WO2016136939A1 - Procédé de production d'un catalyseur supporté exempt de matériaux polymères protecteurs - Google Patents

Procédé de production d'un catalyseur supporté exempt de matériaux polymères protecteurs Download PDF

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WO2016136939A1
WO2016136939A1 PCT/JP2016/055792 JP2016055792W WO2016136939A1 WO 2016136939 A1 WO2016136939 A1 WO 2016136939A1 JP 2016055792 W JP2016055792 W JP 2016055792W WO 2016136939 A1 WO2016136939 A1 WO 2016136939A1
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protective material
supported catalyst
ether
polymer protective
producing
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Japanese (ja)
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康平 草田
北川　宏
池田　泰之
丸子　智弘
竹内　正史
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株式会社フルヤ金属
国立大学法人京都大学
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Priority to JP2017502508A priority Critical patent/JP6675614B2/ja
Publication of WO2016136939A1 publication Critical patent/WO2016136939A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—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
    • 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
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a method for producing a polymer protective material-free supported catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material.
  • a heterogeneous catalyst in which nanoparticles are supported on a carbon-based carrier is used.
  • heterogeneous catalysts in which nanoparticles are supported on a ceramic carrier are used.
  • Pd—Ru alloy nanoparticles are disclosed as nanoparticles used for heterogeneous catalysts (see, for example, Patent Document 1 or Non-Patent Document 1).
  • Patent Document 1 when Pd—Ru alloy nanoparticles are supported on a support and used as a heterogeneous catalyst, the nanoparticles were synthesized and purified using a polymer protective material such as polyvinylpyrrolidone. Nanoparticles are supported on a carrier.
  • the polymer protective material used in the synthesis of the nanoparticles remains in the catalyst, the effect of the catalyst may not be fully exhibited. If the purification of the nanoparticles is repeated for the purpose of removing the polymer protective material, the yield of nanoparticles obtained decreases as the number of purification increases.
  • An object of the present invention is to produce a polymer protective material-free supported catalyst capable of fully exhibiting the effect of the catalyst without using a polymer protective material that lowers the performance of the catalyst, more efficiently than conventional methods. Is to provide a method.
  • the method for producing a polymer protective material-free supported catalyst according to the present invention is a method for producing a polymer protective material-free supported catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material, And synthesizing and supporting the nanoparticles on the carrier, wherein the step 1 includes the carrier and an organic solvent having a reducibility of 2 or more carbon atoms, and Step 1a for heating a mixture that does not contain a molecular protective material, Step 1b for producing a mixture that contains a compound as a raw material for synthesizing the nanoparticles and pure water, and does not contain the polymer protective material, and Step 1a And the step 1c of mixing the mixture of step 1b with the mixture of step 1b.
  • the boiling point of the organic solvent is preferably 100 ° C. or higher. Excellent handleability.
  • the supported catalyst can be obtained more safely.
  • the organic solvent is a polyhydric alcohol, butanol, isobutanol, ethoxyethanol, dimethylformamide, xylene, N-methylpyrrolidinone, dichlorobenzene, toluene, propylene glycol.
  • Monomethyl ether ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene Guri Butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol It is preferably at least one selected from dimethyl ether and polyethylene glycol monomethyl ether.
  • the supported catalyst can be obtained more safely and more efficiently.
  • the polyhydric alcohol is preferably at least one selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and butylene glycol.
  • the supported catalyst can be obtained more safely and more efficiently.
  • the support includes one or both of carbon and ceramics.
  • the support is alumina, silica, silica alumina, calcia, magnesia, titania, ceria, zirconia, ceria zirconia, lantana, lantana alumina, tin oxide, oxidation Tungsten, aluminosilicate, aluminophosphate, borosilicate, phosphotungstic acid, hydroxyapatite, hydrotalcite, perovskite, cordierite, mullite, silicon carbide, activated carbon, carbon black, acetylene black, carbon nanotube and carbon nanohorn The form which is 1 or more types is included.
  • the nanoparticles are Pd—Ru alloy particles, Ag—Rh alloy particles, or Au—Rh alloy particles to form a solid solution.
