh, Pd, Ag, Cu or Au. Compared with the quaternary system or the quaternary system, the production of the ternary solid solution nanoparticles is easy.
  • M1 Ir and M2 is composed of three kinds of metal elements
  • the content ratio of Pt can be in the range of 10 mol% or more and 30 mol% or less.
  • Pt is considered to be the main component that influences the catalytic activity. Therefore, it is predicted that if the Pt content ratio is lowered, the catalytic activity is also lowered.
  • catalysts containing solid solution nanoparticles exhibit the highest methane oxidative degradation activity when the Pt content is reduced. Specifically, the catalytic activity tends to increase as the Pt content ratio decreases to 50 mol%, 40 mol%, and 30 mol%. Regarding the lower limit, the catalytic activity tends to increase as the Pt content ratio increases to 5 mol% and 10 mol%. This becomes clear from the examples described later.
  • the solid solution nanoparticles of the present embodiment can be suitably used as various catalysts.
  • catalytic reactions include chemical reactions such as reduction reaction, oxidation reaction, dehydrogenation reaction, and coupling reaction.
  • the catalyst of this embodiment can be used in a process or apparatus involving these catalytic reactions.
  • Specific applications of the catalyst include environmental applications including purification of exhaust gas, electrode applications, and chemical process applications.
  • catalysts are used in at least one reaction selected from the group consisting of nitrogen oxide reduction reactions, carbon monoxide oxidation reactions, hydrocarbon oxidation reactions, and volatile organic compound (VOC) oxidation reactions.
  • VOC volatile organic compound
  • catalysts are used in at least one reaction selected from the group consisting of hydrogen oxidation reactions, oxygen reduction reactions, and water electrolysis reactions.
  • catalysts are used in at least one reaction selected from the group consisting of hydrogenation reactions of unsaturated hydrocarbons and dehydrogenation reactions of saturated or unsaturated hydrocarbons.
  • the catalyst of the present embodiment can be suitably used for purifying the exhaust gas discharged from the heat engine, generating hydrogen in the fuel cell, and removing the volatile organic compounds.
  • methane may be the main component of hydrocarbons in the exhaust gas, such as the combustion exhaust gas of natural gas.
  • Methane has a greenhouse effect about 25 times that of carbon dioxide. Therefore, it is recommended to reduce the release of methane into the atmosphere as much as possible from the viewpoint of global environmental protection.
  • the catalyst of this embodiment is suitable for oxidative decomposition of hydrocarbons, particularly methane. Although the chemical stability of methane is high, the catalyst of the present embodiment exhibits high activity, so that the oxidative decomposition of methane can proceed sufficiently at a relatively low temperature. In addition, the catalyst of the present embodiment is also excellent in durability against reaction inhibitors such as sulfur oxides (SO x). Examples of heat engines that use natural gas as fuel include gas turbines.
  • the catalyst of this embodiment is suitable for a purification device for combustion exhaust gas of a gas turbine.
  • the catalyst of the present embodiment may further include a carrier supporting solid solution nanoparticles.
  • a carrier supporting solid solution nanoparticles By supporting the solid solution nanoparticles on the carrier, aggregation of the solid solution nanoparticles can be suppressed.
  • the electronic interaction from the carrier can promote the adsorption and activation of the reaction molecule on the surface of the solid solution nanoparticles.
  • the structure of the carrier is not particularly limited.
  • the carrier is typically particles.
  • the shape of the particles is not particularly limited, and particles having various shapes such as spherical, elliptical spherical, and scaly can be used.
  • the material of the carrier is not particularly limited.
  • the carrier material include oxides, nitrides, carbides, carbon materials, and metal materials.
  • Oxides include silica, alumina, ceria, titania, zirconia, niobia, silica-alumina, titania-zirconia, ceria-zirconia, tin oxide, tungsten trioxide, molybdenum trioxide, tantalum pentaoxide, and strontium titanate.
