WO2010131634A1 - 触媒及びその製造方法ならびにその用途 - Google Patents
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- WO2010131634A1 WO2010131634A1 PCT/JP2010/057927 JP2010057927W WO2010131634A1 WO 2010131634 A1 WO2010131634 A1 WO 2010131634A1 JP 2010057927 W JP2010057927 W JP 2010057927W WO 2010131634 A1 WO2010131634 A1 WO 2010131634A1
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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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/08—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using ammonia or derivatives thereof
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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
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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
- H01M4/88—Processes of manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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. More specifically, the present invention relates to an electrode catalyst for a fuel cell, a production method thereof, and an application thereof.
- Catalysts have the function of accelerating the rate of reaction that should proceed in terms of chemical equilibrium by lowering the activation energy of the reaction, and are used in a wide variety of chemical reaction processes such as synthesis and decomposition.
- homogeneous catalysts can be efficiently dissolved in a liquid phase or the like by being dissolved or dispersed in a solvent.
- Heterogeneous catalysts can be synthesized on a support by efficiently synthesizing or decomposing the target substance, and the catalyst can be easily separated and recovered from the product. Especially useful in large chemical synthesis factories.
- a catalyst that is used for an electrochemical reaction by being fixed on the electrode surface and allows the intended reaction to proceed with a smaller overvoltage is called an electrode catalyst.
- Electrocatalysts are particularly needed for fuel cells for the purpose of reducing overvoltage and generating more electrical energy.
- 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, oxygen is reduced at the cathode, and electricity is taken out. is there. 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, an inert or non-oxidizing atmosphere.
- Patent Document 2 is a thin film magnetic head ceramic substrate material, and the use of this oxycarbonitride as a catalyst has not been studied.
- Patent Document 3 discusses the possibility that an oxide having a perovskite structure containing two or more kinds of metals can serve as a platinum substitute catalyst. As shown in the examples, the effect is supplemented by platinum. There was room for improvement in activity, not exceeding its role as a carrier.
- platinum is useful not only as a catalyst for the fuel cell, but also as an exhaust gas treatment catalyst or an organic synthesis catalyst, platinum is expensive and has limited resources. There has been a demand for the development of a catalyst that can be used in various applications.
- JP 2007-031781 A Japanese Patent Laid-Open No. 2003-342058 Japanese Patent Laid-Open No. 2008-04286
- 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 composed of a specific metal M and a metal oxycarbonitride containing titanium does not corrode in an acidic electrolyte or at a high potential.
- the inventors have found that it has excellent durability and high oxygen reducing ability, and has completed the present invention.
- the present invention relates to the following (1) to (16), for example.
- metal M metal oxycarbonitride containing titanium
- a step of obtaining a metal carbonitride by heat-treating a mixture of metal M oxide, titanium oxide and carbon in a mixed gas containing nitrogen or a nitrogen compound (step 1a), and the metal carbonitride containing oxygen The method for producing a catalyst according to any one of (1) to (3), further comprising a step (Step 2a) of obtaining the metal oxycarbonitride by heat treatment in a mixed gas.
- step (10) Any one of (5) to (9), wherein in the step (step 2 or step 2a), the oxygen-containing mixed gas further contains hydrogen at a concentration of 0.01% by volume to 5% by volume.
- the oxygen-containing mixed gas further contains hydrogen at a concentration of 0.01% by volume to 5% by volume.
- a fuel cell catalyst layer comprising the catalyst according to any one of (1) to (3).
- 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 (11) or (12). electrode.
- 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 (13) A membrane electrode assembly.
- a fuel cell comprising the membrane electrode assembly according to (14).
- a polymer electrolyte fuel cell comprising the membrane electrode assembly according to (14).
- 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. 2 is a powder X-ray diffraction spectrum of carbonitride oxide (1) in Example 1.
- FIG. 2 is a powder X-ray diffraction spectrum of carbonitride oxide (2) in Example 2.
- FIG. 3 is a powder X-ray diffraction spectrum of carbonitride oxide (3) in Example 3.
- 4 is a powder X-ray diffraction spectrum of carbonitride oxide (4) in Example 4.
- 3 is a powder X-ray diffraction spectrum of carbonitride oxide (5) in Example 5.
- FIG. 2 is a powder X-ray diffraction spectrum of carbonitride oxide (6) of Example 6.
- 2 is a powder X-ray diffraction spectrum of carbonitride oxide (7) in Example 7.
- 4 is a powder X-ray diffraction spectrum of carbonitride oxide (8) of Example 8.
- 4 is a powder X-ray diffraction spectrum of carbonitride oxide (9) of Example 9.
- 2 is a powder X-ray diffraction spectrum of carbonitride oxide (10) of Example 10.
- 2 is a powder X-ray diffraction spectrum of carbonitride oxide (11) of Example 11.
- 2 is a powder X-ray diffraction spectrum of carbonitride oxide (12) of Example 12.
- 2 is a powder X-ray diffraction spectrum of carbonitride oxide (13 ′) of Reference Example 1.
- 4 is a powder X-ray diffraction spectrum of carbonitride of Comparative Example 1.
- FIG. 2 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (1) in Example 1.
- FIG. 6 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (2) in Example 2.
- FIG. 4 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (3) in Example 3.
- FIG. 6 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (4) in Example 4.
- FIG. 6 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (5) in Example 5.
- FIG. 6 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (6) of Example 6.
- FIG. 6 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (7) in Example 7.
- FIG. 6 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (8) in Example 8.
- FIG. 10 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (9) of Example 9.
- 6 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (10) of Example 10.
- FIG. 6 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (11) in Example 11.
- FIG. 6 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (12) of Example 12.
- 4 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (13 ′) of Reference Example 1.
- 5 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (14 ′) of Comparative Example 1.
- FIG. 10 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (9) of Example 9.
- 6 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell
- FIG. 1 is a powder X-ray diffraction spectrum of carbonitride oxide (13) of Example 13. It is a powder X-ray-diffraction spectrum of the carbonitrous oxide (14) of Example 14. 2 is a powder X-ray diffraction spectrum of carbonitride oxide (15) of Example 15. 4 is a powder X-ray diffraction spectrum of carbonitride oxide (16) of Example 16. 14 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (13) in Example 13. It is the graph which evaluated the oxygen reduction ability of the electrode (14) for fuel cells of Example 14.
- FIG. 18 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (15) in Example 15. 18 is a graph showing an evaluation of the oxygen reducing ability of a fuel cell electrode (16) in Example 16.
- the catalyst of the present invention is selected from the group consisting of silver, calcium, strontium, yttrium, ruthenium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. It is characterized by being composed of oxycarbonitride of two or more different metals containing at least one metal M and titanium.
- the added metal is industrially preferable because it is relatively inexpensive.
- the metal M is yttrium, lanthanum, or samarium because the catalyst performance to be exhibited is particularly high, and among them, lanthanum or samarium is preferable because the oxygen reduction potential is particularly high.
- lanthanum is relatively inexpensive. Therefore, it is preferable.
- a catalyst comprising a metal oxycarbonitride used in the present invention is a single compound in which at least titanium, the metal M, carbon, nitrogen and oxygen are detected when elemental analysis of the catalyst is performed, There is also the possibility of being a mixture.
- an additive for imparting electrical conductivity specifically, carbon black represented by Vulcan XC72, which is an electron conductive particle, Ketjen Black, and the like are used.
- conductive particles may be used in the implementation.
- the catalyst comprising the metal oxycarbonitride of the present invention can detect carbon when elemental analysis is performed without blending this “additive for improving conductivity”. It is characterized by that.
- the catalyst comprising the metal oxycarbonitride used in the present invention is mainly an XRD pattern of an oxide when a diffraction pattern is confirmed by powder X-ray diffraction (Cu-K ⁇ ray).
