WO2014025049A1 - Matériau composite d'alliage de type à solution solide du groupe du fer supporté par un support solide et catalyseur le mettant en œuvre - Google Patents

Matériau composite d'alliage de type à solution solide du groupe du fer supporté par un support solide et catalyseur le mettant en œuvre Download PDF

Info

Publication number
WO2014025049A1
WO2014025049A1 PCT/JP2013/071735 JP2013071735W WO2014025049A1 WO 2014025049 A1 WO2014025049 A1 WO 2014025049A1 JP 2013071735 W JP2013071735 W JP 2013071735W WO 2014025049 A1 WO2014025049 A1 WO 2014025049A1
Authority
WO
WIPO (PCT)
Prior art keywords
iron group
metal
group metal
catalyst
iron
Prior art date
Application number
PCT/JP2013/071735
Other languages
English (en)
Japanese (ja)
Inventor
山内　美穂
Original Assignee
国立大学法人九州大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人九州大学 filed Critical 国立大学法人九州大学
Priority to JP2014529587A priority Critical patent/JP6230126B2/ja
Publication of WO2014025049A1 publication Critical patent/WO2014025049A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/862—Iron and chromium
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a solid support-supported iron group solid solution type alloy composite and a catalyst using the same.
  • a fuel cell directly converts chemical energy into electrical energy by supplying fuel and an oxidant (mainly oxygen) to two electrically connected electrodes and electrochemically oxidizing the fuel. Therefore, the fuel cell exhibits high energy conversion efficiency.
  • a fuel cell generally has a basic structure of a membrane / electrode assembly in which an electrolyte membrane is sandwiched between a pair of electrodes. There are alkaline fuel cells using an anion conductive solid polymer electrolyte membrane as an electrolyte membrane and proton fuel cells using a proton conductive solid polymer electrolyte membrane.
  • Electrons generated in Equation (1) reach the oxygen electrode after working with an external load via an external circuit.
  • the hydroxide ions generated in the formula (2) move from the oxygen electrode side to the fuel electrode side in the solid polymer electrolyte membrane.
  • the water produced by the formula (1) mainly passes through the gas diffusion layer and is discharged to the outside, or permeates the solid polymer electrolyte membrane from the fuel electrode to the oxygen electrode, and the formula (2 ).
  • a direct methanol fuel cell is a typical example. As its name suggests, direct methanol fuel cells react methanol directly at the fuel electrode without producing hydrogen from methanol in the fuel reformer. The cell reaction of a direct methanol fuel cell is shown.
  • the electrode reaction in the fuel cell uses a catalyst for promoting the reaction in both the fuel electrode and the oxygen electrode.
  • a catalyst for electrode reaction of a fuel cell a noble metal such as platinum is mainly used.
  • noble metal catalysts represented by platinum have limited reserves and are relatively expensive.
  • a candidate for a new catalyst material that can replace the noble metal catalyst is an iron group metal.
  • a fuel cell catalyst containing platinum as a main component and further containing nickel and iron is known (Patent Document 1).
  • a catalyst using an iron group metal is known as a catalyst other than a catalyst for an electrode of a fuel cell.
  • a catalyst for Fischer-Tropsch reaction for the production of soft olefins (Patent Document 2)
  • a fuel cell electrode catalyst there is no known fuel cell catalyst composed of only an iron group metal and having a catalytic performance at a practical level.
  • An iron group metal is inexpensive, but a catalyst made only of an iron group metal or a catalyst mainly composed of an iron group metal has lower performance than a noble metal catalyst.
  • a first object of the present invention is to provide a catalyst made of only an iron group metal or a catalyst containing an iron group metal as a main component, which has improved catalyst characteristics as a catalyst for an electrode of a fuel cell.
  • a second object of the present invention is to provide a catalyst composed of only an iron group metal or a catalyst mainly composed of an iron group metal, which has an improved CO (carbon monoxide) conversion rate as a Fischer-Tropsch reaction catalyst. That is.
  • the present inventors considered as follows.
  • One method for improving the chemical reactivity of the base metal is to form an alloy.
  • a new energy (band) state and Fermi energy (chemical potential) are formed.
  • the catalytic properties change greatly depending on the position of the center of gravity of the d-band (d-band center).
  • d-band center By adapting the position of the d-band to the target reaction, a highly active catalyst can be obtained. May be obtained.
  • the present invention from the above viewpoint, a technique capable of producing an iron group alloy in which component metals are dissolved at an atomic level is developed, and the obtained alloy is used as a fuel cell electrode catalyst and a Fischer-Tropsch reaction catalyst.
  • the present invention was completed by finding that the catalytic reaction activity and reaction selectivity were improved.
  • a composite comprising a solid support and any one of the following iron group metal-based alloy particles supported on the solid support (a) to (d).
  • the solid support is a carbon-based material or an inorganic material, and contains particles having a diameter in the range of 1 nm to 10 ⁇ m.
  • a catalyst for a solid oxide alkaline fuel cell comprising the composite according to any one of [4].
  • a Fischer comprising the composite according to any one of the above (except for the composite in which the iron group metal alloy particles are iron group metal alloy particles composed of Fe and Co). ⁇ Tropsch reaction catalyst.
  • Iron group metal-containing compounds where the iron group metal is selected from the group of iron group metals consisting of Fe, Co and Ni
  • transition metal-containing compounds where the transition metals are Cr, Mn, Cu, Mo, Ru, Rh
  • precursor particles containing at least two kinds of metals selected from the group consisting of iron group metals and transition metals and a solid support are obtained.
  • Step (2) of preparing, and heating the precursor particles in a hydrogen-containing atmosphere to reduce the precursor particles, so that at least two metal alloy particles selected from the group consisting of iron group metals and transition metals A production method comprising a step (3) of obtaining a composite supported on a solid support.
  • the at least two compounds used in step (1) are two or three iron group metal-containing compounds, or one or more iron group metal-containing compounds and one or more transition metals.
  • the alkaline fuel cell catalyst to be used can be provided.
  • a catalyst for the Fischer-Tropsch reaction a catalyst composed of only an iron group metal or an iron group metal having improved CO (carbon monoxide) conversion rate and selectivity to an olefin is a main component.
  • a composite capable of providing a catalyst and a catalyst for a Fischer-Tropsch reaction using the composite can be provided.
  • Example 1 According to (a) the conventional (impregnation) method (after 900 ° C. heat treatment) prepared in Reference Example 1, and (b) the present invention (after 900 ° C. heat treatment) obtained in Example 1-1.
  • the TEM image of the prepared Fe-based alloy nanoalloy supported catalyst is shown. 3 shows powder XRD patterns of FexCoyNi (1-x-y) / C obtained in Examples 1-1 to 4. Shows a STEM-EDS (elemental map) image of Fe 50 Co 50 / C precursor obtained in Example 1-2 (a) and the nano-alloy catalyst (b).
  • 1 shows a TEM image (Test Example 4) of a binary nano-alloy (RT to 1000 ° C., 10 K / min, 10 min Keep, N 2 ).
  • Example 3 shows a TEM image (Test Example 4) of metal nanoparticles.
  • the direct glycol inorganic alkaline battery power generation characteristics (Test Example 5) using FexCoyNi (100-xy) / C / as an anode catalyst are shown.
  • the powder XRD pattern (overall image) of Fe33Co33Ni33 / C. Co50Ni50 / C, Fe50Co50 / C, and Fe50Ni50 / C produced in Example 2-1 is shown.
  • the element mapping by STEM-HAADF and EDS of Fe33Co33Ni33 / C of Table 1 produced in Example 2-1 and the result of the one-dimensional analysis are shown. (There are twins and stacking faults in the particles. The particles are covered with an oxide film.
  • Example 2 shows an ASF distribution (an ASF model in an FT reaction) that probabilistically predicts the product distribution obtained by the FT reaction used in Example 3.
  • the product distribution in the FT reaction after 16 hours on Fe50Co50 / Al2O3 obtained in Example 3 is shown.
  • the olefin and paraffin selectivity in the C3-C5 compound in the FT reaction on Fe50Co50 / Al2O3 obtained in Example 3 is shown.
  • the present invention relates to a composite comprising a solid support and any one of the following iron group metal alloy particles (a) to (d) supported on the solid support.
  • the iron group metal alloy particles of (a) are iron group metals composed of two or three kinds of iron group metals selected from the group consisting of Fe, Co and Ni. Based alloy particles. However, the iron group metal alloy is a solid solution type alloy of the two or three kinds of iron group metals. In the present specification, the iron group metal group means a group consisting of Fe, Co and Ni. Fe, Co, and Ni are expressed in atomic% (in the present specification, unless otherwise specified,% with respect to the alloy composition means atomic%) and are contained in the range of 0 to 99%. However, the total of Fe, Co, and Ni is 100 atomic%, and at least two of Fe, Co, and Ni have a content exceeding 0.1 atomic%.