  • the oxide may be a metal oxide.
  • nitride 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.
  • the nitride may be a metal nitride.
  • Examples of the carbide 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 carbide may be a metal carbide.
  • Examples of the carbon material include activated carbon, carbon black, graphite, carbon nanotubes, and activated carbon fiber.
  • Examples of the metal material include pure metals such as iron, copper and aluminum, and alloys such as stainless steel. One kind or a combination of two or more kinds selected from these carriers can be used.
  • metal oxide particles such as zirconia particles can be suitably used as a carrier.
  • the metal oxide has a large specific surface area and is excellent in heat resistance, chemical stability, mechanical strength, and dispersibility.
  • the carrier may contain at least one selected from the group consisting of SnO 2 , WO 3 , MoO 3 , Ta 2 O 5 , and Nb 2 O 5. Since these materials have excellent durability against SO x, they may have the effect of maintaining the activity of the catalyst for a long period of time.
  • the carrier may contain any of these materials as a main component, or may be substantially composed of these materials.
  • the "main component” means the component contained most in the mass ratio. By “substantially consisting of ", it means that no material other than a specific material is intentionally added except for unavoidable impurities.
  • the solid solution nanoparticles may be used as a catalyst without being supported on a carrier.
  • the solid solution nanoparticles may be protected with a protective agent.
  • the solid solution nanoparticles having the composition represented by the formula (1) are produced through a step of adding a solution containing a Pt salt, a salt of M1 and a salt of M2 to a liquid reducing agent heated to a predetermined temperature T and reacting them. ..
  • the composition of the solid solution nanoparticles can be controlled by adjusting the ratio of the metal salt as the raw material.
  • a solution containing a Pt salt, a salt of M1 and a salt of M2 is prepared.
  • the solution is typically an aqueous solution.
  • the salt of M1 is Ru salt or Ir salt.
  • the salt of M2 contains at least one selected from the group consisting of Ir salt, Rh salt, Ag salt, Cu salt and Au salt.
  • the salt of M1 is an Ir salt
  • the salt of M2 contains at least one selected from the group consisting of Rh salt, Pd salt, Ag salt, Cu salt and Au salt.
  • the Pt salt, the salt of M1 and the salt of M2 can be water-soluble, respectively.
  • Examples of the Pt salt, Ru salt, Ir salt, Rh salt, Pd salt, Ag salt, Cu salt and Au salt include the following salts.
  • Pt K 2 PtCl 4 , (NH 4 ) 2 K 2 PtCl 4 , (NH 4 ) 2 PtCl 6 , Na 2 PtCl 6 , [Pt (NO 2 ) 2 (NH 3 ) 2 ]
  • Ru Ruthenium halides such as RuCl 3 , RuBr 3 , Ruthenium nitrate
  • Ir Iridium chloride, iridium acetylacetonate, potassium iridium cyanate, potassium iridium Rh: rhodium acetate, rhodium nitrate, rhodium chloride
  • Pd K 2 PdCl 4 , Na 2 PdCl 4 , K 2 PdBr 4 , Na 2 PdBr 4 , Palladium nitrate Ag: Silver nitrate, Silver
  • the Pt salt, the salt of M1 and the salt of M2 are weighed and added to water to prepare a solution. Acids or alkalis may be added to the water to adjust the pH of the solution.
  • the temperature of the solution is, for example, room temperature (20 ° C. ⁇ 15 ° C.).
  • the carrier to the solution.
  • the timing of adding the carrier to the solution is not particularly limited.
  • the reaction for forming the solid solution nanoparticles is allowed to proceed while the carrier is present in the solution, the solid solution nanoparticles can be directly supported on the carrier without using a protective agent such as a polymer.
  • the liquid reducing agent and the solution are mixed to obtain a reaction solution.
  • the liquid reducing agent and the solution are mixed by spraying the solution onto the liquid reducing agent heated to a predetermined temperature T.
