JPWO2019003788A1 - Support catalyst and method for producing the same - Google Patents
Support catalyst and method for producing the same Download PDFInfo
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- JPWO2019003788A1 JPWO2019003788A1 JP2019526728A JP2019526728A JPWO2019003788A1 JP WO2019003788 A1 JPWO2019003788 A1 JP WO2019003788A1 JP 2019526728 A JP2019526728 A JP 2019526728A JP 2019526728 A JP2019526728 A JP 2019526728A JP WO2019003788 A1 JPWO2019003788 A1 JP WO2019003788A1
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- Prior art keywords
- catalyst
- carrier
- tio
- titanium oxide
- crystal phase
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- 239000003054 catalyst Substances 0.000 title claims abstract description 155
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 137
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000010936 titanium Substances 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 91
- 229960005196 titanium dioxide Drugs 0.000 claims description 78
- 239000013078 crystal Substances 0.000 claims description 60
- 229910052697 platinum Inorganic materials 0.000 claims description 44
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- 239000004408 titanium dioxide Substances 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 28
- 239000000446 fuel Substances 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000002245 particle Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 16
- 238000005259 measurement Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 239000012528 membrane Substances 0.000 description 11
- 239000005518 polymer electrolyte Substances 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 229920000557 Nafion® Polymers 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- -1 for example Chemical compound 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 241000252073 Anguilliformes Species 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910000929 Ru alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000566 Platinum-iridium alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000366 colloid method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- UYXRCZUOJAYSQR-UHFFFAOYSA-N nitric acid;platinum Chemical compound [Pt].O[N+]([O-])=O UYXRCZUOJAYSQR-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical class [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- 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
- H01M8/08—Fuel cells with aqueous electrolytes
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
本発明の担体付き触媒は、触媒が担体に担持されてなる。担体がチタン酸化物を含み、担体に含まれるチタン元素（Ｔｉ）と酸素元素（Ｏ）の含有割合（Ｏ／Ｔｉ）がモル比で表して０．８以上１．６以下であり、担体がＴｉＯ０．５の結晶相又はＴｉＯの結晶相を有する。担体付き触媒は、組成式ＴｉＯａ（式中、ａは０．４以上１以下の数を表す。）で表されるチタン酸化物を有機溶媒中で粉砕し、次いで乾粉化工程を経ることなく有機溶媒中で触媒を担持させ；触媒を担持したチタン酸化物を焼成することで製造される。The carrier-supported catalyst of the present invention comprises a catalyst supported on a carrier. The carrier contains titanium oxide, and the content ratio (O / Ti) of titanium element (Ti) and oxygen element (O) contained in the carrier is 0.8 or more and 1.6 or less in terms of molar ratio, and the carrier is It has a crystalline phase of TiO0.5 or a crystalline phase of TiO. The catalyst with a carrier is obtained by pulverizing a titanium oxide represented by the composition formula TiOa (wherein a represents a number of 0.4 or more and 1 or less) in an organic solvent, and then organic It is produced by supporting a catalyst in a solvent; calcining a titanium oxide supporting the catalyst.
Description
触媒の担体としては様々な無機化合物が用いられている。かかる無機化合物は、触媒の種類や化学反応の種類に応じて導電性を有するものと、非導電性のものが用いられる。無機化合物からなる導電性の担体としては、例えば導電性を有する炭素などの炭素材料が知られている。しかし炭素材料は酸化性の環境下での耐久性に問題があることから、炭素材料の代替材料が種々検討されている。 Various inorganic compounds have been used as catalyst carriers. As such an inorganic compound, an electrically conductive one and a non-conductive one are used depending on the type of catalyst and the type of chemical reaction. As a conductive carrier made of an inorganic compound, for example, a carbon material such as conductive carbon is known. However, since carbon materials have a problem in durability in an oxidizing environment, various alternative materials for carbon materials have been investigated.
炭素材料に代わる導電性の無機化合物の一つとして導電性酸化チタンが知られている。例えば特許文献１には組成式ＴｉＯｘ（式中のｘは１．５＜ｘ＜２の範囲である。）で表され、且つ比表面積が５０ｍ２／ｇ以上である低次酸化チタンに、金属を担持してなる触媒が提案されている。この触媒は、燃料電池の電極触媒として用いた場合に酸化安定性に優れ、また導電性が高いと同文献には記載されている。Conductive titanium oxide is known as one of conductive inorganic compounds that replace carbon materials. For example, in Patent Document 1, a low-order titanium oxide represented by the composition formula TiO x (where x is in the range of 1.5 <x <2) and having a specific surface area of 50 m 2 / g or more, A catalyst supporting a metal has been proposed. This catalyst is described in the literature as being excellent in oxidation stability and having high conductivity when used as an electrode catalyst of a fuel cell.
特許文献１に記載の低次酸化チタンは確かに導電性を有するものの、従来用いられていた炭素材料と比較すると導電性が決して高いとは言えず、更なる導電性の向上が望まれていた。 Although the low-order titanium oxide described in Patent Document 1 certainly has conductivity, it cannot be said that the low-order titanium oxide has high conductivity as compared with the conventionally used carbon materials, and further improvement in conductivity has been desired. .
したがって本発明の課題は、従来知られている酸化チタンより、導電性が一層向上した酸化チタンを担体とする触媒を提供することにある。 Therefore, an object of the present invention is to provide a catalyst having titanium oxide as a carrier, which has a further improved conductivity as compared with the conventionally known titanium oxide.
本発明は、触媒が担体に担持されてなる担体付き触媒であって、
前記担体がチタン酸化物を含み、
前記担体に含まれるチタン元素（Ｔｉ）と酸素元素（Ｏ）の含有割合（Ｏ／Ｔｉ）がモル比で表して０．８以上１．６以下であり、
前記担体がＴｉＯ０．５の結晶相又はＴｉＯの結晶相を有する、担体付き触媒を提供することにより前記の課題を解決したものである。The present invention is a catalyst with a carrier in which the catalyst is supported on a carrier,
The carrier comprises titanium oxide,
The content ratio (O / Ti) of titanium element (Ti) and oxygen element (O) contained in the carrier is 0.8 or more and 1.6 or less in terms of molar ratio,
The above problem is solved by providing a catalyst with a carrier in which the carrier has a TiO 0.5 crystal phase or a TiO crystal phase.
また本発明は、前記の担体付き触媒の好適な製造方法として、
組成式ＴｉＯａ（式中、ａは０．４以上１以下の数を表す。）で表されるチタン酸化物を有機溶媒中で粉砕し、次いで乾粉化工程を経ることなく有機溶媒中で触媒を担持させ、
前記触媒を担持した前記チタン酸化物を焼成する、担体付き触媒の製造方法を提供するものである。The present invention also provides a suitable method for producing the above-mentioned catalyst with a carrier,
Titanium oxide represented by the composition formula TiO a (where a is a number of 0.4 or more and 1 or less) is crushed in an organic solvent, and then the catalyst is catalyzed in the organic solvent without a dry powdering step. Carry
The present invention provides a method for producing a catalyst with a carrier, which comprises firing the titanium oxide carrying the catalyst.
以下、本発明をその好ましい実施形態に基づき説明する。本発明は、触媒が担体に担持されてなる担体付き触媒に関するものである。この担体はチタン酸化物を含む。このチタン酸化物は、チタン元素（Ｔｉ）と酸素元素（Ｏ）とから構成される化合物である。担体は、このチタン酸化物を含み、残部が好ましくは不可避不純物から構成される。チタン酸化物は導電性を有していることが好ましい。 The present invention will be described below based on its preferred embodiments. The present invention relates to a catalyst with a carrier in which a catalyst is supported on a carrier. This carrier comprises titanium oxide. This titanium oxide is a compound composed of titanium element (Ti) and oxygen element (O). The carrier contains this titanium oxide and the balance is preferably composed of unavoidable impurities. The titanium oxide is preferably conductive.
触媒が担持された状態の担体（チタン酸化物）におけるチタン元素（Ｔｉ）と酸素元素（Ｏ）との含有割合は、Ｏ／Ｔｉのモル比で表して、Ｏ／Ｔｉの値が０．８以上１．６以下であることが好ましく、０．８以上１．４以下であることが更に好ましく、０．９以上１．２以下であることが一層好ましい。チタンの酸化物としては、例えば四価のチタンの酸化物である二酸化チタン（ＴｉＯ２）が典型的なものとして知られているところ、Ｏ／Ｔｉの値がモル比で表して０．８以上１．６以下であるチタン酸化物は、二酸化チタンに比べて酸素が欠損した状態になっていると言える。この酸素欠損状態に起因して、本発明で用いるチタン酸化物は導電性を有するものと本発明者は考えている。The content ratio of the titanium element (Ti) and the oxygen element (O) in the carrier (titanium oxide) on which the catalyst is supported is expressed by the molar ratio of O / Ti, and the value of O / Ti is 0.8. It is preferably 1.6 or more and 1.6 or less, more preferably 0.8 or more and 1.4 or less, and further preferably 0.9 or more and 1.2 or less. As a titanium oxide, for example, titanium dioxide (TiO 2 ) which is an oxide of tetravalent titanium is known as a typical one, and the value of O / Ti is 0.8 or more in terms of a molar ratio. It can be said that the titanium oxide having 1.6 or less is in a state of lacking oxygen as compared with titanium dioxide. The present inventor believes that the titanium oxide used in the present invention has conductivity due to this oxygen deficiency state.
