WO2009091043A1 - 触媒およびその製造方法ならびにその用途 - Google Patents
触媒およびその製造方法ならびにその用途 Download PDFInfo
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- WO2009091043A1 WO2009091043A1 PCT/JP2009/050570 JP2009050570W WO2009091043A1 WO 2009091043 A1 WO2009091043 A1 WO 2009091043A1 JP 2009050570 W JP2009050570 W JP 2009050570W WO 2009091043 A1 WO2009091043 A1 WO 2009091043A1
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- oxide
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- fuel cell
- niobium
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- 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
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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- 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 catalyst, a production method thereof, and an application thereof.
- Fuel cells are classified into various types according to the type of electrolyte and the type of electrode, and representative types include alkali type, phosphoric acid type, molten carbonate type, solid electrolyte type, and solid polymer type.
- a polymer electrolyte fuel cell that can operate at a low temperature (about ⁇ 40 ° C.) to about 120 ° C. attracts attention, and in recent years, development and practical application as a low-pollution power source for automobiles is progressing.
- a use of the polymer electrolyte fuel cell a vehicle driving source and a stationary power source are being studied. However, in order to be applied to these uses, durability over a long period of time is required.
- a polymer solid electrolyte is sandwiched between an anode and a cathode, fuel is supplied to the anode, oxygen or air is supplied to the cathode, and oxygen is reduced at the cathode to extract electricity.
- Hydrogen or methanol is mainly used as the fuel.
- the fuel cell cathode (air electrode) surface or anode (fuel electrode) surface has a layer containing a catalyst (hereinafter referred to as “for fuel cell”). Also referred to as “catalyst layer”).
- the noble metal used on the cathode surface may be dissolved in an acidic atmosphere, and there is a problem that it is not suitable for applications that require long-term durability. Therefore, there has been a strong demand for the development of a catalyst that does not corrode in an acidic atmosphere, has excellent durability, and has a high oxygen reducing ability.
- Non-Patent Document 1 reports that a ZrOxN compound based on zirconium exhibits oxygen reducing ability.
- Patent Document 1 discloses an oxygen reduction electrode material containing one or more nitrides selected from the group of elements of Group 4, Group 5, and Group 14 of the long periodic table as a platinum substitute material.
- Patent Document 2 discloses a carbonitride oxide obtained by mixing carbide, oxide, and nitride and performing heat treatment at 500 to 1500 ° C. in a vacuum, inert or non-oxidizing atmosphere.
- Patent Document 2 is a thin film magnetic head ceramic substrate material, and the use of this carbonitrous oxide as a catalyst has not been studied.
- An object of the present invention is to solve such problems in the prior art, and an object of the present invention is to provide a catalyst that does not corrode in an acidic electrolyte or at a high potential, has excellent durability, and has a high oxygen reduction ability. There is.
- a catalyst made of a metal oxynitride containing a specific metal and niobium does not corrode in an acidic electrolyte or at a high potential, The inventors have found that it is excellent in durability and has a high oxygen reducing ability, and has completed the present invention.
- the present invention relates to the following (1) to (21), for example.
- the metal oxycarbonitride is a mixture of several phases, and when the metal oxycarbonitride is measured by a powder X-ray diffraction method (Cu—K ⁇ ray), a peak derived from Nb 12 O 29 is observed.
- the catalyst according to any one of (1) to (3), which is observed.
- a metal carbonitride by heat treatment in a nitrogen atmosphere or an inert gas containing nitrogen, and heat treating the metal carbonitride in an oxygen-containing inert gas.
- a fuel cell catalyst layer comprising the catalyst according to any one of (4).
- An electrode having a fuel cell catalyst layer and a porous support layer, wherein the fuel cell catalyst layer is the fuel cell catalyst layer according to (16) or (17).
- a membrane electrode assembly having a cathode, an anode, and an electrolyte membrane disposed between the cathode and the anode, wherein the cathode and / or the anode is an electrode according to (18) Membrane electrode assembly.
- a fuel cell comprising the membrane electrode assembly according to (19).
- the catalyst of the present invention does not corrode in an acidic electrolyte or at a high potential, is stable, has a high oxygen reducing ability, and is less expensive than platinum. Therefore, the fuel cell including the catalyst is relatively inexpensive and has excellent performance.
- FIG. 1 is a powder X-ray diffraction spectrum of the catalyst (1) of Example 1.
- FIG. FIG. 2 is a powder X-ray diffraction spectrum of the catalyst (2) of Example 2.
- FIG. 3 is a powder X-ray diffraction spectrum of the catalyst (3) of Example 3.
- FIG. 4 is a powder X-ray diffraction spectrum of the catalyst (4) of Example 4.
- FIG. 5 is a powder X-ray diffraction spectrum of the catalyst (5) of Example 5.
- 6 is a powder X-ray diffraction spectrum of the catalyst (6) of Example 6.
- FIG. FIG. 7 is a powder X-ray diffraction spectrum of the catalyst (7) of Example 7.
- FIG. 8 is a powder X-ray diffraction spectrum of the catalyst (8) of Example 8.
- FIG. 9 is a powder X-ray diffraction spectrum of the catalyst (9) of Example 9.
- 10 is a powder X-ray diffraction spectrum of the catalyst (10) of Example 10.
- FIG. FIG. 11 is a powder X-ray diffraction spectrum of the catalyst (11) of Example 11.
- FIG. 12 is the powder X-ray diffraction spectrum of the catalyst (13) of Example 12.
- FIG. 13 is a powder X-ray diffraction spectrum of the catalyst (14) of Example 13.
- FIG. 14 is a peak analysis of the powder X-ray diffraction spectrum of the catalyst (14) of Example 13.
- FIG. 15 is the powder X-ray diffraction spectrum of the catalyst (15) of Example 14.
- FIG. 16 is a graph obtained by performing peak analysis on the powder X-ray diffraction spectrum of the catalyst (15) of Example 14.
- FIG. 17 is the powder X-ray diffraction spectrum of the catalyst (16) of Example 15.
- FIG. 18 is a graph obtained by performing peak analysis on the powder X-ray diffraction spectrum of the catalyst (16) of Example 15.
- FIG. 19 is the powder X-ray diffraction spectrum of the catalyst (17) of Example 16.
- 20 is a graph obtained by peak analysis of the powder X-ray diffraction spectrum of the catalyst (17) of Example 16.
- FIG. FIG. 21 is the powder X-ray diffraction spectrum of the catalyst (18) of Example 17.
- FIG. 22 is a graph obtained by peak analysis of the powder X-ray diffraction spectrum of the catalyst (18) of Example 17.
- FIG. 23 is the powder X-ray diffraction spectrum of the catalyst (19) of Example 18.
- FIG. 24 is the powder X-ray diffraction spectrum of the catalyst (20) of Example 19.
- FIG. 25 is the powder X-ray diffraction spectrum of the catalyst (21) of Example 20.
- FIG. 27 is the powder X-ray diffraction spectrum of the catalyst (22) of Example 21.
- FIG. 29 is the powder X-ray diffraction spectrum of the catalyst (23) of Example 22.
- FIG. 31 is the powder X-ray diffraction spectrum of the catalyst (24) of Example 23.
- FIG. 33 is the powder X-ray diffraction spectrum of the catalyst (25) of Example 24.
- FIG. 35 is the powder X-ray diffraction spectrum of the catalyst (26) of Example 25.
- FIG. 37 is the powder X-ray diffraction spectrum of the catalyst (27) of Example 26.
- FIG. 35 is the powder X-ray diffraction spectrum of the catalyst (26) of Example 25.
- FIG. 36 is an
- FIG. 39 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (1) of Example 1.
- 40 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (2) of Example 2.
- FIG. 41 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (3) of Example 3.
- FIG. 42 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (4) of Example 4.
- FIG. 43 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (5) of Example 5.
- FIG. 39 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (1) of Example 1.
- 40 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (2) of Example 2.
- FIG. 41 is a graph showing an evaluation of the oxygen reducing ability of the fuel
- FIG. 44 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (6) of Example 6.
- FIG. 45 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (7) of Example 7.
- 46 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (8) of Example 8.
- FIG. 47 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (9) of Example 9.
- FIG. 48 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (10) of Example 10.
- FIG. 49 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (11) of Example 11.
- 50 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (12) of Comparative Example 1.
- FIG. 51 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (13) of Example 12.
- 52 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (14) of Example 13.
- FIG. 53 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (15) of Example 14.
- FIG. 54 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (16) of Example 15.
- FIG. 55 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (17) of Example 16.
- FIG. 56 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (18) of Example 17.
- FIG. 57 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (19) of Example 18.
- FIG. 58 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (20) of Example 19.
- FIG. 59 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (21) of Example 20.
- FIG. FIG. 60 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (22) of Example 21.
- 61 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (23) in Example 22.
- FIG. 62 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (24) of Example 23.
- FIG. FIG. 63 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (25) of Example 24.
- 64 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (26) of Example 25.
- FIG. 65 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (27) of Example 26.
- 66 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (28) of Comparative Example 2.
- FIG. 67 is a graph showing an evaluation of the oxygen reducing ability of the fuel cell electrode (29) of Comparative Example 3.
- the catalyst of the present invention is tin, indium, platinum, tantalum, zirconium, copper, iron, tungsten, chromium, molybdenum, hafnium, titanium, vanadium, cobalt, manganese, cerium, mercury, plutonium, gold, silver, iridium, palladium, At least one metal M and niobium selected from the group consisting of yttrium, ruthenium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and nickel It is characterized by comprising a metal oxycarbonitride containing
- 0.05 ⁇ a ⁇ 0.99, 0.01 ⁇ b ⁇ 0.95 (more preferably 0.50 ⁇ a ⁇ 0.99, 0.01 ⁇ b ⁇ 0.50, more preferably 0.80 ⁇ a ⁇ 0.99, 0.01 ⁇ b ⁇ 0.20), 0.01 ⁇ x ⁇ 2, 0.01 ⁇ y ⁇ 2, 0.05 ⁇ z ⁇ 3, and 0.07 It is preferable that ⁇ x + y + z ⁇ 5.
- the ratio of the number of atoms is in the above range, the oxygen reduction potential tends to increase, which is preferable.
- the metal M is platinum
- b in the composition formula (Nb a M b C x N y O z ) is used in order to suppress the use amount of platinum which is expensive and has a limited amount of resources. Is 0.50 or less, preferably 0.20 or less.
- metal oxycarbonitride containing metal M and niobium means a compound whose composition formula is represented by Nb a M b C x N y O z , an oxide of metal M, or metal M Carbide, metal M nitride, metal M carbonitride, metal M carbonate, metal M nitride, niobium oxide, niobium carbide, niobium nitride, niobium carbonitride, niobium Carbon dioxide, niobium nitride oxide, oxide containing metal M and niobium, carbide containing metal M and niobium, nitride containing metal M and niobium, carbonitride containing metal M and niobium, metal A mixture including a carbonate containing M and niobium, a nitrogen oxide containing metal M and niobium, and the like and having a composition formula as a whole represented by
- a diffraction line peak means a peak obtained with a specific diffraction angle and diffraction intensity when a sample (crystalline) is irradiated with X-rays at various angles.
- a signal that can be detected when the ratio (S / N) of the signal (S) to the noise (N) is 2 or more is regarded as one diffraction line peak.
- the noise (N) is the width of the baseline.
- X-ray diffractometer for example, a powder X-ray analyzer: Rigaku RAD-RX can be used.