  • Fe, C and Ni are expressed in atomic%, preferably each in the range of 0.01 to 99.99%, more preferably in the range of 1 to 99%, still more preferably in the range of 5 to 95%, and still more preferably each. It is contained in the range of 10 to 90%, still more preferably in the range of 20 to 80%, and still more preferably in the range of 30 to 70%.
  • the iron group metal alloy particles (a) are composed of four types of alloy particles of Fe—Co, Fe—Ni, Co—Ni, and Fe—Co—Ni.
  • the Fe: Co atomic% ratio ranges from 0.1 to 99.9: 99.9 to 0.1, preferably from 1 to 99:99 to 1, more preferably from 10 to 90:90 to 10, and Preferably in the range of 20-80: 80-20, more preferably in the range of 30-70: 70-30, even more preferably in the range of 40-60: 60-40, even more preferably 45-55: 55-45. Range.
  • the Fe: Co atomic% ratio can be appropriately determined in consideration of product distribution, power density, and current efficiency.
  • the Fe: Ni atomic% ratio ranges from 0.1 to 99.9: 99.9 to 0.1, preferably from 1 to 99:99 to 1, more preferably from 10 to 90:90 to 10, and Preferably in the range of 20-80: 80-20, more preferably in the range of 30-70: 70-30, even more preferably in the range of 40-60: 60-40, even more preferably 45-55: 55-45. Range.
  • the Fe: Ni atomic% ratio can be appropriately determined in consideration of product distribution, power density, current efficiency, and life.
  • the Fe: Ni atomic% ratio can be appropriately determined in consideration of the conversion rate of raw materials, the selectivity of products, and the yield.
  • the Co: Ni atomic% ratio is in the range of 0.1 to 99.9: 99.9 to 0.1, preferably in the range of 1 to 99:99 to 1, more preferably in the range of 10 to 90:90 to 10, and Preferably in the range of 20-80: 80-20, more preferably in the range of 30-70: 70-30, even more preferably in the range of 40-60: 60-40, even more preferably 45-55: 55-45. Range.
  • the Co: Ni atomic% ratio can be appropriately determined in consideration of product distribution, power density, current efficiency, and lifetime.
  • the Co: Ni atomic% ratio can be appropriately determined in consideration of the conversion rate of raw materials, the selectivity of products, and the yield.
  • the Fe: Co: Ni atomic% ratio can be in the range of 0.01 to 999 when Fe is 1, and Ni can be in the range of 0.01 to 999. .
  • the total of the three elements is 100 atomic%.
  • Co is preferably in the range of 0.05 to 99.95, more preferably in the range of 0.1 to 99.9, and still more preferably in the range of 0.5 to 99.5.
  • Ni can be preferably in the range of 0.05 to 99.95, more preferably in the range of 0.1 to 99.9, and still more preferably in the range of 0.5 to 99.9.
  • the Fe: Co: Ni atomic% ratio when used as an electrode catalyst for a fuel cell, can be appropriately determined in consideration of product distribution, power density, current efficiency, and lifetime.
  • the Fe: Co: Ni atomic% ratio when used as a Fischer-Tropsch reaction catalyst, can be appropriately determined in consideration of the conversion rate of raw materials, the selectivity of products, and the yield.
  • Iron group metal alloy particles contain two or three iron group metals selected from the iron group metal group consisting of Fe, Co and Ni. Metal alloy particles.
  • the iron group metal-based alloy is a solid solution type alloy in which at least the two or three kinds of iron group metals are used.
  • the iron group metal-based alloy particles of (b) are described later (c) and ( Additional components other than the transition metal contained in the iron group metal alloy particles of d) may be contained within a range that does not affect the catalyst performance of the iron group metal alloy particles of (b).
  • additional components examples include Al, Zn, V, W, Ta, Y, Re, and Bi.
  • the content of the additional component is not particularly limited, but considering that it does not affect the catalytic performance of the iron group metal alloy particles of (b), it is less than 1%, preferably 0.5%. It is suitable that it is less than.
  • about the part which consists of 2 or 3 types of iron group metals chosen from the iron group metal group which consists of Fe, Co, and Ni it is the same as that of the iron group metal alloy of the iron group metal alloy particle of (a). .
  • the iron group metal alloy particles of (c) are one, two or three kinds of iron group metals selected from the group of iron group metals consisting of Fe, Co and Ni, and These are iron group metal alloy particles composed of one or more transition metals selected from the group of transition metals composed of Cr, Mn, Cu, Mo, Ru, Rh, Pd, Ag, Ir, Pt and Au.
  • the transition metal group means a group consisting of Cr, Mn, Cu, Mo, Ru, Rh, Pd, Ag, Ir, Pt and Au.
  • the said iron group metal-type alloy is a solid solution type alloy in which the said 1 type, 2 type, or 3 type iron group metal and 1 type, or 2 or more types of transition metal are.
  • the iron group metal alloy particles (c) are iron group metal alloy particles composed of one, two or three kinds of iron group metals and one or more kinds of transition metals.
  • any one of iron group metals Fe, Co, and Ni and iron group metal alloy particles composed of one or more transition metals, Fe and Co, Fe and Ni, or Co and Ni and 1 are iron group metal alloy particles composed of seeds or two or more transition metals, and iron group metal alloy particles composed of Fe, Co, and Ni and one or more transition metals.
  • the contents of iron group metals and transition metals are each in the range of 0.1 to 99.9%. However, the total of iron group metals and transition metals is 100 atomic%.
  • the content of iron group metal and transition metal is preferably in the range of 1 to 99%, more preferably in the range of 5 to 95%, and still more preferably in the range of 10 to 90%. More preferably, each is in the range of 20 to 80%, still more preferably in the range of 30 to 70%, and still more preferably in the range of 40 to 60%.
  • the atoms of the iron group metal and transition metal when used as a catalyst for fuel cell electrodes, the atoms of the iron group metal and transition metal are considered in consideration of product distribution, power density, current efficiency and life.
  • The% ratio can be determined as appropriate.
  • the atomic% ratio of the iron group metal and the transition metal can be appropriately determined in consideration of the conversion rate of the raw material, the selectivity of the product, and the yield.
  • the combination and content ratio of the iron group metals in the iron group metal alloy particles (a) can be referred to.
  • the transition metal combination and content ratio can be appropriately determined in consideration of the crystal structure and solid solution state of the alloy and its catalytic properties.
  • the iron group metal alloy particles of (d) are one, two or three types of iron group metals selected from the group of iron group metals consisting of Fe, Co and Ni, and These are iron group metal alloy particles containing one or more transition metals selected from the group of transition metals consisting of Cr, Mn, Cu, Mo, Ru, Rh, Pd, Ag, Ir, Pt and Au.
  • the iron group metal alloy is a solid solution type alloy in which at least one, two or three kinds of iron group metals and one or more kinds of transition metals are used.
  • the iron group metal alloy particles of (d) contain one or more transition metals selected from the two or three types of iron group metals selected from the iron group metal group and the transition metal group.
  • an additional component other than the iron group metal and the transition metal can be contained in a range that does not affect the catalyst performance of the iron group metal alloy particles of (d).
  • additional components include Al, Zn, V, W, Ta, Y, Re, Bi, and the like.
  • the content of the additional component is not particularly limited, but considering that it does not affect the catalytic performance of the iron group metal alloy particles of (d), it is less than 1%, preferably 0.5%. It is suitable that it is less than.
  • the iron group metal alloy particle of (c) This is the same as the iron group metal alloy.
  • iron group metal alloy particles (a) two or three iron group metals are solid solution type alloys.
  • iron group metal alloy particles of (b) at least two or three kinds of iron group metals are solid solution type alloys, and may be a solid solution type alloy together with the iron group metals including additional components.
  • iron group metal alloy particles (c) one, two or three iron group metals and one or more transition metals are solid solution type alloys.
  • iron group metal alloy particles of (d) at least one, two or three kinds of iron group metals and one or more kinds of transition metals are solid solution type alloys, and iron groups including additional components are included. It can be a solid solution type alloy together with a metal.
  • the solid solution type alloy means that the metal atoms constituting the alloy are present uniformly in the alloy particles.
  • the iron group alloy catalyst in which the component metals of the present invention are dissolved at the atomic level is made to be an iron group alloy particle having a small particle size at the nano level, thereby further improving the catalytic reaction activity and reaction selectivity.
  • the atomic level means that at least one iron group metal atom bonded to a different metal atom exists in a volume of 16.7 nm 3 of one alloy particle.
  • the different metal atom is an iron group metal atom different from the iron group metal atom, the transition metal atom, or an iron group metal atom different from the iron group metal atom and the transition metal atom.
  • the different metal atom is an iron group metal atom different from the iron group metal atom or an additional component metal atom.
  • the different metal atom is an iron group metal atom or a transition metal atom different from the iron group metal atom.
