WO2009035163A1 - 微粒子コンポジット、その製造方法、固体高分子型燃料電池用触媒、及び固体高分子型燃料電池 - Google Patents
微粒子コンポジット、その製造方法、固体高分子型燃料電池用触媒、及び固体高分子型燃料電池 Download PDFInfo
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- WO2009035163A1 WO2009035163A1 PCT/JP2008/066937 JP2008066937W WO2009035163A1 WO 2009035163 A1 WO2009035163 A1 WO 2009035163A1 JP 2008066937 W JP2008066937 W JP 2008066937W WO 2009035163 A1 WO2009035163 A1 WO 2009035163A1
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- Prior art keywords
- reaction
- hours
- fine particle
- product
- sulfide
- Prior art date
Links
- 239000010419 fine particle Substances 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims description 36
- 239000000446 fuel Substances 0.000 title claims description 23
- 239000005518 polymer electrolyte Substances 0.000 title claims description 10
- 238000000034 method Methods 0.000 title abstract description 4
- 230000008569 process Effects 0.000 title abstract description 4
- 239000007787 solid Substances 0.000 title description 20
- 239000010948 rhodium Substances 0.000 claims abstract description 82
- 238000004729 solvothermal method Methods 0.000 claims abstract description 76
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 73
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 20
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 16
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000002041 carbon nanotube Substances 0.000 claims description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 22
- 239000006229 carbon black Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011877 solvent mixture Substances 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- DUDJJJCZFBPZKW-UHFFFAOYSA-N [Ru]=S Chemical compound [Ru]=S DUDJJJCZFBPZKW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- USBWXQYIYZPMMN-UHFFFAOYSA-N rhenium;heptasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[Re].[Re] USBWXQYIYZPMMN-UHFFFAOYSA-N 0.000 claims description 2
- BVJAAVMKGRODCT-UHFFFAOYSA-N sulfanylidenerhodium Chemical compound [Rh]=S BVJAAVMKGRODCT-UHFFFAOYSA-N 0.000 claims description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims 2
- 229910052776 Thorium Inorganic materials 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract 2
- 239000000047 product Substances 0.000 description 146
- 238000002441 X-ray diffraction Methods 0.000 description 51
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 46
- 239000002994 raw material Substances 0.000 description 45
- 230000015572 biosynthetic process Effects 0.000 description 37
- 238000003786 synthesis reaction Methods 0.000 description 35
- 238000001354 calcination Methods 0.000 description 32
- 239000007795 chemical reaction product Substances 0.000 description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 23
- 239000000463 material Substances 0.000 description 22
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 19
- 239000008096 xylene Substances 0.000 description 19
- 238000001878 scanning electron micrograph Methods 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 238000000635 electron micrograph Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000002524 electron diffraction data Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 5
- 229910052798 chalcogen Inorganic materials 0.000 description 4
- 150000001787 chalcogens Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000218213 Morus <angiosperm> Species 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 sulfur ions Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910015799 MoRu Inorganic materials 0.000 description 1
- 241000917012 Quercus floribunda Species 0.000 description 1
- 241000084978 Rena Species 0.000 description 1
- 229910019851 Ru—Se Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G47/00—Compounds of rhenium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/923—Compounds thereof with non-metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
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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
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- Fine particle composite Fine particle composite, production method thereof, solid polymer fuel cell catalyst, and solid polymer fuel cell
- the present invention relates to molybdenum (M o), rhodium (R h), ruthenium (R u), renyu
- the present invention relates to a fine particle composite containing a sulfide or composite sulfide fine powder of at least one element selected from the group (R e), and a manufacturing method thereof.
- the present invention also relates to a polymer electrolyte fuel cell catalyst comprising a fine particle composite, and a polymer electrolyte fuel cell.
- Hydrothermal reaction or solvothermal reaction has attracted attention as a means for compound synthesis.
- water is used as a reaction solvent, and sulfur ions and zinc ions are hydrothermally reacted at a particle growth temperature of 1550 to 3700 ° C. to have a multiple twin structure. 5 ⁇ ⁇ !
- a production method for obtaining zinc sulfide particles having an average particle diameter of ⁇ 20 ⁇ m is disclosed.
- Platinum or platinum alloy catalysts are mainly used as the catalyst for polymer electrolyte fuel cells. Specifically, a catalyst in which a noble metal including platinum is supported on carbon black has been used.