- the measurement conditions are X-ray output (Cu-K ⁇ ): 50 kV, 180 mA, scanning axis. : ⁇ / 2 ⁇ , measurement range (2 ⁇ ): 10 ° to 89.98 °, measurement mode: FT, reading width: 0.02 °, sampling time: 0.70 seconds, DS, SS, RS: 0.5 ° 0.5 °, 0.15 mm, Gonometer radius: 185 mm.
- the metal oxycarbonitride is a mixture composed of several phases, and when the metal oxycarbonitride is measured by a powder X-ray diffraction method (Cu—K ⁇ ray), it is derived from Nb 12 O 29 . Preferably a peak is observed. In addition, peaks derived from oxides such as NbO, NbO 2 , Nb 2 O 5 , Nb 25 O 62 , Nb 47 O 116 , and Nb 22 O 54 may be observed.
- the structure of the metal oxycarbonitride is not clear, it is considered that a phase composed of an oxide such as Nb 12 O 29 having an oxygen defect exists in the metal oxycarbonitride. Normally, single Nb 12 O 29 does not exhibit high oxygen reducing ability, but the metal carbonitride oxide is finally obtained because a phase composed of an oxide such as Nb 12 O 29 having oxygen defects exists. We estimate that the resulting catalyst has a high oxygen reduction ability.
- Nb 12 O 29 having an oxygen defect when Nb 12 O 29 having an oxygen defect is regarded as one unit, oxygen is bridged (Nb—O—O—Nb) between Nb and Nb of each unit. It is conceivable that. Although the mechanism of the expression of oxygen reducing ability is not clear, it is presumed that Nb contributing to the bridge coordination (Nb—O—O—Nb) becomes an active site and oxygen reducing ability is expressed. When Nb 12 O 29 having oxygen defects overlaps in each unit, the coupling distance between Nb and Nb between the units is shortened. It is considered that the oxygen reduction ability is improved as the portion having a shorter bond distance is increased.
- the oxygen reduction starting potential of the catalyst used in the present invention is preferably 0.5 V (vs. NHE) or more with respect to the reversible hydrogen electrode.
- the carbon source carbon black (specific surface area: 100 to 300 m 2 / g) (for example, XC-72 manufactured by Cabot Corporation) is used, and the catalyst and carbon are dispersed so that the mass ratio is 95: 5.
- isopropyl alcohol: water (mass ratio) 2: 1 is used.
- the obtained electrode refer to a reversible hydrogen electrode in a sulfuric acid solution of the same concentration at a temperature of 30 ° C. in a 0.5 mol / dm 3 sulfuric acid solution in an oxygen atmosphere and a nitrogen atmosphere.
- the current-potential curve was measured by polarizing the electrode at a potential scanning speed of 5 mV / sec, there was a difference of 0.2 ⁇ A / cm 2 or more between the reduction current in the oxygen atmosphere and the reduction current in the nitrogen atmosphere.
- the potential at which it begins to appear is defined as the oxygen reduction start potential.
- the oxygen reduction starting potential is less than 0.7 V (vs.
- the oxygen reduction starting potential is preferably 0.85 V (vs. NHE) or more in order to suitably reduce oxygen.
- the upper limit of the oxygen reduction start potential is the theoretical value of 1.23 V (vs. NHE).
- the fuel cell catalyst layer of the present invention formed using the above catalyst is preferably used at a potential of 0.4 V (vs. NHE) or more in the acidic electrolyte, and the upper limit of the potential depends on the stability of the electrode. It can be used up to approximately 1.23 V (vs. NHE), which is the potential at which oxygen is generated.
- the method for producing the catalyst is not particularly limited.
- tin, indium, platinum, tantalum, zirconium, copper, iron, tungsten, chromium, molybdenum, hafnium, titanium, vanadium, cobalt, manganese, cerium, mercury, plutonium, gold At least selected from the group consisting of silver, iridium, palladium, yttrium, ruthenium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and nickel
- a metal carbonitride containing one metal M and niobium to heat treatment in an inert gas containing oxygen
- metal carbonitride is obtained by heat-treating a mixture of the metal M oxide, niobium oxide and carbon in a nitrogen atmosphere or an inert gas containing nitrogen.
- a method of manufacturing a metal (I) a method of manufacturing a metal carbonitride by heat-treating a mixture of the metal M oxide, niobium carbide and niobium nitride in an inert gas such as nitrogen gas (II), Or a method (III) for producing a metal carbonitride by heat-treating a mixture of the metal M oxide, niobium carbide, niobium nitride and niobium oxide in an inert gas such as nitrogen gas, or the metal M Compound containing (eg, organic acid salts, chlorides, carbides, nitrides, complexes, etc.), niobium carbide and niobium nitride mixtures are heat-treating a mixture of the metal M oxide, niobi
- the raw material is not particularly limited, and for example, the raw materials in the production methods (I) to (IV) and other raw materials can be used in combination.
- a method (V) for producing a metal carbonitride by heat-treating the mixture thus combined in an inert gas such as nitrogen gas may be used.
- the production method (I) is a method for producing a metal carbonitride by heat-treating a mixture of the metal M oxide, niobium oxide and carbon in a nitrogen atmosphere or an inert gas containing nitrogen.
- the temperature of the heat treatment for producing the metal carbonitride is in the range of 600 ° C. to 1800 ° C., preferably in the range of 800 to 1600 ° C.
- the heat treatment temperature is within the above range, it is preferable in terms of good crystallinity and uniformity. If the heat treatment temperature is less than 600 ° C., the crystallinity tends to be poor and the uniformity tends to deteriorate, and if it is 1800 ° C. or more, it tends to be easy to sinter.
- the raw material metal M oxide is tin oxide, indium oxide, platinum oxide, tantalum oxide, zirconium oxide, copper oxide, iron oxide, tungsten oxide, chromium oxide, molybdenum oxide, hafnium oxide, titanium oxide, vanadium oxide, cobalt oxide.
- Examples include europium, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, and nickel oxide.
- One or more kinds of metal M oxides can be used.
- Examples of the raw material niobium oxide include NbO, NbO 2 and Nb 2 O 5 .
- the raw material carbon examples include carbon, carbon black, graphite, graphite, activated carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, and fullerene. It is preferable that the particle size of the carbon powder is smaller because the specific surface area is increased and the reaction with the oxide is facilitated.
- carbon black specific surface area: 100 to 300 m 2 / g, such as XC-72 manufactured by Cabot is preferably used.
- the catalyst has a high oxygen reduction initiation potential and high activity.
- Controlling the compounding amount (molar ratio) of the metal M oxide, niobium oxide, and carbon provides an appropriate metal carbonitride.
- the compounding amount (molar ratio) is usually 0.01 to 10 mol of the metal M oxide and 1 to 10 mol of carbon, preferably 1 mol of niobium oxide, with respect to 1 mol of niobium oxide.
- the metal M oxide is 0.01 to 4 mol and carbon is 2 to 6 mol.
- the production method (II) is a method for producing a metal carbonitride by heat-treating a mixture of the metal M oxide, niobium carbide and niobium nitride in an inert gas such as nitrogen gas.
- the temperature of the heat treatment for producing the metal carbonitride is in the range of 600 ° C. to 1800 ° C., preferably in the range of 800 to 1600 ° C.
- the heat treatment temperature is within the above range, it is preferable in terms of good crystallinity and uniformity. If the heat treatment temperature is less than 600 ° C., the crystallinity tends to be poor and the uniformity tends to deteriorate, and if it is 1800 ° C. or more, it tends to sinter easily.
- the metal M oxide, niobium carbide and niobium nitride are used as the raw material.
- the raw material metal M oxide is tin oxide, indium oxide, platinum oxide, tantalum oxide, zirconium oxide, copper oxide, iron oxide, tungsten oxide, chromium oxide, molybdenum oxide, hafnium oxide, titanium oxide, vanadium oxide, cobalt oxide.
- Examples include europium, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, and nickel oxide.
- One or more kinds of metal M oxides can be used.
- NbC etc. are mentioned as a raw material niobium carbide.
- Examples of the raw material niobium nitride include NbN.
- the metal carbonitride obtained from the metal M oxide, niobium carbide and niobium nitride is heat-treated in an inert gas containing oxygen.
- the resulting catalyst has a high oxygen reduction starting potential and high activity.
- the blending amount (molar ratio) is usually 0.01 to 500 mol of niobium carbide (NbC) and 0.01 to 50 mol of the metal M oxide with respect to 1 mol of niobium nitride (NbN).
- niobium carbide (NbC) is 0.1 to 300 mol and the metal M oxide is 0.1 to 30 mol with respect to 1 mol of niobium nitride (NbN).
- the production method (III) is a method for producing a metal carbonitride by heat-treating a mixture of the metal M oxide, niobium carbide, niobium nitride and niobium oxide in an inert gas such as nitrogen gas.
- the temperature of the heat treatment for producing the metal carbonitride is in the range of 600 ° C. to 1800 ° C., preferably in the range of 800 to 1600 ° C.
- the heat treatment temperature is within the above range, it is preferable in terms of good crystallinity and uniformity. If the heat treatment temperature is less than 600 ° C., the crystallinity tends to be poor and the uniformity tends to deteriorate, and if it is 1800 ° C. or more, it tends to sinter easily.
- the metal M oxide, niobium carbide, niobium nitride and niobium oxide are used as the raw material.
- the raw material metal M oxide is tin oxide, indium oxide, platinum oxide, tantalum oxide, zirconium oxide, copper oxide, iron oxide, tungsten oxide, chromium oxide, molybdenum oxide, hafnium oxide, titanium oxide, vanadium oxide, cobalt oxide.
- Examples include europium, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, and nickel oxide.
- One or more kinds of metal M oxides can be used.
- NbC etc. are mentioned as a raw material niobium carbide.
- Examples of the raw material niobium nitride include NbN.
- Examples of the raw material niobium oxide include NbO, NbO 2 and Nb 2 O 5 .
- metal carbonitride obtained by heat-treating metal carbonitride obtained from the oxide of metal M, niobium carbide, niobium nitride and niobium oxide in an inert gas containing oxygen A catalyst made of an oxide has a high oxygen reduction starting potential and high activity.
- the blending amount (molar ratio) is usually 0.01 to 500 moles of niobium carbide (NbC) with respect to 1 mole of niobium nitride (NbN), and 0.01% of the metal M oxide and niobium oxide.
- NbC niobium carbide
- NbN niobium nitride
- Production method (IV) is a method for producing a metal carbonitride by heat-treating a mixture of the compound containing metal M, niobium carbide and niobium nitride in an inert gas such as nitrogen gas.
- the temperature of the heat treatment for producing the metal carbonitride is in the range of 600 ° C. to 1800 ° C., preferably in the range of 800 to 1600 ° C.
- the heat treatment temperature is within the above range, it is preferable in terms of good crystallinity and uniformity. If the heat treatment temperature is less than 600 ° C., the crystallinity tends to be poor and the uniformity tends to deteriorate, and if it is 1800 ° C. or more, it tends to be easy to sinter.
- a compound containing the metal M, niobium carbide and niobium nitride are used as the raw material.
- the compounds containing the raw material metal M are tin, indium, platinum, tantalum, zirconium, copper, iron, tungsten, chromium, molybdenum, hafnium, titanium, vanadium, cobalt, manganese, cerium, mercury, plutonium, gold, silver, Organic salts such as iridium, palladium, yttrium, ruthenium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium or nickel, carbonates, chlorides , Organic complexes, carbides, nitrides and the like.