- the main component of the metal in the compound of the present invention is titanium, and as an XRD pattern, a diffraction line peak of rutile titanium oxide is a main peak (a peak appearing between 27 ° and 28 ° obtained by a method described later). can get.
- the diffraction line peak height of this rutile type titanium oxide is 2 times or more, more preferably 5 times or more, more preferably 10 times or more compared to the strongest peak not identified as rutile type titanium oxide.
- the catalyst characterized by containing the carbonitride oxide of the present invention is a mixture, the crystalline substance has a rutile structure and may contain an amorphous compound. is there.
- the diffraction line peak is 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 diffraction measurement apparatus for example, a powder X-ray analysis apparatus: 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, read width: 0.02 °, sampling time: 0.70 seconds, DS, SS, RS: 0.5 ° 0.5 °, 0.15 mm, goniometer radius: 185 mm.
- the crystalline component has at least the crystal structure of the oxide. That is, it may be a compound in which part of the oxygen element of the [1] rutile oxide is replaced with a carbon element or a nitrogen element.
- [2] only titanium and oxygen may exist as crystalline compounds, that is, oxides that may contain oxygen defects, and carbon and nitrogen may exist as amorphous compounds. Although it may be a mixture of 1] and [2], it is difficult to separate and identify them.
- the catalyst of the present invention may be a mixture, the ratio of carbon, nitrogen, and oxygen contained in each metal carbonitride oxide, or crystalline oxide or amorphous carbonitride compound It is difficult to determine individually.
- the oxygen reduction initiation 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.
- carbon black (specific surface area: 100 to 300 m 2 / g) (for example, XC-72 manufactured by Cabot) is used, and the catalyst and carbon are dispersed so that the weight ratio is 95: 5.
- 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 sulfuric acid solution of 0.5 mol / dm 3 in an oxygen atmosphere and a nitrogen atmosphere.
- a current-potential curve was measured by polarizing the electrode at a potential scanning speed of 5 mV / sec, there was a difference of 0.5 ⁇ A / cm 2 or more between the reduction current in the oxygen atmosphere and the reduction current in the nitrogen atmosphere.
- the potential that 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. Further, the oxygen reduction starting potential is preferably as high as possible. Although there is no particular upper limit, the theoretical value is 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 production method of the catalyst is not particularly limited.
- the production method includes a step of obtaining the metal carbonitride oxide from a metal carbonitride containing metal M and titanium ([Production step of metal carbonitride oxide]).
- Including selected from the group consisting of silver, calcium, strontium, yttrium, ruthenium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
- a metal carbonitride containing at least one metal M as well as titanium is heat-treated in an oxygen-containing mixed gas, whereby silver, calcium, strontium, yttrium, ruthenium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, At least one metal M selected from the group consisting of gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium Manufacturing method comprising the steps of obtaining a metal oxycarbonitride containing titanium are listed.
- Step 1 a metal containing a compound containing the metal M and a compound containing titanium is heat-treated.
- Method for producing carbonitride step 1), among which a method for producing metal carbonitride by heat-treating a mixture of the metal M oxide, titanium oxide and carbon in a nitrogen atmosphere (step 1a) Is preferred.
- Step 1 is a method for producing a metal carbonitride (heat treated product) by heat-treating a mixture containing the compound containing the metal M and the compound containing titanium.
- the temperature of the heat treatment for producing the metal carbonitride is usually in the range of 500 ° C. to 2200 ° C., preferably in the range of 600 ° C. to 2200 ° C., more preferably in the range of 800 to 2000 ° C.
- the heat treatment temperature is within the above range, it is preferable in terms of good crystallinity and uniformity.
- the heat treatment temperature is less than 500 ° C., the crystallinity is poor and the uniformity tends to deteriorate, and when it exceeds 2200 ° C., the crystal tends to be sintered and become larger. It is possible to supply nitrogen in the synthesized carbonitride by supplying nitrogen or a nitrogen compound-containing mixed gas during the reaction.
- Examples of the compound containing the raw material metal M include oxides, carbides, nitrides, carbonates, nitrates, acetates, oxalates, carboxylates such as citrates, citrates, phosphates, and the like.
- oxides silver oxide, calcium oxide, calcium hydroxide, strontium oxide, yttrium oxide, ruthenium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide Holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, and the like.
- carbides include silver carbide, calcium carbide, strontium carbide, yttrium carbide, ruthenium carbide, lanthanum carbide, praseodymium carbide, neodymium carbide, promethium carbide, samarium carbide, europium carbide, gadolinium carbide, terbium carbide, dysprosium carbide, holmium carbide, carbonized. Examples thereof include erbium, thulium carbide, ytterbium carbide, and lutetium carbide.
- nitride examples include silver nitride, calcium nitride, strontium nitride, yttrium nitride, ruthenium nitride, lanthanum nitride, praseodymium nitride, neodymium nitride, promethium nitride, samarium nitride, europium nitride, gadolinium nitride, terbium nitride, dysprosium nitride, holmium nitride, Examples thereof include erbium nitride, thulium nitride, ytterbium nitride, and lutetium nitride.
- Examples of carbonates include silver carbonate, calcium carbonate, strontium carbonate, yttrium carbonate, ruthenium carbonate, lanthanum carbonate, praseodymium carbonate, neodymium carbonate, promethium carbonate, samarium carbonate, europium carbonate, gadolinium carbonate, terbium carbonate, dysprosium carbonate, holmium carbonate, Examples thereof include erbium carbonate, thulium carbonate, ytterbium carbonate, and lutetium carbonate.
- the compound containing the metal M can be used alone or in combination of two or more, and is not particularly limited.
- Examples of the raw material containing titanium include oxides, carbides, nitrides, carbonates, nitrates, acetates, oxalates, citrates, carboxylates, phosphates, oxychlorides and the like.
- TiO, Ti 3 O 4 , TiO 2 , Ti 3 O 5 , Ti n O 2n-1 (where n is an integer from 2 to 10), TiC, TiN, TiCl 2 O, TiCl 4 and the like can be mentioned.
- the compound containing titanium can be used singly or in combination of two or more, and may contain a plurality of phases in a single particle, and is not particularly limited.
- the raw material may contain carbon.
- Examples of carbon 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.
- an appropriate metal carbonitride By controlling the amount (molar ratio) of the compound containing metal M and the compound containing titanium, an appropriate metal carbonitride can be obtained.
- a metal carbonitride made with an optimum blending amount (molar ratio) is used, an active metal carbonitride oxide tends to be obtained with a high oxygen reduction starting potential.
- nitrogen gas or nitrogen compound gas may be used, or nitrogen gas and nitrogen compound gas may be mixed and used.
- an inert gas may be mixed with nitrogen gas and / or nitrogen compound gas. Examples of the inert gas include helium gas, neon gas, argon gas, krypton gas, xenon gas, and radon gas.
- nitrogen compound ammonia, nitric oxide, nitrogen dioxide, nitrous oxide, dinitrogen trioxide, dinitrogen tetroxide, dinitrogen pentoxide, acetonitrile, acrylonitrile, aniline, pyrrole, monomethylamine, dimethylamine
- examples include trimethylamine, pyridine, imidazole, methanolamine, ethanolamine, formamide, and dimethylformamide.
- Step 1a Among (Step 1), in particular, (Step 1a) is a metal carbonitride (heat treatment) by heat-treating a mixture of the metal M oxide and titanium oxide and carbon in a mixed gas atmosphere containing nitrogen or a nitrogen compound.
- the catalytic activity of the metal carbonitride obtained from this step is particularly high and preferable.
- the temperature of the heat treatment for producing the metal carbonitride is usually in the range of 600 ° C. to 2200 ° C., preferably in the range of 800 to 2000 ° C. More preferably, it is in the range of 1000 to 1900 ° C.
- the heat treatment temperature is within the above range, it is preferable in terms of good crystallinity and uniformity.