  • the reaction is allowed to proceed over a predetermined time t while maintaining the reaction solution at a predetermined temperature T.
  • the solution may be added dropwise to the liquid reducing agent.
  • the reaction solution is allowed to cool to perform solid-liquid separation, whereby solid solution nanoparticles having a desired composition can be obtained.
  • the predetermined temperature T is, for example, in the range of 150 ° C. or higher and 250 ° C. or lower.
  • the predetermined time t is, for example, in the range of 1 minute or more and 12 hours or less.
  • the liquid reducing agent include polyhydric alcohols such as ethylene glycol, glycerin, diethylene glycol, and triethylene glycol.
  • One or both of the liquid reducing agent and the solution may be preheated and mixed.
  • the reaction solution may contain a protective agent.
  • the protective agent has a role of suppressing the aggregation of solid solution nanoparticles.
  • Protective agents include polymers, amines, and carboxylic acids. Polymers include poly (N-vinyl-2-pyrrolidone) (PVP) and polyethylene glycol (PEG). Examples of the amine include oleylamine. Examples of the carboxylic acid include oleic acid.
  • the solid-liquid separation process may be omitted. That is, the solid solution nanoparticles may be provided in the form of a dispersion.
  • the dispersion liquid contains a solvent and solid solution nanoparticles dispersed in the solvent. Depending on the application, it is desirable to provide solid solution nanoparticles in the form of a dispersion.
  • Example 1 PtRuIr solid solution nanoparticles >> Dilute hydrochloric acid was prepared by adding 0.117 ml of hydrochloric acid to 40 ml of water. The pH of dilute hydrochloric acid was 1.64 and the temperature was 24.7 ° C. 0.1025 mmol of K 2 PtCl 4 was dissolved in 8 ml of dilute hydrochloric acid to obtain a Pt salt aqueous solution. 0.205 mmol of RuCl 3 ⁇ nH 2 O was dissolved in 8 ml of dilute hydrochloric acid to obtain an aqueous Ru salt solution.
  • an aqueous NaOH solution was prepared by dissolving 1.3 mmol of NaOH in 2 ml of water.
  • the pH of the triethylene glycol was adjusted to 7 by slowly adding an aqueous NaOH solution to 400 ml of triethylene glycol. Then, the triethylene glycol was heated to 232 ° C.
  • the raw material solution was sprayed on the heated triethylene glycol over 19 minutes.
  • the temperature of triethylene glycol at the time of spraying was 229 to 232 ° C.
  • the reaction solution containing triethylene glycol and the raw material solution was stirred over 10 minutes while maintaining the temperature at 232 ° C.
  • the precipitate was separated by centrifugation and washed with water. Then, the separated solid matter was vacuum dried. As a result, PtRuIr solid solution nanoparticles supported on ZrO 2 were obtained.
  • composition analysis, TEM observation The composition of PtRuIr solid solution nanoparticles was identified using a fluorescent X-ray analyzer. The results are shown in Table 1. PtRuIr solid solution nanoparticles supported on ZrO 2 were observed by a transmission electron microscope. The obtained TEM image is shown in FIG.
  • the amount of Pt supported was 1.08 wt%, which was almost the same as the target value (1 wt%).
  • HfO 2 is an impurity inevitably contained in zirconia particles.
  • the large particles are ZrO 2 particles.
  • the small particles attached to the surface of the ZrO 2 particles are PtRuIr solid solution nanoparticles.
  • the PtRuIr solid solution nanoparticles were uniformly attached to the surface of the ZrO 2 particles.
  • the average particle size of the PtRuIr solid solution nanoparticles was 2.2 ⁇ 0.4 nm. In the notation of "A ⁇ Bnm", A represents the average particle size and B represents the standard deviation.
  • FIGS. 2A to 2D The image by HAADF-STEM (High-Angle Annular Dark-Field Scanning Transmission Electron Microscopy) and the result of element mapping are shown in FIGS. 2A to 2D.