- One or more compounds containing the metal M can be used.
- NbC etc. are mentioned as a raw material niobium carbide.
- Examples of the raw material niobium nitride include NbN.
- the catalyst consisting of has a high oxygen reduction starting potential and high activity.
- the compounding amount (molar ratio) of the compound containing metal M, niobium carbide and niobium nitride is controlled, an appropriate metal carbonitride can be obtained.
- the compounding amount (molar ratio) is usually 0.01 to 500 mol of niobium carbide (NbC) and 0.001 to 50 mol of the compound containing the metal M with respect to 1 mol of niobium nitride (NbN). Yes, preferably 0.1 to 300 mol of niobium carbide (NbC) and 0.01 to 30 mol of the compound containing the metal M with respect to 1 mol of niobium nitride (NbN).
- NbC niobium carbide
- NbN niobium nitride
- the raw material is not particularly limited as long as the metal carbonitride can be obtained, and the raw materials in the production methods (I) to (IV) and other raw materials can be used in various combinations.
- the production method (V) is a method for producing a metal carbonitride by heat-treating a raw material mixture other than the raw material combination in the production methods (I) to (IV) in an inert gas such as nitrogen gas. .
- the temperature of the heat treatment for producing the metal carbonitride is in the range of 600 ° C. to 1800 ° C., preferably in the range of 800 to 1600 ° C.
- the heat treatment temperature is within the above range, it is preferable in terms of good crystallinity and uniformity. If the heat treatment temperature is less than 600 ° C., the crystallinity tends to be poor and the uniformity tends to deteriorate, and if it is 1800 ° C. or more, it tends to sinter easily.
- the raw material for example, a mixture containing various combinations of the metal M-containing compound, niobium carbide, niobium nitride, niobium oxide, niobium precursor, carbon, or the like can be used as the raw material mixture.
- the compounds containing the raw material metal M are tin, indium, platinum, tantalum, zirconium, copper, iron, tungsten, chromium, molybdenum, hafnium, titanium, vanadium, cobalt, manganese, cerium, mercury, plutonium, gold, silver, Organic salts such as iridium, palladium, yttrium, ruthenium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium or nickel, carbonates, chlorides , Organic complexes, carbides, nitrides, precursors and the like.
- One or more compounds containing the metal M can be used.
- NbC etc. are mentioned as a raw material niobium carbide.
- Examples of the raw material niobium nitride include NbN.
- Examples of the raw material niobium oxide include NbO, NbO 2 and Nb 2 O 5 .
- niobium precursors examples include niobium organic acid salts, carbonates, chlorides, organic complexes, carbides, nitrides, and alkoxy compounds.
- the raw material carbon examples include carbon, carbon black, graphite, graphite, activated carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, and fullerene. It is preferable that the particle size of the carbon powder is smaller because the specific surface area is increased and the reaction with the oxide is facilitated.
- carbon black specific surface area: 100 to 300 m 2 / g, such as XC-72 manufactured by Cabot is preferably used.
- a catalyst made of metal carbonitride obtained by heat-treating the obtained metal carbonitride in an inert gas containing oxygen has a high oxygen reduction starting potential and is active. high.
- the compounding amount (molar ratio) of the compound containing metal M, niobium carbide and niobium nitride an appropriate metal carbonitride can be obtained.
- the compounding amount (molar ratio) is usually 0.01 to 500 mol of niobium carbide (NbC) and 0.001 to 50 mol of the compound containing the metal M with respect to 1 mol of niobium nitride (NbN). Yes, preferably 0.1 to 300 mol of niobium carbide (NbC) and 0.01 to 30 mol of the compound containing the metal M with respect to 1 mol of niobium nitride (NbN).
- NbC niobium carbide
- NbN niobium nitride
- the inert gas includes nitrogen, helium gas, neon gas, argon gas, krypton gas, xenon gas or radon gas. Nitrogen, argon gas or helium gas is particularly preferable because it is relatively easy to obtain.
- the concentration of the oxygen gas in the inert gas depends on the heat treatment time and the heat treatment temperature, but is preferably 0.1 to 10% by volume, particularly preferably 0.5 to 5% by volume. When the concentration of the oxygen gas is within the above range, it is preferable in that a uniform carbonitride oxide is formed. Further, when the concentration of the oxygen gas is less than 0.1% by volume, it tends to be in an unoxidized state, and when it exceeds 10% by volume, oxidation tends to proceed excessively.
- hydrogen gas is contained in the inert gas in a range of 5% by volume or less.
- the hydrogen gas content is more preferably 0.01 to 4% by volume, still more preferably 0.1 to 4% by volume.
- the capacity% in the present invention is a value in a standard state.
- the temperature of the heat treatment in this step is usually in the range of 400 to 1400 ° C., preferably in the range of 600 to 1200 ° C.
- the heat treatment temperature is within the above range, it is preferable in that a uniform metal oxynitride is formed.
- the heat treatment temperature is less than 400 ° C., the oxidation tends not to proceed, and when it is 1400 ° C. or more, the oxidation proceeds excessively and the crystal tends to grow.
- Examples of the heat treatment method in the process include a stationary method, a stirring method, a dropping method, and a powder trapping method.
- the dropping method is a method of heating a furnace to a predetermined heat treatment temperature while flowing an inert gas containing a small amount of oxygen gas in an induction furnace, maintaining a thermal equilibrium at the temperature, and then a crucible which is a heating area of the furnace.
- This is a method of dropping a metal carbonitride into a heat treatment.
- the dropping method is preferable in that aggregation and growth of metal carbonitride particles can be suppressed to a minimum.
- the powder trapping method captures metal carbonitrides in a vertical tube furnace maintained at a prescribed heat treatment temperature by suspending metal carbonitrides in an inert gas atmosphere containing a small amount of oxygen gas.
- the heat treatment method captures metal carbonitrides in a vertical tube furnace maintained at a prescribed heat treatment temperature by suspending metal carbonitrides in an inert gas atmosphere containing a small amount of oxygen gas.
- the heat treatment time of the metal carbonitride is usually 0.5 to 10 minutes, preferably 0.5 to 3 minutes. It is preferable that the heat treatment time be within the above range because a uniform metal oxycarbonitride tends to be formed. If the heat treatment time is less than 0.5 minutes, metal oxycarbonitride tends to be partially formed, and if it exceeds 10 minutes, oxidation tends to proceed excessively.
- the heat treatment time of the metal carbonitride is 0.2 second to 1 minute, preferably 0.2 to 10 seconds. It is preferable that the heat treatment time be within the above range because a uniform metal oxycarbonitride tends to be formed. If the heat treatment time is less than 0.2 seconds, metal oxycarbonitride tends to be partially formed, and if it exceeds 1 minute, oxidation tends to proceed excessively.
- the heat treatment time of the metal carbonitride is 0.1 to 10 hours, preferably 0.5 to 5 hours. It is preferable that the heat treatment time be within the above range because a uniform metal oxycarbonitride tends to be formed. If the heat treatment time is less than 0.1 hour, metal oxycarbonitride tends to be partially formed, and if it exceeds 10 hours, oxidation tends to proceed excessively.
- the metal oxycarbonitride obtained by the above-described production method or the like may be used as it is, but the obtained metal oxycarbonitride is further pulverized into a finer powder. It may be used.
- Examples of the method for crushing the metal carbonitride oxide include a roll rolling mill, a ball mill, a medium agitation mill, an airflow crusher, a mortar, a method using a tank disintegrator, and the like.
- the method using an airflow pulverizer is preferable, and the method using a mortar is preferable from the viewpoint that a small amount of processing is easy.
- the catalyst of the present invention can be used as an alternative catalyst for a platinum catalyst.
- it can be used as a fuel cell catalyst, exhaust gas treatment catalyst or organic synthesis catalyst.
- the fuel cell catalyst layer of the present invention is characterized by containing the catalyst.
- the fuel cell catalyst layer includes an anode catalyst layer and a cathode catalyst layer, and the catalyst can be used for both. Since the catalyst is excellent in durability and has a large oxygen reducing ability, it is preferably used in the cathode catalyst layer.
- the fuel cell catalyst layer of the present invention preferably further contains electron conductive particles.
- the reduction current can be further increased.
- the electron conductive particles are considered to increase the reduction current because they generate an electrical contact for inducing an electrochemical reaction in the catalyst.
- the electron conductive particles are usually used as a catalyst carrier.
- the material constituting the electron conductive particles examples include carbon, conductive polymers, conductive ceramics, metals, and conductive inorganic oxides such as tungsten oxide or iridium oxide, which can be used alone or in combination. .
- carbon particles having a large specific surface area alone or a mixture of carbon particles having a large specific surface area and other electron conductive particles are preferable. That is, the fuel cell catalyst layer preferably includes the catalyst and carbon particles having a large specific surface area.
- carbon carbon black, graphite, graphite, activated carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, fullerene and the like can be used. If the particle size of the carbon is too small, it becomes difficult to form an electron conduction path, and if it is too large, the gas diffusibility of the catalyst layer for the fuel cell tends to be reduced or the utilization factor of the catalyst tends to be reduced. A range of 1000 nm is preferable, and a range of 10 to 100 nm is more preferable.
- the mass ratio of the catalyst to carbon is preferably 4: 1 to 1000: 1.
- the conductive polymer is not particularly limited.
- polypyrrole, polyaniline, and polythiophene are preferable, and polypyrrole is more preferable.
- the polymer electrolyte is not particularly limited as long as it is generally used in a fuel cell catalyst layer.
- a perfluorocarbon polymer having a sulfonic acid group for example, Nafion (DuPont 5% Nafion solution (DE521))
- a hydrocarbon polymer compound having a sulfonic acid group for example, an inorganic acid such as phosphoric acid.
- Nafion DuPont 5% Nafion solution (DE521)
- Nafion DuPont 5% Nafion solution (DE521)
- the fuel cell catalyst layer of the present invention can be used for either an anode catalyst layer or a cathode catalyst layer.
- the catalyst layer for a fuel cell of the present invention includes a catalyst layer (catalyst catalyst for cathode) provided on the cathode of a fuel cell because it contains a catalyst having high oxygen reducing ability and hardly corroded even in a high potential in an acidic electrolyte. Layer).
- a catalyst layer provided on the cathode of a membrane electrode assembly provided in a polymer electrolyte fuel cell.
- Examples of the method for dispersing the catalyst on the electron conductive particles as a support include air flow dispersion and dispersion in liquid. Dispersion in liquid is preferable because a catalyst and electron conductive particles dispersed in a solvent can be used in the fuel cell catalyst layer forming step. Examples of the dispersion in the liquid include a method using an orifice contraction flow, a method using a rotating shear flow, and a method using an ultrasonic wave.
- the solvent used for dispersion in the liquid is not particularly limited as long as it does not erode the catalyst or electron conductive particles and can be dispersed, but a volatile liquid organic solvent or water is generally used.
- the electrolyte and the dispersant may be further dispersed at the same time.
- the method for forming the catalyst layer for the fuel cell is not particularly limited. For example, a method of applying a suspension containing the catalyst, the electron conductive particles, and the electrolyte to the electrolyte membrane or the gas diffusion layer to be described later. It is done. Examples of the application method include a dipping method, a screen printing method, a roll coating method, and a spray method. In addition, after forming a catalyst layer for a fuel cell on a base material by a coating method or a filtration method using a suspension containing the catalyst, electron conductive particles, and an electrolyte, the catalyst layer for a fuel cell is formed on the electrolyte membrane by a transfer method. The method of forming is mentioned.