- the heat treatment temperature is less than 600 ° C., the crystallinity is poor and the uniformity tends to be poor, and when it exceeds 2200 ° C., the crystal tends to be sintered and become large.
- nitrogen in the synthesized carbonitride by supplying nitrogen or a nitrogen compound-containing mixed gas during the reaction.
- carbon of the carbonitride synthesized by the carbon of the raw material is possible.
- the oxide of metal M which is a raw material of (Step 1a) is silver oxide, calcium oxide, strontium oxide, yttrium oxide, ruthenium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide, europium oxide, gadolinium oxide. Terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide or lutetium oxide. One type or two or more types of metal M oxides can be used.
- Examples of the raw material titanium oxide include TiO, Ti 3 O 4 , TiO 2, Ti 3 O 5 , and Ti n O 2n-1 (where n is an integer of 2 or more and 10 or less).
- One type or two or more types of titanium oxide can be used, and a single particle may contain a plurality of phases, and is not particularly limited.
- Examples of the raw material carbon in (Step 1a) include carbon, carbon black, graphite, graphite, activated carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, and fullerene.
- carbon black is particularly preferable. 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 metal carbonitride obtained in the presence of nitrogen or a nitrogen compound-containing mixed gas from the metal M oxide, titanium oxide and carbon is heat-treated in a mixed gas containing oxygen.
- the resulting catalyst composed of metal oxycarbonitride has a high oxygen reduction starting potential and is active.
- the compounding amount (molar ratio) is usually 0.0001 to 1 mol of the metal M oxide and 1 to 10 mol of carbon, and preferably 1 mol of titanium oxide with respect to 1 mol of titanium oxide.
- the metal M oxide is 0.001 to 0.4 mol and carbon is 2 to 6 mol. More preferably, the metal M oxide is 0.001 to 0.1 mol and the carbon is 2 to 3 mol with respect to 1 mol of titanium oxide.
- the metal M is calcium, strontium, yttrium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the metal is 1 mol of titanium oxide.
- M oxide is preferably 0.001 to 0.05 mol. More preferably, the amount is 0.005 to 0.03 mol.
- nitrogen gas or nitrogen compound gas may be used, or nitrogen gas and nitrogen compound gas may be mixed and used.
- an inert gas may be mixed with nitrogen gas and / or nitrogen compound gas. Examples of the inert gas include helium gas, neon gas, argon gas, krypton gas, xenon gas, and radon gas.
- nitrogen compound ammonia, nitric oxide, nitrogen dioxide, nitrous oxide, dinitrogen trioxide, dinitrogen tetroxide, dinitrogen pentoxide, acetonitrile, acrylonitrile, aniline, pyrrole, monomethylamine, dimethylamine
- examples include trimethylamine, pyridine, imidazole, methanolamine, ethanolamine, formamide, and dimethylformamide.
- step (1) or step (1a) The step (step (2) or step (2a)) of obtaining the metal carbonitride by heat-treating the metal carbonitride obtained in (1) in a mixed gas containing oxygen will be described.
- the oxygen-containing mixed gas contains an inert gas in addition to the oxygen gas.
- the inert gas include nitrogen, helium gas, neon gas, argon gas, krypton gas, xenon gas, and radon gas. Nitrogen or argon gas is particularly preferred because it is relatively easy to obtain.
- the oxygen-containing mixed gas may further contain hydrogen gas.
- the oxygen concentration in the oxygen-containing mixed gas in this step depends on the heat treatment time and the heat treatment temperature, but is preferably 0.005 to 10% by volume, more preferably 0.1 to 7.0% by volume, 5% by volume is more preferable, 1.0-5% by volume is particularly preferable, and 1.5-2.5% by volume is most preferable.
- the oxygen concentration is within the above range, it is preferable in that a uniform carbonitride oxide is formed.
- the oxygen concentration is less than 0.005% by volume, it tends to be in an unoxidized state, and when it exceeds 10% by volume, oxidation tends to proceed excessively.
- the hydrogen concentration depends on the heat treatment time and the heat treatment temperature, but is preferably 0.01 to 10% by volume, particularly preferably 0.1 to 5% by volume. .
- Hydrogen is preferable in that the hydrogen concentration is within the above range, a uniform carbonitride oxide is formed. If it exceeds 10% by volume, the reduction tends to proceed too much.
- the oxygen-containing mixed gas is composed of oxygen gas and inert gas
- the remainder of the oxygen concentration is the concentration of inert gas.
- the oxygen-containing mixed gas is composed of oxygen gas, inert gas, and hydrogen gas
- the oxygen concentration and the remainder of the hydrogen concentration are the concentration of the inert gas.
- the temperature of the heat treatment in this step is usually 400 to 1500 ° C., preferably 400 to 1400 ° C., more preferably 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., oxidation tends not to proceed, and when it exceeds 1500 ° C., oxidation proceeds and crystal growth tends to occur.
- Examples of the heat treatment method in this step include a leveling method, a stirring method, a dropping method, a powder trapping method, and the like.
- a dropping method an inert gas containing a small amount of oxygen flows through an induction furnace, the furnace is heated to a predetermined heat treatment temperature, and after maintaining a thermal equilibrium at the temperature, the furnace is heated in a crucible that is a heating area of the furnace.
- the metal carbonitride is dropped and heat-treated.
- 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 carbonitride in a vertical tubular furnace maintained at a prescribed heat treatment temperature by suspending the metal carbonitride in the atmosphere of an inert gas containing a small amount of oxygen. This is a heat treatment method.
- the heat treatment time of the metal carbonitride is usually 0.5 to 10 minutes, preferably 1.0 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 usually 0.2 seconds to 1 minute, preferably 0.5 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 catalyst for fuel cells, a catalyst for exhaust gas treatment, or a catalyst for organic synthesis.
- 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 an electron conductive powder.
- the reduction current can be further increased.
- the electron conductive powder is considered to increase the reduction current because it causes an electrical contact for inducing an electrochemical reaction in the catalyst.
- the electron conductive particles are usually used as a catalyst carrier.
- the electron conductive particles include carbon, conductive polymers, conductive ceramics, metals, and conductive inorganic oxides such as tungsten oxide or iridium oxide, and these can be used alone or in combination.
- carbon since carbon has a large specific surface area, carbon alone or a mixture of carbon and other electron conductive particles is preferable. That is, the fuel cell catalyst layer preferably contains the catalyst and 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 20 to 100 nm is more preferable.
- the weight 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 catalyst layer for fuel cells of this invention contains a polymer electrolyte further.
- 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 (registered trademark) (DuPont 5% Nafion (registered trademark) solution (DE521), etc.)
- a hydrocarbon polymer compound having a sulfonic acid group Polymer compounds doped with inorganic acids such as phosphoric acid, organic / inorganic hybrid polymers partially substituted with proton-conducting functional groups, proton conduction with polymer matrix impregnated with phosphoric acid solution or sulfuric acid solution
- Nafion (registered trademark) DuPont 5% Nafion (registered trademark) solution (DE521)
- Nafion (registered trademark) DuPont 5% Nafion (registered trademark) 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 dispersing agent 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.
- 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 industrially superior when used as 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. Materials and aluminum foil coated with stainless steel and corrosion-resistant materials for weight reduction are used.
- 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 used.
- a membrane filled with a polymer electrolyte may be used.
- the fuel cell according to the present invention includes 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.
- Titanium 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 (Ti a La b C x N y O z)] 1. Preparation of catalyst 3.53 g of titanium oxide (manufactured by Showa Denko, Super Titania F6), and 0.144 g of lanthanum oxide (manufactured by Shin-Etsu Chemical Co., Ltd., La 2 O 3 ) were sufficiently pulverized with 1.33 g of carbon (manufactured by Cabot, Vulcan 72) And mixed.