  • a supported catalyst with higher catalytic activity can be obtained.
  • the nanoparticles are Pd—Ru alloy particles, and the compound as a raw material for synthesizing the nanoparticles is Ru chloride and Pd chloride. preferable.
  • a supported catalyst can be obtained more efficiently.
  • the nanoparticles are Ag-Rh alloy particles, and the compound as a raw material for synthesizing the nanoparticles is Ag nitrate and Rh acetate. .
  • the nanoparticles are Au—Rh alloy particles, and the compound as a raw material for synthesizing the nanoparticles is Au chloride and Rh chloride. preferable.
  • the present invention provides a production method capable of obtaining a polymer protective material-free supported catalyst capable of fully exhibiting the effect of the catalyst without using a polymer protective material that lowers the performance of the catalyst more efficiently than the conventional method. Can be provided.
  • Example 1B It is a TEM image of Example 1B. It is an XRD pattern of Example 1B. It is the temperature rising XRD pattern of Example 1B. It is a STEM image of Example 1B. It is an EDS mapping of Example 1B. It is a STEM image of Example 4B. It is an EDS mapping of Example 4B. It is a TEM image of Example 4B. It is a STEM image of Example 5B. It is an EDS mapping of Example 5B. It is a TEM image of Example 5B.
  • a method for producing a polymer protective material-free supported catalyst is a method for producing a polymer protective material-free supported catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material,
  • the method includes a step 1 for supporting nanoparticles on a carrier, and the step 1 includes a carrier and an organic solvent having a reducing property having 2 or more carbon atoms, and a polymer protective material.
  • Step 1a for heating the mixture not to be prepared Step 1b for producing a mixture containing a compound and pure water as a raw material for synthesizing nanoparticles and not containing a polymer protective material, and a mixture of Step 1a and Step 1b And 1c of mixing.
  • the method for producing a supported catalyst according to the present embodiment is, for example, that nanoparticle synthesis is performed without using a polymer protective material, and that nanoparticle synthesis and nanoparticle support are performed simultaneously. This is a point different from the conventional manufacturing method described in Patent Document 1. By not using the polymer protective material, it is possible to produce a supported catalyst that can sufficiently exert the action of the catalyst. In addition, by simultaneously performing the synthesis of the nanoparticles and the loading of the nanoparticles on the carrier, the number of manufacturing steps can be reduced as compared with the conventional manufacturing method.
  • a nanoparticle means the fine particle whose average particle diameter is 100 nm or less.
  • the average particle diameter of the nanoparticles was calculated by measuring the particle diameter of at least 30 particles, more preferably 100 particles or more from the particle image obtained by a transmission electron microscope (TEM), and calculating the average. Value.
  • TEM transmission electron microscope
  • the observation magnification of TEM is not specifically limited, For example, it is preferable that it is 80000 times, 120,000 times, or 150,000 times.
  • the minimum of the average particle diameter of a nanoparticle is not specifically limited, It is preferable that it is 1 nm or more, and it is more preferable that it is 0.5 nm or more.
  • step 1 each substance used in step 1 will be described.
  • the synthetic raw materials are a Ru compound and a Pd compound.
  • the Ru compound is, for example, Ru chloride or Ru nitride.
  • the Pd compound is, for example, Pd chloride or Pd nitride. Of these, the Ru compound and the Pd compound are preferably Ru chloride and Pd chloride.
  • a supported catalyst can be obtained more efficiently.
  • Ru chloride is, for example, ruthenium (III) chloride n hydrate or ruthenium (IV) chloride n hydrate. Further, sodium ruthenate may be used as the Ru compound.
  • Pd chloride is, for example, potassium tetrachloropalladate (II). Further, as the Pd compound, dinitrodiammine palladium (II) may be used.
  • the synthetic raw materials are an Ag compound and an Rh compound.
  • the Ag compound is, for example, Ag nitrate or Ag acetate.
  • the Rh compound is, for example, Rh sulfate, Rh acetate, or Rh nitrate. Among these, it is more preferable that the compound used as the raw material for synthesizing the nanoparticles is Ag nitrate and Rh acetate. A supported catalyst can be obtained more efficiently.