  • the different metal atom is an iron group metal atom or transition metal atom different from the iron group metal atom, or is an additional component metal atom.
  • the number of iron group metal atoms bonded to different metal atoms present in a volume of 16.7 nm 3 of one alloy particle is in proportion to the alloy composition.
  • the iron group metal alloy particles are preferably alloy particles having a particle volume of 16.7 nm 3 or more and 10,466.7 nm 3 or less from the viewpoint that they can be used as a highly active catalyst.
  • Viewpoint volume one particle is preferably 20 nm 3 or more 5,000 nm 3 or less, more preferably 50 nm 3 or more 1,000 nm 3 or less, still more preferably used as a catalyst is highly active is at 50 nm 3 or more 1,000 nm 3 or less To preferred.
  • any alloy particles containing at least 10% by mass or more of alloy particles having a volume within the above range may be supported on a solid support.
  • the loading amount of the alloy particles having a volume within the above range on the solid support is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and more preferably 90% by mass or more. It is.
  • the composite of the present invention comprises a solid support and any one of iron group metal alloy particles (a) to (d) supported on the solid support.
  • the solid carrier can be appropriately selected from materials that can exhibit suitable activity and durability when the composite of the present invention is used as various catalysts.
  • the solid support used in the composite of the present invention is preferably at least partially made of a porous material, and it is appropriate that iron group metal alloy particles are supported on the surface of the porous material. Therefore, it is appropriate for the solid support used in the composite of the present invention that at least the surface of the portion on which the iron group metal alloy particles are supported is made of a porous material, and the entire solid support is made of a porous material.
  • the surface of a support made of a non-porous material may be coated with a porous material.
  • the support may be made of another porous material.
  • the solid support used in the composite of the present invention can be at least partially made of, for example, a carbon-based material or an inorganic material.
  • the carbon-based material include activated carbon and carbon nanotubes.
  • An inorganic oxide material can be mentioned as an inorganic material.
  • the inorganic oxide material include silica, alumina, silica-alumina, zeolite, titania, zirconia and the like.
  • the solid support preferably has a large surface area, for example, a specific surface area of 500 to 2000 m 2 / g is preferred.
  • the shape and form of the solid carrier are not particularly limited, and can be, for example, powder, particle, granule, pellet, honeycomb or the like.
  • the carrier in the form of powder, particles, granules, or pellets can be composed of, for example, only the above-mentioned porous material carrier material.
  • the carrier having a honeycomb structure may be a non-porous material, for example, a surface of a support made of cordierite or the like and coated with the porous material carrier material. Further, as described above, the support may be made of another porous material.
  • the solid carrier When the shape of the solid carrier is, for example, powder, particle or granule, the solid carrier suitably contains particles having a diameter in the range of 1 nm to 10 ⁇ m, and the diameter is in the range of 10 nm to 10 ⁇ m. It is preferable to contain particles, and it is more preferable to contain particles having a diameter in the range of 10 nm to 500 ⁇ m.
  • the particle size of the solid support can be appropriately selected according to the use of the composite of the present invention.
  • the amount of iron group metal alloy particles supported on the solid support can be appropriately determined in consideration of the type of iron group metal alloy particles, the type of solid support, the use of the composite, and the like.
  • the supported amount of iron group metal-based alloy particles can be in the range of 0.01 to 50 with respect to the solid support 100 in terms of mass ratio.
  • the amount of iron group metal alloy particles supported on the solid support 100 is 0.1. It is preferably in the range of ⁇ 30, more preferably in the range of 0.5-15, and even more preferably in the range of 1-10. However, it is not intended to be limited to this range.
  • the composite of the present invention can be produced by a method including steps (1) to (3).
  • a solution in which a water-soluble polymer is mixed as an inhibitor of the aggregation of iron group metal ions and / or transition metal ions and particles is used. It is expected that the iron group metal ions and / or transition metal ions interact with the polymer to suppress aggregation between the same type of metals.
  • a reducing agent was added to this mixed solution to reduce it to a metal once, and it was re-oxidized as it was, thereby mixing the iron group metal and its oxide and / or transition metal or transition metal oxide with a water-soluble polymer.
  • a nanoalloy precursor is prepared.
  • the precursor Even in the precursor, solid solution (mixing) of metal ions at the atomic level is maintained. Furthermore, by heating the precursor in a hydrogen atmosphere, it becomes possible to simultaneously reduce the constituent metal ions, the component metal is dissolved at the atomic level, and the nano-alloy catalyst whose particle size is controlled (for example, 1-50 nm) can be produced.
  • Step (1) is a step of preparing a mixture by mixing at least two metal-containing compounds selected from the group consisting of an iron group metal-containing compound and a transition metal-containing compound, a protective polymer, a solvent, and a solid support.
  • the iron group metal is selected from the iron group metal group consisting of Fe, Co and Ni
  • the transition metal group is composed of Cr, Mn, Cu, Mo, Ru, Rh, Pd, Ag, Ir, Pt and Au. Chosen from.
  • the at least two compounds used in step (1) are two or three iron group metal-containing compounds, or one or more iron group metal-containing compounds and one or more transition metals. Containing compounds.
  • the iron group metal-containing compound is not particularly limited as long as it is a compound containing an iron group metal. Appropriate solubility in the solvent used in step (1) is appropriate. Examples of such compounds include inorganic iron group metal-containing compounds such as iron group metal chlorides, sulfates, nitrates, and hydrates thereof, and complexes containing iron group metals. When the iron group metal is iron, examples thereof include inorganic iron-containing compounds such as iron chloride, iron sulfate, iron nitrate, and hydrates thereof, and also complexes containing iron.
  • Examples of the complex containing iron include iron acetate, iron acetylacetonate, tetraethylammonium tetrachloroiron (II), tetraethylammonium tetrachloroiron (III), bis (sulfide) tetranitrosyl and iron (2-) sodium.
  • the iron group metal is nickel
  • inorganic nickel-containing compounds such as nickel chloride, nickel nitrate and hydrates thereof, and further complexes containing nickel
  • the complex containing nickel include nickel acetate, nickel acetylacetonate, tetraethylammonium tetrachloronickel (II), tetraethylammonium tetrabromonickel (II), hexaamminenickel (II) chloride, dinitrotetraamminenickel ( II), potassium tetracyanonickel (II) monohydrate, potassium barium hexanitronickel (II), tris (ethylenediamine) nickel (II) sulfate, bis (ethylenediamine) diaquanickel nitrate, ethylenediaminetetraaquanickel (II) Sulfate monohydrate, dinitro (ethylenediamine) nickel (II), bis (N, N-dimethylethylenediamine
  • iron group metal when the iron group metal is cobalt, examples thereof include inorganic cobalt-containing compounds such as cobalt chloride, cobalt sulfate, cobalt nitrate and hydrates thereof, and further complexes containing cobalt.
  • the complex containing cobalt include cobalt acetate (II) tetrahydrate, cobalt acetylacetonate, potassium hexacyanocobalt (III), calcium (ethylenediaminetetraacetato) cobalt (III), pentachlorohydrate (chloro ( Ethylenediaminetetraacetato) cobalt (III) potassium, dichlorobis (ethylenediamine) cobalt (III) chloride, carbonatotetraamminecobalt (III) chloride, tris (ethylenediamine) cobalt (III) chloride trihydrate, ethylenediaminetetra Nitrocobalt (III) potassium, diamminebis (oxalato)
  • the transition metal-containing compound is not particularly limited as long as it is a compound containing a transition metal. Appropriate solubility in the solvent used in step (1) is appropriate. Examples of such compounds include inorganic transition metal-containing compounds such as transition metal chlorides, sulfates, nitrates, and hydrates thereof, and complexes containing transition metals. Examples of the complex containing a transition metal include chromium (III) acetate monohydrate, chromium (III) oxalate hexahydrate, hexaammine chromium (III) chloride, and chromium (III) ammonium dodecahydrate.
  • the protective polymer exhibits affinity for the iron group metal-containing compound and / or transition metal-containing compound, and further exhibits solubility in a solvent, such as the iron group metal-containing compound and / or transition metal-containing compound.
  • a polymer having a functional group moiety having an affinity for the metal-containing compound for example, a polymer having a polar functional group, is suitable, and a water-soluble polymer is preferred.
  • the protective polymer include polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyvinyl ether, polyacrylate, poly (mercaptomethylenethrylene-N-vinyl-2-pyrrolidone), polyacrylonitrile. And so on.