- This mixed powder was heat-treated in a tube furnace at 1800 ° C. for 3 hours in a nitrogen atmosphere to obtain 2.52 g of carbonitride (1) containing titanium and lanthanum (about 2 mol% with respect to 100 mol% of titanium). Obtained. This was crushed with a mortar.
- the powder X-ray diffraction spectrum of the catalyst (1) is shown in FIG. 2.
- the produced 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 0.5 ⁇ 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. That is, the higher the oxygen reduction start potential and the larger the oxygen reduction current, the higher the catalytic ability (oxygen reducing ability) of the fuel cell electrode (1).
- FIG. 15 shows an oxygen reduction current-oxygen reduction potential curve (hereinafter referred to as a current-potential curve) obtained by the above measurement.
- the fuel cell electrode (1) produced in Example 1 had an oxygen reduction starting potential of 0.89 V (vs. NHE) and was found to have a high oxygen reducing ability.
- Example 2 (Ti a Sm b C x N y O z)] 1. Preparation of catalyst Titanium oxide 3.57g (manufactured by Showa Denko, Super Titania F6), samarium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., Sm 2 O 3 ) 0.077g, carbon (Cabot Co., Vulcan 72) 1.34g sufficiently pulverized And mixed.
- This mixed powder was heat-treated in a tube furnace at 1700 ° C. for 3 hours in a nitrogen atmosphere to obtain 2.48 g of carbonitride (2) containing titanium and samarium (about 1 mol% with respect to 100 mol% of titanium). Obtained. This was crushed with a mortar.
- catalyst (2) carbonitride oxide containing titanium and samarium was prepared from 1.00 g of the carbonitride (2).
- Table 1 shows the results of elemental analysis of the obtained catalyst (2).
- the powder X-ray diffraction spectrum of the catalyst (2) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (2) was obtained in the same manner as in Example 1 except that the catalyst (2) was used.
- FIG. 16 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (2) produced in Example 2 had an oxygen reduction starting potential of 0.90 V (vs. NHE), and was found to have a high oxygen reducing ability.
- catalyst (3) carbonitride oxide containing titanium and praseodymium was prepared from 1.00 g of the carbonitride (3).
- Table 1 shows the results of elemental analysis of the obtained catalyst (3).
- the powder X-ray diffraction spectrum of the catalyst (3) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (3) was obtained in the same manner as in Example 1 except that the catalyst (3) was used.
- FIG. 17 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (3) produced in Example 3 had an oxygen reduction starting potential of 0.89 V (vs. NHE) and was found to have a high oxygen reducing ability.
- Example 4 (Ti a Nd b C x N y O z )] 1. Preparation of catalyst 3.53 g of titanium oxide (manufactured by Showa Denko, Super Titania F6) and neodymium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., Nd 2 O 3 ) 0.150 g were sufficiently pulverized with 1.33 g of carbon (manufactured by Cabot, Vulcan 72). And mixed. This mixed powder is heat-treated in a tube furnace at 1700 ° C. for 3 hours in a nitrogen atmosphere, whereby 2.50 g of carbonitride (4) containing titanium and neodymium (about 2 mol% with respect to 100 mol% of titanium) is obtained. Obtained. This was crushed with a mortar.
- the powder X-ray diffraction spectrum of the catalyst (4) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (4) was obtained in the same manner as in Example 1 except that the catalyst (4) was used.
- FIG. 18 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (4) produced in Example 4 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and was found to have a high oxygen reducing ability.
- the powder X-ray diffraction spectrum of the catalyst (5) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (5) was obtained in the same manner as in Example 1 except that the catalyst (5) was used.
- FIG. 19 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (5) produced in Example 5 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and was found to have a high oxygen reducing ability.
- Example 6 (Ti a Gd b C x N y O z )] 1. Preparation of catalyst 3.52 g of titanium oxide (manufactured by Showa Denko, Super Titania F6), 0.12 g of gadolinium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., Gd 2 O 3 ) and 1.32 g of carbon (manufactured by Cabot, Vulcan 72) are sufficiently pulverized And mixed. This mixed powder was heat-treated in a tube furnace at 1700 ° C. for 3 hours in a nitrogen atmosphere to obtain 2.55 g of carbonitride (6) containing titanium and gadolinium (about 2 mol% relative to 100 mol% of titanium). Obtained. This was crushed with a mortar.
- catalyst (6) carbonitride oxide containing titanium and gadolinium
- the powder X-ray diffraction spectrum of the catalyst (6) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (6) was obtained in the same manner as in Example 1 except that the catalyst (6) was used.
- FIG. 20 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (6) produced in Example 6 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and was found to have a high oxygen reducing ability.
- the powder X-ray diffraction spectrum of the catalyst (7) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (7) was obtained in the same manner as in Example 1 except that the catalyst (7) was used.
- FIG. 21 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (7) produced in Example 7 had an oxygen reduction starting potential of 0.86 V (vs. NHE) and was found to have a high oxygen reducing ability.
- the powder X-ray diffraction spectrum of the catalyst (8) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (8) was obtained in the same manner as in Example 1 except that the catalyst (8) was used.
- FIG. 22 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (8) produced in Example 8 had an oxygen reduction starting potential of 0.87 V (vs. NHE), and was found to have high oxygen reducing ability.
- the powder X-ray diffraction spectrum of the catalyst (9) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (9) was obtained in the same manner as in Example 1 except that the catalyst (9) was used.
- FIG. 23 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (9) produced in Example 9 had an oxygen reduction starting potential of 0.87 V (vs. NHE), and was found to have a high oxygen reducing ability.
- Example 10 (Ti a Yb b C x N y O z )] 1. Catalyst preparation 3.51 g of titanium oxide (manufactured by Showa Denko, Super Titania F6), 0.173 g of ytterbium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., Yb 2 O 3 ), 1.32 g of carbon (manufactured by Cabot Corporation, Vulcan 72) sufficiently pulverized And mixed. This mixed powder was heat-treated in a tube furnace at 1700 ° C. for 3 hours in a nitrogen atmosphere to obtain 2.70 g of carbonitride (10) containing titanium and ytterbium (about 2 mol% relative to 100 mol% of titanium). Obtained. This was crushed with a mortar.
- titanium oxide manufactured by Showa Denko, Super Titania F6
- ytterbium oxide manufactured by Shin-Etsu Chemical Co., Ltd., Yb 2 O 3
- carbon
- the powder X-ray diffraction spectrum of the catalyst (10) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (10) was obtained in the same manner as in Example 1 except that the catalyst (10) was used.
- FIG. 24 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (10) produced in Example 10 had an oxygen reduction starting potential of 0.86 V (vs. NHE) and was found to have a high oxygen reducing ability.
- the powder X-ray diffraction spectrum of the catalyst (11) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (11) was obtained in the same manner as in Example 1 except that the catalyst (11) was used.
- FIG. 25 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (11) produced in Example 11 had an oxygen reduction starting potential of 0.87 V (vs. NHE), and was found to have a high oxygen reducing ability.
- Example 12 (Ti a Ca b C x N y O z)] 1. Preparation of catalyst 3.60 g of titanium oxide (manufactured by Showa Denko, Super Titania F6), 0.045 g of calcium carbonate (manufactured by Ube Materials, CS-4NA), 1.35 g of carbon (manufactured by Cabot, Vulcan 72) sufficiently Milled and mixed. This mixed powder was heat-treated in a tube furnace at 1700 ° C. for 3 hours in a nitrogen atmosphere to obtain 2.47 g of carbonitride (12) containing titanium and calcium (about 1 mol% with respect to 100 mol% of titanium). Obtained. This was crushed with a mortar.
- the powder X-ray diffraction spectrum of the catalyst (12) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (12) was obtained in the same manner as in Example 1 except that the catalyst (12) was used.