  • FIG. 2A shows a HAADF-STEM image.
  • 2B, 2C and 2D show elemental mapping data for Pt, Ir and Ru, respectively.
  • the results of the line analysis are shown in FIGS. 3A and 3B.
  • FIG. 3B shows the results of line analysis of PtRuIr solid solution nanoparticles appearing in the STEM image of FIG. 3A.
  • FIGS. 2B to 2D corresponds to the portion of small particles in FIG. 2A.
  • PtRuIr solid solution nanoparticles were uniformly formed on the ZnO 2 particles.
  • the results of the line analysis of FIGS. 3A and 3B show that Pt, Ir and Ru are not present separately from each other, but that Pt, Ir and Ru are uniformly distributed throughout the particles. .. That is, the data in FIGS. 2A-2D, 3A and 3B show that Pt, Ir and Ru are solid-solved at the atomic level in the PtRuIr nanoparticles.
  • Examples 2 to 6 PtRuIr solid solution nanoparticles >> PtRuIr solid solution nanoparticles of Examples 2 to 6 having different composition ratios were prepared by the same method as in Example 1 except that the charging ratios of Pt salt, Ru salt and Ir salt were changed.
  • the target composition in each example was as follows.
  • the target value of the amount of Pt supported in each example was 1 wt%.
  • Example 2 Pt 0.2 Ru 0.6 Ir 0.2
  • Example 3 Pt 0.2 Ru 0.2 Ir 0.6
  • Example 4 Pt 0.25 Ru 0.25 Ir 0.5
  • Example 5 Pt 0.3 Ru 0.3 Ir 0.3
  • Example 6 Pt 0.6 Ru 0.2 Ir 0.2
  • the raw material solution was sprayed on 300 ml of triethylene glycol heated to 232 ° C. over 19 minutes.
  • the temperature of triethylene glycol at the time of spraying was 228 to 233 ° C.
  • the reaction solution containing triethylene glycol and the raw material solution was stirred over 10 minutes while maintaining the temperature at 230 ° C.
  • the precipitate was separated by centrifugation and washed with water. Then, the separated solid matter was vacuum dried.
  • the amount of Pt supported was 1.02 wt%, which was almost the same as the target value (1 wt%).
  • FIG. 4 is a TEM image of Pt nanoparticles supported on ZrO 2 of Reference Example 1.
  • the large particles are ZrO 2 particles.
  • the small particles attached to the surface of the ZrO 2 particles are Pt nanoparticles.
  • the average particle size of the Pt nanoparticles was 2.9 ⁇ 0.8 nm.
  • Reference example 2 Ru nanoparticles >> Dilute hydrochloric acid was prepared by adding 0.088 ml of hydrochloric acid to 30 ml of water. 0.07689 mmol of RuCl 3 ⁇ nH 2 O was dissolved in 8 ml of dilute hydrochloric acid to obtain an aqueous Ru salt solution. Using an ultrasonic homogenizer, 1462.45 mg of ZrO 2 powder was dispersed in 12 ml of dilute hydrochloric acid to obtain a ZrO 2 dispersion. The Ru salt solution was added to ZrO 2 dispersion with stirring ZrO 2 dispersion, to obtain a raw material solution. Stirring of the raw material solution was continued for 15 minutes.
  • the raw material solution was sprayed on the heated triethylene glycol over 13 minutes.
  • the temperature of triethylene glycol at the time of spraying was 229 to 232 ° C.
  • the reaction solution containing triethylene glycol and the raw material solution was stirred over 10 minutes while maintaining the temperature at 230 ° C.
  • the precipitate was separated by centrifugation and washed with water. Then, the separated solid matter was vacuum dried.
  • Ru nanoparticles supported on ZrO 2 were obtained.
  • the amount of Ru carried was 0.43 wt%, which was almost the same as the target value (0.5 wt%).