  • the protective polymer has a solubility in water and a solvent that is equivalent to that of the iron group metal-containing compound and the transition metal-containing compound, and may be a substance that interacts with the metal complex raw material and may be complexed.
  • the role of the protective polymer is mainly to prevent aggregation between the precursor particles and / or alloy particles produced in the steps (2) and (3), and to reduce the size of the precursor particles and / or alloy particles produced. Is to control.
  • the average particle diameter of the precursor particles and / or alloy nanoparticles is, for example, 1 to 200000 nm, desirably 1 to 5000 nm, preferably 1 to 1000 nm, more preferably 1 to 200 nm, and still more preferably. 1-100 nm, even more preferably 1-50 nm, even more preferably 1-20 nm, even more preferably 1-10 nm, and most preferably the average particle size is in the range of 1-4 nm. It is.
  • the particle size of the alloy can be controlled by adjusting the ratio of metal to protective polymer. For example, when the amount of the protective polymer in the solvent is relatively increased, the particle size of the precipitated precursor particles and / or alloy particles is reduced. By utilizing this phenomenon, the particle size of the precursor particles and / or alloy particles can be controlled.
  • the particle size of the alloy particle to precipitate can be adjusted also by adjusting the density
  • the solvent is a solvent capable of dissolving the iron group metal-containing compound and / or the transition metal-containing compound and the protective polymer.
  • dissolution is a state in which the iron group metal-containing compound and / or the transition metal-containing compound and the protective polymer are dissolved in a solvent, and the solution is preferably transparent.
  • water and / or an organic solvent or a mixed solvent thereof can be used as the solvent.
  • the organic solvent is preferably an organic solvent having an affinity for water or an organic solvent having a polar site from the viewpoint of excellent solubility in an iron group metal-containing compound and / or transition metal-containing compound and a protective polymer.
  • the solvent can also be a mixed solvent of water and an organic solvent having an affinity for water.
  • the organic solvent may be appropriately selected according to the type of the iron group metal-containing compound and / or transition metal-containing compound and the protective polymer.
  • polyhydric alcohols such as ethanol, propanol, ethylene glycol, triethylene glycol, and glycerin are used. Can be used. Even when using a mixed solvent of water and an organic solvent, considering the solubility of the iron group metal-containing compound and / or transition metal-containing compound and the protective polymer, the type of organic solvent and the mixing ratio of the organic solvent and water Can be adjusted as appropriate.
  • the presence state of the iron group metal-containing compound and / or transition metal-containing compound and the protective polymer in the solvent is not particularly limited, and may be in a dispersed and / or dissolved state.
  • the dispersed state is a dispersion
  • the dissolved state is a solution.
  • the solid carrier is dispersed in a solvent.
  • the mixture can also be heated during dissolution. This includes cases where dispersion and dissolution coexist. Whether the iron group metal-containing compound and / or the transition metal-containing compound and the protective polymer are in a dispersed state, a dissolved state, or a coexistence state of both, the iron group metal-containing compound and / or the transition metal is contained.
  • the concentrations of the iron group metal-containing compound and / or transition metal-containing compound and the protective polymer in the solvent are determined in consideration of the composition of the precursor, the particle diameter, and the like.
  • the concentration of the protective polymer, the concentration of the iron group metal ion and / or the concentration of the transition metal ion in the dispersion or solution is, for example, in the range of 1 ⁇ 10 ⁇ 7 to 10 mol / L for the protective polymer, 1 ⁇ 10 -10 ⁇ 10mol / L range, and transition metal ions can be in the range of 1 ⁇ 10 -10 ⁇ 10mol / L .
  • the dispersion or solution can be prepared by adding a protective polymer and an iron group metal-containing compound and / or a transition metal-containing compound to the solvent and dissolving or dispersing it.
  • a protective polymer and an iron group metal containing compound and / or a transition metal containing compound There is no restriction
  • the solid carrier can be added to and mixed with the dispersion or solution thus obtained to prepare a mixture, and when the protective polymer and the iron group metal-containing compound and / or transition metal-containing compound are added to the solvent.
  • a mixture can be prepared by adding a solid carrier.
  • the operation of dispersing or dissolving the iron group metal-containing compound, transition metal-containing compound and protective polymer in a solvent can be carried out at room temperature or under heating or cooling. Furthermore, the operation of dispersion or dissolution in the solvent may be performed in a stationary state or in a stirred state. Furthermore, the mixture can be prepared by adding a solid carrier at room temperature or under heating or cooling.
  • step (2) a reducing agent for the metal ions contained in the metal-containing compound is added to the mixture obtained in step (1), so that the supported precursor containing iron group metal or iron group metal and transition metal is added. This is a process for preparing body particles.
  • the reducing agent is selected from substances whose oxidation-reduction potential is lower than the oxidation-reduction potential of the metal to be reduced.
  • the reducing agent it is appropriate to use a compound whose standard reduction potential is more negative than hydrogen (0 eV) at room temperature from the viewpoint of strong ability to reduce iron group metal ions to metals.
  • BH 3 ⁇ L (L is a ligand, such as THF (tetrahydrofuran), SMe 2 (dimethyl sulfide)), triethylsilane Et 3 SiH, sodium bis (2-methoxyethoxy) aluminum hydride (Sodium Bis (2-methoxyethoxy ) Alminium Hydride; Red-Al).
  • THF tetrahydrofuran
  • SMe 2 dimethyl sulfide
  • triethylsilane Et 3 SiH sodium bis (2-methoxyethoxy) aluminum hydride
  • sodium bis (2-methoxyethoxy ) Alminium Hydride Red-Al
  • a solvent other than water for example, an aprotic polar solvent such as tetrahydrofuran, N, N-dimethylformamide, dimethylsulfoxide
  • the amount of reducing agent used is appropriately determined in consideration of the amount of iron group metal and / or transition metal contained in the metal raw material, for example, the total amount of iron group metal and / or transition metal ions to be reduced. It can be in the range of equivalent to 200 times equivalent or less. Preferably, it is in the range of the equivalent of the total amount of iron group metal and / or transition metal ion to 50 times equivalent or less
  • the method for adding the reducing agent is not particularly limited, but for example, a powdery or granular reducing agent can be added to the mixture.
  • a powdery or granular reducing agent may be dissolved and / or dispersed in the solvent used in the step (1), and the dissolved and / or dispersed liquid may be added to the mixture.
  • the solvent used is preferably inert to the reducing agent from the viewpoint of reduction efficiency.
  • the precursor particles are prepared by reducing the iron group metal and / or transition metal ions with the above reducing agent.
  • the reduction temperature with the reducing agent is determined in consideration of the crystal structure of the alloy to be prepared by reduction, and is suitably in the range of 0 to 200 ° C., for example. The range of 25 to 160 ° C. is preferable.
  • the obtained precursor particles containing an iron group metal and / or transition metal are particles containing an iron group metal oxide and / or a transition metal oxide, or an iron group metal alloy. Alternatively, it is a particle containing an iron group metal and a transition metal alloy, and an iron group metal oxide or an iron group metal oxide and a transition metal oxide.
  • the iron group metal and / or the transition metal ion may be reduced to the metal (alloy) correspondingly by the reduction during the preparation of the precursor particles.
  • the precursor particles containing metal are oxidized by being exposed to an atmosphere containing oxygen. Therefore, the precursor particles immediately after the synthesis have a relatively high metal (alloy) content, and the amount thereof decreases with time.
  • the ratio of iron group metal alloy or iron group metal and transition metal alloy, and iron group metal oxide or iron group metal oxide and transition metal oxide varies depending on the reduction conditions.
  • the range can be: 0.1 to 100: 0.1 to 100. However, it is not intended to be limited to this range.
  • the ratio of the iron group metal or the ratio of the iron group metal and the transition metal in the precursor particles can be appropriately determined by adjusting the composition ratio of the raw materials according to the composition of the target alloy particles.
  • the precursor particles containing the iron group metal obtained in the step (2) can be, for example, particles containing at least one of iron oxide, cobalt oxide, and nickel oxide.
  • the reaction product in the step (2) can be appropriately washed with an organic solvent or the like after completion of the reaction and before being subjected to the step (3).
  • an organic solvent or the like for example, a mixed solution of acetone and diethyl ether is used as an organic solvent, and this solution is added to the solid phase and the liquid phase until separation occurs, and then centrifuged to recover the solid phase.