- the electrode of the present invention is characterized by having the fuel cell catalyst layer and a porous support layer.
- the electrode of the present invention can be used as either a cathode or an anode. Since the electrode of the present invention is excellent in durability and has a large catalytic ability, it is more effective when used for a cathode.
- the porous support layer is a layer that diffuses gas (hereinafter also referred to as “gas diffusion layer”).
- gas diffusion layer may be anything as long as it has electron conductivity, high gas diffusibility, and high corrosion resistance.
- carbon-based porous materials such as carbon paper and carbon cloth are used.
- Aluminum foil coated with stainless steel or corrosion resistant material is used for the material and weight reduction.
- the membrane electrode assembly of the present invention is a membrane electrode assembly having a cathode, an anode, and an electrolyte membrane disposed between the cathode and the anode, wherein the cathode and / or the anode is the electrode. It is characterized by that.
- an electrolyte membrane using a perfluorosulfonic acid system or a hydrocarbon electrolyte membrane is generally used.
- a membrane or porous body in which a polymer microporous membrane is impregnated with a liquid electrolyte is impregnated with a liquid electrolyte.
- a membrane filled with a polymer electrolyte may be used.
- the fuel cell of the present invention is characterized by comprising the membrane electrode assembly.
- Fuel cell electrode reactions occur at the so-called three-phase interface (electrolyte-electrode catalyst-reaction gas). Fuel cells are classified into several types depending on the electrolyte used, etc., and include molten carbonate type (MCFC), phosphoric acid type (PAFC), solid oxide type (SOFC), and solid polymer type (PEFC). . Especially, it is preferable to use the membrane electrode assembly of this invention for a polymer electrolyte fuel cell.
- MCFC molten carbonate type
- PAFC phosphoric acid type
- SOFC solid oxide type
- PEFC solid polymer type
- the number of diffraction line peaks in powder X-ray diffraction of each sample was counted by regarding a signal that can be detected with a ratio (S / N) of signal (S) to noise (N) of 2 or more as one peak.
- the noise (N) is the width of the baseline.
- Nitrogen / oxygen About 0.1 g of a sample was weighed and sealed in Ni-Cup, and then measured with an ON analyzer.
- Niobium and other metals M About 0.1 g of a sample was weighed in a platinum dish, and acid was added for thermal decomposition. This thermally decomposed product was fixed, diluted, and quantified by ICP-MS.
- Example 1 Preparation niobium oxide catalyst (IV) (NbO 2) 4.95g (39.6mmol), tin oxide (IV) (SnO 2) 60mg (0.4mmol) of carbon (Cabot Corporation, Vulcan72) 1.2g (100mmol ) was sufficiently pulverized and mixed. This mixed powder was heat-treated in a tube furnace at 1400 ° C. for 3 hours in a nitrogen atmosphere to obtain 4.23 g of carbonitride (1) containing tin (1 mol%) and niobium.
- the obtained carbonitride (1) (1.02 g) was heat-treated at 800 ° C. for 1 hour in a tubular furnace while flowing an argon gas containing 1% by volume of oxygen gas, whereby tin (1 mol%) and niobium 1.10 g of oxycarbonitride containing nitrogen (hereinafter also referred to as “catalyst (1)”) was obtained.
- the prepared fuel cell electrode (1) was polarized in an oxygen atmosphere and a nitrogen atmosphere in a 0.5 mol / dm 3 sulfuric acid solution at 30 ° C. and a potential scanning rate of 5 mV / sec, and a current-potential curve was obtained. It was measured. At that time, a reversible hydrogen electrode in a sulfuric acid solution having the same concentration was used as a reference electrode.
- the potential at which a difference of 0.2 ⁇ A / cm 2 or more appears between the reduction current in the oxygen atmosphere and the reduction current in the nitrogen atmosphere was defined as the oxygen reduction start potential, and the difference between the two was defined as the oxygen reduction current.
- the catalytic ability (oxygen reducing ability) of the fuel cell electrode (1) produced by this oxygen reduction starting potential and oxygen reducing current was evaluated.
- FIG. 39 shows a current-potential curve obtained by the above measurement.
- Example 1 It was found that the fuel cell electrode (1) produced in Example 1 had an oxygen reduction starting potential of 0.78 V (vs. NHE) and high oxygen reducing ability.
- Example 2 Catalyst Preparation 4.75 g (38 mmol) of niobium oxide (IV) (NbO 2 ), 302 mg (2 mmol) of tin oxide (IV) (SnO 2), and 1.2 g (100 mmol) of carbon (Cabot Corporation, Vulcan 72) were sufficiently ground. And mixed. This mixed powder was heat-treated in a tube furnace at 1400 ° C. for 3 hours in a nitrogen atmosphere to obtain 4.10 g of carbonitride (2) containing tin (5 mol%) and niobium.
- a fuel cell electrode (2) was obtained in the same manner as in Example 1 except that the catalyst (2) was used.
- FIG. 40 shows a current-potential curve obtained by the measurement.
- the electrode for fuel cell (2) produced in Example 2 has an oxygen reduction starting potential of 0.72 V (vs. NHE) and was found to have a high oxygen reducing ability.
- Example 3 Preparation of catalyst In the same manner as in Example 1 except that 4.00 g (32 mmol) of niobium oxide (IV) (NbO 2 ) and 1.21 g (8 mmol) of tin (IV) oxide (SnO 2 ) were used, tin (20 Mol%) and niobium-containing carbonitride (3) (4.23 g), and carbonitride oxide containing tin (20 mol%) and niobium (hereinafter “ Also referred to as “catalyst (3)”.) 1.09 g was prepared. Table 1 shows the results of elemental analysis of the obtained catalyst (3).
- a fuel cell electrode (3) was obtained in the same manner as in Example 1 except that the catalyst (3) was used.
- FIG. 41 shows a current-potential curve obtained by the measurement.
- Example 3 It was found that the fuel cell electrode (3) produced in Example 3 had an oxygen reduction starting potential of 0.65 V (vs. NHE) and high oxygen reducing ability.
- Example 4 Preparation of catalyst In the same manner as in Example 1 except that 55 mg (0.2 mmol) of indium (III) oxide (In 2 O 3 ) was used instead of 60 mg (0.4 mmol) of tin (IV) oxide (SnO 2 ). , 4.23 g of carbonitride (4) containing indium (0.4 mol%) and niobium was produced, and 1.02 g of carbonitride (4) contained indium (0.4 mol%) and niobium 1.10 g of carbonitride oxide (hereinafter also referred to as “catalyst (4)”) was prepared.
- a fuel cell electrode (4) was obtained in the same manner as in Example 1 except that the catalyst (4) was used.
- FIG. 42 shows a current-potential curve obtained by the measurement.
- Example 4 It was found that the fuel cell electrode (4) produced in Example 4 had an oxygen reduction starting potential of 0.80 V (vs. NHE) and high oxygen reducing ability.
- Example 5 Preparation of catalyst The amount of niobium (IV) oxide (NbO 2 ) was changed from 4.95 g (39.6 mmol) to 4.75 g (38 mmol), and 60 mg (0.4 mmol) of tin (IV) oxide (SnO 2 ) was added.
- a fuel cell electrode (5) was obtained in the same manner as in Example 1 except that the catalyst (5) was used.
- FIG. 43 shows a current-potential curve obtained by the measurement.
- Example 5 It was found that the fuel cell electrode (5) produced in Example 5 had an oxygen reduction starting potential of 0.80 V (vs. NHE) and high oxygen reducing ability.
- Example 6 Preparation of catalyst The amount of niobium (IV) oxide (NbO 2 ) was changed from 4.95 g (39.6 mmol) to 4.00 g (32 mmol), and 60 mg (0.4 mmol) of tin (IV) oxide (SnO 2 ) was added. Carbonitride (6) 3 containing indium (20 mol%) and niobium in the same manner as in Example 1 except that 1.11 g (8 mmol) of indium (III) oxide (In 2 O 3 ) was used instead.
- catalyst (6) carbonitride oxide containing indium (20 mol%) and niobium was prepared from 1.02 g of the carbonitride (6).
- Table 1 shows the elemental analysis results of the obtained catalyst (6).
- a fuel cell electrode (6) was obtained in the same manner as in Example 1 except that the catalyst (6) was used.
- FIG. 44 shows a current-potential curve obtained by the measurement.
- Example 6 It was found that the fuel cell electrode (6) produced in Example 6 had an oxygen reduction starting potential of 0.80 V (vs. NHE) and high oxygen reducing ability.
- Example 7 Preparation of catalyst 4.96 g (42.5 mmol) of niobium carbide (NbC), 0.60 g (2.5 mmol) of indium oxide (In 2 O 3 ), 0.27 g (2.5 mmol) of niobium nitride (NbN) Milled and mixed. This mixed powder was heat-treated in a tube furnace at 1400 ° C. for 3 hours in a nitrogen atmosphere to obtain 5.12 g of carbonitride (7) containing indium and niobium. The sintered carbonitride (7) was pulverized with a ball mill.
- a fuel cell electrode (7) was obtained in the same manner as in Example 1 except that the catalyst (7) was used.
- FIG. 45 shows a current-potential curve obtained by the measurement.
- Example 7 It was found that the fuel cell electrode (7) produced in Example 7 had an oxygen reduction starting potential of 0.82 V (vs. NHE) and high oxygen reducing ability.
- Example 8 1. Preparation of catalyst 4.96 g (42.5 mmol) of niobium carbide (NbC), 1.11 g (2.5 mmol) of tantalum oxide (Ta 2 O 5 ), 0.27 g (2.5 mmol) of niobium nitride (NbN) are mixed well. Then, the mixture was heat treated at 1500 ° C. for 3 hours in a nitrogen atmosphere to obtain 5.94 g of carbonitride (8) containing tantalum and niobium. The sintered carbonitride (8) was pulverized with a ball mill.
- a fuel cell electrode (8) was obtained in the same manner as in Example 1 except that the catalyst (8) was used.
- FIG. 46 shows a current-potential curve obtained by the measurement.
- Example 8 It was found that the fuel cell electrode (8) produced in Example 8 had an oxygen reduction starting potential of 0.83 V (vs. NHE) and high oxygen reducing ability.
- Example 9 Preparation of catalyst 4.96 g (42.5 mmol) of niobium carbide (NbC), 0.31 g (2.5 mmol) of niobium oxide (NbO 2 ), 0.57 g (2.5 mmol) of platinum oxide (PtO 2 ), niobium nitride ( NbN) 0.27 g (2.5 mmol) was mixed well, and the mixture was heat-treated in a nitrogen atmosphere at 1600 ° C. for 3 hours to obtain 5.87 g of carbonitride (9) containing platinum and niobium. Obtained. The sintered carbonitride (9) was pulverized with a ball mill.
- a fuel cell electrode (9) was obtained in the same manner as in Example 1 except that the catalyst (9) was used.
- FIG. 47 shows a current-potential curve obtained by the measurement.
- Example 9 It was found that the fuel cell electrode (9) produced in Example 9 had an oxygen reduction starting potential of 0.90 V (vs. NHE) and high oxygen reducing ability.