担体（チタン酸化物）におけるＯ／Ｔｉのモル比の値は、次の方法で測定される。熱重量分析装置（ＴＧ−ＤＴＡ）（日立ハイテクサイエンス社製ＳＴＡ７３００）を用いて、大気中にて１０℃／分の昇温速度で１３００℃まで昇温することで、重量増加率を測定する。増加した重量のすべてが、担体を構成するチタン酸化物（ＴｉＯａ）の二酸化チタン（ＴｉＯ２）への酸化によるものであると仮定し、測定した重量増加率により、Ｏ／Ｔｉのモル比の値を算出する。The value of the O / Ti molar ratio in the carrier (titanium oxide) is measured by the following method. Using a thermogravimetric analyzer (TG-DTA) (STA7300 manufactured by Hitachi High-Tech Science Co., Ltd.), the rate of increase in weight is measured by increasing the temperature to 1300 ° C. at a temperature increasing rate of 10 ° C./min in the atmosphere. It is assumed that all of the increased weight is due to the oxidation of the titanium oxide (TiO a ) that constitutes the support to titanium dioxide (TiO 2 ), and the measured weight gain rate indicates that the molar ratio of O / Ti Calculate the value.
担体（チタン酸化物）は、Ｏ／Ｔｉのモル比の値が上述のとおりであることに加えて、ＴｉＯ０．５の結晶相又はＴｉＯの結晶相を有していることが好ましい。結晶性のＴｉＯ０．５及びＴｉＯは、背景技術の項で述べたＴｉＯｘ（式中のｘは１．５＜ｘ＜２である。）に比べて導電性の高い物質である。したがって、担体が結晶性のＴｉＯ０．５又はＴｉＯを含むことで、担体の導電性が高まり、該担体に担持されている触媒はその性能を十分に発揮することができる。The carrier (titanium oxide) preferably has a crystal phase of TiO 0.5 or a crystal phase of TiO, in addition to the value of the O / Ti molar ratio as described above. Crystalline TiO 0.5 and TiO are materials having higher conductivity than TiO x ( x in the formula is 1.5 <x <2) described in the section of background art. Therefore, since the carrier contains crystalline TiO 0.5 or TiO, the conductivity of the carrier is enhanced, and the catalyst supported on the carrier can sufficiently exhibit its performance.
特に担体（チタン酸化物）がＴｉＯ０．５の結晶相を有する場合には、該結晶相の結晶子サイズは１０ｎｍ以上１００ｎｍ以下であることが好ましく、１５ｎｍ以上８０ｎｍ以下であることが更に好ましく、２０ｎｍ以上６５ｎｍ以下であることが一層好ましい。ＴｉＯ０．５の結晶相の結晶子サイズがこの範囲内であることによって、担体の導電性が一層高まり、担体に担持されている触媒はその性能を十分に発揮することができる。Particularly when the carrier (titanium oxide) has a crystal phase of TiO 0.5 , the crystallite size of the crystal phase is preferably 10 nm or more and 100 nm or less, more preferably 15 nm or more and 80 nm or less, It is more preferably 20 nm or more and 65 nm or less. When the crystallite size of the crystal phase of TiO 0.5 is within this range, the conductivity of the carrier is further enhanced, and the catalyst supported on the carrier can sufficiently exhibit its performance.
担体（チタン酸化物）に含まれるＴｉＯ０．５の結晶相の結晶子サイズは、粉末Ｘ線回折によって得られる回折ピークからシェラー（Ｓｃｈｅｒｒｅｒ）の式によって算出される。粉末Ｘ線回折による測定には例えば株式会社リガク製のＳｍａｒｔＬａｂを用い、ＣｕＫα１線を使用して、測定範囲２０°〜１００°でＴｉＯ０．５のＸ線回折強度を測定したときの結晶面（１０１）Ｘ線回折ピークのピーク幅（半値幅）から、下記のシェラーの式により算出する。
シェラーの式：Ｄ＝Ｋλ／βｃｏｓθ
Ｄ：結晶子サイズ
Ｋ：シェラー定数（１．３３３）
λ：Ｘ線の波長
β：半値幅［ｒａｄ］
θ：回折角The crystallite size of the crystal phase of TiO 0.5 contained in the carrier (titanium oxide) is calculated by the Scherrer formula from the diffraction peak obtained by powder X-ray diffraction. For measurement by powder X-ray diffraction, for example, SmartLab manufactured by Rigaku Co., Ltd. is used, and CuKα1 rays are used to measure the crystal plane (when measuring the X-ray diffraction intensity of TiO 0.5 in a measurement range of 20 ° to 100 ° ( 101) It is calculated from the peak width (half-width) of the X-ray diffraction peak by the Scherrer's formula below.
Scherrer's formula: D = Kλ / β cos θ
D: Crystallite size K: Scherrer constant (1.333)
λ: wavelength of X-ray β: full width at half maximum [rad]
θ: Diffraction angle
担体（チタン酸化物）が、ＴｉＯ０．５の結晶相又はＴｉＯの結晶相を有することは、該担体の粉末Ｘ線回折（ＸＲＤ）測定によって確認することができる。担体は、Ｘ線回折測定によってＴｉＯ０．５の結晶相の存在のみが確認されてもよく、ＴｉＯの結晶相の存在のみが確認されてもよく、あるいはＴｉＯ０．５の結晶相及びＴｉＯの結晶相の双方の存在が確認されてもよい。担体の導電性の一層の向上の観点からは、担体がＴｉＯ０．５の結晶相を少なくとも有することが好ましい。担体に、ＴｉＯ０．５の結晶相及びＴｉＯの結晶相以外の酸化チタンの結晶相や非晶質相が存在してもよい。そのような酸化物の例としてはＴｉＯ２やＴｉ２Ｏ３などが挙げられる。ＴｉＯ２が結晶相として存在している場合には、ＴｉＯ２はルチル型及びアナターゼ型、ブルッカイト型のいずれであってもよい。また、ＴｉＯ０．５の結晶相以外の結晶相を有する場合、担体の導電性の一層の向上の観点から、ＴｉＯ０．５の結晶相は主結晶相として存在することが好ましい。It can be confirmed by powder X-ray diffraction (XRD) measurement of the carrier that the carrier (titanium oxide) has a crystal phase of TiO 0.5 or a crystal phase of TiO. Carrier may be only in the presence of a crystalline phase of TiO 0.5 is confirmed by X-ray diffraction measurement may be only in the presence of TiO crystalline phase is confirmed, or the TiO 0.5 crystalline phase and the TiO The presence of both crystalline phases may be confirmed. From the viewpoint of further improving the conductivity of the carrier, it is preferable that the carrier has at least a crystal phase of TiO 0.5 . A crystal phase of titanium oxide other than the crystal phase of TiO 0.5 and the crystal phase of TiO 2 or an amorphous phase may be present in the carrier. Examples of such oxides include TiO 2 and Ti 2 O 3 . When TiO 2 exists as a crystal phase, TiO 2 may be any of rutile type, anatase type, and brookite type. Also, when having a crystal phase other than the crystalline phase of TiO 0.5, from the viewpoint of further improvement of the conductivity of the carrier, the crystalline phase of TiO 0.5 are preferably present as the predominant crystal phase.
ＴｉＯ０．５の結晶相やＴｉＯの結晶相は、Ｔｉの一部が他の元素（例えば、Ｎｂ，Ｔａ，Ｍｏ，Ｗ，Ｇｅ，Ｓｂ，Ｂｉ，Ｈｆ，Ｚｒ，Ｍｇ，Ｃａ，Ｓｒ，Ｂａ，Ｚｎ，Ａｌなどの金属元素）で置換されていてもよいし、またＴｉの一部が欠損していてもよい。また、本発明の効果を奏する程度において、担体はチタン酸化物以外の化合物を含有してもよい。In the crystal phase of TiO 0.5 or the crystal phase of TiO, a part of Ti is contained in another element (for example, Nb, Ta, Mo, W, Ge, Sb, Bi, Hf, Zr, Mg, Ca, Sr, Ba). , Zn, Al, etc.), or a part of Ti may be missing. In addition, the carrier may contain a compound other than titanium oxide to the extent that the effects of the present invention are exhibited.
担体が有する結晶相の同定は次のように行う。測定装置として例えば株式会社リガク製のＳｍａｒｔＬａｂを用い、ＣｕＫα１線を使用して、測定範囲２０°〜１００°で、粉末Ｘ線回折の測定を行う。そして、粉末Ｘ線回折の測定によって得られた回折パターンを観察することにより、結晶相の同定を行う。担体がＴｉＯ０．５の結晶相を主結晶相として有するか否かは、粉末Ｘ線回折の測定で得られる回折パターンにおいて、ＴｉＯ０．５の結晶相に由来する回折ピークの最大強度が、他のいずれの結晶相に由来する回折ピークの最大強度よりも大きいか否かで判断する。The crystal phase of the carrier is identified as follows. As the measuring device, for example, SmartLab manufactured by Rigaku Corporation is used, and the powder X-ray diffraction is measured in the measurement range of 20 ° to 100 ° using CuKα1 ray. Then, the crystal phase is identified by observing the diffraction pattern obtained by the powder X-ray diffraction measurement. Whether or not the carrier has the crystal phase of TiO 0.5 as the main crystal phase is determined by the maximum intensity of the diffraction peak derived from the crystal phase of TiO 0.5 in the diffraction pattern obtained by the measurement of powder X-ray diffraction. It is judged by whether it is larger than the maximum intensity of the diffraction peak derived from any of the other crystal phases.