  • the synthetic raw materials are Au compound and Rh compound.
  • the Au compound is, for example, Au chloride or Au nitrate.
  • the Rh compound is, for example, Rh chloride, Rh acetate or Rh nitrate. Among these, it is more preferable that the compound used as the raw material for synthesizing the nanoparticles is Au chloride and Rh chloride.
  • a supported catalyst can be obtained more efficiently.
  • Au chloride is, for example, tetrachloroauric (III) acid tetrahydrate.
  • Rh chloride is, for example, rhodium (III) chloride trihydrate.
  • the support includes a form that is one or both of carbon and ceramics.
  • Ceramics include, for example, alumina, silica, silica alumina, calcia, magnesia, titania, ceria, zirconia, ceria zirconia, lantana, lantana alumina, tin oxide, tungsten oxide, aluminosilicate, aluminophosphate, borosilicate, phosphotungstic acid, hydroxy Apatite, hydrotalcite, perovskite, cordierite, mullite or silicon carbide.
  • the carbon is, for example, activated carbon, carbon black, acetylene black, carbon nanotube, or carbon nanohorn.
  • only 1 type may be used from these support bodies, or 2 or more types may be used together.
  • two or more types are used in combination, two or more types from ceramics may be used in combination, two or more types from carbon may be used in combination, or one or more types from ceramics and one or more types from carbon may be used in combination.
  • at least one selected from alumina, silica, titania, ceria, zirconia, activated carbon and carbon black is used.
  • Organic solvent has 2 or more carbon atoms and has reducibility. More preferably, the organic solvent has 4 or more carbon atoms.
  • the upper limit of the carbon number of the organic solvent is not particularly limited, but is preferably liquid at room temperature.
  • the boiling point of the organic solvent is preferably 100 ° C. or higher. Excellent handleability. In addition, the supported catalyst can be obtained more safely.
  • the boiling point of the organic solvent is more preferably 160 ° C. or higher.
  • the upper limit of the boiling point of the organic solvent is not particularly limited, it is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, from the viewpoint that the solvent can be more easily removed from the supported catalyst.
  • Organic solvents are polyhydric alcohol, butanol, isobutanol, ethoxyethanol, dimethylformamide, xylene, N-methylpyrrolidinone, dichlorobenzene, toluene, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethyl lactate, Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl Among ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, tri
  • the polyhydric alcohol is preferably at least one selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and butylene glycol. Of these, triethylene glycol is more preferable.
  • the supported catalyst can be obtained more safely and more efficiently.
  • Polymer protective material In this embodiment, a polymer protective material is not used.
  • the polymer protective material is, for example, polyvinyl pyrrolidone (PVP).
  • Step 1 will be described by taking an example in which the nanoparticles are Pd—Ru alloy particles.
  • the nanoparticles are Pd—Ru alloy particles
  • step 1 heats the mixture containing the support and the organic solvent and not containing the polymer protective material.
  • step 1a first, a mixture containing a carrier and an organic solvent and not containing a polymer protective material is prepared.
  • the support is suspended in an organic solvent and then dispersed using, for example, an ultrasonic disperser.
  • the heating method is not particularly limited, and is, for example, an external heating method such as an oil bath, a mantle heater, a block heater or a heat medium circulation jacket, or a microwave irradiation method.
  • the heating temperature is preferably 100 to 300 ° C, more preferably 180 to 230 ° C.
  • a mixture containing a Pd compound, a Ru compound, and pure water and containing no polymer protective material is prepared.
  • the mixture may be a solution in which the Pd compound and the Ru compound are dissolved in pure water, or a dispersion in which the Pd compound and the Ru compound are dispersed in pure water.
  • the mixture is more preferably a solution in which a Pd compound and a Ru compound are dissolved in pure water.
  • the ratio of the Pd compound and the Ru compound is adjusted so that the atomic ratio of Ru and Pd is within a predetermined range in the obtained Pd—Ru alloy particles. It is particularly preferable that Ru: Pd is in the range of 0.1: 0.9 to 0.9: 0.1 in atomic ratio.