- Example 10 Catalyst Preparation 5.05 g (40 mmol) of niobium (IV) oxide (NbO 2 ) and 1.5 g (Pt: 1.6 mmol) of 20% Pt carbon (made by Tanaka Kikinzoku) were mixed well, and the mixture was heated to 1600 ° C. Then, 4.47 g of carbonitride (10) containing platinum and niobium was obtained by heat treatment in a nitrogen atmosphere for 1 hour. The sintered carbonitride (10) was pulverized with a ball mill.
- niobium (IV) oxide NbO 2
- Pt 1.6 mmol
- 20% Pt carbon made by Tanaka Kikinzoku
- a fuel cell electrode (10) was obtained in the same manner as in Example 1 except that the catalyst (10) was used.
- FIG. 48 shows a current-potential curve obtained by the measurement.
- Example 10 It was found that the fuel cell electrode (10) produced in Example 10 had an oxygen reduction starting potential of 0.95 V (vs. NHE) and high oxygen reducing ability.
- Example 11 Preparation of catalyst 4.96 g (42.5 mmol) of niobium carbide (NbC), indium tin oxide (In 2 O 2 —SnO 2 ) (ITO) (powder made by Catalyst Kasei Kogyo Co., Ltd.) 0.69 g (2.5 mmol), Niobium nitride (NbN) 0.27 g (2.5 mmol) was sufficiently pulverized and mixed. This mixed powder was heat-treated in a tube furnace at 1400 ° C. for 3 hours in a nitrogen atmosphere to obtain 5.94 g of carbonitride (11) containing indium, tin and niobium.
- the sintered carbonitride (11) was pulverized with a ball mill. Thereafter, in the same manner as in Example 1, 1.10 g of carbonitride oxide containing indium, tin and niobium (hereinafter also referred to as “catalyst (11)”) from 1.02 g of the carbonitride (11). Prepared.
- a fuel cell electrode (11) was obtained in the same manner as in Example 1 except that the catalyst (11) was used.
- FIG. 49 shows a current-potential curve obtained by the measurement.
- Example 11 It was found that the fuel cell electrode (11) produced in Example 11 had an oxygen reduction starting potential of 0.85 V (vs. NHE) and high oxygen reducing ability.
- Table 1 shows the elemental analysis results of the ground catalyst (12).
- a fuel cell electrode (12) was obtained in the same manner as in Example 1 except that the obtained niobium carbonitride was used.
- FIG. 50 shows a current-potential curve obtained by the measurement.
- Example 12 Preparation of catalyst 5.88 g (56 mmol) of niobium carbide (NbC), 0.40 g (2.5 mmol) of ferric oxide (Fe 2 O 3 ), and 5.14 g (48 mmol) of niobium nitride (NbN) were sufficiently pulverized. And mixed. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 11.19 g of carbonitride (13) containing iron and niobium. The sintered carbonitride (13) was pulverized with a ball mill. By heat-treating 1.00 g of the obtained carbonitride (13) at 900 ° C.
- a fuel cell electrode (13) was obtained in the same manner as in Example 1 except that the catalyst (13) was used.
- FIG. 51 shows a current-potential curve obtained by the measurement.
- Example 12 It was found that the fuel cell electrode (13) produced in Example 12 had an oxygen reduction starting potential of 0.90 V (vs. NHE) and high oxygen reducing ability.
- Example 13 Preparation of catalyst 5.88 g (56 mmol) of niobium carbide (NbC), 0.36 g (5 mmol) of manganese oxide (MnO), and 5.14 g (48 mmol) of niobium nitride (NbN) were sufficiently pulverized and mixed. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 10.93 g of carbonitride (14) containing manganese and niobium. The sintered carbonitride (14) was pulverized with a ball mill.
- NbC niobium carbide
- MnO manganese oxide
- NbN niobium nitride
- a fuel cell electrode (14) was obtained in the same manner as in Example 1 except that the catalyst (14) was used.
- FIG. 52 shows a current-potential curve obtained by the measurement.
- Example 13 It was found that the fuel cell electrode (14) produced in Example 13 had an oxygen reduction starting potential of 0.85 V (vs. NHE) and high oxygen reducing ability.
- Example 14 Preparation of catalyst 5.88 g (56 mmol) of niobium carbide (NbC), 0.86 g (5 mmol) of cerium oxide (CeO 2 ), and 5.14 g (48 mmol) of niobium nitride (NbN) were sufficiently pulverized and mixed. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 11.69 g of carbonitride (15) containing cerium and niobium. The sintered carbonitride (15) was pulverized with a ball mill.
- NbC niobium carbide
- CeO 2 cerium oxide
- NbN niobium nitride
- a peak derived from Nb 12 O 29 was observed as shown in FIG.
- a fuel cell electrode (15) was obtained in the same manner as in Example 1 except that the catalyst (15) was used.
- FIG. 53 shows a current-potential curve obtained by the measurement.
- Example 14 It was found that the fuel cell electrode (15) produced in Example 14 had an oxygen reduction starting potential of 0.86 V (vs. NHE) and high oxygen reducing ability.
- Example 15 Preparation of catalyst 5.88 g (56 mmol) of niobium carbide (NbC), 0.38 g (2.5 mmol) of chromium oxide (Cr 2 O 3 ), 5.14 g (48 mmol) of niobium nitride (NbN) were sufficiently pulverized and mixed. did. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 11.17 g of carbonitride (16) containing chromium and niobium. The sintered carbonitride (16) was pulverized with a ball mill.
- a fuel cell electrode (16) was obtained in the same manner as in Example 1 except that the catalyst (16) was used.
- FIG. 54 shows a current-potential curve obtained by the measurement.
- Example 15 It was found that the fuel cell electrode (16) produced in Example 15 had an oxygen reduction starting potential of 0.85 V (vs. NHE) and high oxygen reducing ability.
- Example 16 Preparation of catalyst Niobium carbide (NbC) 5.88 g (56 mmol), iron acetate (C 4 H 6 O 4 Fe) 0.87 g (5 mmol), niobium nitride (NbN) 5.14 g (48 mmol) were sufficiently pulverized. Mixed. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 10.89 g of carbonitride (17) containing iron and niobium. The sintered carbonitride (17) was pulverized with a ball mill.
- a fuel cell electrode (17) was obtained in the same manner as in Example 1 except that the catalyst (17) was used.
- FIG. 55 shows a current-potential curve obtained by the measurement.
- Example 16 It was found that the fuel cell electrode (17) produced in Example 16 had an oxygen reduction starting potential of 0.90 V (vs. NHE) and high oxygen reducing ability.
- Example 17 1. Preparation of catalyst 5.88 g (56 mmol) of niobium carbide (NbC), 1.29 g (5 mmol) of cobalt acetylacetone complex (C 10 H 14 O 4 Co), and 5.14 g (48 mmol) of niobium nitride (NbN) were sufficiently pulverized. And mixed. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 10.94 g of carbonitride (18) containing cobalt and niobium. The sintered carbonitride (18) was pulverized with a ball mill.
- a peak derived from Nb 12 O 29 was observed as shown in FIG.
- FIG. 56 shows a current-potential curve obtained by the measurement.
- Example 17 It was found that the fuel cell electrode (18) produced in Example 17 had an oxygen reduction starting potential of 0.87 V (vs. NHE) and high oxygen reducing ability.
- Example 18 Catalyst Preparation 5.88 g (56 mmol) of niobium carbide (NbC) and 5.14 g (48 mmol) of niobium nitride (NbN) were mixed, and tetrachloroauric acid (HAuCl 4 .nH 2 O) dissolved in 1 ml of ethanol was added. 203 g (0.5 mmol) was added and thoroughly pulverized and mixed. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 11.33 g of carbonitride (19) containing gold and niobium.
- NbC niobium carbide
- NbN niobium nitride
- the sintered carbonitride (19) was pulverized with a ball mill. Thereafter, in the same manner as in Example 12, 1.25 g of carbonitride oxide (hereinafter also referred to as “catalyst (19)”) containing gold and niobium was prepared from 1.02 g of the carbonitride (19). . Table 1 shows the results of elemental analysis of the obtained catalyst (19).
- a fuel cell electrode (19) was obtained in the same manner as in Example 1 except that the catalyst (19) was used.
- FIG. 57 shows a current-potential curve obtained by the measurement.
- Example 18 It was found that the fuel cell electrode (19) produced in Example 18 had an oxygen reduction starting potential of 0.90 V (vs. NHE) and high oxygen reducing ability.
- Example 19 Preparation of catalyst Niobium carbide (NbC) 5.88 g (56 mmol), silver acetate (C 2 H 3 O 2 Ag) 0.835 g (5 mmol), niobium nitride (NbN) 5.14 g (48 mmol) were sufficiently pulverized. Mixed. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 10.82 g of carbonitride (20) containing silver and niobium. The sintered carbonitride (20) was pulverized with a ball mill.
- a fuel cell electrode (20) was obtained in the same manner as in Example 1 except that the catalyst (20) was used.
- FIG. 58 shows a current-potential curve obtained by the measurement.
- Example 19 It was found that the fuel cell electrode (20) produced in Example 19 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and high oxygen reducing ability.
- Example 20 Catalyst Preparation 5.88 g (56 mmol) of niobium carbide (NbC), 0.61 g (5 mmol) of palladium oxide (PdO), and 5.14 g (48 mmol) of niobium nitride (NbN) were sufficiently pulverized and mixed. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 11.63 g of carbonitride (21) containing palladium and niobium. The sintered carbonitride (21) was pulverized with a ball mill.
- a fuel cell electrode (21) was obtained in the same manner as in Example 1 except that the catalyst (21) was used.
- FIG. 59 shows a current-potential curve obtained by the measurement.
- Example 20 It was found that the fuel cell electrode (21) produced in Example 20 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and high oxygen reducing ability.
- Example 21 Preparation of catalyst 5.88 g (56 mmol) of niobium carbide (NbC), 1.12 g (5 mmol) of iridium oxide (IrO 2 ) and 5.14 g (48 mmol) of niobium nitride (NbN) were sufficiently pulverized and mixed. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 11.29 g of carbonitride (22) containing iridium and niobium. The sintered carbonitride (22) was pulverized with a ball mill.
- NbC niobium carbide
- IrO 2 iridium oxide
- NbN niobium nitride
- a fuel cell electrode (22) was obtained in the same manner as in Example 1 except that the catalyst (22) was used.
- FIG. 60 shows a current-potential curve obtained by the measurement.
- Example 21 It was found that the fuel cell electrode (22) produced in Example 21 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and high oxygen reducing ability.
- Example 22 Preparation of catalyst 5.88 g (56 mmol) of niobium carbide (NbC), 0.67 g (5 mmol) of ruthenium oxide (RuO 2 ), and 5.14 g (48 mmol) of niobium nitride (NbN) were sufficiently pulverized and mixed. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain 11.29 g of carbonitride (23) containing ruthenium and niobium. The sintered carbonitride (23) was pulverized with a ball mill.
- NbC niobium carbide
- RuO 2 ruthenium oxide
- NbN niobium nitride
- a fuel cell electrode (23) was obtained in the same manner as in Example 1 except that the catalyst (23) was used.
- FIG. 61 shows a current-potential curve obtained by the measurement.
- Example 22 It was found that the fuel cell electrode (23) produced in Example 22 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and high oxygen reducing ability.
- Example 23 Preparation of catalyst 5.17 g (49 mmol) of niobium carbide (NbC), 0.30 g (0.9 mmol) of lanthanum oxide (La 2 O 3 ), and 4.52 g (42 mmol) of niobium nitride (NbN) were sufficiently pulverized and mixed. did. The mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain a carbonitride (24) containing niobium and lanthanum.