  • the recovered solid phase is dispersed in water, and acetone is added to the dispersion to separate the solid phase and the liquid phase again, followed by centrifugation to obtain a washed sample.
  • the complex composed of the metal supported on the solid support can be separated from impurities such as Na and boric acid.
  • step (3) the precursor particles are heated in a hydrogen-containing atmosphere to reduce the precursor particles, and alloy particles having a volume of 16.7 nm 3 or more and 10466.7 nm 3 or less are supported on a solid support. This is a step of obtaining a complex.
  • the heat treatment in the hydrogen atmosphere can be performed at a predetermined temperature and hydrogen pressure after removing the solvent from the precursor particles obtained in the step (2) or together with the solvent.
  • the temperature can be, for example, in the range of 200 ° C. to 1000 ° C., and the hydrogen pressure can be in the range of 0.01 Pa to 100 MPa.
  • the conditions for the heat treatment in the hydrogen atmosphere are preferably in the range of 300 to 950 ° C. and the hydrogen pressure in the range of 0.01 MPa to 5 MPa.
  • the conditions of the heat treatment in the hydrogen atmosphere are more preferably in the range of 400 to 900 ° C. and the hydrogen pressure in the range of 0.1 MPa to 3 MPa.
  • the heating temperature is more preferably in the range of 500 to 900 ° C.
  • the treatment time can be appropriately set according to the temperature and pressure, and can be, for example, in the range of 0.05 to 10 hours. However, it is not intended to be limited to this range.
  • the hydrogen content of the hydrogen-containing atmosphere can be, for example, in the range of more than 1 vol% and not more than 100 vol%, and can contain an inert gas such as argon or nitrogen in addition to hydrogen.
  • the hydrogen atmosphere heat treatment in the step (3) is preferably performed under the condition that the obtained iron group nanoalloy particles have a crystallite size having a volume of 16.7 nm 3 or more and 10466.7 nm 3 or less.
  • alloy particles having a crystallite size having the above volume range can be obtained.
  • the composite of the present invention can be used as a catalyst for a solid oxide alkaline fuel cell.
  • the alkaline fuel cell can be, for example, a fuel cell that uses hydrogen as a fuel as described above.
  • the alkaline fuel cell can be, for example, a fuel cell using a glycol as a fuel (an alkaline direct ethylene glycol fuel cell).
  • a selective oxidation catalyst that generates oxalic acid from glycol and does not oxidize to carbon dioxide is preferable, and the complex of the present invention includes a catalyst exhibiting such selective oxidation activity. Yes.
  • the present invention includes an anode for a fuel cell having a layer comprising an anode composition containing the composite of the present invention and an anion conductive material on a substrate surface.
  • the ion-conducting material used for the anode composition has a function as an ion-conducting medium for conducting hydroxide ions generated by an electrochemical reaction to the solid polymer electrolyte at the cathode. It has a function as a binder that binds the catalyst particles made of the composite to the conductive porous substrate as an electrode catalyst layer.
  • a material made of the same material as the solid polymer electrolyte or the solid oxide electrolyte can be used, for example, known as Flemillon (Asahi Glass). Not only is the catalyst particles excellent in binding properties but also ion conductivity.
  • the ion conductive material that can be used in the present invention is not limited to the solid polymer electrolyte.
  • the ratio of the mass of the catalyst particles to the mass of the ion conductive material (hereinafter sometimes referred to as “catalyst particle / polymer mass ratio”) is, for example, 3/1 to 20 / 1 and preferably in the range of 4/1 to 18/1.
  • the electrode catalyst layer may contain a small amount of other resin as a binder for the catalyst particles in addition to the ion conductive material.
  • the other resin include a fluorine resin having no proton conductivity, and more specifically, for example, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, polytetrafluoroethylene. Mention may be made of ethylene fluoride.
  • the proportion of the resin in the binder is preferably 30% by weight or less, and particularly preferably 10% by weight or less in the binder.
  • examples of the conductive porous substrate include paper, nonwoven fabric, woven fabric, knitted fabric, and conductive porous membrane made of fibers such as porous carbon powder and conductive polymer.
  • the present invention further includes a membrane electrode assembly for a fuel cell in which the anode and the cathode of the present invention are laminated with a polymer electrolyte membrane interposed therebetween.
  • the cathode is formed by binding and supporting an electrode catalyst together with a binder as an electrode catalyst layer on a conductive porous substrate, and its configuration is not particularly limited.
  • the electrode catalyst layer is, for example, a carbon black powder carrying platinum fine particles, a carbon black powder as a conductive auxiliary agent, a binder for bringing them together, and an ion conductor that becomes a conductor of ions generated by an electrochemical reaction.
  • a functional material or the like is a functional material or the like.
  • the cathode may be a paste using, for example, carbon black powder supporting platinum fine particles and, if necessary, carbon black as a conductive aid using a suitable binder, and this is described above. It can obtain by apply
  • each conductive porous substrate constituting the cathode and the anode can have a conductive water repellent layer on the side on which the electrode catalyst is supported in order to prevent so-called flooding.
  • the present invention includes a fuel cell including the fuel cell membrane electrode assembly of the present invention.
  • the operating temperature of the fuel cell according to the present invention is usually 0 ° C. or higher, preferably in the range of 15 to 200 ° C., more preferably in the range of 30 to 100 ° C. When the operating temperature is too high, the material used may be deteriorated or peeled off.
  • the composite of the present invention can be used as a catalyst for the fuel electrode (anode).
  • the solid support is preferably a conductive material, for example, a carbon-based material (for example, activated carbon, carbon black, carbon nanotube, porous carbon material, etc.).
  • the complex of the present invention exhibits ethylene glycol oxidation reaction (EOR) activity.
  • EOR ethylene glycol oxidation reaction
  • Fuel electrode HOCH 2 CH 2 OH + 8 OH - ⁇ (COOH) 2 + 6 H 2 O + 8 e -
  • Oxygen electrode 2 O 2 + 4 H 2 O + 8 e - ⁇ 8 OH -
  • Total reaction HOCH 2 CH 2 OH + 2 O 2 ⁇ (COOH) 2 + 2 H 2 O
  • An alkaline direct ethylene glycol fuel cell can be constructed by using the composite of the present invention as a catalyst for a fuel electrode (anode). Furthermore, by reducing oxalic acid, which is an emission from a fuel cell that uses ethylene glycol as a fuel, to ethylene glycol using, for example, a photocatalyst, a fuel cell capable of reusing the fuel can be provided.
  • the composite of the present invention can be used as a catalyst for a Fischer-Tropsch (FT) reaction.
  • FT reaction catalyst the composite in which the iron group metal alloy particles are iron group metal alloy particles made of Fe and Co are excluded from the composite of the present invention.
  • the FT reaction is a method of synthesizing hydrocarbons from synthesis gas (a mixed gas containing carbon monoxide and hydrogen as main components).
  • Examples of the FT reaction include a reaction in which a linear saturated or unsaturated hydrocarbon is produced from synthesis gas (CO + H 2 ) using the complex of the present invention as a catalyst.
  • the reaction formula at this time is as follows. nCO + (2n + 1) H 2 ⁇ C n H 2n + 2 + nH 2 O nCO + 2nH 2 ⁇ C n H 2n + nH 2 O
  • the catalyst for FT reaction comprising the composite of the present invention has a high CO conversion rate and efficiency when used for the production of light olefins having 2 to 4 carbon atoms such as ethylene, propylene and butene by FT reaction. It can be obtained well.
  • the FT reaction catalyst comprising the composite of the present invention is particularly suitable for the production of propylene.
  • the pressure in the FT reaction can be, for example, in the range of normal pressure to 10 MPa, preferably in the range of 0.5 to 5 MPa, and the temperature is in the range of 200 to 450 ° C., preferably in the range of 200 to 350 ° C. be able to.
  • Example 1-1 Fe 33 Co 33 Ni 33 / C50wt% 0.0747 g of iron (II) acetate, 0.0706 g of cobalt (II) acetate, 0.0996 g of nickel (II) acetate tetrahydrate, 0.0515 g of polyethylene glycol (hereinafter referred to as PEG) and 0.0692 g of vulcan (registered) (Trademark) was mixed with 200 ml of triethylene glycol (hereinafter referred to as TEG). The mixed solution was heated to 80 ° C., 0.75 g of NaBH 4 was added, and the mixture was stirred for 5 minutes and then allowed to cool.
  • PEG polyethylene glycol
  • TEG triethylene glycol
  • the resulting black precipitate was dispersed in water.
  • Acetone was added to this mixture to separate the black sample from the colorless and transparent solution, and the operation of centrifuging was repeated three times to obtain a black sample.
  • This sample is called a catalyst precursor.
  • the catalyst precursor was dried in a vacuum desiccator.
  • the dried catalyst precursor was pulverized into a powder.
  • 500 mg of the precursor powder was transferred to a quartz boat, and a catalyst was prepared by raising the temperature to 700 ° C. while 5% H 2 —Ar gas was circulated.