- FIG. 26 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (12) produced in Example 12 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and was found to have a high oxygen reducing ability.
- Example 13 (Ti a La b C x N y O z)] 1. Preparation of titanium oxide 3.57g of catalyst (manufactured by Showa Denko KK, super Thailand Titania F6), lanthanum oxide (manufactured by Shin-Etsu Chemical Co., La 2 O 3) 0.036g of carbon (Cabot Corporation, Vulcan72) 1.34g sufficiently crushed And mixed.
- the mixed powder is heat-treated in a tube furnace at 1700 ° C. for 3 hours in a nitrogen atmosphere to thereby obtain a carbonitride (13) containing titanium and lanthanum (about 0.5 mol% with respect to 100 mol% of titanium) 2. 49 g was obtained. This was crushed with a mortar.
- the powder X-ray diffraction spectrum of the catalyst (13) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (13) was obtained in the same manner as in Example 1 except that the catalyst (13) was used.
- FIG. 33 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (13) produced in Example 13 had an oxygen reduction starting potential of 0.89 V (vs. NHE), and was found to have high oxygen reducing ability.
- Example 14 (Ti a La b C x N y O z)] 1. Preparation of catalyst Titanium oxide 3.57g (manufactured by Showa Denko, Super Titania F6), lanthanum oxide (manufactured by Shin-Etsu Chemical Co., Ltd., La 2 O 3 ) 0.72g, 1.34g of carbon (Cabot Co., Vulcan 72) sufficiently pulverized And mixed. This mixed powder was heat-treated in a tube furnace at 1700 ° C. for 3 hours in a nitrogen atmosphere to obtain 2.48 g of carbonitride (14) containing titanium and lanthanum (about 10 mol% relative to 100 mol% of titanium). Obtained. This was crushed with a mortar.
- the powder X-ray diffraction spectrum of the catalyst (14) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (14) was obtained in the same manner as in Example 1 except that the catalyst (14) was used.
- FIG. 34 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (14) produced in Example 14 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and was found to have a high oxygen reducing ability.
- Example 15 (Ti a Smb b C x N y O z )] 1. Preparation of catalyst 3.57 g of titanium oxide (manufactured by Showa Denko, Super Titania F6), 0.038 g of samarium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., Sm 2 O 3 ), 1.34 g of carbon (manufactured by Cabot Corp., Vulcan 72) sufficiently pulverized And mixed. This mixed powder is heat-treated in a tube furnace at 1700 ° C. for 3 hours in a nitrogen atmosphere, so that carbonitride (15) containing titanium and samarium (about 0.5 mol% with respect to 100 mol% of titanium) 2. 51 g was obtained. This was crushed with a mortar.
- catalyst (15) carbonitride oxide containing titanium and samarium
- the powder X-ray diffraction spectrum of the catalyst (15) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (15) was obtained in the same manner as in Example 1 except that the catalyst (15) was used.
- FIG. 35 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (15) produced in Example 15 had an oxygen reduction starting potential of 0.88 V (vs. NHE) and was found to have a high oxygen reducing ability.
- Example 16 (Ti a Sm b C x N y O z)] 1. Preparation of catalyst Titanium oxide 3.57g (manufactured by Showa Denko, Super Titania F6) and samarium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., Sm 2 O 3 ) 0.154 g were sufficiently pulverized 1.34 g of carbon (Cabot Co., Vulcan 72) And mixed. This mixed powder was heat-treated in a tube furnace at 1700 ° C. for 3 hours in a nitrogen atmosphere to obtain 2.48 g of carbonitride (16) containing titanium and samarium (about 10 mol% relative to 100 mol% of titanium). Obtained. This was crushed with a mortar.
- the powder X-ray diffraction spectrum of the catalyst (16) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (16) was obtained in the same manner as in Example 1 except that the catalyst (16) was used.
- FIG. 36 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (16) produced in Example 16 had an oxygen reduction starting potential of 0.86 V (vs. NHE) and was found to have a high oxygen reducing ability.
- the powder X-ray diffraction spectrum of the catalyst (13 ′) is shown in FIG. 2.
- Production of Fuel Cell Electrode A fuel cell electrode (13 ′) was obtained in the same manner as in Example 1 except that the catalyst (13 ′) was used.
- FIG. 27 shows a current-potential curve obtained by the measurement.
- the fuel cell electrode (13 ′) produced in Reference Example 1 had an oxygen reduction starting potential of 0.80 V (vs. NHE), and was found to have oxygen reducing ability.
- a fuel cell electrode (14 ') was obtained in the same manner as in Example 1 except that the carbonitride was used as a catalyst.
- FIG. 28 shows a current-potential curve obtained by the measurement. It was found that the fuel cell electrode (14 ′) produced in Example 2 had an oxygen reduction starting potential of 0.51 V (vs. NHE) and a low potential for oxygen reduction.
- the catalyst of the present invention does not corrode in an acidic electrolyte or at a high potential, has excellent 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
特許文献1では、白金代替材料として長周期表4族,5族及び14族の元素群から選ばれる1種以上の窒化物をふくむ酸素還元電極材料が開示されている。
また、特許文献2では、炭化物、酸化物、窒化物を混合し、真空、不活性または非酸化性雰囲気下、500~1500℃で熱処理をした炭窒酸化物が開示されている。
特許文献3では、二種類の以上の金属を含むペロブスカイト構造をとる酸化物が白金代替の触媒となる可能性について検討されているが、実施例に示されているように、効能は白金を補助する担体としての役割を超えるものではなく、活性には改善の余地があった。