  • the atomic ratio of the alloy can be measured by, for example, high frequency inductively coupled plasma emission spectrometry or atomic absorption spectrophotometry.
  • step 1c the mixture of step 1a and the mixture of step 1b are mixed while the mixture of step 1a is kept at the heating temperature described above.
  • the mixing method is not particularly limited, but is preferably a method in which the mixture of step 1b is sprayed onto the mixture of step 1a.
  • step 1c it is preferable to maintain the heated state after mixing the mixture of step 1a and the mixture of step 1b.
  • the time during which the heated state is maintained after mixing the entire amount of the mixed solution is preferably 5 to 60 minutes, and more preferably 10 to 30 minutes.
  • the ratio between the total amount of the Ru compound and the Pd compound and the amount of the support is adjusted so that the supported amount of the Pd—Ru alloy particles in the supported catalyst falls within a predetermined range.
  • the supported amount of Pd—Ru alloy particles in the supported catalyst is preferably 0.001 to 60% by mass.
  • the supported amount is the ratio of the mass of the nanoparticles to the mass of the supported catalyst in the dry state, and can be measured by, for example, high frequency inductively coupled plasma emission spectrometry or atomic absorption spectrophotometry.
  • step 1 the Ru compound and the Pd compound are reduced by an organic solvent, and nucleation and grain growth of Pd—Ru alloy particles occur on the surface of the support.
  • a supported catalyst in which Pd—Ru alloy particles are supported on a support is obtained.
  • the Ru content in the Pd—Ru alloy particles is 10 to 90 atomic%, a solid solution of the Pd—Ru alloy is not formed, but in this embodiment, a solid solution of the Pd—Ru alloy can be formed. Since the Pd—Ru alloy particles form a solid solution, the catalytic activity is further increased. More preferably, the Pd—Ru alloy particles form a solid solution single phase.
  • the state of the Pd—Ru alloy particles can be confirmed, for example, by elemental mapping of energy dispersive X-ray fluorescence (EDS) using scanning transmission electron microscopy (STEM).
  • EDS energy dispersive X-ray fluorescence
  • STEM scanning transmission electron microscopy
  • the average particle diameter of the Pd—Ru alloy particles is preferably 30 nm or less, and more preferably 20 nm or less.
  • the lower limit of the average particle diameter of the Pd—Ru alloy particles is not particularly limited, but is preferably 1 nm or more.
  • the average particle diameter of the Ag—Rh alloy particles is preferably 20 nm or less, and more preferably 10 nm or less.
  • the lower limit of the average particle diameter of the Ag—Rh alloy particles is not particularly limited, but is preferably 0.5 nm or more.
  • the average particle diameter of the Au—Rh alloy particles is preferably 20 nm or less, and more preferably 10 nm or less.
  • the lower limit of the average particle diameter of the Au—Rh alloy particles is not particularly limited, but is preferably 0.5 nm or more.
  • the method for separating and purifying the supported catalyst is not particularly limited.
  • the method is a method of filtering, washing and drying a mixture having a lowered temperature.
  • XRD pattern X-ray diffraction pattern
  • Example 1B 50 mL of pure water was charged into the flask. Ruthenium (III) chloride n hydrate (hereinafter RuCl 3 ⁇ nH 2 O) 0.1177 g and potassium tetrachloropalladate (II) (hereinafter K 2 PdCl 4 ) 0.1635 g were weighed and the pure An aqueous solution dissolved in water was prepared. No polymer protective material was added to the aqueous solution. Further, 1.15 g of activated carbon (FAM-50, manufactured by Nippon Enviro Chemicals) was weighed and added to 100 mL of triethylene glycol (hereinafter referred to as TEG), and dispersed with an ultrasonic wave to prepare a mixed solution.
  • RuCl 3 ⁇ nH 2 O 0.1177 g
  • potassium tetrachloropalladate (II) hereinafter K 2 PdCl 4
  • the polymer protective material was not added to the mixed solution.