- NbC niobium carbide
- La 2 O 3 lanthanum oxide
- NbN niobium nitride
- a fuel cell electrode (24) was obtained in the same manner as in Example 1 except that the catalyst (24) was used.
- FIG. 62 shows a current-potential curve obtained by the measurement.
- Example 23 It was found that the fuel cell electrode (24) produced in Example 23 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and high oxygen reducing ability.
- Example 24 Preparation of catalyst Niobium carbide (NbC) 5.17 g (49 mmol), praseodymium oxide (Pr 6 O 11 ) 0.31 g (0.3 mmol), niobium nitride (NbN) 4.52 g (42 mmol) were sufficiently pulverized and mixed. did. This mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain a carbonitride (25) containing niobium and praseodymium.
- a fuel cell electrode (25) was obtained in the same manner as in Example 1 except that the catalyst (25) was used.
- FIG. 63 shows a current-potential curve obtained by the measurement.
- Example 24 It was found that the fuel cell electrode (25) produced in Example 24 had an oxygen reduction starting potential of 0.85 V (vs. NHE) and high oxygen reducing ability.
- Example 25 Preparation of catalyst 5.17 g (49 mmol) of niobium carbide (NbC), 0.31 g (0.9 mmol) of neodymium oxide (Nd 2 O 3 ), and 4.51 g (42 mmol) of niobium nitride (NbN) were sufficiently pulverized and mixed. did. The mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain a carbonitride (26) containing niobium and neodymium.
- NbC niobium carbide
- Nd 2 O 3 neodymium oxide
- NbN niobium nitride
- a fuel cell electrode (26) was obtained in the same manner as in Example 1 except that the catalyst (26) was used.
- FIG. 64 shows a current-potential curve obtained by the measurement.
- Example 25 It was found that the fuel cell electrode (26) produced in Example 25 had an oxygen reduction starting potential of 0.85 V (vs. NHE) and high oxygen reducing ability.
- Example 26 1. Preparation of catalyst 5.17 g (49 mmol) of niobium carbide (NbC), 0.32 g (0.9 mmol) of samarium oxide (Sm 2 O 3 ), and 4.51 g (42 mmol) of niobium nitride (NbN) were sufficiently pulverized and mixed. did. The mixed powder was heat-treated in a tube furnace at 1600 ° C. for 3 hours in a nitrogen atmosphere to obtain a carbonitride (27) containing niobium and samarium.
- NbC niobium carbide
- Sm 2 O 3 samarium oxide
- NbN niobium nitride
- a fuel cell electrode (27) was obtained in the same manner as in Example 1 except that the catalyst (27) was used.
- FIG. 65 shows a current-potential curve obtained by the measurement.
- the electrode for fuel cell (27) produced in Example 26 has an oxygen reduction starting potential of 0.90 V (vs. NHE) and was found to have a high oxygen reducing ability.
- Table 1 shows the elemental analysis results of the ground catalyst (28).
- a fuel cell electrode (28) was obtained in the same manner as in Example 1 except that the catalyst (28) was used.
- FIG. 66 shows a current-potential curve obtained by the measurement.
- Table 1 shows the elemental analysis results of the ground catalyst (29).
- a fuel cell electrode (29) was obtained in the same manner as in Example 1 except that the catalyst (29) was used.
- FIG. 67 shows a current-potential curve obtained by the measurement.
- the catalyst of the present invention does not corrode in an acidic electrolyte or at a high potential, is excellent in durability, and has a high oxygen reducing ability. Therefore, it can be used in a fuel cell catalyst layer, an electrode, an electrode assembly or a fuel cell.
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Abstract
Description
錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属(以下「金属M」または「M」と記す。)ならびにニオブを含有する金属炭窒酸化物からなることを特徴とする触媒。
前記金属炭窒酸化物の組成式が、NbaMbCxNyOz(ただし、a、b、x、y、zは原子数の比を表し、0.01≦a<1、0<b≦0.99、0.01≦x≦2、0.01≦y≦2、0.01≦z≦3、a+b=1、かつx+y+z≦5である。)で表されることを特徴とする(1)に記載の触媒。
粉末X線回折法(Cu-Kα線)によって前記金属炭窒酸化物を測定した際に、回折角2θ=33°~43°の間に、回折線ピークが2つ以上観測されることを特徴とする(1)または(2)に記載の触媒。
前記金属炭窒酸化物がいくつかの相からなる混合物であって、粉末X線回折法(Cu-Kα線)によって前記金属炭窒酸化物を測定した際に、Nb12O29由来のピークが観測されることを特徴とする(1)~(3)のいずれかに記載の触媒。
錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mの酸化物、酸化ニオブおよび炭素の混合物を窒素雰囲気または窒素を含有する不活性ガス中で熱処理することにより金属炭窒化物を得る工程(ia)と、前記金属炭窒化物を酸素含有不活性ガス中で熱処理することにより金属炭窒酸化物からなる触媒を得る工程(ii)とを含むことを特徴とする金属炭窒酸化物からなる触媒の製造方法。
錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mの酸化物、炭化ニオブおよび窒化ニオブの混合物を不活性ガス中で熱処理することにより金属炭窒化物を得る工程(ib)と、前記金属炭窒化物を酸素含有不活性ガス中で熱処理することにより金属炭窒酸化物からなる触媒を得る工程(ii)とを含むことを特徴とする金属炭窒酸化物からなる触媒の製造方法。
錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mの酸化物、炭化ニオブ、窒化ニオブおよび酸化ニオブの混合物を不活性ガス中で熱処理することにより金属炭窒化物を得る工程(ic)と、前記金属炭窒化物を酸素含有不活性ガス中で熱処理することにより金属炭窒酸化物からなる触媒を得る工程(ii)とを含むことを特徴とする金属炭窒酸化物からなる触媒の製造方法。
錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mを含有する化合物、炭化ニオブおよび窒化ニオブの混合物を不活性ガス中で熱処理することにより金属炭窒化物を得る工程(id)と、前記金属炭窒化物を酸素含有不活性ガス中で熱処理することにより金属炭窒酸化物からなる触媒を得る工程(ii)とを含むことを特徴とする金属炭窒酸化物からなる触媒の製造方法。
前記工程(ia)における熱処理の温度が600~1800℃の範囲であることを特徴とする(5)に記載の製造方法。
前記工程(ib)における熱処理の温度が600~1800℃の範囲であることを特徴とする(6)に記載の製造方法。
前記工程(ic)における熱処理の温度が600~1800℃の範囲であることを特徴とする(7)に記載の製造方法。
前記工程(id)における熱処理の温度が600~1800℃の範囲であることを特徴とする(8)に記載の製造方法。
前記工程(ii)における熱処理の温度が400~1400℃の範囲であることを特徴とする(5)~(12)のいずれかに記載の製造方法。
前記工程(ii)における不活性ガス中の酸素ガス濃度が0.1~10容量%の範囲であることを特徴とする(5)~(13)のいずれかに記載の製造方法。
前記工程(ii)における不活性ガスが、水素ガスを5容量%以下の範囲で含有していることを特徴とする(5)~(14)のいずれかに記載の製造方法。
(1)~(4)のいずれかに記載の触媒を含むことを特徴とする燃料電池用触媒層。
さらに電子伝導性粒子を含むことを特徴とする(16)に記載の燃料電池用触媒層。
燃料電池用触媒層と多孔質支持層とを有する電極であって、前記燃料電池用触媒層が(16)または(17)に記載の燃料電池用触媒層であることを特徴とする電極。
カソードとアノードと前記カソードおよび前記アノードの間に配置された電解質膜とを有する膜電極接合体であって、前記カソードおよび/または前記アノードが(18)に記載の電極であることを特徴とする膜電極接合体。
(19)に記載の膜電極接合体を備えることを特徴とする燃料電池。
(19)に記載の膜電極接合体を備えることを特徴とする固体高分子形燃料電池。
本発明の触媒は、錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mならびにニオブを含有する金属炭窒酸化物からなることを特徴としている。
電子伝導性粒子である炭素に分散させた触媒が1質量%となるように、該触媒および炭素を溶剤中に入れ、超音波で攪拌し懸濁液を得る。なお、炭素源としては、カーボンブラック(比表面積:100~300m2/g)(例えばキャボット社製 XC-72)を用い、触媒と炭素とが質量比で95:5になるように分散させる。また、溶剤としては、イソプロピルアルコール:水(質量比)=2:1を用いる。
上記酸素還元開始電位が0.7V(vs.NHE)未満であると、前記触媒を燃料電池のカソード用の触媒として用いた際に過酸化水素が発生することがある。また酸素還元開始電位は0.85V(vs.NHE)以上であることが、好適に酸素を還元するために好ましい。また、酸素還元開始電位は高い程好ましく、特に上限は無いが、酸素還元開始電位の上限は、理論値の1.23V(vs.NHE)である。
上記触媒の製造方法は特に限定されないが、例えば、錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mならびにニオブを含有する金属炭窒化物を、酸素を含む不活性ガス中で熱処理することにより、錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mならびにニオブを含有する金属炭窒酸化物得る工程を含む製造方法が挙げられる。
製造方法(I)は、前記金属Mの酸化物、酸化ニオブおよび炭素との混合物を、窒素雰囲気または窒素を含有する不活性ガス中で熱処理することにより金属炭窒化物を製造する方法である。
製造方法(II)は、前記金属Mの酸化物、炭化ニオブおよび窒化ニオブの混合物を、窒素ガスなどの不活性ガス中で熱処理することにより金属炭窒化物を製造する方法である。
製造方法(III)は、前記金属Mの酸化物、炭化ニオブ、窒化ニオブおよび酸化ニオブの混合物を、窒素ガスなどの不活性ガス中で熱処理することにより金属炭窒化物を製造する方法である。