本発明の担体付き触媒において、該担体を構成するチタン酸化物には、上述のとおり、ＴｉＯ２が存在していてもよい。特にＴｉＯ２は、担体の表面の少なくとも一部に露出していることが好ましい。この理由は次のとおりである。すなわち、本発明において担体として用いられるチタン酸化物にはＴｉＯ０．５の結晶相又はＴｉＯの結晶相が含まれるところ、ＴｉＯ０．５やＴｉＯは、背景技術の項で述べた特許文献１に記載のＴｉＯｘ（式中のｘは１．５＜ｘ＜２の範囲である。）に比べて酸化されやすい性質を有している。そこで、担体の表面部分にＴｉＯ２を配置することで、担体の内部に含まれるＴｉＯ０．５の結晶相又はＴｉＯの結晶相が酸化されることが効果的に防止される。ＴｉＯ２の表層は、例えば、チタン酸化物を含む担体に触媒を担持させる工程において、該担体が酸素と触れて酸化が生じることに起因して形成される。In the catalyst with a carrier of the present invention, TiO 2 may be present in the titanium oxide constituting the carrier as described above. Particularly, TiO 2 is preferably exposed on at least a part of the surface of the carrier. The reason for this is as follows. That is, the titanium oxide used as a carrier in the present invention includes a crystal phase of TiO 0.5 or a crystal phase of TiO, and TiO 0.5 and TiO are described in Patent Document 1 described in the background art section. Compared with the described TiO x ( x in the formula is in the range of 1.5 <x <2), it has a property of being easily oxidized. Therefore, by disposing TiO 2 on the surface of the carrier, it is possible to effectively prevent the crystal phase of TiO 0.5 or the crystal phase of TiO contained in the carrier from being oxidized. The surface layer of TiO 2 is formed, for example, because the carrier is brought into contact with oxygen to be oxidized in the step of supporting the catalyst on the carrier containing titanium oxide.
本発明の担体付き触媒は、担体として用いられるチタン酸化物の導電性が高いことに起因して体積抵抗率が低いものである。詳細には、本発明の担体付き触媒は、その体積抵抗率が、１０Ω・ｃｍ以下、特に５Ω・ｃｍ以下、とりわけ２Ω・ｃｍ以下という低い値を示す。かかる低体積抵抗率を示す本発明の担体付き触媒は、その低体積抵抗率を利用して、例えば自動車用燃料電池、家庭用燃料電池に使用される固体高分子形燃料電池（ＰＥＦＣ）やリン酸形燃料電池（ＰＡＦＣ）の電極触媒などとして有用なものとなる。 The catalyst with a carrier of the present invention has a low volume resistivity due to the high conductivity of titanium oxide used as a carrier. Specifically, the catalyst with a carrier of the present invention has a low volume resistivity of 10 Ω · cm or less, particularly 5 Ω · cm or less, and particularly 2 Ω · cm or less. The carrier-supported catalyst of the present invention exhibiting such a low volume resistivity utilizes the low volume resistivity, for example, a polymer electrolyte fuel cell (PEFC) or phosphorus used in a fuel cell for automobiles, a fuel cell for household use. It is useful as an electrode catalyst for an acid fuel cell (PAFC).
前記の体積抵抗率は次のようにして測定される。測定には圧粉抵抗測定システム（三菱化学アナリティック社製 ＰＤ−４１）と抵抗率測定器（三菱化学アナリティック社製 ＭＣＰ−Ｔ６００）を用いる。試料１ｇをプローブシリンダへ投入し、プローブユニットをＰＤ−４１へセットする。油圧ジャッキによって３．２ＭＰａの荷重をかけたときの抵抗値を、抵抗率測定器を用いて測定する。測定した抵抗値と試料厚みから、体積抵抗率を算出する。 The volume resistivity is measured as follows. A dust resistance measuring system (PD-41 manufactured by Mitsubishi Chemical Analytical Co., Ltd.) and a resistivity measuring device (MCP-T600 manufactured by Mitsubishi Chemical Analytical Co., Ltd.) are used for the measurement. 1 g of the sample is put into the probe cylinder, and the probe unit is set to PD-41. The resistance value when a load of 3.2 MPa is applied by the hydraulic jack is measured using a resistivity measuring device. The volume resistivity is calculated from the measured resistance value and the sample thickness.
本発明の担体付き触媒において、該触媒が本来的に有する性能を十分に発揮させるためには、担体の表面の一部にＴｉＯ０．５の結晶相又はＴｉＯの結晶相が露出しており、且つ触媒が、露出しているＴｉＯ０．５の結晶相又はＴｉＯの結晶相に直接に接していることが好ましい。これらの結晶相と触媒とが直接に接していることで、例えば触媒が導電性を有する場合には、これらの結晶相と触媒との間で電気的な導通が確保されるという利点がある。このような接触状態を実現するためには、例えば後述する方法に従い本発明の担体付き触媒を製造すればよい。In the carrier-supported catalyst of the present invention, in order to fully exhibit the inherent performance of the catalyst, the crystal phase of TiO 0.5 or the crystal phase of TiO is exposed on a part of the surface of the carrier, Further, it is preferable that the catalyst is in direct contact with the exposed crystal phase of TiO 0.5 or the crystal phase of TiO. Since these crystal phases and the catalyst are in direct contact with each other, for example, when the catalyst has conductivity, there is an advantage that electrical conduction is secured between the crystal phases and the catalyst. In order to achieve such a contact state, for example, the catalyst with the carrier of the present invention may be produced according to the method described later.
ところで、担体に含まれるＴｉＯ０．５の結晶相又はＴｉＯの結晶相の酸化を効果的に防止するためには、上述のとおり、該担体が表層にＴｉＯ２を有していることが好ましい。尤もＴｉＯ２は、ＴｉＯ０．５やＴｉＯに比べると導電性の低い物質なので、触媒がＴｉＯ２を介して間接的にＴｉＯ０．５の結晶相又はＴｉＯの結晶相に接していることは、触媒活性上有利とは言えない。そこで、上述のとおり触媒は、担体の表面の一部に露出しているＴｉＯ０．５の結晶相又はＴｉＯの結晶相に直接に接していることが好ましく、且つ担体の表面のうち触媒と接触していない部分は、ＴｉＯ２が露出している、すなわちＴｉＯ２の表層が配置されていることが好ましい。担体がこのような表面状態になっていることは、例えばＴＥＭ（透過型電子顕微鏡）のＥＥＬＳ分析や、ＸＰＳ（Ｘ線光電子分光法）による表面のチタンの価数測定によって確認できる。By the way, in order to effectively prevent the oxidation of the crystal phase of TiO 0.5 or the crystal phase of TiO contained in the carrier, it is preferable that the carrier has TiO 2 in the surface layer as described above. Since TiO 2 is a substance having a lower conductivity than TiO 0.5 or TiO, the catalyst is indirectly contacted with the crystal phase of TiO 0.5 or the crystal phase of TiO 2 through TiO 2 . It cannot be said to be advantageous in terms of catalytic activity. Therefore, as described above, the catalyst is preferably in direct contact with the crystal phase of TiO 0.5 or the crystal phase of TiO exposed on a part of the surface of the carrier, and in contact with the catalyst on the surface of the carrier. It is preferable that TiO 2 is exposed in a portion not formed, that is, a surface layer of TiO 2 is arranged. The surface state of the carrier can be confirmed by, for example, EELS analysis of a TEM (transmission electron microscope) or valence measurement of titanium on the surface by XPS (X-ray photoelectron spectroscopy).
本発明の担体付き触媒は、触媒活性を高める観点からＢＥＴ比表面積が大きいことが好ましい。具体的には、本発明の担体付き触媒のＢＥＴ比表面積は、１ｍ２／ｇ以上２０ｍ２／ｇ以下であることが好ましく、２ｍ２／ｇ以上２０ｍ２／ｇ以下であることが更に好ましく、４ｍ２／ｇ以上２０ｍ２／ｇ以下であることが一層好ましい。このような範囲のＢＥＴ比表面積を実現するためには、例えば後述する方法に従い本発明の担体付き触媒を製造すればよい。The catalyst with a carrier of the present invention preferably has a large BET specific surface area from the viewpoint of enhancing the catalytic activity. Specifically, BET specific surface area of the support with the catalyst of the present invention is preferably from 1 m 2 / g or more 20 m 2 / g, more preferably at most 2m 2 / g or more 20 m 2 / g, It is more preferably 4 m 2 / g or more and 20 m 2 / g or less. In order to achieve a BET specific surface area in such a range, the catalyst with a carrier of the present invention may be produced according to, for example, the method described below.
ＢＥＴ比表面積は、例えば島津製作所社製の「フローソーブ２３００」を用い、ＢＥＴ１点法に従い窒素吸着法で測定することができる。測定粉末の量は０．３ｇとし、予備脱気条件は大気圧下、８０℃で１０分間とする。 The BET specific surface area can be measured by a nitrogen adsorption method according to the BET one-point method, using "Flowsorb 2300" manufactured by Shimadzu Corporation. The amount of powder to be measured is 0.3 g, and the preliminary deaeration conditions are atmospheric pressure and 80 ° C. for 10 minutes.
ＢＥＴ比表面積に関連して、本発明の担体付き触媒の粒径は、レーザー回折散乱式粒度分布測定法（例えば、堀場製作所社製のレーザー回折/散乱式粒子径分布測定装置「ＬＡ−９２０」を用いて測定する。）による累積体積５０容量％における体積累積粒径Ｄ５０で表して０．５μｍ以上１００μｍ以下であることが好ましく、１μｍ以上５０μｍ以下であることが更に好ましく、３μｍ以上２０μｍ以下であることが一層好ましい。本発明の担体付き触媒の粒径をこの範囲内に設定することで、触媒活性を十分に高くすることができる。Regarding the BET specific surface area, the particle size of the catalyst with a carrier of the present invention is determined by a laser diffraction / scattering particle size distribution measuring method (for example, laser diffraction / scattering particle size distribution measuring apparatus “LA-920” manufactured by Horiba Ltd.). In terms of the volume cumulative particle diameter D 50 at a cumulative volume of 50% by volume, the particle diameter is preferably 0.5 μm or more and 100 μm or less, more preferably 1 μm or more and 50 μm or less, and 3 μm or more and 20 μm or less. Is more preferable. By setting the particle size of the catalyst with carrier of the present invention within this range, the catalytic activity can be sufficiently increased.