  • FIG. 5 is a TEM image of Ru nanoparticles supported on ZrO 2 of Reference Example 2.
  • the large particles are ZrO 2 particles.
  • the small particles attached to the surface of the ZrO 2 particles are Ru nanoparticles.
  • the average particle size of the Ru nanoparticles was 4.2 ⁇ 0.8 nm.
  • the raw material solution was sprayed on 300 ml of triethylene glycol heated to 232 ° C. over 12 minutes.
  • the temperature of triethylene glycol at the time of spraying was 228 to 232 ° C.
  • the reaction solution containing triethylene glycol and the raw material solution was stirred over 10 minutes while maintaining the temperature at 230 ° C.
  • the precipitate was separated by centrifugation and washed with water. Then, the separated solid matter was vacuum dried.
  • Ir nanoparticles supported on ZrO 2 were obtained.
  • the amount of Ir carried was 1.1 wt%, which was almost the same as the target value (1 wt%).
  • FIG. 6 is a TEM image of Ir nanoparticles supported on ZrO 2 of Reference Example 3.
  • the large particles are ZrO 2 particles.
  • the small particles attached to the surface of the ZrO 2 particles are Ir nanoparticles.
  • the average particle size of the Ir nanoparticles was 1.3 ⁇ 0.3 nm.
  • the raw material solution was sprayed on 300 ml of triethylene glycol heated to 232 ° C. over 22 minutes.
  • the temperature of triethylene glycol at the time of spraying was 228 to 233 ° C.
  • the reaction solution containing triethylene glycol and the raw material solution was stirred over 10 minutes while maintaining the temperature at 230 ° C.
  • the precipitate was separated by centrifugation and washed with water. Then, the separated solid matter was vacuum dried.
  • the amount of Pd supported was 1.06 wt%, which was almost the same as the target value (1 wt%).
  • FIG. 7 is a TEM image of Pd nanoparticles supported on ZrO 2 of Reference Example 4.
  • the large particles are ZrO 2 particles.
  • the small particles attached to the surface of the ZrO 2 particles are Pd nanoparticles.
  • the average particle size of the Pd nanoparticles was 3.9 ⁇ 0.8 nm.
  • the methane oxidation activity of the catalysts of Example 5, Reference Examples 1 to 4 and Comparative Example 1 was evaluated using a fixed bed flow type reactor. First, a pellet-shaped 50 mg catalyst was filled in a quartz reaction tube having an inner diameter of 7 mm using quartz wool. A reaction gas (CH 4 : 0.1%, O 2 : 10%, SO 2 : 5 volppm, H 2 O: 3%, He: balance) that simulates the combustion exhaust gas of natural gas by connecting the reaction tube to the gas supply device. Gas) was supplied towards the catalyst.
  • the catalyst was heated to 600 ° C. in the above reaction gas and held for 1 hour. Then, the temperature of the catalyst was lowered to 200 ° C., and the reaction gas was supplied at a flow rate of 100 ml / min. The temperature of the catalyst was increased by 50 ° C. from 200 ° C. to 600 ° C. The temperature of the catalyst was maintained at each temperature for 20 minutes, and the concentration of methane in the reaction gas that passed through the catalyst in a steady state was measured. The methane conversion rate (%) was calculated from the measured concentration. The results are shown in FIG. The "methane conversion rate" on the vertical axis indicates the ratio of oxidatively decomposed methane. The higher the methane conversion rate, the higher the methane-oxidizing activity of the catalyst.
  • the methane conversion rate of the catalyst of Example 5 at 400 ° C. was 41% (FIG. 8).
  • the methane conversion rate of the catalyst of Comparative Example 1 at 400 ° C. was 29%.
  • the rate constant k was calculated based on the following formula, the rate constant of the catalyst of Example 5 was 4.71 ⁇ 10 -5 mol / min / g-cat.
  • the rate constant of the catalyst of Comparative Example 1 was 3.06 ⁇ 10 -5 mol / min / g-cat.