(1) 銀、カルシウム、ストロンチウム、イットリウム、ルテニウム、ランタン、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、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、イッテルビウムおよびルテチウム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」または単に「M」ともいう。)ならびにチタン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。
(4) 金属Mおよびチタンを含有する金属炭窒化物から前記金属炭窒酸化物を得る工程を含むことを特徴とする(1)~(3)のいずれかに記載の触媒の製造方法。
(8) 前記工程(工程2または工程2a)における熱処理の温度が600~1500℃の範囲であることを特徴とする(5)~(6)のいずれかに記載の触媒の製造方法。
(12) さらに電子伝導性粒子を含むことを特徴とする(12)に記載の燃料電池用触媒層。
(16) (14)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型燃料電池。
本発明の触媒は、銀、カルシウム、ストロンチウム、イットリウム、ルテニウム、ランタン、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、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、イッテルビウム及びルテチウムからなる群より選択された少なくとも1種の金属Mならびにチタンを含有する、異なる2種以上の金属の炭窒酸化物からなることを特徴としている。
本発明に用いる触媒の、下記測定法(A)に従って測定される酸素還元開始電位は、可逆水素電極を基準として好ましくは0.5V(vs.NHE)以上である。
〔測定法(A):
電子伝導性粒子であるカーボンに分散させた触媒が0.9重量%となるように、該触媒及びカーボンを溶剤中に入れ、超音波で攪拌し懸濁液を得る。なお、カーボンとしては、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、触媒とカーボンとが重量比で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(重量比)=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、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、例えば該製造方法は金属Mおよびチタンを含有する金属炭窒化物から前記金属炭窒酸化物を得る工程(〔金属炭窒酸化物の製造工程〕)を含む。具体的には、銀、カルシウム、ストロンチウム、イットリウム、ルテニウム、ランタン、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、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、及びルテチウムからなる群より選択された少なくとも1種の金属Mならびにチタンを含有する金属炭窒化物を、酸素含有混合ガス中で熱処理することにより、銀、カルシウム、ストロンチウム、イットリウム、ルテニウム、ランタン、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、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、及びルテチウムからなる群より選択された少なくとも1種の金属Mならびにチタンを含有する金属炭窒酸化物を得る工程を含む製造方法が挙げられる。
上記工程(〔金属炭窒酸化物の製造工程〕)に用いる前記金属炭窒化物を得る方法としては、前記金属Mを含有する化合物及びチタンを含有する化合物を含んだ混合物を熱処理することにより金属炭窒化物を製造する方法(工程1)、その中でも前記金属Mの酸化物、酸化チタン及び炭素との混合物を、窒素雰囲気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(工程1a)が好ましい。
(工程1)は、前記金属Mを含有する化合物及びチタンを含有する化合物を含んだ混合物を熱処理することにより金属炭窒化物(熱処理物)を製造する方法である。
酸化物としては、酸化銀、酸化カルシウム、水酸化カルシウム、酸化ストロンチウム、酸化イットリウム、酸化ルテニウム、酸化ランタン、酸化プラセオジム、酸化ネオジム、酸化プロメチウム、酸化サマリウム、酸化ユウロピウム、酸化ガドリニウム、酸化テルビウム、酸化ジスプロシウム、酸化ホルミウム、酸化エルビウム、酸化ツリウム、酸化イッテルビウム、または酸化ルテチウム等が挙げられる。
炭素には、カーボン、カーボンブラック、グラファイト、黒鉛、活性炭、カーボンナノチューブ、カーボンナノファイバー、カーボンナノホーン、フラーレンが挙げられる。カーボンの粉末の粒径がより小さいと、比表面積が大きくなり、酸化物との反応がしやすくなるため好ましい。例えば、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)などが好適に用いられる。
最適な配合量(モル比)で作られた金属炭窒化物を用いると、酸素還元開始電位が高く、活性がある金属炭窒酸化物が得られる傾向がある。
(工程1)の中でも、特に(工程1a)は、前記金属Mの酸化物及び酸化チタン及び炭素との混合物を、窒素または窒素化合物含有混合ガス雰囲気中で熱処理することにより金属炭窒化物(熱処理物)を製造する方法であり、この工程から得られる金属炭窒酸化物の触媒活性が特に高く好ましい。
前記配合量(モル比)は、通常、酸化チタン1モルに対して、前記金属Mの酸化物が0.0001~1モル、炭素が1~10モルであり、好ましくは、酸化チタン1モルに対して、前記金属Mの酸化物が0.001~0.4モル、炭素が2~6モルである。さらに好ましくは、酸化チタン1モルに対して、前記金属Mの酸化物が0.001~0.1モル、炭素が2~3モルである。金属Mがカルシウム、ストロンチウム、イットリウム、ランタン、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、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、ルテチウムの場合には、酸化チタン1モルに対して、金属Mの酸化物が0.001~0.05モルであることが好ましい。より好ましくは、0.005~0.03モルであることが好ましい。上記範囲を満たす配合モル比で作られた金属炭窒化物を用いると、酸素還元開始電位が高く、活性がある金属炭窒酸化物が得られる傾向がある。
次に、金属Mおよびチタンを含有する金属炭窒化物から前記金属炭窒酸化物を得る工程(〔金属炭窒酸化物の製造工程〕)について、具体的には工程(1)または工程(1a)で得られた金属炭窒化物を、酸素を含む混合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(工程(2)または工程(2a))について説明する。
当該工程における酸素含有混合ガス中の酸素濃度は、熱処理時間と熱処理温度に依存するが、0.005~10容量%が好ましく、0.1~7.0容量%がより好ましく、0.5~5容量%がさらに好ましく、1.0~5容量%が特に好ましく、1.5~2.5容量%が最も好ましい。前記酸素濃度が前記範囲内であると、均一な炭窒酸化物が形成する点で好ましい。また、前記酸素濃度が0.005容量%未満であると未酸化状態になる傾向があり、10容量%を超えると酸化が進み過ぎてしまう傾向がある。
落下法とは、誘導炉中に微量の酸素を含む不活性ガスを流しながら、炉を所定の熱処理温度まで加熱し、該温度で熱的平衡を保った後、炉の加熱区域である坩堝中に金属炭窒化物を落下させ、熱処理する方法である。落下法の場合は、金属炭窒化物の粒子の凝集及び成長を最小限度に抑制することができる点で好ましい。
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。
例えば、燃料電池用触媒、排ガス処理用触媒または有機合成用触媒として使用できる。
燃料電池用触媒層には、アノード触媒層、カソード触媒層があるが、前記触媒はいずれにも用いることができる。前記触媒は、耐久性に優れ、酸素還元能が大きいので、カソード触媒層に用いることが好ましい。
電子伝導性粒子としては、炭素、導電性高分子、導電性セラミクス、金属または酸化タングステンもしくは酸化イリジウムなどの導電性無機酸化物が挙げられ、それらを単独または組み合わせて用いることができる。特に、炭素は比表面積が大きいため、炭素単独または炭素とその他の電子伝導性粒子との混合物が好ましい。すなわち燃料電池用触媒層としては、前記触媒と、炭素とを含むことが好ましい。
導電性高分子としては特に限定は無いが、例えばポリアセチレン、ポリ-p-フェニレン、ポリアニリン、ポリアルキルアニリン、ポリピロール、ポリチオフェン、ポリインドール、ポリ-1,5-ジアミノアントラキノン、ポリアミノジフェニル、ポリ(o-フェニレンジアミン)、ポリ(キノリニウム)塩、ポリピリジン、ポリキノキサリン、ポリフェニルキノキサリン等が挙げられる。これらの中でも、ポリピロール、ポリアニリン、ポリチオフェンが好ましく、ポリピロールがより好ましい。
高分子電解質としては、燃料電池用触媒層において一般的に用いられているものであれば特に限定されない。具体的には、スルホン酸基を有するパーフルオロカーボン重合体(例えば、ナフィオン(登録商標)(デュポン社 5%ナフィオン(登録商標)溶液(DE521)など)、スルホン酸基を有する炭化水素系高分子化合物、リン酸などの無機酸をドープさせた高分子化合物、一部がプロトン伝導性の官能基で置換された有機/無機ハイブリッドポリマー、高分子マトリックスにリン酸溶液や硫酸溶液を含浸させたプロトン伝導体などが挙げられる。これらの中でも、ナフィオン(登録商標)(デュポン社 5%ナフィオン(登録商標)溶液(DE521))が好ましい。
燃料電池用触媒層の形成方法としては、特に制限はないが、たとえば、前記触媒と電子伝導性粒子と電解質とを含む懸濁液を、後述する電解質膜またはガス拡散層に塗布する方法が挙げられる。前記塗布する方法としては、ディッピング法、スクリーン印刷法、ロールコーティング法、スプレー法などが挙げられる。また、前記触媒と電子伝導性粒子と電解質とを含む懸濁液を、塗布法またはろ過法により基材に燃料電池用触媒層を形成した後、転写法で電解質膜に燃料電池用触媒層を形成する方法が挙げられる。
本発明の電極はカソードまたはアノードのいずれの電極にも用いることができる。本発明の電極は、耐久性に優れ、触媒能が大きいので、カソードに用いるとより産業上の優位性が高い。
燃料電池の電極反応はいわゆる3相界面(電解質‐電極触媒‐反応ガス)で起こる。燃料電池は、使用される電解質などの違いにより数種類に分類され、溶融炭酸塩型(MCFC)、リン酸型(PAFC)、固体酸化物型(SOFC)、固体高分子型(PEFC)等がある。中でも、本発明の膜電極接合体は、固体高分子型燃料電池に使用することが好ましい。
また、実施例及び比較例における各種測定は、下記の方法により行なった。
1.粉末X線回折
理学電機株式会社製 ロータフレックスを用いて、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。
窒素・酸素:試料約0.1gを量り取り、Ni-Cupに封入後、ON分析装置で測定を行った。
[実施例1、(TiaLabCxNyOz)]
1.触媒の調製
酸化チタン3.53g(昭和電工製、スーパータイタニアF6)、酸化ランタン(信越化学工業製、La2O3)0.144gにカーボン(キャボット社製、Vulcan72)1.33gを十分に粉砕して混合した。この混合粉末を管状炉において、1800℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びランタン(チタン100mol%に対して約2mol%)を含有する炭窒化物(1)2.52gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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の重量比で混合した溶液10gに入れ、超音波で撹拌、縣濁して混合した。この混合物10μl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5分間乾燥した。この滴下及び乾燥操作を、カーボン電極表面に1.0mg以上の燃料電池触媒層が形成されるまで行った。さらに、ナフィオン(登録商標)(デゥポン社 5%ナフィオン(登録商標)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。