本発明の担体付き触媒において、触媒の担持量は、触媒の種類にもよるが一般に、担体付き触媒に対して１質量％以上５０質量％以下であることが好ましく、５質量％以上４０質量％以下であることが更に好ましく、１０質量％以上３０質量％以下であることが一層好ましい。触媒の担持量がこの範囲内であることによって、必要最低限の使用量で十分な触媒活性を発現させることができる。触媒の担持量は、担体付き触媒を例えば酸で溶解した溶液を調製し、その溶液を対象としたＩＣＰ発光分光分析によって測定できる。 In the catalyst with a carrier of the present invention, the supported amount of the catalyst depends on the type of the catalyst, but generally, it is preferably 1% by mass or more and 50% by mass or less, and 5% by mass or more and 40% by mass or less with respect to the catalyst with a carrier. It is more preferable that the amount is 10% by mass or more and 30% by mass or less. When the amount of the catalyst carried is within this range, sufficient catalytic activity can be expressed with the minimum necessary amount. The supported amount of the catalyst can be measured by preparing a solution of a catalyst with a carrier, for example, in an acid, and subjecting the solution to ICP emission spectroscopy.
本発明で用いられる触媒の種類に特に制限はなく、対象とする化学反応を活性化する物質が適切に用いられる。本発明の担体付き触媒を例えば燃料電池の電極触媒として用いる場合には、触媒として各種金属を用いることが好ましい。金属としては、例えば白金、金、パラジウム、銀、イリジウム、ロジウム及びルテニウムなどからなる貴金属触媒が好適なものとして挙げられる。これらの金属は合金として用いることもできる。触媒として水素酸化活性を有するものを用いる場合には、白金、イリジウム及びルテニウムからなる群より選ばれる少なくとも１種の金属又はその合金を含む触媒を用いることが好ましい。例えば白金又は白金を含む合金、イリジウムやイリジウムを含む合金、ルテニウムやルテニウムを含む合金を用いることが好ましい。具体的には、白金、イリジウム、ルテニウム、白金−イリジウム合金、白金−ルテニウム合金、白金−鉄合金、イリジウム−ルテニウム合金などが挙げられるが、これらに限られない。 The type of catalyst used in the present invention is not particularly limited, and a substance that activates a target chemical reaction is appropriately used. When the carrier-supported catalyst of the present invention is used as, for example, an electrode catalyst for a fuel cell, it is preferable to use various metals as the catalyst. Preferable examples of the metal include noble metal catalysts composed of platinum, gold, palladium, silver, iridium, rhodium, ruthenium and the like. These metals can also be used as an alloy. When a catalyst having hydrogen oxidation activity is used as the catalyst, it is preferable to use a catalyst containing at least one metal selected from the group consisting of platinum, iridium and ruthenium, or an alloy thereof. For example, it is preferable to use platinum or an alloy containing platinum, iridium, an alloy containing iridium, ruthenium, or an alloy containing ruthenium. Specific examples thereof include, but are not limited to, platinum, iridium, ruthenium, platinum-iridium alloy, platinum-ruthenium alloy, platinum-iron alloy, and iridium-ruthenium alloy.
次に本発明の担体付き触媒の好適な製造方法について説明する。本製造方法は、（１）担体の製造工程、（２）触媒の担持工程、（３）焼成工程の３工程に大別される。以下、それぞれの工程について詳述する。 Next, a suitable method for producing the catalyst with carrier of the present invention will be described. This production method is roughly divided into three steps: (1) carrier production step, (2) catalyst loading step, and (3) calcination step. Hereinafter, each step will be described in detail.
担体の製造工程においては、チタン酸化物を製造する。このチタン酸化物は組成式ＴｉＯａ（式中、ａは０．４以上１以下の数を表す。）で表されるものである。このチタン酸化物を生成させるため、本製造方法では出発原料として金属チタン及び二酸化チタンを用いる。金属チタンとしては、Ｄ５０が０．５μｍ以上３００μｍ以下である金属チタンの粉末を用いることが、金属チタンと二酸化チタンとの反応性を高める観点から好ましい。同様の観点から、二酸化チタンとしてＤ５０が０．０１μｍ以上５．０μｍ以下である粉末を用いることが好ましい。二酸化チタンとしてはルチル型、アナターゼ型、及びブルッカイト型のいずれであっても用いることができる。比表面積の高い担体を得る観点からは、アナターゼ型の二酸化チタンを用いることが好ましい。In the manufacturing process of the carrier, titanium oxide is manufactured. This titanium oxide is represented by the composition formula TiO a (in the formula, a represents a number of 0.4 or more and 1 or less). In order to produce this titanium oxide, titanium metal and titanium dioxide are used as starting materials in this production method. As the metallic titanium, it is preferable to use metallic titanium powder having a D 50 of 0.5 μm or more and 300 μm or less from the viewpoint of enhancing the reactivity between the metallic titanium and titanium dioxide. From the same viewpoint, it is preferable to use a powder having D 50 of 0.01 μm or more and 5.0 μm or less as titanium dioxide. As titanium dioxide, any of rutile type, anatase type and brookite type can be used. From the viewpoint of obtaining a carrier having a high specific surface area, it is preferable to use anatase type titanium dioxide.
担体の製造工程において、金属チタンと二酸化チタンとを混合させる割合は、ＴｉＯａ（式中、ａは０．４以上１以下の数を表す。）で表されるチタン酸化物が得られるように適切に調整される。この観点から、金属チタン１００質量部に対して二酸化チタンを好ましくは２０質量部以上３００質量部以下、更に好ましくは４０質量部以上２３０質量部以下、一層好ましくは５０質量部以上１８０質量部以下の量で混合する。混合に際しては乳鉢、自動乳鉢、ボールミル、スタンプミル、Ｖ型混合器、タンブラー型混合器など一般的に乾式で混合可能な装置を用いることができる。In the production process of the carrier, the mixing ratio of metallic titanium and titanium dioxide is such that a titanium oxide represented by TiO a (in the formula, a represents a number of 0.4 or more and 1 or less) is obtained. Adjusted appropriately. From this viewpoint, titanium dioxide is preferably 20 parts by mass or more and 300 parts by mass or less, more preferably 40 parts by mass or more and 230 parts by mass or less, and further preferably 50 parts by mass or more and 180 parts by mass or less with respect to 100 parts by mass of metallic titanium. Mix by volume. For mixing, a generally dry type mixing device such as a mortar, an automatic mortar, a ball mill, a stamp mill, a V-type mixer, and a tumbler-type mixer can be used.
金属チタンと二酸化チタンとを混合したら、混合物を焼成してチタン酸化物を生成させる。焼成は一般に真空中で行うことができる。この場合の真空度は、絶対圧で表して１×１０−１Ｐａ以下であることが、目的とするチタン酸化物を首尾よく得る点から好ましい。同様の観点から、焼成温度は、６００℃以上１３００℃以下であることが好ましく、７５０℃以上１１００℃以下であることが更に好ましい。焼成時間は、焼成温度が上述の範囲であることを条件として５時間以上３０時間以下であることが好ましく、５時間以上１５時間以下であることが更に好ましい。Once the titanium metal and titanium dioxide are mixed, the mixture is fired to form titanium oxide. Firing can generally be performed in vacuum. In this case, the degree of vacuum is preferably 1 × 10 −1 Pa or less expressed in absolute pressure in terms of successfully obtaining the target titanium oxide. From the same viewpoint, the firing temperature is preferably 600 ° C. or higher and 1300 ° C. or lower, and more preferably 750 ° C. or higher and 1100 ° C. or lower. The firing time is preferably 5 hours or more and 30 hours or less, more preferably 5 hours or more and 15 hours or less, provided that the firing temperature is within the above range.
チタン酸化物の担体において、その表面の少なくとも一部に二酸化チタンを存在させるためには、例えば上述した金属チタンと二酸化チタンとの混合物の焼成条件を調整して、一部の二酸化チタンが残存するようにすればよい。 In order to allow titanium dioxide to be present on at least a part of the surface of the titanium oxide carrier, for example, the firing conditions of the above-mentioned mixture of metallic titanium and titanium dioxide are adjusted so that a part of titanium dioxide remains. You can do it like this.
以上の工程によってチタン酸化物の担体が得られる。この担体は、上述のとおりＴｉＯａ（式中、ａは０．４以上１以下の数を表す。）で表されるチタン酸化物からなるものである。また、このチタン酸化物中は好ましくはＴｉＯ０．５の結晶相又はＴｉＯの結晶相を有する。Through the above steps, a titanium oxide carrier is obtained. As described above, this carrier is made of titanium oxide represented by TiO a (in the formula, a represents a number of 0.4 or more and 1 or less). The titanium oxide preferably has a TiO 0.5 crystal phase or a TiO crystal phase.