  • the rate constant of the catalyst of Example 5 was about 1.5 times the rate constant of the catalyst of Comparative Example 1.
  • the PtRuIr catalyst of Example 5 (Pt 0.3 Ru 0.3 Ir 0.3 / ZnO 2 ) showed a high activity equal to or higher than that of the Pd catalyst of Reference Example 4. In the low temperature range of 350 to 500 ° C., the activity of the PtRuIr catalyst of Example 5 exceeded that of the catalyst of Comparative Example 1.
  • the activity of the PtRuIr catalyst of Example 5 was significantly higher than that of the Pt catalyst, Ru catalyst and Ir catalyst of Reference Examples 1 to 3.
  • the methane conversion rates of the Pt catalyst, Ru catalyst and Ir catalyst of Reference Examples 1 to 3 were less than 10%.
  • the methane conversion rate of the catalyst of Example 5 at 400 ° C. was about 40%.
  • 400 ° C is, for example, a temperature sufficiently lower than the temperature of the exhaust gas of a general gas turbine. Therefore, it can be said that a catalyst capable of exhibiting sufficient activity at 400 ° C. is suitable for use in removing methane from the exhaust gas of a gas turbine.
  • the total supported amount (wt%) of the noble metal is different from each other.
  • the amount of Pt supported is equal at 1 wt%.
  • the activity at 400 ° C. methane conversion rate
  • the activity of the PtRuIr catalyst of Example 1 Pt 0.2 Ru 0.4 Ir 0.4
  • the activity of the PtRuIr catalyst of Example 6 Pt 0.6 Ru 0.2 Ir 0.2
  • the amount of Pt supported in Example 1 and the amount of Pt supported in Example 6 are approximately 1 wt% and equal. When the Pt content was relatively low, the PtRuIr catalyst showed high activity.
  • the PtRuIr catalyst having various compositions has the same tendency as that of the above example. Presumed to show.
  • FIG. 10 is a triangular graph showing the relationship between the methane conversion rate at 400 ° C. and the composition of the solid solution nanoparticles.
  • the PtRuIr catalyst showed the highest activity (77.3%).
  • the catalytic activity tended to increase as the Pt content ratio decreased to 50 mol%, 40 mol%, and 30 mol%.
  • the catalytic activity tended to increase as the Pt content ratio increased to 5 mol% and 10 mol%. Therefore, the upper limit of the Pt content ratio in the PtRuIr solid solution nanoparticles is, for example, 50 mol%, 40 mol% or 30 mol%.
  • the lower limit of the Pt content ratio in the PtRuIr solid solution nanoparticles is, for example, 5 mol% or 10 mol%.
  • the content ratio of Pt in the PtRuIr solid solution nanoparticles may be in the range of 10 mol% or more and 30 mol% or less.
  • Example 1 The activity of the catalysts of Example 1, Example 5, and Comparative Example 1 was substantially constant over the test period of 30 hours, respectively. This result indicates that the PtRuIr catalyst is less susceptible to sulfur poisoning. Moreover, the activity of the catalysts of Examples 1 and 5 was much higher than that of the catalyst of Comparative Example 1.
  • the activity of the catalysts of Reference Examples 1 to 3 decreased slightly with the passage of time. However, the activity of the catalysts of Reference Examples 1 to 3 was low from the initial stage. Comparing the rate of decrease based on the initial activity, the rate of decrease in the activity of the catalysts of Reference Examples 1 to 3 was large. This indicates that Pt, Ru and Ir are also subject to sulfur poisoning, though not as much as Pd. Since the activity of the catalyst of Example 1 was hardly reduced, it is considered that the PtRuIr catalyst newly acquired excellent durability against sulfur poisoning by forming a solid solution of Pt, Ru and Ir.