- material costs One way to solve this is to reduce the amount of platinum. ⁇
- Non-Patent Document 1 discloses that a catalyst having a chalcogen element is excellent in four-electron reducibility and suggests application to a fuel cell. Specifically, Non-Patent Document 1 below discloses a Mo-Ru-Se ternary electrode catalyst and a synthesis method thereof. ' T / JP2008 / 066937
- Patent Document 2 there is an electrocatalyst composed of at least one transition metal and a chalcogen as a platinum substitute catalyst, and the electrocatalyst composed of Ru as the transition metal and S or Se as the chalcogen. It is disclosed.
- the molar ratio of Ru: Se is in the range of 0.5 to 2 and the stoichiometric number n of (Ru) n Se is 1.5 to 2.
- Patent Document 3 discloses a fuel cell catalyst material having a transition metal selected from Fe or Ru, a nitrogen-containing organometallic transition complex, and a chalcogen component such as S as a Pt substitute catalyst. ing.
- Non-Patent Document 2 discloses Ru-S, Mo-S, Mo-Ru-S binary and ternary electrode catalysts, and a synthesis method thereof.
- Non-Patent Document 3 discloses a ternary force rucogenide electrode catalyst of Ru—Mo—S and Ru—Mo—Se.
- An object of the present invention is to provide a fine particle composite containing fine powder of a sulfide or a complex sulfide of a specific element, and a method for producing the same.
- the present invention is intended to apply the fine particle composite to a fuel cell catalyst, and relates to a solid polymer fuel cell catalyst containing the fine particle composite, and a solid polymer fuel cell.
- the present inventors have found that the above problems can be solved by using a hydrothermal reaction or a solvothermal reaction, and have reached the present invention.
- the present invention is an invention of a fine particle composite, and sulfidation of one or more elements selected from molypden (M.), rhodium (Rh), ruthenium (Ru), and rhenium (R e). Or composite sulfide fine particles and conductive fine particles.
- the fine particle composite of the present invention is a composite containing at least the above components. Fine particles of sulfide or composite sulfide of one or more elements selected from molypden (Mo), rhodium (R h), ruthenium (R u), rhenium (R e) can catalyze the oxygen reduction reaction.
- the conductive fine particles act as a support for the catalyst. For this reason, in the fine particle composite of the present invention, the fine particle composite itself has a carrier, and no other carrier is required.
- the fine particle composite of the present invention has an average particle size of 1 nil! ⁇ 1 im is preferred.
- the fine particle composite of the present invention there are various sulfides or composite sulfides of one or more elements selected from molypden (Mo), rhodium (Rh), ruthenium (Ru), and rhenium (R e).
- Mo molypden
- Rh rhodium
- Ru ruthenium
- R e rhenium
- a single crystal fine powder state can also be taken.
- the single crystal fine powder of the present invention can take various shapes, and among them, a substantially spherical one can be obtained.
- the sulfide which is a component of the fine particle composite of the present invention, includes sulfide sulfide (M o 2 S 2 , Mo S 2 , Mo 2 S 3 s Mo S 3 , Mo S 4 ), rhodium sulfide (R h 17 S 15 , Rh 9 S 8 , Rh 3 S 4 , Rh 2 S 3 , Rh 2 S 5 ), ruthenium sulfide (R u S 2 ), or rhenium sulfide (R e S 2 , R e 2 S 7 )
- Preferred examples are binary compounds selected.
- Rh- X- SX is ternary compound represented by Ru- X- S
- X is molybdenum (Mo), palladium (P d), selenium (S e), PT / JP2008 / 066937
- Rh or Ru acts as a catalyst and X acts as a promoter.
- R h—Mo—S or Ru—Mo—S is particularly preferable.
- carpump racks and / or carbon nanotubes are preferably exemplified.
- the present invention provides fine particles of sulfide or composite sulfide of one or more elements selected from the above molybdenum (Mo), rhodium (Rh), ruthenium (R u ), and rhenium (R e ),
- the solvent used for the sorbosa single reaction is not limited, xylene, acetone, chloroform and the like are exemplified.
- the hydrothermal reaction or the sopothermal reaction is preferably carried out at 200 ° C to 600 ° C.
- the conductive carbon powder is preferably exemplified by a car pump rack and / or a carbon nanotube.
- the method for producing a fine particle composite of the present invention can be produced by carrying out the reaction i n-si t u. It is a great advantage of the present invention that all the reactions can be carried out in i—s i t ti, compared to the conventional combination of several reactions in the preparation of fuel cell catalysts.
- the present invention provides a polymer electrolyte fuel cell comprising the fine particle composite described above. Catalyst.
- the catalyst of the present invention is an alternative to expensive platinum-based catalysts.