  • the dried catalyst precursor was pulverized into a powder. 500 mg of the precursor powder was transferred to a quartz boat, and a catalyst was prepared by raising the temperature to 700 ° C. while 5% H 2 —Ar gas was circulated.
  • the dried catalyst precursor was pulverized into a powder. 500 mg of the precursor powder was transferred to a quartz boat, and a catalyst was prepared by raising the temperature to 700 ° C. while 5% H 2 —Ar gas was circulated.
  • the dried catalyst precursor was pulverized into a powder. 500 mg of the precursor powder was transferred to a quartz boat, and a catalyst was prepared by raising the temperature to 700 ° C. while 5% H 2 —Ar gas was circulated.
  • Example 1-5 Fe 25 Co 75 / C20wt% 0.135 g of iron (II) acetate, 0.4 g of cobalt (II) acetate, 1.33 g of polyethylene glycol (hereinafter referred to as PEG) and 0.71 g of Vulcan (registered trademark) in 200 ml of triethylene glycol (hereinafter referred to as TEG) Mixed). After heating the mixed solution to 120 ° C., 1.1 g of NaBH 4 was added and stirred for 5 minutes, and then allowed to cool.
  • PEG polyethylene glycol
  • TEG triethylene glycol
  • the resulting black precipitate was dispersed in water.
  • Acetone was added to this mixture to separate the black sample from the colorless and transparent solution, and the operation of centrifuging was repeated three times to obtain a black sample.
  • This sample is called a catalyst precursor.
  • the catalyst precursor was dried in a vacuum desiccator.
  • the dried catalyst precursor was pulverized into a powder. 500 mg of the precursor powder was transferred to a quartz boat, and a catalyst was prepared by raising the temperature to 700 ° C. while 5% H 2 —Ar gas was circulated.
  • the dried catalyst precursor was pulverized into a powder. 500 mg of precursor powder was transferred to a quartz boat, and a catalyst was prepared by raising the temperature to 700 ° C. in a state where 5% H2-Ar soot gas was circulated.
  • This sample is called a catalyst precursor.
  • the catalyst precursor was dried in a vacuum desiccator.
  • the dried catalyst precursor was pulverized into a powder.
  • 500 mg of the precursor powder was transferred to a quartz boat, and a catalyst was prepared by raising the temperature to 700 ° C. while 5% H 2 —Ar gas was circulated.
  • the dried catalyst precursor was pulverized into a powder. 500 mg of the precursor powder was transferred to a quartz boat and heated to 800 ° C. in a state where 5% H 2 —Ar gas was circulated to prepare a catalyst.
  • the dried catalyst precursor was pulverized into a powder. 500 mg of the precursor powder was transferred to a quartz boat and heated to 800 ° C. in a state where 5% H 2 —Ar gas was circulated to prepare a catalyst.
  • the particle size of the Fe nanoparticles supported on Vulcan was 28.1 ⁇ 12.3 nm.
  • the Fe nanoparticles in the prepared catalyst have a bcc structure and an fcc structure, and from the ICP-AES measurement, it is clear that the catalyst contains 28.5 wt% Fe.
  • the dried catalyst precursor was pulverized into a powder. 500 mg of the precursor powder was transferred to a quartz boat and heated to 800 ° C. in a state where 5% H 2 —Ar gas was circulated to prepare a catalyst.
  • Fig. 1 shows the conventional (impregnation) method (after 900 ° C heat treatment) preparation obtained in Reference Example 1, and (b) shows the present invention obtained in Example 1-1 (900 ° C heat treatment).
  • the TEM image of the Fe-based alloy nanoalloy-supported catalyst prepared in the latter step is shown.
  • FIG. 2 shows the powder XRD patterns of FexCoyNi (1-xy) / C obtained in Examples 1-1 to 4.
  • FIG. 3 shows an STEM-EDS (element map) image of the Fe 50 Co 50 / C precursor (a) and the nanoalloy catalyst (b) obtained in Example 1-2. It can be seen that iron and cobalt are dispersed within 16.7 nm 3 .
  • FIG. 4 shows a TEM image of FexCoyNi (100-xy) / C and metal composition analysis result by TEM-EDS Fig. 4 shows a TEM image of the binary nano-alloy (RT-1000 ° C, 10 K / min, 10 min Keep, N 2 ).
  • FIG. 5 shows a TEM image of the metal nanoparticles.
  • FIG. 6 shows the power generation characteristics of a direct glycol inorganic alkaline battery using FexCoyNi (100-xy) / C as an anode catalyst. The output characteristics change depending on the composition.
  • Example 2-1 Preparation of Fe-Co-Ni nanoalloy catalyst (1) A weight / g of (2) metal salt raw material A, (3) B weight / g of (4) metal salt raw material B, ( 5) C weight / g (6) Metal salt raw material C, (7) D weight / g (8) Protective agent D and (9) E weight / g (10) Carrier E (11) F capacity / Mixed with ml (12) Solvent F. The mixed solution was heated to (13) temperature / ° C., (14) weight / g NaBH 4 was added, and the mixture was stirred for (15) hours and then allowed to cool.
  • a mixed solution of acetone: diethyl ether composition (16): (17) was added to the reaction mixture until separation occurred between the black layer and the colorless and transparent solution layer, followed by centrifugation to obtain a black sample.
  • the resulting black precipitate was dispersed in water.
  • Acetone and diethyl ether were added to the mixture to again separate the black sample from the colorless and transparent solution, and centrifuged to obtain a black sample.
  • This sample is called a catalyst precursor.
  • the catalyst precursor was dried in a vacuum desiccator. The dried catalyst precursor was pulverized into a powder.
  • Example 2-2 Preparation of Fe-Co-Cr nanoalloy catalyst An Fe-Co-Cr nanoalloy catalyst was prepared in the same manner as in Example 2-1. Each explanation of (1) to (25) is shown in Table 2.
  • Example 2-3 Preparation of Fe-Cr nanoalloy catalyst An Fe-Cr nanoalloy catalyst was prepared in the same manner as in Example 2-1. However, (1) to (4) in Example 2-1 correspond to (1) to (4) in Table 3, and (7) to (25) correspond to (5) to (22) in Table 3. To do.
  • Example 2-4 Preparation of Fe-Mn nanoalloy catalyst An Fe-Mn nanoalloy catalyst was prepared in the same manner as in Example 2-1. However, (1) to (4) in Example 2-1 correspond to (1) to (4) in Table 4, and (7) to (25) correspond to (5) to (22) in Table 4. To do.
  • Co / C, Fe / C, and Ni / C are samples obtained in Reference Examples 1 to 3. An overall image of the XRD pattern is shown in FIG. For all nanoalloy catalysts, diffraction patterns from a single crystalline phase were obtained, suggesting that all samples had a solid solution structure.
  • each point of element mapping is 0.773 nm in both the x-axis and y-axis directions, and the distance between each point of line analysis is around 0.2-0.5 nm.
  • the results are shown in FIGS. From the obtained TEM photograph, the constituent elements of the nano-alloy in the range of resolution measured any nano alloys are uniformly distributed throughout the particle, that constituent molecules is present in the volume of 16.7 nm 3 Show. Further, when the characteristic X-ray counts from the elements were measured on a straight line plotted on the BF STEM image, it was found that the same was true for all constituent elements at any position. This revealed that the constituent elements were uniformly distributed in the nanoalloy.
  • the gas phase components in the cell in the initial state before the start of the reaction were analyzed by gas chromatography analysis after N 2 bubbling. Further, about 50 mL of the cell solution on the working electrode and counter electrode side is collected, and the sample diluted with 450 mL of deionized water is analyzed with a liquid chromatograph (LC-20AD) manufactured by Shimadzu Corporation. analyzed. Subsequently, electrode oxidation was performed at a constant potential for about 125 minutes while applying a voltage of 1.0 V vs. RHE. After applying the voltage, the gas phase component in the reaction solution on the working electrode side was analyzed by GC analysis.
  • LC-20AD liquid chromatograph
  • anode electrodes and Na x CoO 2 electrolyte pellets As the cathode electrode, P50T carbon paper coated with 9.44 mg / cm 2 of a powder obtained by mixing Na x CoO 2 electrolyte powder and Vulcan XC-72R carbon powder in a weight ratio of 2: 1 was used. Anode and cathode electrodes each having a diameter of 5 mm ⁇ were used. The prepared anode electrode catalyst, electrolyte pellet, and cathode electrode were installed in a fuel cell evaluation cell manufactured by ElectroChem, and the fuel cell characteristics were evaluated.
  • the anode electrode side was filled with an aqueous solution containing 10 wt% ethylene glycol and 10 wt% potassium hydroxide, 70 ° C wet O 2 gas was circulated at 200 ml / min on the cathode electrode side, and the evaluation cell was 70 ° C Held on.
  • the current-voltage characteristics were measured with a Solartron Electrochemical Test System 1280C. As a result of open circuit voltage measurement, an electromotive force of 0.6-0.7 (V) was confirmed. The result of the current-voltage characteristic measurement is shown in FIG. It was confirmed that the power density showed a maximum of 46.0 (mW / cm 2 ) on Fe50Co50 / C. Co / C, Fe / C, and Ni / C are the results for the samples obtained in Reference Examples 1 to 3.
  • Example 3 FT reaction was performed using Fe50Co50 / Al2O3 prepared in Example 2-1.
  • the reaction device used was BEL-REA manufactured by Nippon Bell.
  • a reaction tube having a diameter of 1.0 cm was filled with 0.5 g of an Al 2 O 3 supported FeCo catalyst.
  • Pretreatment was performed for 5 hours under conditions of H 2 at 400 ° C, 0.1 MPa, 50 sccm.
  • CO conversion and lower hydrocarbon selectivity were determined using a gas chromatograph connected to BEL-REA.
  • a toluene trap was placed after the reaction tube, and after completion of the reaction, the product was assigned by gas chromatography.
  • the present invention is useful in fields related to metal alloy composites useful for fuel cell electrode catalysts and Fischer-Tropsch reaction catalysts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