製造方法(IV)は、前記金属Mを含有する化合物、炭化ニオブおよび窒化ニオブの混合物を、窒素ガスなどの不活性ガス中で熱処理することにより金属炭窒化物を製造する方法である。
前記金属炭窒化物を得ることができれば、原料としては特に制限されず、前記製造方法(I)~(IV)における原料、その他の原料を様々に組み合わせて用いることができる。
次に、上記製造方法(I)~(V)で得られた金属炭窒化物を、酸素含有不活性ガス中で熱処理することにより、金属炭窒酸化物を得る工程について説明する。
本発明の触媒は、白金触媒の代替触媒として使用することができる。
1.粉末X線回折
理学電機株式会社製 ロータフレックスおよびPANalytical 製 X’Pert Proを用いて、試料の粉末X線回折を行った。
炭素:試料約0.1gを量り取り、堀場製作所 EMIA-110で測定を行った。
1.触媒の調製
酸化ニオブ(IV)(NbO2)4.95g(39.6mmol)、酸化スズ(IV)(SnO2)60mg(0.4mmol)にカーボン(キャボット社製、Vulcan72)1.2g(100mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1400℃で3時間、窒素雰囲気中で熱処理することにより、スズ(1モル%)およびニオブを含有する炭窒化物(1)4.23gが得られた。
酸素還元能の測定は、次のように行った。触媒(1)0.095gとカーボン(キャボット社製 XC-72)0.005gをイソプロピルアルコール:純水=2:1の質量比で混合した溶液10gに入れ、超音波で攪拌、縣濁して混合した。この混合物30μlをグラッシーカーボン電極(東海カーボン社製、径:5.2mm)に塗布し、120℃で1時間乾燥した。さらに、ナフィオン(デュポン社 5%ナフィオン溶液(DE521))を10倍に純水で希釈したもの10μlを塗布し、120℃で1時間乾燥し、燃料電池用電極(1)を得た。
このようにして作製した燃料電池用電極(1)の触媒能(酸素還元能)を以下の方法で評価した。
1.触媒の調製
酸化ニオブ(IV)(NbO2)4.75g(38mmol)、酸化スズ(IV)(SnO2)302mg(2mmol)にカーボン(キャボット社製、Vulcan72)1.2g(100mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1400℃で3時間、窒素雰囲気中で熱処理することにより、スズ(5モル%)およびニオブを含有する炭窒化物(2)4.10gが得られた。
得られた触媒(2)の元素分析結果を表1に示す。
前記触媒(2)を用いた以外は実施例1と同様にして燃料電池用電極(2)を得た。
前記燃料電池用電極(2)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
酸化ニオブ(IV)(NbO2)4.00g(32mmol)、酸化スズ(IV)(SnO2)1.21g(8mmol)を用いた以外は実施例1と同様にして、スズ(20モル%)およびニオブを含有する炭窒化物(3)4.23gを製造し、該炭窒化物(3)1.02gからスズ(20モル%)およびニオブを含有する炭窒酸化物(以下「触媒(3)」とも記す。)1.09gを調製した。得られた触媒(3)の元素分析結果を表1に示す。
前記触媒(3)を用いた以外は実施例1と同様にして燃料電池用電極(3)を得た。
前記燃料電池用電極(3)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
酸化スズ(IV)(SnO2)60mg(0.4mmol)の代わりに酸化インジウム(III)(In2O3)55mg(0.2mmol)を用いた以外は実施例1と同様にして、インジウム(0.4モル%)およびニオブを含有する炭窒化物(4)4.23gを製造し、該炭窒化物(4)1.02gからインジウム(0.4モル%)およびニオブを含有する炭窒酸化物(以下「触媒(4)」とも記す。)1.10gを調製した。
前記触媒(4)を用いた以外は実施例1と同様にして燃料電池用電極(4)を得た。
前記燃料電池用電極(4)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
酸化ニオブ(IV)(NbO2)の量を4.95g(39.6mmol)から4.75g(38mmol)と変更し、酸化スズ(IV)(SnO2)60mg(0.4mmol)の代わりに酸化インジウム(III)(In2O3)278mg(2mmol)を用いた以外は実施例1と同様にして、インジウム(5モル%)およびニオブを含有する炭窒化物(5)3.94gを製造し、該炭窒化物(5)1.02gからインジウム(5モル%)およびニオブを含有する炭窒酸化物(以下「触媒(5)」とも記す。)1.10gを調製した。得られた触媒(5)の元素分析結果を表1に示す。
前記触媒(5)を用いた以外は実施例1と同様にして燃料電池用電極(5)を得た。
前記燃料電池用電極(5)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
酸化ニオブ(IV)(NbO2)の量を4.95g(39.6mmol)から4.00g(32mmol)と変更し、酸化スズ(IV)(SnO2)60mg(0.4mmol)の代わりに酸化インジウム(III)(In2O3)1.11g(8mmol)を用いた以外は実施例1と同様にして、インジウム(20モル%)およびニオブを含有する炭窒化物(6)3.34gを製造し、該炭窒化物(6)1.02gからインジウム(20モル%)およびニオブを含有する炭窒酸化物(以下「触媒(6)」とも記す。)1.11gを調製した。得られた触媒(6)の元素分析結果を表1に示す。
前記触媒(6)を用いた以外は実施例1と同様にして燃料電池用電極(6)を得た。
前記燃料電池用電極(6)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)4.96g(42.5mmol)、酸化インジウム(In2O3)0.60g(2.5mmol)、窒化ニオブ(NbN)0.27g(2.5mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1400℃で3時間、窒素雰囲気中で熱処理することにより、インジウムおよびニオブを含有する炭窒化物(7)5.12gが得られた。焼結体の炭窒化物(7)をボールミルで粉砕した。これ以降は実施例1と同様にして、該炭窒化物(7)1.02gからインジウムおよびニオブを含有する炭窒酸化物(以下「触媒(7)」とも記す。)1.11gを調製した。
前記触媒(7)を用いた以外は実施例1と同様にして燃料電池用電極(7)を得た。
前記燃料電池用電極(7)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)4.96g(42.5mmol)、酸化タンタル(Ta2O5)1.11g(2.5mmol)、窒化ニオブ(NbN)0.27g(2.5mmol)をよく混合して、該混合物を1500℃で3時間、窒素雰囲気中で熱処理することにより、タンタルおよびニオブを含有する炭窒化物(8)5.94gが得られた。焼結体の炭窒化物(8)をボールミルで粉砕した。これ以降は実施例1と同様にして、該炭窒化物(8)1.02gからタンタルおよびニオブを含有する炭窒酸化物(以下「触媒(8)」とも記す。)1.11gを調製した。
前記触媒(8)を用いた以外は実施例1と同様にして燃料電池用電極(8)を得た。
前記燃料電池用電極(8)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)4.96g(42.5mmol)、酸化ニオブ(NbO2)0.31g(2.5mmol)、酸化白金(PtO2)0.57g(2.5mmol)、窒化ニオブ(NbN)0.27g(2.5mmol)をよく混合して、該混合物を1600℃で3時間、窒素雰囲気中で熱処理することにより、白金およびニオブを含有する炭窒化物(9)5.87gが得られた。焼結体の炭窒化物(9)をボールミルで粉砕した。これ以降は実施例1と同様にして、該炭窒化物(9)1.02gから白金およびニオブを含有する炭窒酸化物(以下「触媒(9)」とも記す。)1.10gを調製した。
前記触媒(9)を用いた以外は実施例1と同様にして燃料電池用電極(9)を得た。
前記燃料電池用電極(9)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
酸化ニオブ(IV)(NbO2)5.05g(40mmol)、に20%Ptカーボン(田中貴金属製)1.5g(Pt:1.6mmol)をよく混合して、該混合物を1600℃で1時間、窒素雰囲気中で熱処理することにより、白金およびニオブを含有する炭窒化物(10)4.47gが得られた。焼結体の炭窒化物(10)をボールミルで粉砕した。
前記触媒(10)を用いた以外は実施例1と同様にして燃料電池用電極(10)を得た。
前記燃料電池用電極(10)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)4.96g(42.5mmol)、酸化インジウムスズ(In2O2-SnO2)(ITO)(触媒化成工業株式会社製粉末)0.69g(2.5mmol)、窒化ニオブ(NbN)0.27g(2.5mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1400℃で3時間、窒素雰囲気中で熱処理することにより、インジウム、錫およびニオブを含有する炭窒化物(11)5.94gが得られた。焼結体の炭窒化物(11)をボールミルで粉砕した。これ以降は実施例1と同様にして、該炭窒化物(11)1.02gからインジウム、錫およびニオブを含有する炭窒酸化物(以下「触媒(11)」とも記す。)1.10gを調製した。
前記触媒(11)を用いた以外は実施例1と同様にして燃料電池用電極(11)を得た。
前記燃料電池用電極(11)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)4.96g(81mmol)、酸化ニオブ(NbO2)1.25g(10mmol)、窒化ニオブ(NbN)0.54g(5mmol)をよく混合して、1500℃で3時間、窒素雰囲気中で熱処理を行うことにより、焼結体のニオブの炭窒化物(以下「触媒(12)」とも記す。)2.70gが得られた。焼結体になるため、ボールミルで粉砕した。
得られたニオブの炭窒化物を用いた以外は実施例1と同様にして燃料電池用電極(12)を得た。
前記燃料電池用電極(12)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酸化第二鉄(Fe2O3)0.40g(2.5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、鉄およびニオブを含有する炭窒化物(13)11.19gが得られた。焼結体の炭窒化物(13)をボールミルで粉砕した。得られた炭窒化物(13)1.00gを、1容量%の酸素ガスおよび0.8容量%の水素ガスを含む窒素ガスを流しながら、管状炉で、900℃で6時間熱処理することにより、鉄(5モル%)およびニオブを含有する炭窒酸化物(以下「触媒(13)」とも記す。)1.24gが得られた。得られた触媒(13)の元素分析結果を表1に示す。
前記触媒(13)を用いた以外は実施例1と同様にして燃料電池用電極(13)を得た。
前記燃料電池用電極(13)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酸化マンガン(MnO)0.36g(5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、マンガンおよびニオブを含有する炭窒化物(14)10.93gが得られた。焼結体の炭窒化物(14)をボールミルで粉砕した。これ以降は実施例12と同様にして、該炭窒化物(14)1.04gからマンガンおよびニオブを含有する炭窒酸化物(以下「触媒(14)」とも記す。)1.33gを調製した。得られた触媒(14)の元素分析結果を表1に示す。
前記触媒(14)を用いた以外は実施例1と同様にして燃料電池用電極(14)を得た。
前記燃料電池用電極(14)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酸化セリウム(CeO2)0.86g(5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、セリウムおよびニオブを含有する炭窒化物(15)11.69gが得られた。焼結体の炭窒化物(15)をボールミルで粉砕した。これ以降は実施例12と同様にして、該炭窒化物(15)1.03gから、セリウムおよびニオブを含有する炭窒酸化物(以下「触媒(15)」とも記す。)1.31gを調製した。得られた触媒(15)の元素分析結果を表1に示す。
前記触媒(15)を用いた以外は実施例1と同様にして燃料電池用電極(15)を得た。
前記燃料電池用電極(15)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酸化クロム(Cr2O3)0.38g(2.5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、クロムおよびニオブを含有する炭窒化物(16)11.17gが得られた。焼結体の炭窒化物(16)をボールミルで粉砕した。これ以降は実施例12と同様にして、該炭窒化物(16)0.97gからクロムおよびニオブを含有する炭窒酸化物(以下「触媒(16)」とも記す。)1.20gを調製した。得られた触媒(16)の元素分析結果を表1に示す。
前記触媒(16)を用いた以外は実施例1と同様にして燃料電池用電極(16)を得た。
前記燃料電池用電極(16)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酢酸鉄(C4H6O4Fe)0.87g(5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、鉄およびニオブを含有する炭窒化物(17)10.89gが得られた。焼結体の炭窒化物(17)をボールミルで粉砕した。これ以降は実施例12と同様にして、該炭窒化物(17)1.05gから鉄およびニオブを含有する炭窒酸化物(以下「触媒(17)」とも記す。)1.34gを調製した。得られた触媒(17)の元素分析結果を表1に示す。
前記触媒(17)を用いた以外は実施例1と同様にして燃料電池用電極(17)を得た。
前記燃料電池用電極(17)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、コバルトアセチルアセトン錯体(C10H14O4Co)1.29g(5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、コバルトおよびニオブを含有する炭窒化物(18)10.94gが得られた。焼結体の炭窒化物(18)をボールミルで粉砕した。これ以降は実施例12と同様にして、該炭窒化物(18)1.05gからコバルトおよびニオブを含有する炭窒酸化物(以下「触媒(18)」とも記す。)1.35gを調製した。得られた触媒(18)の元素分析結果を表1に示す。