  • Example 7 PtRuIr solid solution nanoparticles / SnO 2 >> The same method as in Example 5 except that 1438.5 mg of SnO 2 powder was used instead of ZrO 2 powder and the amount of metal salt charged was adjusted so that the total amount of metal after support was 4.1 wt%. Obtained PtRuIr solid solution nanoparticles supported on SnO 2. That is, the composition of the PtRuIr solid solution nanoparticles in Example 7 is Pt 0.3 Ru 0.3 Ir 0.3 .
  • Example 3 catalyst (Pt 0.2 Ru 0.2 Ir 0.6 / ZrO 2 ) 200 mg 50 mg of catalyst of Example 5 (Pt 0.3 Ru 0.3 Ir 0.3 / ZrO 2)
  • Example 7 catalyst (Pt 0.3 Ru 0.3 Ir 0.3 / SnO 2 ) 200 mg
  • Example 7 catalyst (Pt 0.3 Ru 0.3 Ir 0.3 / SnO 2 ) 50 mg
  • FIG. 12 is a graph showing the time course of the methane oxidation activity of the catalysts of Examples 3, 5 and 7 at 400 ° C.
  • the initial activity (0 to 50 hours) of 200 mg of the catalyst of Example 3 using ZrO 2 as a carrier was superior to the initial activity of 200 mg of the catalyst of Example 7 using SnO 2 as a carrier.
  • the activity of the catalyst of Example 7 exceeded that of the catalyst of Sample 1. That is, the catalyst using SnO 2 as a carrier was excellent in durability.
  • the composition of the PtRuIr solid solution nanoparticles in the catalyst of Example 5 is the same as the composition of the PtRuIr solid solution nanoparticles in the catalyst of Example 7.
  • the activity of 50 mg of the catalyst of Example 5 decreased immediately after the start of the test, and then remained around 40%.
  • 50 mg of the catalyst of Example 7 maintained the initial activity (60%) even after the lapse of 100 hours. That is, the catalyst using SnO 2 as a carrier was excellent in durability.
  • Preprocessing 100 mg of ZrO 2 particles or SnO 2 particles were filled in a reaction tube as a sample, the temperature was raised to 600 ° C. while flowing Ar, and Ar treatment was carried out over 30 minutes. Then, after switching to 100% O 2 and performing the treatment for 30 minutes, switching to Ar and performing the treatment for 30 minutes. The sample was then cooled to 100 ° C. (NH 3- TPD) or 50 ° C. (CO 2-TPD). NH 3 at a concentration of 0.5 vol% for 1 hour at -TPD at 100 ° C. was circulated NH 3 / Ar mixed gas containing NH 3 and was adsorbed NH 3 in the sample.
  • CO 2- TPD a CO 2 / Ar mixed gas containing 0.5 vol% concentration of CO 2 was circulated at 50 ° C. for 1 hour to adsorb CO 2 to the sample. Then, it was switched to Ar, and the physically adsorbed species was desorbed from the sample over 30 minutes.
  • FIG. 13A is a graph showing the measurement results of NH 3-TPD.
  • FIG. 13B is a graph showing the measurement results of CO 2-TPD.
  • the horizontal axis shows the temperature of the sample.
  • the vertical axis shows the MS signal intensity.
  • ZrO 2 showed desorption of NH 3 and CO 2 over a wide temperature range. That is, ZrO 2 had both an acid point and a base point.
  • SnO 2 showed desorption of NH 3 over a wide temperature range, but showed almost no desorption of CO 2.
  • No CO 2 signal was detected above 200 ° C. That is, there were almost no base points in SnO 2.
  • Example 8 PtIrPd solid solution nanoparticles >> Using an ultrasonic homogenizer, 0.3 mmol of K 2 PtCl 4 , 0.3 mmol of IrCl 4 ⁇ nH 2 O, and 0.3 mmol of K 2 PdCl 4 were dissolved in 40 ml of water. As a result, a raw material liquid containing a noble metal salt was obtained.