  • This mixed solution was heated to 205 ° C., and the aqueous solution was added in the form of a mist under the condition that the temperature of the mixed solution was maintained at 200 ° C. or higher.
  • the entire amount of the aqueous solution was heated and held for 15 minutes after the addition was completed, and then cooled.
  • the cooled mixture was filtered under reduced pressure, and the solid component (filtrate) was thoroughly washed with H 2 O and ethanol and then dried under reduced pressure to obtain the target Pd—Ru alloy-supported catalyst.
  • Example 2B 50 mL of pure water was charged into the flask. An aqueous solution in which 0.0582 g of RuCl 3 ⁇ nH 2 O and 0.0779 g of K 2 PdCl 4 were weighed and dissolved in the pure water was prepared. No polymer protective material was added to the aqueous solution. Further, 0.959 g of activated carbon (FAM-50) was weighed and added to 100 mL of TEG, and dispersed with ultrasonic waves to prepare a mixed solution. The polymer protective material was not added to the mixed solution.
  • FAM-50 activated carbon
  • This mixed solution was heated to 205 ° C., and the aqueous solution was added in the form of a mist under the condition that the temperature of the mixed solution was maintained at 200 ° C. or higher. The whole amount of the aqueous solution was kept heated for 15 minutes after the addition was completed, and then cooled. The solid component is precipitated from the cooled mixed solution using centrifugal separation, the supernatant is removed, the solid component is thoroughly washed with H 2 O and ethanol, and then dried under reduced pressure to carry the target Pd—Ru alloy. A catalyst was obtained.
  • Example 3B 50 mL of pure water was charged into the flask. An aqueous solution in which 0.3535 g of RuCl 3 .nH 2 O and 0.4917 g of K 2 PdCl 4 were weighed and dissolved in the pure water was prepared. No polymer protective material was added to the aqueous solution. In addition, 0.7023 g of Ketjen Black (EC300J, manufactured by Lion Corporation) was weighed and added to 100 mL of TEG, and dispersed with ultrasonic waves to prepare a mixed solution. The polymer protective material was not added to the mixed solution.
  • Ketjen Black EC300J, manufactured by Lion Corporation
  • This mixed solution was heated to 205 ° C., and the aqueous solution was added in the form of a mist under the condition that the temperature of the mixed solution was maintained at 200 ° C. or higher. The entire amount of the aqueous solution was heated and held for 15 minutes after the addition was completed, and then cooled. The solid component is precipitated from the cooled mixed solution using centrifugal separation, the supernatant is removed, the solid component is thoroughly washed with H 2 O and ethanol, and then dried under reduced pressure to carry the target Pd—Ru alloy. A catalyst was obtained.
  • Example 1B Average particle diameter of Pd—Ru alloy particles
  • the supported catalyst of Example 1B was observed with a TEM at a magnification of 150,000 times, the particle diameter of 100 particles was measured from the obtained particle image, the average was obtained, and the TEM image of Example 1B is shown in FIG.
  • the average particle size of Example 1B was 6.71 nm. Further, from FIG. 1, the presence of aggregated particles was not confirmed.
  • Example 1B (Alloy state) The supported catalyst of Example 1B was subjected to XRD measurement and elevated temperature XRD measurement.
  • FIG. 2 shows the XRD pattern of Example 1B.
  • FIG. 3 shows the temperature rise XRD pattern of Example 1B. 2 and 3, it was confirmed that Pd—Ru alloy nanoparticles were synthesized.
  • STEM measurement was performed on the supported catalyst of Example 1B.
  • FIG. 4 shows an STEM image of Example 1B
  • FIG. 5 shows an EDS mapping of Example 1B. From FIG.
  • FIG. 5 shows that particles in which Pd and Ru are mixed at a mixing ratio exceeding the solid solution limit of Pd and Ru are formed, and that the Pd—Ru alloy forms a solid solution.
  • FIG. 5 shows an image in which element mapping is processed to gray gradation, but element mapping is more accurately expressed by a color image before processing in gray tone.
  • Example 4B 40 mL of pure water was charged into the flask.