La présente invention concerne un support solide et un composite comprenant des particules d'alliage à base d'un métal du groupe du fer supportées par le support solide. Lesdites particules d'alliage à base d'un métal du groupe du fer sont, par exemple des particules d'alliage à base d'un métal du groupe du fer comprenant deux ou trois métaux du groupe du fer sélectionnés dans le groupe constitué par les métaux du groupe du fer (a) Fe, Co et Ni (où lesdits deux ou trois métaux du groupe du fer sont des alliages de type à solution solide), ou des particules d'alliage à base d'un métal du groupe du fer comprenant un, deux ou trois métaux du groupe du fer sélectionnés dans le groupe constitué par les métaux du groupe du fer (c) Fe, Co et Ni, et un, deux ou plusieurs métaux de transition sélectionnés dans le groupe constitué par les métaux de transition Cr, Mn, Cu, Mo, Ru, Rh, Pd, Ag, Ir, Pt et Au (où ledit/lesdits métaux du groupe du fer et ledit/lesdits métaux de transition sont des alliages du type à solution solide). L'invention concerne en outre un catalyseur présentant des caractéristiques de catalyseur améliorées, un catalyseur pour électrodes d'une pile à combustible et un catalyseur à taux de conversion amélioré du monoxyde de carbone, présentant un nombre supérieur d'atomes de carbone et une sélectivité en oléfines supérieure en tant que catalyseur pour réaction Fischer-Tropsch.
PCT/JP2013/071735 2012-08-10 2013-08-09 Matériau composite d'alliage de type à solution solide du groupe du fer supporté par un support solide et catalyseur le mettant en œuvre WO2014025049A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014529587A JP6230126B2 (ja) 2012-08-10 2013-08-09 固体担体担持鉄族固溶体型合金複合体及びそれを用いた触媒