  • composition analysis, TEM observation The composition of PtIrPd solid solution nanoparticles was identified using a fluorescent X-ray analyzer. The results are shown in Table 2. PtIrPd solid solution nanoparticles were observed with a transmission electron microscope. The obtained TEM image is shown in FIG.
  • the quantitative result (wt%) is a value calculated on the assumption that the balance other than the precious metal is PVP.
  • FIG. 14 is a TEM image of the PtIrPd solid solution nanoparticles of Example 8. As shown in FIG. 14, nano-sized PtIrPd solid solution nanoparticles were obtained. The average particle size of the PtIrPd solid solution nanoparticles was 4.4 ⁇ 0.9 nm. The average particle size was calculated by measuring the particle size (major axis) of the particles (100 particles) in the TEM image and calculating the average. A in the notation A ⁇ Bnm represents the average particle size, and B represents the standard deviation. "Major axis" means the longest distance between two points on the outer edge of a particle.
  • FIG. 15 is an X-ray diffraction pattern of the PtIrPd solid solution nanoparticles of Example 8.
  • X-ray diffraction measurement was performed at room temperature using CuK ⁇ rays.
  • the X-ray diffraction pattern showed a single fcc pattern. This indicates that the sample is a solid solution rather than a mixture of Pt, Ir and Pd.
  • the lattice constant of each single noble metal is Since they are different, a plurality of fcc patterns having different peak positions are observed.
  • the lattice constant is determined by the composition ratio of each element and the atomic radius to a single value, so that only a single fcc pattern is observed.
  • Example 9 PtIrPdRh solid solution nanoparticles >> Using an ultrasonic homogenizer, 0.25mmol of K 2 PtCl 4, IrCl 4 ⁇ nH 2 O of 0.25mmol, K 2 PdCl 4 of 0.25mmol, and RhCl 3 ⁇ 3H 2 O of 0.25mmol in 40ml water was dissolved in. As a result, a raw material liquid containing a noble metal salt was obtained.
  • composition analysis, TEM observation The composition of PtIrPdRh solid solution nanoparticles was identified using a fluorescent X-ray analyzer. The results are shown in Table 3. PtIrPdRh solid solution nanoparticles were observed with a transmission electron microscope. The obtained TEM image is shown in FIG.
  • the quantitative result (wt%) is a value calculated on the assumption that the balance other than the precious metal is PVP.
  • FIG. 16 is a TEM image of the PtIrPdRh solid solution nanoparticles of Example 9. As shown in FIG. 16, nano-sized PtIrPdRh solid solution nanoparticles were obtained. The average particle size of the PtIrPdRh solid solution nanoparticles was 3.9 ⁇ 1.2 nm.
  • FIG. 17 is an X-ray diffraction pattern of the PtIrPdRh solid solution nanoparticles of Example 9.
  • the X-ray diffraction pattern showed a single fcc pattern. This indicates that the sample is a solid solution rather than a mixture of Pt, Ir, Pd and Rh.
  • the lattice constant of each single noble metal is Since they are different, a plurality of fcc patterns having different peak positions are observed.
  • the lattice constant is determined by the composition ratio of each element and the atomic radius to a single value, so that only a single fcc pattern is observed.
  • the solid solution nanoparticles of the present invention are useful as electronic materials, magnetic materials, catalyst materials, pharmaceutical materials, cosmetic materials or food materials.

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Abstract

Les nanoparticules solides en solution selon la présente invention ont un maquillage de composition représenté par la formule PtxM1yM21-x-y (0<x<1, 0<y<1, x+y<1). M1 représente Ru ou Ir. Lorsque M1 représente Ru, M2 représente au moins un élément choisi dans le groupe constitué par Ir, Rh, Ag, Cu et Au. Lorsque M1 représente Ir, M2 représente au moins un élément choisi dans le groupe constitué par Rh, Pd, Ag, Cu et Au. Pt, M1 et M2 forment une solution solide.
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