このようにしてチタン酸化物の担体が得られたら、この担体に触媒を担持させる。触媒の担持に先立ち触媒の粒径を調整することが好ましい。粒径の調整には、例えばペイントシェイカーやビーズミルなどの粉砕装置を用いることができる。この場合、担体が酸素に触れて酸化されることを防止する目的で、担体を有機溶媒中で粉砕することが好ましい。この目的で用いられる有機溶媒としては、例えばエタノール、２−プロパノール、ブタノールなどの脂肪族一価アルコール類、トルエンやベンゼンなどの芳香族炭化水素、ヘキサンなどの脂肪族炭化水素、その他ケトン類やエステル類、エーテル類などが挙げられる。担体と有機溶媒との使用割合は、粉砕を首尾よく行う観点から、担体１００質量部に対する有機溶媒の使用量が１００質量部以上９９００質量部以下であることが好ましく、１００質量部以上９００質量部以下であることが更に好ましい。 After the titanium oxide carrier is obtained in this manner, the catalyst is supported on the carrier. It is preferable to adjust the particle size of the catalyst before supporting the catalyst. A crushing device such as a paint shaker or a bead mill can be used to adjust the particle size. In this case, it is preferable to grind the carrier in an organic solvent for the purpose of preventing the carrier from being oxidized by being exposed to oxygen. Examples of the organic solvent used for this purpose include aliphatic monohydric alcohols such as ethanol, 2-propanol and butanol, aromatic hydrocarbons such as toluene and benzene, aliphatic hydrocarbons such as hexane, and other ketones and esters. And ethers. The use ratio of the carrier and the organic solvent is preferably 100 parts by mass or more and 9900 parts by mass or less, and 100 parts by mass or more and 900 parts by mass, with respect to 100 parts by mass of the carrier, from the viewpoint of successfully performing pulverization. The following is more preferable.
有機溶媒中での担体の粉砕が完了したら、引き続き触媒の担持工程を行う。この場合、粉砕から触媒の担持までの間でも触媒を酸素に極力触れさせないことが、触媒の酸化を防止する観点から好ましい。この目的のために、粉砕が完了した担体に対して乾粉化工程を行うことなく、有機溶媒中に分散した状態の担体に触媒を担持させることが有利である。つまり、担体を有機溶媒中で粉砕し、次いで乾粉化工程を経ることなく有機溶媒中で触媒を担持させることが有利である。粉砕に用いる有機溶媒と、触媒の担持に用いる有機溶媒とは同一のものであってもよく、あるいは異なるものであってもよい。 After the pulverization of the carrier in the organic solvent is completed, the step of supporting the catalyst is subsequently performed. In this case, it is preferable from the viewpoint of preventing oxidation of the catalyst that the catalyst is not exposed to oxygen as much as possible during the period from crushing to loading the catalyst. For this purpose, it is advantageous to support the catalyst on a carrier in a state of being dispersed in an organic solvent, without performing a dry powdering process on the carrier after pulverization. That is, it is advantageous to grind the carrier in an organic solvent and then carry the catalyst in the organic solvent without going through a dry powdering step. The organic solvent used for pulverization and the organic solvent used for supporting the catalyst may be the same or different.
触媒の担持には、触媒を構成する元素を含む原料を用いることができる。かかる原料と、有機溶媒中に分散されている担体とを混合することで、担体の表面に、触媒を構成する元素を付着させる。この場合、必要に応じて分散液を加熱してもよい。触媒を構成する元素を含む原料としては、例えば触媒が白金を含む場合には、ヘキサクロロ白金酸塩、ジニトロアンミン白金塩、ヘキサアンミン白金クロライド、テトラアンミン白金水酸塩、アセチルアセトナト白金塩などを用いることができる。触媒がイリジウムを含む場合には、酸化イリジウム、塩化イリジウム、アセチルアセトナトイリジウム塩などを用いることができる。触媒がルテニウムを含む場合には、塩化ルテニウム、酸化ルテニウム、硝酸ルテニウム、ヘキサアンミンルテニウムクロライド、アセチルアセトナトルテニウム塩などを用いることができる。 A raw material containing an element constituting the catalyst can be used for supporting the catalyst. By mixing such a raw material and a carrier dispersed in an organic solvent, the elements constituting the catalyst are attached to the surface of the carrier. In this case, the dispersion may be heated if necessary. As the raw material containing the element constituting the catalyst, for example, when the catalyst contains platinum, hexachloroplatinate, dinitroammineplatinum salt, hexaammineplatinum chloride, tetraammineplatinum hydrochloride, acetylacetonatoplatinum salt, etc. are used. be able to. When the catalyst contains iridium, iridium oxide, iridium chloride, acetylacetonatoiridium salt and the like can be used. When the catalyst contains ruthenium, ruthenium chloride, ruthenium oxide, ruthenium nitrate, hexaammine ruthenium chloride, acetylacetonatoruthenium salt and the like can be used.
このようにして、触媒を構成する元素を担体に担持させたら、これを焼成工程に付して、担体の表面に触媒を生成させる。また、必要に応じ、担体中にＴｉＯ０．５の結晶相又はＴｉＯの結晶相を生成させる。焼成は一般に還元性雰囲気中で行うことができる。還元性雰囲気としては、水素ガス及びアルゴンガスや窒素ガス等の不活性ガスとの混合ガスを用いることが好ましい。この場合、混合ガス中の水素ガスと不活性ガスとの割合を調整することで、還元の程度をコントロールできる。焼成温度は、還元の程度を適切にコントロールする観点から４００℃以上１２００℃以下であることが好ましく、５５０℃以上９００℃以下であることが更に好ましい。焼成時間は、焼成温度が上述の範囲であることを条件として０．１時間以上２０時間以下であることが好ましく、１時間以上１０時間以下であることが更に好ましい。After the elements constituting the catalyst are supported on the carrier in this manner, the carrier is subjected to a firing step to generate the catalyst on the surface of the carrier. If necessary, a TiO 0.5 crystal phase or a TiO crystal phase is generated in the carrier. Firing can generally be performed in a reducing atmosphere. As the reducing atmosphere, it is preferable to use a mixed gas of hydrogen gas and an inert gas such as argon gas or nitrogen gas. In this case, the degree of reduction can be controlled by adjusting the ratio of hydrogen gas and inert gas in the mixed gas. The firing temperature is preferably 400 ° C. or higher and 1200 ° C. or lower, and more preferably 550 ° C. or higher and 900 ° C. or lower, from the viewpoint of appropriately controlling the degree of reduction. The firing time is preferably 0.1 hours or more and 20 hours or less, more preferably 1 hour or more and 10 hours or less, provided that the firing temperature is in the above range.
担体の表面の一部にＴｉＯ０．５の結晶相又はＴｉＯの結晶相が露出している場合、上述の方法を用いれば、該ＴｉＯ０．５の結晶相又はＴｉＯの結晶相に直接触媒を担持させることができる。一方、担体の表面のうち触媒と接していない部分にＴｉＯ２を露出させるためには、例えば担体の製造において、上述した金属ＴｉとＴｉＯ２との混合物の焼成条件を調整して、一部のＴｉＯ２が残存するようにすればよい。When the crystal phase of TiO 0.5 or the crystal phase of TiO is exposed on a part of the surface of the carrier, the above method is used to directly attach the catalyst to the crystal phase of TiO 0.5 or the crystal phase of TiO. It can be supported. On the other hand, in order to expose TiO 2 to a portion of the surface of the support that is not in contact with the catalyst, for example, in the production of the support, the firing conditions of the above-described mixture of metal Ti and TiO 2 are adjusted to allow a part of It is sufficient that TiO 2 remains.
以上の工程によって目的とする担体付き触媒を得ることができる。この触媒は、担体の導電性が高いことを活かして種々の用途に用いることができる。そのような用途としては、例えば自動車用燃料電池、家庭用燃料電池に使用される固体高分子形燃料電池（ＰＥＦＣ）やリン酸形燃料電池（ＰＡＦＣ）の電極触媒などが挙げられる。特に、本発明の担体付き触媒は、固体高分子形燃料電池の電極触媒として有用である。 The target catalyst with a carrier can be obtained by the above steps. This catalyst can be used for various purposes by taking advantage of the high conductivity of the carrier. Such applications include, for example, fuel cells for automobiles, polymer electrolyte fuel cells (PEFC) used in household fuel cells, and electrode catalysts for phosphoric acid fuel cells (PAFC). In particular, the carrier-supported catalyst of the present invention is useful as an electrode catalyst for polymer electrolyte fuel cells.
本発明の担体付き触媒を燃料電池の電極触媒として用いる場合、該電極触媒は、例えば固体高分子電解質膜の一方の面に配置された酸素極及び他方の面に配置された燃料極を有する膜電極接合体における酸素極又は燃料極の少なくとも一方に含有させることができる。電極触媒は、好適には燃料極に含有させることができる。 When the carrier-supported catalyst of the present invention is used as an electrode catalyst of a fuel cell, the electrode catalyst is, for example, a membrane having an oxygen electrode arranged on one surface of a solid polymer electrolyte membrane and a fuel electrode arranged on the other surface. It can be contained in at least one of the oxygen electrode and the fuel electrode in the electrode assembly. The electrode catalyst can be preferably contained in the fuel electrode.
特に、燃料極は、本発明の担体付き触媒を含む触媒層と、ガス拡散層とを含んでいることが好ましい。電極反応を円滑に進行させるために、担体付き触媒は固体高分子電解質膜に接していることが好ましい。ガス拡散層は、集電機能を有する支持集電体として機能するものである。更に、本発明の担体付き触媒にガスを十分に供給する機能を有するものである。ガス拡散層としては、この種の技術分野において従来用いられてきたものと同様のものを用いることができる。例えば多孔質材料であるカーボンペーパー、カーボンクロスを用いることができる。具体的には、例えば表面をポリ四フッ化エチレンでコーティングした炭素繊維と、当該コーティングがなされていない炭素繊維とを所定の割合とした糸で織成したカーボンクロスにより形成することができる。 In particular, the fuel electrode preferably includes a catalyst layer containing the carrier-supported catalyst of the present invention and a gas diffusion layer. In order to allow the electrode reaction to proceed smoothly, the catalyst with a carrier is preferably in contact with the solid polymer electrolyte membrane. The gas diffusion layer functions as a supporting current collector having a current collecting function. Further, it has a function of sufficiently supplying gas to the catalyst with a carrier of the present invention. As the gas diffusion layer, the same one as that conventionally used in this kind of technical field can be used. For example, carbon paper or carbon cloth, which is a porous material, can be used. Specifically, for example, it can be formed by a carbon cloth woven from yarns in which carbon fibers whose surfaces are coated with polytetrafluoroethylene and carbon fibers which are not coated are woven in a predetermined ratio.