すなわち、酸素還元開始電位が高いほど、また、酸素還元電流が大きいほど、燃料電池用電極(1)の触媒能(酸素還元能)が高いことを示す。
実施例1で作製した燃料電池用電極(1)は、酸素還元開始電位が0.89V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.57g(昭和電工製、スーパータイタニアF6)、酸化サマリウム(信越化学工業製、Sm2O3)0.077gにカーボン(キャボット社製、Vulcan72)1.34gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びサマリウム(チタン100mol%に対して約1mol%)を含有する炭窒化物(2)2.48gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例2で作製した燃料電池用電極(2)は、酸素還元開始電位が0.90V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.52g(昭和電工製、スーパータイタニアF6)、酸化プラセオジム(信越化学工業製、Pr6O11)0.144gにカーボン(キャボット社製、Vulcan72)1.33gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びプラセオジム(チタン100mol%に対して約2mol%)を含有する炭窒化物(3)2.53gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例3で作製した燃料電池用電極(3)は、酸素還元開始電位が0.89V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.53g(昭和電工製、スーパータイタニアF6)、酸化ネオジム(信越化学工業製、Nd2O3)0.150gにカーボン(キャボット社製、Vulcan72)1.33gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びネオジム(チタン100mol%に対して約2mol%)を含有する炭窒化物(4)2.50gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例4で作製した燃料電池用電極(4)は、酸素還元開始電位が0.88V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.52g(昭和電工製、スーパータイタニアF6)、酸化ユウロピウム(信越化学工業製、Eu2O3)0.155gにカーボン(キャボット社製、Vulcan72)1.32gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びユウロピウム(チタン100mol%に対して約2mol%)を含有する炭窒化物(5)2.49gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例5で作製した燃料電池用電極(5)は、酸素還元開始電位が0.88V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.52g(昭和電工製、スーパータイタニアF6)、酸化ガドリニウム(信越化学工業製、Gd2O3)0.160gにカーボン(キャボット社製、Vulcan72)1.32gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びガドリニウム(チタン100mol%に対して約2mol%)を含有する炭窒化物(6)2.55gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例6で作製した燃料電池用電極(6)は、酸素還元開始電位が0.88V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.52g(昭和電工製、スーパータイタニアF6)、酸化テルビウム(信越化学工業製、Tb2O3)0.164gにカーボン(キャボット社製、Vulcan72)1.32gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びテルビウム(チタン100mol%に対して約2mol%)を含有する炭窒化物(7)2.60gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例7で作製した燃料電池用電極(7)は、酸素還元開始電位が0.86V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.52g(昭和電工製、スーパータイタニアF6)、酸化ジスプロシウム(信越化学工業製、Dy2O3)0.164gにカーボン(キャボット社製、Vulcan72)1.32gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びジスプロシウム(チタン100mol%に対して約2mol%)を含有する炭窒化物(8)2.61gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例8で作製した燃料電池用電極(8)は、酸素還元開始電位が0.87V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.57g(昭和電工製、スーパータイタニアF6)、酸化エルビウム(信越化学工業製、Er2O3)0.077gにカーボン(キャボット社製、Vulcan72)1.34gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びエルビウム(チタン100mol%に対して約2mol%)を含有する炭窒化物(9)2.65gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例9で作製した燃料電池用電極(9)は、酸素還元開始電位が0.87V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.51g(昭和電工製、スーパータイタニアF6)、酸化イッテルビウム(信越化学工業製、Yb2O3)0.173gにカーボン(キャボット社製、Vulcan72)1.32gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びイッテルビウム(チタン100mol%に対して約2mol%)を含有する炭窒化物(10)2.70gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例10で作製した燃料電池用電極(10)は、酸素還元開始電位が0.86V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.54g(昭和電工製、スーパータイタニアF6)、炭酸ストロンチウム(堺化学製、SW-K)0.131gにカーボン(キャボット社製、Vulcan72)1.33gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びストロンチウム(チタン100mol%に対して約2mol%)を含有する炭窒化物(11)2.46gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例11で作製した燃料電池用電極(11)は、酸素還元開始電位が0.87V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.60g(昭和電工製、スーパータイタニアF6)、炭酸カルシウム(宇部マテリアルズ製、CS-4N-A)0.045gにカーボン(キャボット社製、Vulcan72)1.35gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びカルシウム(チタン100mol%に対して約1mol%)を含有する炭窒化物(12)2.47gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
前記触媒(12)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。
実施例12で作製した燃料電池用電極(12)は、酸素還元開始電位が0.88V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.57g(昭和電工製、スーパータイタニアF6)、酸化ランタン(信越化学工業製、La2O3)0.036gにカーボン(キャボット社製、Vulcan72)1.34gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びランタン(チタン100mol%に対して約0.5mol%)を含有する炭窒化物(13)2.49gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例13で作製した燃料電池用電極(13)は、酸素還元開始電位が0.89V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.57g(昭和電工製、スーパータイタニアF6)、酸化ランタン(信越化学工業製、La2O3)0.72gにカーボン(キャボット社製、Vulcan72)1.34gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びランタン(チタン100mol%に対して約10mol%)を含有する炭窒化物(14)2.48gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例14で作製した燃料電池用電極(14)は、酸素還元開始電位が0.88V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.57g(昭和電工製、スーパータイタニアF6)、酸化サマリウム(信越化学工業製、Sm2O3)0.038gにカーボン(キャボット社製、Vulcan72)1.34gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びサマリウム(チタン100mol%に対して約0.5mol%)を含有する炭窒化物(15)2.51gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例15で作製した燃料電池用電極(15)は、酸素還元開始電位が0.88V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.57g(昭和電工製、スーパータイタニアF6)、酸化サマリウム(信越化学工業製、Sm2O3)0.154gにカーボン(キャボット社製、Vulcan72)1.34gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタン及びサマリウム(チタン100mol%に対して約10mol%)を含有する炭窒化物(16)2.48gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
実施例16で作製した燃料電池用電極(16)は、酸素還元開始電位が0.86V(vs.NHE)であり、高い酸素還元能を有することがわかった。
1.触媒の調製
酸化チタン3.63g(昭和電工製、スーパータイタニアF6)、カーボン(キャボット社製、Vulcan72)1.37gを十分に粉砕して混合した。この混合粉末を管状炉において、1700℃で3時間、窒素雰囲気中で熱処理することにより、チタンの炭窒化物(13’)2.51gが得られた。これを乳鉢により破砕した。
2.燃料電池用電極の製造
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。
参考例1で作製した燃料電池用電極(13’)は、酸素還元開始電位が0.80V(vs.NHE)であり、酸素還元能を有することがわかった。
1.触媒の準備
炭窒化チタン(和光純薬株式会社、40nm)を入手したままの状態で触媒として使用した。粉末X線回折スペクトルを図14に示す。
上記炭窒化物を触媒として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。