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261681741P 2012-08-10 2012-08-10
US61/681,741 2012-08-10

Publications (1)

Publication Number Publication Date
WO2014025049A1 true WO2014025049A1 (fr) 2014-02-13

Family

ID=50068265

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/071735 WO2014025049A1 (fr) 2012-08-10 2013-08-09 Matériau composite d'alliage de type à solution solide du groupe du fer supporté par un support solide et catalyseur le mettant en œuvre

Country Status (2)

Country Link
JP (1) JP6230126B2 (fr)
WO (1) WO2014025049A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11039619B2 (en) 2014-02-19 2021-06-22 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
CN113451588A (zh) * 2021-06-29 2021-09-28 深圳大学 一种共生型燃料电池阳极及其制备方法与应用
CN113559879A (zh) * 2021-07-27 2021-10-29 大连理工大学 一种耐腐蚀型高熵合金纳米催化剂低温合成方法及应用
WO2022080142A1 (fr) * 2020-10-14 2022-04-21 国立大学法人筑波大学 Électrode, procédé de production associé, électrolyseur d'eau et pile à combustible
CN115939424A (zh) * 2022-11-25 2023-04-07 大连理工大学 一种负载型亚纳米铁硫簇催化剂、制备方法及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006504232A (ja) * 2002-10-21 2006-02-02 イディア ラボ ソシエタ ア レスポンサビリタ リミタータ 白金不含有電極触媒材料
JP2008288006A (ja) * 2007-05-17 2008-11-27 Kyushu Institute Of Technology エタノール燃料電池電極用触媒、エタノール燃料電池用膜・電極接合体およびエタノール燃料電池
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
JP2012164608A (ja) * 2011-02-09 2012-08-30 Toyota Motor Corp Ｆｅ、Ｃｏ及びＮｉを含む電極触媒及びその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5751516B2 (ja) * 2011-09-07 2015-07-22 国立研究開発法人産業技術総合研究所 水素発生用触媒及び水素発生方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006504232A (ja) * 2002-10-21 2006-02-02 イディア ラボ ソシエタ ア レスポンサビリタ リミタータ 白金不含有電極触媒材料
JP2008288006A (ja) * 2007-05-17 2008-11-27 Kyushu Institute Of Technology エタノール燃料電池電極用触媒、エタノール燃料電池用膜・電極接合体およびエタノール燃料電池
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
JP2012164608A (ja) * 2011-02-09 2012-08-30 Toyota Motor Corp Ｆｅ、Ｃｏ及びＮｉを含む電極触媒及びその製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11039619B2 (en) 2014-02-19 2021-06-22 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
WO2022080142A1 (fr) * 2020-10-14 2022-04-21 国立大学法人筑波大学 Électrode, procédé de production associé, électrolyseur d'eau et pile à combustible
EP4230774A4 (fr) * 2020-10-14 2024-07-31 Univ Tsukuba Électrode, procédé de production associé, électrolyseur d'eau et pile à combustible
CN113451588A (zh) * 2021-06-29 2021-09-28 深圳大学 一种共生型燃料电池阳极及其制备方法与应用
CN113559879A (zh) * 2021-07-27 2021-10-29 大连理工大学 一种耐腐蚀型高熵合金纳米催化剂低温合成方法及应用
CN115939424A (zh) * 2022-11-25 2023-04-07 大连理工大学 一种负载型亚纳米铁硫簇催化剂、制备方法及应用
CN115939424B (zh) * 2022-11-25 2024-04-19 大连理工大学 一种负载型亚纳米铁硫簇催化剂、制备方法及应用

Also Published As

Publication number Publication date
JP6230126B2 (ja) 2017-11-15
JPWO2014025049A1 (ja) 2016-07-25

Similar Documents

Publication Publication Date Title
Hu et al. Porosity-induced high selectivity for CO2 electroreduction to CO on Fe-doped ZIF-derived carbon catalysts
Xiong et al. Synergistic bimetallic metallic organic framework-derived Pt–Co oxygen reduction electrocatalysts
Wu et al. Ultrafine Pt nanoparticles and amorphous nickel supported on 3D mesoporous carbon derived from Cu-metal–organic framework for efficient methanol oxidation and nitrophenol reduction
EP1922777B1 (fr) Electrocatalyseurs à monocouches en or sur noyaux de nanoparticules en platine, et utilisations
Singh et al. Synergistic catalysis over bimetallic alloy nanoparticles
US7855021B2 (en) Electrocatalysts having platium monolayers on palladium, palladium alloy, and gold alloy core-shell nanoparticles, and uses thereof
Long et al. Synthesis and characterization of Pt–Pd alloy and core-shell bimetallic nanoparticles for direct methanol fuel cells (DMFCs): Enhanced electrocatalytic properties of well-shaped core-shell morphologies and nanostructures
CA2585542C (fr) Procede de fabrication de catalyseurs constitues d'un alliage a base de metal noble et catalyseurs obtenus a l'aide dudit procede
EP1849201B1 (fr) Particules de palladium-cobalt a titre d'electrocatalyseurs de reduction d'oxygene
JP2008525638A (ja) 水素吸収により誘起されるパラジウム及びパラジウム合金粒子上への金属堆積
El-Nagar et al. Propitious dendritic Cu2O–Pt nanostructured anodes for direct formic acid fuel cells
JP6230126B2 (ja) 固体担体担持鉄族固溶体型合金複合体及びそれを用いた触媒
Gao et al. Evidence of the strong metal support interaction in a palladium-ceria hybrid electrocatalyst for enhancement of the hydrogen evolution reaction
JP5531125B1 (ja) 固体高分子形燃料電池用の触媒及びその製造方法
Fu et al. 3D robust carbon aerogels immobilized with Pd3Pb nanoparticles for oxygen reduction catalysis
JP3870282B2 (ja) 分散安定化された触媒ナノ粒子含有液
Parkash Copper doped zeolitic imidazole frameworks (ZIF-8): a new generation of single-atom catalyst for oxygen reduction reaction in alkaline media
Urbańczyk et al. NiPt sinter as a promising electrode for methanol electrocatalytic oxidation
JP5015489B2 (ja) 燃料電池用電極触媒及び燃料電池
Sharma et al. Graphene-manganite-Pd hybrids as highly active and stable electrocatalysts for methanol oxidation and oxygen reduction
Parkash Incorporation of Pt–Cr nanoparticles into highly porous MOF-5 as efficient oxygen reduction electrocatalysts
KR101688524B1 (ko) 연료전지용 전극촉매, 이 전극촉매를 포함하는 막 전극 접합체와 연료전지, 및 연료전지용 전극촉매의 제조방법
Tie et al. 3D Self-Supported Binary PtCu Aerogel Boosted Methanol Oxidation
JP2007042519A (ja) 燃料電池用触媒及びその製造方法並びに燃料電池用電極及び燃料電池
Huang et al. MOF-derived Cu embedded into N-doped mesoporous carbon as a robust support of PdAu nanocatalysts for ethanol electrooxidation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13827641

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014529587

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13827641

Country of ref document: EP

Kind code of ref document: A1