- the present invention is a polymer electrolyte fuel cell provided with the fine particle composite as a catalyst.
- Mo molypden
- Rh rhodium
- Ru ruthenium
- R e rhenium
- conductive fine particles Fine particle composites containing and can be expected as various reaction catalysts by taking advantage of their catalytic properties that do not require the support.
- it can be used as a fuel cell catalyst capable of reducing the cost as an alternative to a conventional platinum catalyst.
- the catalyst characteristics can be improved by selecting the dopant element to be doped.
- FIG. 1 is a flow chart showing the synthesis method by hydrothermal reaction or solvothermal reaction of the present invention.
- Figure 2 shows the XRD pattern of Mo S 2 synthesized by solvothermal reaction.
- Figure 3 shows a S EM photographs of Mo S 2 powder synthesized from Mo C 1 5 (calcined 400 ° C, 5 h).
- Figure 4 shows the XRD pattern of Mo S 2 synthesized from the Sorpozamar reaction.
- Fig. 5 shows a SEM photograph (calcined 400 ° C, 5 h) of Mo S 2 powder synthesized from thiourea.
- Figure 6 shows the XRD pattern of Mo S 2 (a) synthesized by solvothermal reaction and its calcined product (b, c).
- Fig. 7 shows the XRD pattern of Mo S 2 product synthesized from Mo (CO) 6 and S by solvothermal reaction at 220 ° C for 10 hours with varying SZMo ratio.
- Fig. 8 shows that the calcined product of Mo S 2 synthesized by Mo (CO) 6 and S at 220 ° C for 10 hours at 400 ° C for 5 hours with varying S / Mo ratio at 220 ° C for 10 hours.
- XRD pattern is shown.
- Fig. 9A shows the product Mo S 2 from the sorporotherm reaction
- Fig. 9B shows its 40 JP2008 / 066937
- FIG. 10 shows a transmission electron micrograph of the calcined product of Mo S 2 produced by the sopothermal reaction at 400 ° C for 5 hours.
- Figure 11 shows the XRD pattern of the product Mo S 2 produced by the sopothermal reaction.
- Figures 12A and B show electron micrographs of the product Mo S 2 produced by the solvothermal reaction.
- Figure 13 shows the XRD pattern of Mo S 2 hydrothermally synthesized with ammonia added (220 ° C, 10 hours).
- Figure 14 shows the XRD pattern of Mo S 2 obtained by calcining Mo S 2 hydrothermally synthesized with ammonia in an argon stream (400 ° C, 5 hours).
- Figure 18 shows the XRD pattern of the product obtained by hydrothermal reaction of (NH 4 ) 3 [ ⁇ 0 4 ⁇ 12 0] ⁇ 3 ⁇ 2 0 and thiourea and its calcined product
- Figures 19A and B show scanning electron micrographs of the product obtained by hydrothermal reaction of ( ⁇ 4 ) 3 [ ⁇ 0 4 ⁇ 12 0] ⁇ 3 ⁇ 20 and thiourea and its calcined product.
- Figure 20 shows the FT IR spectrum of the product obtained by hydrothermal reaction of (NH 4 ) 3 [ ⁇ 0 4 ⁇ 12 0] ⁇ 3 ⁇ 20 and thiourea and its calcined product.
- Figure 21 shows the XRD pattern of the product obtained by hydrothermal reaction of ( ⁇ 4 ) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 20 with thiourea and its calcined product.
- 22A and 22B show scanning electron micrographs of the product obtained by hydrothermal reaction of ( ⁇ 4 ) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 20 and thiourea and the calcined product.
- Figure 23 shows the FT IR spectrum of the product obtained by hydrothermal reaction of ( ⁇ 4 ) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 2 0 with thiourea and its calcined product. ' 2008/066937
- Fig. 24 shows the XRD pattern of Ru S 2 synthesized by sopothermal reaction (220 ° C, 10 hours) with varying SZRu ratio.
- Figure 25 shows the XRD pattern of the Ru S 2 calcined material (Ar flow, 400 ° C, 5 hours) synthesized by solvothermal reaction (220 ° C, 10 hours).
- Figures 26A, B, and C show scanning electron micrographs of Ru S 2 calcined material (Ar flow, 400 ° C, 5 hours) synthesized by the sopothermal reaction (220 ° C, 10 hours).
- FIGS. 27A, B, C, and D show transmission electron micrographs of the R u S 2 calcined product.
- Figure 29 shows the XRD pattern of the product RuS 2 (220 ° C, 10 hours) from the hydrothermal reaction.