実施例2で作製した燃料電池用電極(14’)は、酸素還元開始電位が0.51V(vs.NHE)であり、酸素還元の電位が低いことが分かった。
Claims (16)
- 銀、カルシウム、ストロンチウム、イットリウム、ルテニウム、ランタン、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、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、イッテルビウムおよびルテチウム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」または単に「M」ともいう。)ならびにチタン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、TiaMbCxNyOz(ただし、a、b、x、y、zは原子数の比を表し、0.7≦a≦0.9999、0.0001≦b≦0.3、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。
- 請求項1または2に記載の燃料電池用触媒。
- 金属Mおよびチタンを含有する金属炭窒化物から前記金属炭窒酸化物を得る工程を含むことを特徴とする請求項1~3のいずれか一項に記載の触媒の製造方法。
- 金属Mを含有する化合物及びチタンを含有する化合物の混合物を窒素または窒素化合物含有混合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(工程1)と、前記金属炭窒化物を酸素含有混合ガス中で熱処理することにより前記金属炭窒酸化物を得る工程(工程2)とを含むことを特徴とする請求項1~3のいずれか一項に記載の触媒の製造方法。
- 金属Mの酸化物、酸化チタン及び炭素の混合物を窒素または窒素化合物含有混合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(工程1a)と、前記金属炭窒化物を酸素含有混合ガス中で熱処理することにより前記金属炭窒酸化物を得る工程(工程2a)とを含むことを特徴とする請求項1~3のいずれか一項に記載の触媒の製造方法。
- 前記工程(工程1または工程1a)における熱処理の温度が600~2200℃の範囲であることを特徴とする請求項5~6のいずれか一項に記載の触媒の製造方法。
- 前記工程(工程2または工程2a)における熱処理の温度が600~1500℃の範囲であることを特徴とする請求項5~6のいずれか一項に記載の触媒の製造方法。
- 前記工程(工程2または工程2a)における酸素含有混合ガス中の酸素濃度が0.005~2.5容量%の範囲であることを特徴とする請求項5~8のいずれか一項に記載の触媒の製造方法。
- 前記工程(工程2または工程2a)において酸素含有混合ガスが水素を0.01容量%以上5容量%以下の濃度でさらに含むことを特徴とする請求項5~9のいずれか一項に記載の触媒の製造方法。
- 請求項1~3のいずれか一項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11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11または12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及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、前記カソード及び/または前記アノードが請求項13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14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14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型燃料電池。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013146453A1 (ja) | 2012-03-26 | 2013-10-03 | 昭和電工株式会社 | 燃料電池用電極触媒の製造方法、燃料電池用電極触媒およびその用途 |
JP2017013022A (ja) * | 2015-07-03 | 2017-01-19 | 昭和電工株式会社 | 酸素還元触媒の評価方法および選択方法並びに酸素還元触媒 |
Families Citing this family (5)
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WO2009119523A1 (ja) * | 2008-03-24 | 2009-10-01 | 昭和電工株式会社 | 触媒及びその製造方法ならびにその用途 |
US8703638B2 (en) * | 2008-10-06 | 2014-04-22 | Showa Denko K.K. | Process for production and use of carbonitride mixture particles or oxycarbonitride mixture particles |
WO2013035191A1 (ja) * | 2011-09-09 | 2013-03-14 | 昭和電工株式会社 | 燃料電池用触媒層及びその用途 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002095976A (ja) * | 2000-07-17 | 2002-04-02 | Toyota Central Res & Dev Lab Inc | 光触媒体 |
JP2006107967A (ja) * | 2004-10-07 | 2006-04-20 | Toyota Central Res & Dev Lab Inc | 固体高分子型燃料電池 |
JP2006198570A (ja) * | 2005-01-24 | 2006-08-03 | Sumitomo Chemical Co Ltd | 電極触媒の製造方法 |
WO2009031383A1 (ja) * | 2007-09-07 | 2009-03-12 | Showa Denko K.K. | 触媒およびその製造方法ならびにその用途 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5811624A (en) * | 1995-09-05 | 1998-09-22 | Exxon Research And Engineering Company | Selective opening of five and six membered rings |
JP3451878B2 (ja) | 1997-03-10 | 2003-09-29 | 三菱マテリアル株式会社 | 耐摩耗性のすぐれた表面被覆超硬合金製切削工具 |
JP3933523B2 (ja) | 2002-05-23 | 2007-06-20 | 株式会社Neomax | 薄膜磁気ヘッド用セラミックス基板材料 |
JP2005271190A (ja) | 2003-12-05 | 2005-10-06 | Sumitomo Electric Hardmetal Corp | 表面被覆切削工具 |
JP2007031781A (ja) | 2005-07-27 | 2007-02-08 | Yokohama National Univ | 酸素還元電極 |
JP5214117B2 (ja) | 2006-06-20 | 2013-06-19 | トヨタ自動車株式会社 | ペロブスカイト型酸化物微粒子、ペロブスカイト型酸化物担持粒子、触媒材料、燃料電池用電極 |
WO2007145216A1 (ja) | 2006-06-13 | 2007-12-21 | Hitachi Maxell, Ltd. | ペロブスカイト型酸化物微粒子、ペロブスカイト型酸化物担持粒子、触媒材料、酸素還元用触媒材料、燃料電池用触媒材料、燃料電池用電極 |
JP4875410B2 (ja) | 2006-06-13 | 2012-02-15 | トヨタ自動車株式会社 | 微粒子担持カーボン粒子およびその製造方法ならびに燃料電池用電極 |
KR101202130B1 (ko) * | 2008-02-20 | 2012-11-15 | 쇼와 덴코 가부시키가이샤 | 촉매용 담체, 촉매 및 그 제조 방법 |
-
2010
- 2010-05-11 TW TW099114954A patent/TW201111039A/zh unknown
- 2010-05-11 US US13/319,617 patent/US9048499B2/en not_active Expired - Fee Related
- 2010-05-11 JP JP2011513333A patent/JP5713891B2/ja not_active Expired - Fee Related
- 2010-05-11 WO PCT/JP2010/057927 patent/WO2010131634A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002095976A (ja) * | 2000-07-17 | 2002-04-02 | Toyota Central Res & Dev Lab Inc | 光触媒体 |
JP2006107967A (ja) * | 2004-10-07 | 2006-04-20 | Toyota Central Res & Dev Lab Inc | 固体高分子型燃料電池 |
JP2006198570A (ja) * | 2005-01-24 | 2006-08-03 | Sumitomo Chemical Co Ltd | 電極触媒の製造方法 |
WO2009031383A1 (ja) * | 2007-09-07 | 2009-03-12 | Showa Denko K.K. | 触媒およびその製造方法ならびにその用途 |
Non-Patent Citations (1)
Title |
---|
YOSHIRO OSHIRO ET AL.: "Bubun Sanka shita Sen'i Kinzoku Tanchikkabutsu no Sanso Kangen Shokubaino", THE ELECTROCHEMICAL SOCIETY OF JAPAN DAI 74 KAI TAIKAI KOEN YOSHISHU, 29 March 2007 (2007-03-29), pages 94 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013146453A1 (ja) | 2012-03-26 | 2013-10-03 | 昭和電工株式会社 | 燃料電池用電極触媒の製造方法、燃料電池用電極触媒およびその用途 |
JP5635212B2 (ja) * | 2012-03-26 | 2014-12-03 | 昭和電工株式会社 | 燃料電池用電極触媒の製造方法、燃料電池用電極触媒およびその用途 |
US20150044595A1 (en) * | 2012-03-26 | 2015-02-12 | Showa Denko K.K. | Production process of electrode catalyst for fuel cells, electrode catalyst for fuel cells and uses thereof |
JP2017013022A (ja) * | 2015-07-03 | 2017-01-19 | 昭和電工株式会社 | 酸素還元触媒の評価方法および選択方法並びに酸素還元触媒 |
Also Published As
Publication number | Publication date |
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TW201111039A (en) | 2011-04-01 |
US20120058415A1 (en) | 2012-03-08 |
JP5713891B2 (ja) | 2015-05-07 |
JPWO2010131634A1 (ja) | 2012-11-01 |
US9048499B2 (en) | 2015-06-02 |
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