  • An aqueous solution was prepared by weighing 0.0852 g of Ag (NO 3 ) and 0.1402 g of Rh (CH 3 COOH) 3 and adding them to the pure water to dissolve them. No polymer protective material was added to the aqueous solution.
  • 5.2670 g of alumina manufactured by Sasol North America was weighed and added to 300 mL of ethylene glycol (hereinafter referred to as EG), and dispersed with ultrasonic waves to prepare a mixed solution. The polymer protective material was not added to the mixed solution.
  • This mixed solution was heated to 180 ° C., and the aqueous solution was added in the form of a mist under the condition that the temperature of the mixed solution was maintained at 175 ° C. or higher. The entire amount of the aqueous solution was heated and held for 10 minutes after the addition was completed, and then cooled. The solid component is precipitated from the mixture after cooling by centrifugation and the supernatant is removed. The solid component is thoroughly washed with H 2 O and ethanol and then dried under reduced pressure to carry the target Ag-Rh alloy. A catalyst was obtained.
  • FIG. 6 shows an STEM image of Example 4B
  • FIG. 7 shows an EDS mapping of Example 4B. From FIG. 6, it was confirmed that Ag—Rh alloy particles were formed on the support. Further, FIG. 7 shows that Ag and Rh mixed particles are formed at a mixing ratio exceeding the solid solution limit of Ag and Rh, and that the Ag—Rh alloy forms a solid solution. Was confirmed.
  • FIG. 7 shows an image obtained by processing element mapping to gray gradation, the element mapping is more accurately expressed by a color image before processing gray.
  • Example 4B Particle diameter of Ag-Rh alloy particles
  • the supported catalyst of Example 4B was observed with a TEM at a magnification of 120,000 times, 30 particle diameters were measured from the obtained particle images, the average was obtained, and the TEM image of Example 4B is shown in FIG.
  • the average particle size of Example 4B was 8.11 nm. Moreover, the presence of aggregated particles was not confirmed from FIG.
  • Example 5B 20 mL of pure water was charged into the flask. An aqueous solution was prepared by weighing out 0.0214 g of HAuCl 4 .4H 2 O and 0.0144 g of RhCl 3 .3H 2 O and adding them to the pure water to dissolve them. No polymer protective material was added to the aqueous solution. Further, 0.7301 g of alumina (PURALOX SCFa140 / L3 Sasol) was weighed out and added to 200 mL of EG, and a mixed liquid dispersed with ultrasonic waves was prepared. The polymer protective material was not added to the mixed solution.
  • alumina PRALOX SCFa140 / L3 Sasol
  • This mixed solution was heated to 180 ° C., and the aqueous solution was added in the form of a mist under the condition that the temperature of the mixed solution was maintained at 175 ° C. or higher. The entire amount of the aqueous solution was heated and held for 10 minutes after the addition was completed, and then cooled. The solid component is precipitated from the cooled mixed solution using centrifugation and the supernatant is removed. The solid component is thoroughly washed with H 2 O and ethanol and then dried under reduced pressure to carry the target Au—Rh alloy. A catalyst was obtained.
  • FIG. 9 shows an STEM image of Example 5B
  • FIG. 10 shows an EDS mapping of Example 5B. From FIG. 9, it was confirmed that Au—Rh alloy particles were formed on the support.
  • FIG. 10 also shows that Au and Rh mixed particles are formed at a mixing ratio exceeding the solid solution limit of Au and Rh, and that the Au—Rh alloy forms a solid solution.
  • FIG. 10 shows an image in which element mapping is processed to gray gradation, but element mapping is more accurately expressed by a color image before processing in gray tone.
  • Example 5B Particle diameter of Au-Rh alloy particles
  • the supported catalyst of Example 5B was observed with a TEM at a magnification of 80000 times, 30 particle diameters were measured from the obtained particle images, the average was obtained, and the TEM image of Example 5B is shown in FIG.
  • the average particle size of Example 5B was 5.54 nm. Moreover, the presence of aggregated particles was not confirmed from FIG.