固体高分子電解質としては、この種の技術分野において従来用いられてきたものと同様のものを用いることができる。例えばパーフルオロスルホン酸ポリマー系のプロトン伝導体膜、リン酸などの無機酸を炭化水素系高分子化合物にドープさせたもの、一部がプロトン伝導体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。 As the solid polymer electrolyte, the same ones conventionally used in this kind of technical field can be used. For example, a perfluorosulfonic acid polymer-based proton conductor membrane, a hydrocarbon polymer compound doped with an inorganic acid such as phosphoric acid, or an organic / inorganic hybrid polymer partially substituted with a proton conductor functional group. A proton conductor obtained by impregnating a polymer matrix with a phosphoric acid solution or a sulfuric acid solution may be used.
前記膜電極接合体は、その各面にセパレータが配されて固体高分子形燃料電池となされる。セパレータとしては、例えばガス拡散層との対向面に、一方向に延びる複数個の凸部（リブ）が所定間隔をおいて形成されているものを用いることができる。隣り合う凸部間は、断面が矩形の溝部となっている。この溝部は、燃料ガス及び空気等の酸化剤ガスの供給排出用流路として用いられる。燃料ガス及び酸化剤ガスは、燃料ガス供給手段及び酸化剤ガス供給手段からそれぞれ供給される。膜電極接合体の各面に配されるそれぞれのセパレータは、それに形成されている溝部が互いに直交するように配置されることが好ましい。以上の構成が燃料電池の最小単位を構成しており、この構成を数十個〜数百個並設してなるセルスタックから燃料電池を構成することができる。 The membrane electrode assembly has a separator on each surface thereof to form a polymer electrolyte fuel cell. As the separator, for example, a separator in which a plurality of convex portions (ribs) extending in one direction are formed at predetermined intervals on the surface facing the gas diffusion layer can be used. A groove having a rectangular cross section is formed between the adjacent convex portions. This groove is used as a flow path for supplying and discharging a fuel gas and an oxidant gas such as air. The fuel gas and the oxidant gas are supplied from the fuel gas supply means and the oxidant gas supply means, respectively. The respective separators arranged on the respective surfaces of the membrane electrode assembly are preferably arranged such that the groove portions formed therein are orthogonal to each other. The above configuration constitutes the minimum unit of the fuel cell, and the fuel cell can be constructed from a cell stack in which several tens to several hundreds of this configuration are arranged in parallel.
以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲は、かかる実施例に制限されない。特に断らない限り、「％」は「質量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the invention is not limited to such embodiments. Unless otherwise specified, "%" means "% by mass".
〔実施例１〕
（１）担体の製造工程
６．７ｇの金属チタンと３．７ｇのアナターゼ型二酸化チタンとを混合し、真空炉で９００℃にて１０時間にわたり焼成を行った。真空炉内の絶対圧は１０−１Ｐａ以下になるよう設定した。金属チタンの粒径Ｄ５０は１３μｍであった。二酸化チタンの粒径Ｄ５０は０．２μｍであった。この焼成によってＴｉＯａ（式中、ａは０．４７である）で表されるチタン酸化物を得た。[Example 1]
(1) Support manufacturing process 6.7 g of metallic titanium and 3.7 g of anatase type titanium dioxide were mixed and baked in a vacuum furnace at 900 ° C. for 10 hours. The absolute pressure in the vacuum furnace was set to 10 -1 Pa or less. The particle size D 50 of titanium metal was 13 μm. The particle size D 50 of titanium dioxide was 0.2 μm. By this firing, a titanium oxide represented by TiO a (in the formula, a is 0.47) was obtained.
（２）触媒の担持工程
前記（１）で得られたチタン酸化物４．０ｇとエタノール１６．０ｇと混合し、それによって得られたスラリーをペイントシェイカーにより、１０時間にわたりチタン酸化物の粉砕を行った。次いでチタン酸化物を乾粉化させず、酸素に触れさせることなく、該チタン酸化物を含むスラリーに、３００ｇのエタノール及び３．９ｍｌのジニトロアンミン白金硝酸水溶液（白金濃度１５％）を添加して混合液を得た。この混合液を四つ口フラスコに投入した。フラスコ中の混合液を、液温が７５℃になるようにオイルバスで６時間にわたり加温した。その後、液を冷却し、更に水洗することで、エタノール及び副塩成分を除去した。これによって得られたケーキを真空乾燥して乾粉を得た。(2) Catalyst loading step 4.0 g of the titanium oxide obtained in (1) above and 16.0 g of ethanol were mixed, and the resulting slurry was pulverized with a paint shaker for 10 hours. went. Next, 300 g of ethanol and 3.9 ml of a dinitroammine platinum nitric acid aqueous solution (platinum concentration: 15%) were added to and mixed with the slurry containing the titanium oxide without drying the titanium oxide and exposing it to oxygen. A liquid was obtained. This mixed solution was placed in a four-necked flask. The mixed liquid in the flask was heated in an oil bath for 6 hours so that the liquid temperature became 75 ° C. Then, the liquid was cooled and further washed with water to remove ethanol and by-salt components. The cake thus obtained was vacuum dried to obtain a dry powder.
（３）焼成工程
前記（２）で得られた乾粉を焼成した。焼成の雰囲気は２ｖｏｌ％Ｈ２／Ａｒ混合ガスとした。焼成温度は６００℃とした。焼成時間は２時間とした。このようにして担体付き白金触媒を得た。この担体付き白金触媒の粒径Ｄ５０は６．２μｍであった。なお、粒径Ｄ５０は次の方法で測定した。担体付き白金触媒の粒子を水と混合し、一般的な超音波バスを用いて１分間分散処理を行った。次いでベックマンコールター社製ＬＳ１３ ３２０を用いてＤ５０を測定した。(3) Firing step The dry powder obtained in (2) above was fired. The firing atmosphere was a 2 vol% H 2 / Ar mixed gas. The firing temperature was 600 ° C. The firing time was 2 hours. Thus, a platinum catalyst with a carrier was obtained. The particle diameter D 50 of this platinum catalyst with a carrier was 6.2 μm. The particle size D 50 was measured by the following method. Particles of the platinum catalyst with a carrier were mixed with water, and a dispersion treatment was performed for 1 minute using a general ultrasonic bath. It was then measured D 50 using the Beckman Coulter LS13 320.
〔実施例２〕
実施例１において（３）の焼成工程における焼成温度を、以下の表１に示すとおりに変更した。これ以外は実施例１と同様にして担体付き白金触媒を得た。実施例１と同様に測定した結果、実施例２の担体付き白金触媒の粒径Ｄ５０は７．５μｍであった。[Example 2]
In Example 1, the firing temperature in the firing step (3) was changed as shown in Table 1 below. A platinum catalyst with a carrier was obtained in the same manner as in Example 1 except for this. As a result of measurement in the same manner as in Example 1, the particle diameter D 50 of the platinum catalyst with the carrier of Example 2 was 7.5 μm.
〔実施例３〕
実施例１において（３）の焼成工程における焼成温度を、以下の表１に示すとおりに変更した。これ以外は実施例１と同様にして担体付き白金触媒を得た。実施例１と同様に測定した結果、実施例３の担体付き白金触媒の粒径Ｄ５０は５．３μｍであった。[Example 3]
In Example 1, the firing temperature in the firing step (3) was changed as shown in Table 1 below. A platinum catalyst with a carrier was obtained in the same manner as in Example 1 except for this. As a result of measurement in the same manner as in Example 1, the particle diameter D 50 of the platinum catalyst with the carrier of Example 3 was 5.3 μm.
〔実施例４〕
実施例１において（１）の担体の製造工程における金属チタン及び二酸化チタンの使用量を表１に示すとおりとし、且つ（１）担体の製造工程における焼成温度を、以下の表１に示すとおりに変更した。これ以外は実施例１と同様にして担体付き白金触媒を得た。実施例１と同様に測定した結果、実施例４の担体付き白金触媒の粒径Ｄ５０は８．９μｍであった。[Example 4]
In Example 1, the amounts of titanium metal and titanium dioxide used in the manufacturing process of the carrier of (1) are as shown in Table 1, and the firing temperature in the manufacturing process of the carrier of (1) is as shown in Table 1 below. changed. A platinum catalyst with a carrier was obtained in the same manner as in Example 1 except for this. As a result of measurement in the same manner as in Example 1, the particle diameter D 50 of the platinum catalyst with the carrier of Example 4 was 8.9 μm.
〔比較例１〕
（１）担体の製造工程
実施例１と同様に行った。[Comparative Example 1]
(1) Manufacturing process of carrier The same process as in Example 1 was carried out.
（２）触媒の担持工程
前記（１）で得られたチタン酸化物４．０ｇとエタノール１６．０ｇと混合し、それによって得られたスラリーをペイントシェイカーにより、１０時間にわたりチタン酸化物の粉砕を行った。粉砕後、エタノール及び副塩成分を除去した。これによって得られたケーキを真空乾燥してチタン酸化物の乾粉を得た。この乾粉２．０ｇと、３００ｇのエタノール及び３．９ｍｌのジニトロアンミン白金水溶液（白金濃度１５％）を添加して混合液を得た。その後は実施例１と同様の操作を行った。(2) Catalyst loading step 4.0 g of the titanium oxide obtained in (1) above and 16.0 g of ethanol were mixed, and the resulting slurry was pulverized with a paint shaker for 10 hours. went. After grinding, ethanol and by-salt components were removed. The cake thus obtained was vacuum dried to obtain a dry powder of titanium oxide. 2.0 g of this dry powder, 300 g of ethanol and 3.9 ml of a dinitroammine platinum aqueous solution (platinum concentration 15%) were added to obtain a mixed solution. After that, the same operation as in Example 1 was performed.