前記触媒(18)を用いた以外は実施例1と同様にして燃料電池用電極(18)を得た。
前記燃料電池用電極(18)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)および窒化ニオブ(NbN)5.14g(48mmol)を混合し、さらにエタノール1mlに溶解したテトラクロロ金酸(HAuCl4・nH2O)0.203g(0.5mmol)を加えて、充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、金およびニオブを含有する炭窒化物(19)11.33gが得られた。焼結体の炭窒化物(19)をボールミルで粉砕した。これ以降は実施例12と同様にして、該炭窒化物(19)1.02gから金およびニオブを含有する炭窒酸化物(以下「触媒(19)」とも記す。)1.25gを調製した。得られた触媒(19)の元素分析結果を表1に示す。
前記触媒(19)を用いた以外は実施例1と同様にして燃料電池用電極(19)を得た。
前記燃料電池用電極(19)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酢酸銀(C2H3O2Ag)0.835g(5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、銀およびニオブを含有する炭窒化物(20)10.82gが得られた。焼結体の炭窒化物(20)をボールミルで粉砕した。これ以降は実施例12と同様にして、該炭窒化物(20)0.98gから銀およびニオブを含有する炭窒酸化物(以下「触媒(20)」とも記す。)1.27gを調製した。得られた触媒(20)の元素分析結果を表1に示す。
前記触媒(20)を用いた以外は実施例1と同様にして燃料電池用電極(20)を得た。
前記燃料電池用電極(20)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酸化パラジウム(PdO)0.61g(5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、パラジウムおよびニオブを含有する炭窒化物(21)11.63gが得られた。焼結体の炭窒化物(21)をボールミルで粉砕した。これ以降は実施例12と同様にして、該炭窒化物(21)0.99gからパラジウムおよびニオブを含有する炭窒酸化物(以下「触媒(21)」とも記す。)1.26gを調製した。得られた触媒(21)の元素分析結果を表1に示す。
前記触媒(21)を用いた以外は実施例1と同様にして燃料電池用電極(21)を得た。
前記燃料電池用電極(21)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酸化イリジウム(IrO2)1.12g(5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、イリジウムおよびニオブを含有する炭窒化物(22)11.29gが得られた。焼結体の炭窒化物(22)をボールミルで粉砕した。これ以降は実施例12と同様にして、該炭窒化物(22)1.01gからイリジウムおよびニオブを含有する炭窒酸化物(以下「触媒(22)」とも記す。)1.27gを調製した。得られた触媒(22)の元素分析結果を表1に示す。
前記触媒(22)を用いた以外は実施例1と同様にして燃料電池用電極(22)を得た。
前記燃料電池用電極(22)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酸化ルテニウム(RuO2)0.67g(5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、ルテニウムおよびニオブを含有する炭窒化物(23)11.29gが得られた。焼結体の炭窒化物(23)をボールミルで粉砕した。これ以降は実施例12と同様にして、該炭窒化物(23)1.02gからルテニウムおよびニオブを含有する炭窒酸化物(以下「触媒(23)」とも記す。)1.29gを調製した。得られた触媒(23)の元素分析結果を表1に示す。
前記触媒(23)を用いた以外は実施例1と同様にして燃料電池用電極(23)を得た。
前記燃料電池用電極(23)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.17g(49mmol)、酸化ランタン(La2O3)0.30g(0.9mmol)、窒化ニオブ(NbN)4.52g(42mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、ニオブおよびランタンを含有する炭窒化物(24)を得た。
前記触媒(24)を用いた以外は実施例1と同様にして燃料電池用電極(24)を得た。
前記燃料電池用電極(24)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.17g(49mmol)、酸化プラセオジウム(Pr6O11)0.31g(0.3mmol)、窒化ニオブ(NbN)4.52g(42mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、ニオブおよびプラセオジウムを含有する炭窒化物(25)を得た。
前記触媒(25)を用いた以外は実施例1と同様にして燃料電池用電極(25)を得た。
前記燃料電池用電極(25)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.17g(49mmol)、酸化ネオジム(Nd2O3)0.31g(0.9mmol)、窒化ニオブ(NbN)4.51g(42mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、ニオブおよびネオジムを含有する炭窒化物(26)を得た。
前記触媒(26)を用いた以外は実施例1と同様にして燃料電池用電極(26)を得た。
前記燃料電池用電極(26)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.17g(49mmol)、酸化サマリウム(Sm2O3)0.32g(0.9mmol)、窒化ニオブ(NbN)4.51g(42mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、ニオブおよびサマリウムを含有する炭窒化物(27)を得た。
前記触媒(27)を用いた以外は実施例1と同様にして燃料電池用電極(27)を得た。
前記燃料電池用電極(27)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酸化第二鉄(Fe2O3)0.40g(2.5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、鉄およびニオブを含有する炭窒化物(以下「触媒(28)」とも記す。)11.19gが得られた。焼結体の触媒(28)をボールミルで粉砕した。
前記触媒(28)を用いた以外は実施例1と同様にして燃料電池用電極(28)を得た。
前記燃料電池用電極(28)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
1.触媒の調製
炭化ニオブ(NbC)5.88g(56mmol)、酸化セリウム(CeO2)0.86g(5mmol)、窒化ニオブ(NbN)5.14g(48mmol)を充分に粉砕して混合した。この混合粉末を管状炉において、1600℃で3時間、窒素雰囲気中で熱処理することにより、セリウムおよびニオブを含有する炭窒化物(以下「触媒(29)」とも記す。)11.69gが得られた。焼結体の触媒(29)をボールミルで粉砕した。
前記触媒(29)を用いた以外は実施例1と同様にして燃料電池用電極(29)を得た。
前記燃料電池用電極(29)を用いた以外は実施例1と同様にして触媒能(酸素還元能)を評価した。
Claims (21)
- 錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属(以下「金属M」または「M」と記す。)ならびにニオブを含有する金属炭窒酸化物からなることを特徴とする触媒。
- 前記金属炭窒酸化物の組成式が、NbaMbCxNyOz(ただし、a、b、x、y、zは原子数の比を表し、0.01≦a<1、0<b≦0.99、0.01≦x≦2、0.01≦y≦2、0.01≦z≦3、a+b=1、かつx+y+z≦5である。)で表されることを特徴とする請求項1に記載の触媒。
- 粉末X線回折法(Cu-Kα線)によって前記金属炭窒酸化物を測定した際に、回折角2θ=33°~43°の間に、回折線ピークが2つ以上観測されることを特徴とする請求項1または2に記載の触媒。
- 前記金属炭窒酸化物がいくつかの相からなる混合物であって、粉末X線回折法(Cu-Kα線)によって前記金属炭窒酸化物を測定した際に、Nb12O29由来のピークが観測されることを特徴とする請求項1~3のいずれかに記載の触媒。
- 錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mの酸化物、酸化ニオブおよび炭素の混合物を窒素雰囲気または窒素を含有する不活性ガス中で熱処理することにより金属炭窒化物を得る工程(ia)と、前記金属炭窒化物を酸素含有不活性ガス中で熱処理することにより金属炭窒酸化物からなる触媒を得る工程(ii)とを含むことを特徴とする金属炭窒酸化物からなる触媒の製造方法。
- 錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mの酸化物、炭化ニオブおよび窒化ニオブの混合物を不活性ガス中で熱処理することにより金属炭窒化物を得る工程(ib)と、前記金属炭窒化物を酸素含有不活性ガス中で熱処理することにより金属炭窒酸化物からなる触媒を得る工程(ii)とを含むことを特徴とする金属炭窒酸化物からなる触媒の製造方法。
- 錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mの酸化物、炭化ニオブ、窒化ニオブおよび酸化ニオブの混合物を不活性ガス中で熱処理することにより金属炭窒化物を得る工程(ic)と、前記金属炭窒化物を酸素含有不活性ガス中で熱処理することにより金属炭窒酸化物からなる触媒を得る工程(ii)とを含むことを特徴とする金属炭窒酸化物からなる触媒の製造方法。
- 錫、インジウム、白金、タンタル、ジルコニウム、銅、鉄、タングステン、クロム、モリブデン、ハフニウム、チタニウム、バナジウム、コバルト、マンガン、セリウム、水銀、プルトニウム、金、銀、イリジウム、パラジウム、イットリウム、ルテニウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムおよびニッケルからなる群より選択された少なくとも1種の金属Mを含有する化合物、炭化ニオブおよび窒化ニオブの混合物を不活性ガス中で熱処理することにより金属炭窒化物を得る工程(id)と、前記金属炭窒化物を酸素含有不活性ガス中で熱処理することにより金属炭窒酸化物からなる触媒を得る工程(ii)とを含むことを特徴とする金属炭窒酸化物からなる触媒の製造方法。
- 前記工程(ia)における熱処理の温度が600~1800℃の範囲であることを特徴とする請求項5に記載の製造方法。
- 前記工程(ib)における熱処理の温度が600~1800℃の範囲であることを特徴とする請求項6に記載の製造方法。
- 前記工程(ic)における熱処理の温度が600~1800℃の範囲であることを特徴とする請求項7に記載の製造方法。
- 前記工程(id)における熱処理の温度が600~1800℃の範囲であることを特徴とする請求項8に記載の製造方法。
- 前記工程(ii)における熱処理の温度が400~1400℃の範囲であることを特徴とする請求項5~12のいずれかに記載の製造方法。
- 前記工程(ii)における不活性ガス中の酸素ガス濃度が0.1~10容量%の範囲であることを特徴とする請求項5~13のいずれかに記載の製造方法。
- 前記工程(ii)における不活性ガスが、水素ガスを5容量%以下の範囲で含有していることを特徴とする請求項5~14のいずれかに記載の製造方法。
- 請求項1~4のいずれかに記載の触媒を含むことを特徴とする燃料電池用触媒層。
- さらに電子伝導性粒子を含むことを特徴とする請求項16に記載の燃料電池用触媒層。
- 燃料電池用触媒層と多孔質支持層とを有する電極であって、前記燃料電池用触媒層が請求項16または17に記載の燃料電池用触媒層であることを特徴とする電極。
- カソードとアノードと前記カソードおよび前記アノードの間に配置された電解質膜とを有する膜電極接合体であって、前記カソードおよび/または前記アノードが請求項18に記載の電極であることを特徴とする膜電極接合体。
- 請求項19に記載の膜電極接合体を備えることを特徴とする燃料電池。
- 請求項19に記載の膜電極接合体を備えることを特徴とする固体高分子形燃料電池。
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WO2010041650A1 (ja) * | 2008-10-06 | 2010-04-15 | 昭和電工株式会社 | 触媒およびその製造方法ならびにその用途 |
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CN113839056B (zh) * | 2021-08-28 | 2024-04-09 | 西安交通大学 | 用于直接甲醇和甲酸燃料电池的碳载钯氮化铌纳米电催化剂及其制备方法 |
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Also Published As
Publication number | Publication date |
---|---|
CN101909749A (zh) | 2010-12-08 |
US20110053040A1 (en) | 2011-03-03 |
EP2239054B1 (en) | 2014-01-08 |
EP2239054A1 (en) | 2010-10-13 |
KR20100103700A (ko) | 2010-09-27 |
KR101249135B1 (ko) | 2013-03-29 |
CN101909749B (zh) | 2013-08-07 |
EP2239054A4 (en) | 2012-02-01 |
JP5495798B2 (ja) | 2014-05-21 |
US8642495B2 (en) | 2014-02-04 |
CA2721912A1 (en) | 2009-07-23 |
JPWO2009091043A1 (ja) | 2011-05-26 |
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