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Abstract

L'objectif de la présente invention est de proposer un procédé de production qui permet d'obtenir, de manière plus efficace que par des procédés classiques, un catalyseur supporté exempt de matériaux polymères protecteurs et qui présente un effet catalyseur suffisant sans recours à des matériaux polymères protecteurs qui ont pour effet de faire baisser les performances du catalyseur. Ce procédé de production d'un catalyseur supporté exempt de matériaux polymères protecteurs et qui comprend des nanoparticules supportées sur un support, mais pas de matériaux polymères protecteurs, comprend une étape 1 au cours de laquelle des nanoparticules sont synthétisées et amenées à être supportées sur le support, l'étape 1 comprenant : une étape 1a de chauffage d'un mélange contenant un support et un solvant organique réducteur comportant au moins 2 atomes de carbone, mais pas de matériaux polymères protecteurs ; une étape 1b de production d'un mélange contenant de l'eau pure et un composé servant de matériau de départ pour la synthèse des nanoparticules et qui ne contient pas de matériaux polymères protecteurs ; et une étape 1c de mélange du mélange de l'étape 1a et du mélange de l'étape 1b.
PCT/JP2016/055792 2015-02-28 2016-02-26 Procédé de production d'un catalyseur supporté exempt de matériaux polymères protecteurs WO2016136939A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN108854576A (zh) * 2018-07-31 2018-11-23 哈工大（威海）创新创业园有限责任公司 一种环保的生物相容多孔膜及其制备方法

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JPH01307445A (ja) * 1988-06-02 1989-12-12 Matsushita Electric Ind Co Ltd 触媒調整法
JP2004121983A (ja) * 2002-10-02 2004-04-22 Ishifuku Metal Ind Co Ltd 白金−ルテニウム合金担持触媒の製造方法
WO2010122811A1 (fr) * 2009-04-24 2010-10-28 独立行政法人科学技術振興機構 Particules fines d'alliage à l'état de solution solide et leur procédé de production
US20110065025A1 (en) * 2009-08-10 2011-03-17 Korea University Research And Business Foundation Process of preparing pt/support or pt alloy/support catalyst, thus-prepared catalyst and fuel cell comprising the same
WO2012013940A2 (fr) * 2010-07-29 2012-02-02 Isis Innovation Limited Catalyseurs pour la génération d'hydrogène et piles à combustible
WO2013038674A1 (fr) * 2011-09-16 2013-03-21 独立行政法人科学技術振興機構 Microparticules de ruthénium ayant une structure sensiblement cubique à faces centrées et son procédé de fabrication
WO2014045570A1 (fr) * 2012-09-18 2014-03-27 独立行政法人科学技術振興機構 Catalyseur utilisant des particules d'alliage de type solution solide de pd-ru

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01307445A (ja) * 1988-06-02 1989-12-12 Matsushita Electric Ind Co Ltd 触媒調整法
JP2004121983A (ja) * 2002-10-02 2004-04-22 Ishifuku Metal Ind Co Ltd 白金−ルテニウム合金担持触媒の製造方法
WO2010122811A1 (fr) * 2009-04-24 2010-10-28 独立行政法人科学技術振興機構 Particules fines d'alliage à l'état de solution solide et leur procédé de production
US20110065025A1 (en) * 2009-08-10 2011-03-17 Korea University Research And Business Foundation Process of preparing pt/support or pt alloy/support catalyst, thus-prepared catalyst and fuel cell comprising the same
WO2012013940A2 (fr) * 2010-07-29 2012-02-02 Isis Innovation Limited Catalyseurs pour la génération d'hydrogène et piles à combustible
WO2013038674A1 (fr) * 2011-09-16 2013-03-21 独立行政法人科学技術振興機構 Microparticules de ruthénium ayant une structure sensiblement cubique à faces centrées et son procédé de fabrication
WO2014045570A1 (fr) * 2012-09-18 2014-03-27 独立行政法人科学技術振興機構 Catalyseur utilisant des particules d'alliage de type solution solide de pd-ru

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108854576A (zh) * 2018-07-31 2018-11-23 哈工大（威海）创新创业园有限责任公司 一种环保的生物相容多孔膜及其制备方法

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