（３）焼成工程
実施例１と同様に行った。これによって担体付き白金触媒を得た。実施例１と同様に測定した結果、比較例１の担体付き白金触媒の粒径Ｄ５０は３．１μｍであった。(3) Firing step The same process as in Example 1 was performed. As a result, a platinum catalyst with a carrier was obtained. As a result of measurement in the same manner as in Example 1, the particle diameter D 50 of the platinum catalyst with a carrier of Comparative Example 1 was 3.1 μm.
〔比較例２〕
比較例１において（３）の焼成工程を行わなかった点以外は、比較例１と同様にして担体付き白金触媒を得た。実施例１と同様に測定した結果、比較例２の担体付き白金触媒の粒径Ｄ５０は１．１μｍであった。[Comparative Example 2]
A platinum catalyst with a carrier was obtained in the same manner as in Comparative Example 1 except that the firing step (3) in Comparative Example 1 was not performed. As a result of measurement in the same manner as in Example 1, the particle diameter D 50 of the platinum catalyst with a carrier of Comparative Example 2 was 1.1 μm.
〔比較例３〕
（１）担体の製造工程
実施例１と同様に行った。[Comparative Example 3]
(1) Manufacturing process of carrier The same process as in Example 1 was carried out.
（２）触媒の担持工程
前記（１）で得られたチタン酸化物４．０ｇとエタノール１６．０ｇと混合し、それによって得られたスラリーをペイントシェイカーにより、１０時間にわたりチタン酸化物の粉砕を行った。粉砕後、エタノール及び副塩成分を除去した。これによって得られたケーキを真空乾燥してチタン酸化物の乾粉を得た。この乾粉を用いてコロイド法で白金を担持させた。詳細には、５ｍｌのＨ２ＰｔＣｌ６溶液（Ｐｔ１ｇに相当）を蒸留水２９５ｍｌに溶解させ、１５．３ｇのＮａＨＳＯ３を加えた後、１４００ｍｌの蒸留水で希釈した。５％ＮａＯＨ水溶液を加えて、ｐＨを約５に調整を行いながら３５％過酸化水素水（１２０ｍｌ）を滴下し白金のコロイドを含む液を得た。このとき、５％ＮａＯＨ水溶液を適宜加えて液のｐＨを約５に維持した。得られた液からＰｔ０．６０ｇに相当する量を分取し、３．０ｇのチタン酸化物粒子を添加し、９０℃で３時間混合した。その後、液を冷却し、更に固液分離した。固液分離により得られた含水した粉体中から塩化物イオンを除去するために、１５００ｍｌの蒸留水で再び希釈し９０℃で１時間煮沸を行い、液を冷却し固液分離した。この洗浄作業を４回実施した。最後に、固液分離後、大気下にて６０℃で１２時間にわたり乾燥させた。これによって、チタン酸化物粒子の表面に不定比の白金酸化物を含む白金を担持させた。次いで、このチタン酸化物粒子を２ｖｏｌ％Ｈ２／Ａｒ雰囲気下に８０℃で２時間にわたり熱処理することによって白金の還元を行った。(2) Catalyst loading step 4.0 g of the titanium oxide obtained in (1) above and 16.0 g of ethanol were mixed, and the resulting slurry was pulverized with a paint shaker for 10 hours. went. After grinding, ethanol and by-salt components were removed. The cake thus obtained was vacuum dried to obtain a dry powder of titanium oxide. This dry powder was used to support platinum by the colloid method. In detail, 5 ml of H 2 PtCl 6 solution (corresponding to 1 g of Pt) was dissolved in 295 ml of distilled water, 15.3 g of NaHSO 3 was added, and then diluted with 1400 ml of distilled water. A 5% NaOH aqueous solution was added to adjust the pH to about 5, and 35% hydrogen peroxide solution (120 ml) was added dropwise to obtain a liquid containing a platinum colloid. At this time, the pH of the solution was maintained at about 5 by appropriately adding a 5% NaOH aqueous solution. An amount corresponding to 0.60 g of Pt was separated from the obtained liquid, 3.0 g of titanium oxide particles was added, and mixed at 90 ° C. for 3 hours. Then, the liquid was cooled and further solid-liquid separated. In order to remove chloride ions from the hydrated powder obtained by solid-liquid separation, it was diluted again with 1500 ml of distilled water and boiled at 90 ° C. for 1 hour, and the liquid was cooled and solid-liquid separated. This cleaning work was carried out four times. Finally, after solid-liquid separation, it was dried in the atmosphere at 60 ° C. for 12 hours. As a result, platinum containing a non-stoichiometric ratio of platinum oxide was supported on the surface of the titanium oxide particles. Next, the titanium oxide particles were heat-treated at 80 ° C. for 2 hours in a 2 vol% H 2 / Ar atmosphere to reduce platinum.
（３）焼成工程
実施例１と同様に行った。これによって担体付き白金触媒を得た。実施例１と同様に測定した結果、比較例３の担体付き白金触媒の粒径Ｄ５０は５．８μｍであった。(3) Firing step The same process as in Example 1 was performed. As a result, a platinum catalyst with a carrier was obtained. As a result of measurement in the same manner as in Example 1, the particle diameter D 50 of the platinum catalyst with a carrier of Comparative Example 3 was 5.8 μm.
〔比較例４〕
（１）担体の製造工程
実施例１において（１）の担体の製造工程における金属チタン及び二酸化チタンの使用量を表１に示すとおりとし、且つ（１）担体の製造工程における焼成温度を、以下の表１に示すとおりに変更した。これ以外は実施例１と同様にしてチタン酸化物を得た。この焼成によってＴｉＯａ（式中、ａは１．７９である）で表されるチタン酸化物を得た。[Comparative Example 4]
(1) Carrier manufacturing process In Example 1, the amounts of titanium metal and titanium dioxide used in the carrier manufacturing process of (1) are as shown in Table 1, and (1) the firing temperature in the carrier manufacturing process is as follows. It was changed as shown in Table 1 of. A titanium oxide was obtained in the same manner as in Example 1 except for this. By this firing, a titanium oxide represented by TiO a (in the formula, a is 1.79) was obtained.
（２）触媒の担持工程
実施例１と同様に行った。(2) Catalyst loading step The same procedure as in Example 1 was performed.
（３）焼成工程
実施例１と同様に行った。これによって担体付き白金触媒を得た。実施例１と同様に測定した結果、比較例４の担体付き白金触媒の粒径Ｄ５０は２．２μｍであった。(3) Firing step The same process as in Example 1 was performed. As a result, a platinum catalyst with a carrier was obtained. As a result of measurement in the same manner as in Example 1, the particle diameter D 50 of the platinum catalyst with a carrier of Comparative Example 4 was 2.2 μm.
〔評価〕
実施例及び比較例で得られた担体付き白金触媒について、Ｏ／Ｔｉのモル比、結晶相の種類及び結晶相の結晶子サイズを上述の方法で測定した。また、担体付き白金触媒のＢＥＴ比表面積、体積抵抗率、白金担持量を上述の方法で測定した。更に、担体付き白金触媒を用いたＭＥＡのセル電圧を以下の方法で測定した。それらの結果を以下の表１に示す。[Evaluation]
With respect to the platinum catalysts with supports obtained in Examples and Comparative Examples, the O / Ti molar ratio, the type of crystal phase and the crystallite size of the crystal phase were measured by the above-mentioned methods. Further, the BET specific surface area, volume resistivity, and amount of platinum supported of the platinum catalyst with a carrier were measured by the above-mentioned methods. Furthermore, the cell voltage of MEA using a platinum catalyst with a carrier was measured by the following method. The results are shown in Table 1 below.
〔ＭＥＡのセル電圧〕
実施例及び比較例で得られた担体付き白金触媒を用いて作製した燃料電池について、膜電極接合体（ＭＥＡ）の発電特性を評価した。[MEA cell voltage]
The power generation characteristics of the membrane electrode assembly (MEA) were evaluated for the fuel cells produced using the platinum catalysts with a carrier obtained in Examples and Comparative Examples.
得られた担体付き白金触媒０．３５ｇと、直径１０ｍｍのイットリウム安定化ジルコニア製ボールを容器に入れ、更に純水、エタノール及びイソプロパノールを３５：４５：２０の質量比（混合液として０．８７５ｇ）で順に加えた。このようにして得られたインクを、超音波で３分間にわたり分散した。次いで、遊星ボールミル（シンキーＡＲＥ３１０）で８００ｒｐｍ、２０分間撹拌した。更にインクに５％ナフィオン（登録商標）（２７４７０４−１００ＭＬ、Ｓｉｇｍａ−Ａｌｄｒｉｃｈ社製）を加え、超音波分散と遊星ボールミルにより前記と同様な撹拌を行った。ナフィオンの添加量は、ナフィオン／実施例及び比較例の担体付き白金触媒の質量比が７．４となるような量とした。このようにして得られたインクを、ポリ四フッ化エチレンのシート上にバーコーターを用いて塗工し、塗膜を６０℃で乾燥させ、アノード用の触媒層とした。 0.35 g of the obtained platinum catalyst with a carrier and yttrium-stabilized zirconia balls having a diameter of 10 mm were placed in a container, and pure water, ethanol and isopropanol were mixed in a mass ratio of 35:45:20 (0.875 g as a mixed solution). In order. The ink thus obtained was ultrasonically dispersed for 3 minutes. Then, the mixture was stirred with a planetary ball mill (Sinky ARE310) at 800 rpm for 20 minutes. Further, 5% Nafion (registered trademark) (274704-100 ML, manufactured by Sigma-Aldrich) was added to the ink, and the same stirring as above was performed by ultrasonic dispersion and a planetary ball mill. The amount of Nafion added was such that the mass ratio of Nafion / platinum catalyst with carrier in Examples and Comparative Examples was 7.4. The ink thus obtained was applied onto a sheet of polytetrafluoroethylene using a bar coater, and the coating film was dried at 60 ° C. to form a catalyst layer for the anode.
一方、カソード触媒用の触媒層は次の方法で得た。田中貴金属工業株式会社製の白金担持カーボンブラック（ＴＥＫ１０Ｅ５０Ｅ）１．００ｇと、直径１０ｍｍのイットリウム安定化ジルコニア製ボールを容器に入れ、更に純水、エタノール及びイソプロパノールを４５：３５：２０の質量比（混合液として１０．２ｇ）で順に加えた。このようにして得られたインクを、超音波で３分間にわたり分散した。次いで、遊星ボールミル（シンキーＡＲＥ３１０）を用い、８００ｒｐｍで２０分間撹拌した。更にインクに５％ナフィオン（登録商標）（２７４７０４−１００ＭＬ、Ｓｉｇｍａ−Ａｌｄｒｉｃｈ社製）を加え、超音波分散と遊星ボールミルにより前記と同様な撹拌を引き続き行った。ナフィオンの添加量は、ナフィオン／白金担持カーボンブラックの質量比が７０．０となるような量とした。このようにして得られたインクを、ポリ四フッ化エチレンのシート上にバーコーターを用いて塗工し、塗膜を６０℃で乾燥させた。 On the other hand, the catalyst layer for the cathode catalyst was obtained by the following method. Platinum-supporting carbon black (TEK10E50E) manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., and yttrium-stabilized zirconia balls with a diameter of 10 mm were placed in a container, and pure water, ethanol and isopropanol were added at a mass ratio of 45:35:20 ( As a mixed solution, 10.2 g) was sequentially added. The ink thus obtained was ultrasonically dispersed for 3 minutes. Then, using a planetary ball mill (Sinkey ARE310), the mixture was stirred at 800 rpm for 20 minutes. Furthermore, 5% Nafion (registered trademark) (274704-100 ML, manufactured by Sigma-Aldrich) was added to the ink, and the same stirring as above was continuously performed by ultrasonic dispersion and a planetary ball mill. The amount of Nafion added was such that the mass ratio of Nafion / carbon black supporting platinum was 70.0. The ink thus obtained was applied onto a sheet of polytetrafluoroethylene using a bar coater, and the coating film was dried at 60 ° C.
得られたアノード用及びカソード用電極触媒層付ポリ四フッ化エチレンのシートを５４ｍｍ四方の正方形状に切り出し、ナフィオン（登録商標）（ＮＲＥ−２１２、Ｄｕ−Ｐｏｎｔ社製）の電解質膜と重ね合わせ、１４０℃、２５ｋｇｆ／ｃｍ２の条件下に２分間大気中で熱プレスし、転写を行った。このようにして、ナフィオンからなる固体高分子電解質膜の各面にカソード及びアノード触媒層を形成し、触媒層被覆電解質膜（Ｃａｔａｌｙｓｔ Ｃｏａｔｅｄ Ｍｅｍｂｒａｎｅ；ＣＣＭ）を作製した。電極触媒層における白金の量は、カソード触媒層では０．１３８ｍｇ−Ｐｔ／ｃｍ２で、アノード触媒層では０．１１６ｍｇ−Ｐｔ／ｃｍ２であった。The obtained sheet of polytetrafluoroethylene with an electrode catalyst layer for anode and cathode was cut out into a square shape of 54 mm square and superposed with an electrolyte membrane of Nafion (registered trademark) (NRE-212, manufactured by Du-Pont). , 140 ° C., 25 kgf / cm 2 for 2 minutes in the atmosphere, and hot pressed in the atmosphere to perform transfer. In this manner, the cathode and anode catalyst layers were formed on each surface of the solid polymer electrolyte membrane made of Nafion, and a catalyst layer-coated electrolyte membrane (Catalyst Coated Membrane; CCM) was produced. The amount of the platinum in the electrode catalyst layer, the cathode catalyst layer 0.138mg -Pt / cm 2, the anode catalyst layer was 0.116mg -Pt / cm 2.
前記で得られたＣＣＭを一対のガス拡散層（ＳＧＬカーボン社製、型番：２９ＢＣ）で挟んだ。更にガス流路が形成された一対のカーボン板からなるセパレータで挟み、固体高分子形燃料電池を作製した。このようにして得られた燃料電池は、ＪＡＲＩ標準セルに相当するものである。 The CCM obtained above was sandwiched between a pair of gas diffusion layers (manufactured by SGL Carbon Co., model number: 29BC). Further, it was sandwiched between separators composed of a pair of carbon plates in which gas flow paths were formed, to produce a polymer electrolyte fuel cell. The fuel cell thus obtained corresponds to a JARI standard cell.
得られた固体高分子形燃料電池について、出力特性（Ｉ−Ｖ特性）を以下の方法で測定した。固体高分子形燃料電池のアノード側に水素ガスを供給するとともに、カソード側に酸素ガスを供給した。水素ガスの利用率は７０％に、酸素利用率は４０％になるように流量を設定した。ガスはそれぞれ外部加湿器で加湿を行ってから燃料電池に供給した。また燃料電池の温度は８０℃になるように温度調整を行い、供給ガスの湿度については、相対湿度が１００％ＲＨとなるように調整した。このときのセル電圧と電流密度との関係（Ｉ−Ｖ特性）を測定した。得られたセル電圧と電流密度との関係から、０．１Ａ／ｃｍ２におけるセル電圧値Ｖを得た。そして、得られたセル電圧値に基づき、性能を以下の基準で評価した。
◎：セル電圧が０．８Ｖ以上
○：セル電圧が０．７９Ｖ以上０．８Ｖ未満
×：セル電圧が０．７９Ｖ未満The output characteristics (IV characteristics) of the obtained polymer electrolyte fuel cell were measured by the following method. Hydrogen gas was supplied to the anode side of the polymer electrolyte fuel cell, and oxygen gas was supplied to the cathode side. The flow rate was set so that the utilization rate of hydrogen gas was 70% and the utilization rate of oxygen was 40%. Each gas was humidified by an external humidifier and then supplied to the fuel cell. The temperature of the fuel cell was adjusted to 80 ° C., and the humidity of the supply gas was adjusted to a relative humidity of 100% RH. At this time, the relationship between the cell voltage and the current density (IV characteristic) was measured. The cell voltage value V at 0.1 A / cm 2 was obtained from the obtained relationship between the cell voltage and the current density. Then, based on the obtained cell voltage value, the performance was evaluated according to the following criteria.
⊚: Cell voltage is 0.8 V or more O: Cell voltage is 0.79 V or more and less than 0.8 V ×: Cell voltage is less than 0.79 V
表１に示す結果から明らかなとおり、各実施例の担体付き白金触媒は、比較例の触媒に比べて、触媒性能が高いことが判る。
また、表には示していないが、各実施例の担体付き白金触媒は、白金がＴｉＯ０．５の結晶相又はＴｉＯの結晶相に直接に接しており、且つ白金に接触していないＴｉＯ０．５の結晶相又はＴｉＯの結晶相の表面がＴｉＯ２で被覆されていることが、ＴＥＭのＥＥＬＳ分析による測定の結果確認された。As is clear from the results shown in Table 1, the carrier-supported platinum catalyst of each example has higher catalytic performance than the catalyst of the comparative example.
Further, although not shown in the table, in the platinum catalyst with a carrier of each example, platinum is in direct contact with the crystal phase of TiO 0.5 or the crystal phase of TiO, and TiO 0 which is not in contact with platinum. the surface of the crystal phase or TiO crystalline phase of .5 is that is coated with TiO 2, was confirmed the results of measurement by EELS analysis TEM.
本発明によれば、導電性が高く、担持する触媒の性能が十分に発揮される担体付き触媒が提供される。 According to the present invention, there is provided a catalyst with a carrier that has high conductivity and can sufficiently exert the performance of the catalyst to be supported.
Claims (10)
前記担体がチタン酸化物を含み、
前記担体に含まれるチタン元素（Ｔｉ）と酸素元素（Ｏ）の含有割合（Ｏ／Ｔｉ）がモル比で表して０．８以上１．６以下であり、
前記担体がＴｉＯ０．５の結晶相又はＴｉＯの結晶相を有する、担体付き触媒。A catalyst with a carrier in which the catalyst is supported on a carrier,
The carrier comprises titanium oxide,
The content ratio (O / Ti) of titanium element (Ti) and oxygen element (O) contained in the carrier is 0.8 or more and 1.6 or less in terms of molar ratio,
A catalyst with a carrier, wherein the carrier has a crystalline phase of TiO 0.5 or a crystalline phase of TiO 2.
前記触媒が、露出している前記結晶相に直接に接している請求項１ないし５のいずれか一項に記載の担体付き触媒。A crystal phase of TiO 0.5 or a crystal phase of TiO is exposed on a part of the surface of the carrier,
The catalyst with a carrier according to any one of claims 1 to 5, wherein the catalyst is in direct contact with the exposed crystal phase.
前記触媒を担持した前記チタン酸化物を焼成する、担体付き触媒の製造方法。Titanium oxide represented by the composition formula TiO a (where a is a number of 0.4 or more and 1 or less) is crushed in an organic solvent, and then the catalyst is catalyzed in the organic solvent without a dry powdering step. Carry
A method for producing a catalyst with a carrier, comprising calcining the titanium oxide carrying the catalyst.
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