- FIG. 30 shows the XRD pattern of the calcined product (400 ° C, 5 hours) of the product Ru S 2 (220 ° C, 10 hours) resulting from the hydrothermal reaction.
- Figure 3 1 A, B show a R u S 2 a scanning electron micrograph of a resultant of precalcination thereof.
- Figure 32 shows the XRD pattern of Rh 2 S 3 synthesized by solvothermal reaction (2 20 ° C, 10 hours).
- Figure 33 shows the XRD pattern of the Rh 2 S 3 calcined product (Ar in air current, 400 ° C, 5 hours) synthesized by solvothermal reaction (220 ° C, 10 hours).
- Figures 3A, B, C, and D show scanning electron micrographs of the solvothermal reaction product Rh 2 S 3 and its calcined product.
- Figure 36 shows the XRD pattern of the product R h 2 S 3 and its calcined product from the hydrothermal reaction.
- Figures 37A and B show electron micrographs of the hydrothermal reaction product Rh 2 S 3 and its calcined product.
- Figures 38A and B show the electron microscope of the Rh 2 S 3 product of the hydrothermal reaction of SZRh-3.0 8066937
- Figure 3 9 A, B is the product of S // R11-3.0 hydrothermal reaction R h 2 S 3 4 0 0. An electron micrograph and an electron diffraction pattern of the C sintered product are shown.
- Figure 41 shows the XRD pattern of Re S 2 synthesized by a solvothermal reaction (2 20 ° C, 10 hours).
- Fig. 42 shows the XRD pattern of the pre-calcined product of Re S 2 synthesized in a solvothermal reaction (220 ° C, 10 hours) (in Ar flow, 400 ° C, 5 hours).
- FIG. 43 shows the XRD pattern of the product Re S 2 and calcined product obtained at an S / R e ratio of 4.
- Figure 44 shows the XRD pattern of the product Re S 2 and calcined product with an S / R e ratio of 9.
- Fig. 45 A, B, C and D show scanning electron micrographs of the Sorphothermal reaction product Re S 2 and calcined product.
- Figure 48 shows the XRD pattern of R e S 2 synthesized by hydrothermal reaction (220 ° C, 10 hours) and R e synthesized by hydrothermal reaction (220 ° C, 10 hours).
- XRD pattern of S 2 calcined product (Ar in airflow, 400 ° C, 5 hours).
- Fig. 49 A, B, C and D show scanning electron micrographs of the hydrothermal reaction product Re S 2 and calcined product.
- Figure 50 shows Rh— synthesized by solvothermal reaction (220 ° C, 10 hours).
- FIG. 51 shows the oxygen reduction current values of R h 2 S 3 / C and R h—M o—S / C.
- FIG. 52 shows the results of the acid * reduction catalyst performance of a fine particle composite of the present invention containing fine particles of sulfide or composite sulfide of several elements and conductive fine particles.
- Figure 53 shows the results of the RDE evaluation of Mo RuS / C-1 and Mo Ru S / C_2, which are R ⁇ 1-Mo-S synthesized by solvothermal reaction.
- Figure 54 shows the TEM observation results of Mo R S / C-1 synthesized by solvothermal reaction.
- Figure 55 shows the results of RDE evaluation of Mo Ru S / C—1, Mo Ru S / C—4, and Mo Ru S / C—5, which are Ru—Mo—S synthesized by solvothermal reaction. .
- Fig. 56 shows the results of R D E evaluation of Mo Ru S / C-5, which is Ru-Mo-S, synthesized by solvothermal reaction, and Paper.
- Figure 57 shows the results of the R D E evaluation of Mo Ru S / C— 1 1 1 C 2 and Mo Ru S / C — 1 1 — C 4, which are Ru—Mo—S synthesized by the sopothermal reaction.
- FIG. 58 shows the results of R D E evaluation of Mo Ru S / C-12 and Mo Ru S / C-14, which are Ru—Mo—S synthesized by a sopothermal reaction.
- Figure 59 shows the results of the RDE evaluation of Mo Ru—HI—CNT—C-11 and Mo Ru—H2—CNT—CI, which are Ru—Mo—S synthesized by solvothermal reaction.
- FIG. 60 shows the result of TEM observation of Mo Ru—HI—C NT—C 1 which is Ru—Mo—S synthesized by hydrothermal reaction.
- Figure 61 shows the results of the R D E evaluation of Mo Ru HI—CB—CI and Mo Ru_H2—CB—Cl, which are Ru—Mo—S synthesized by a sopothermal reaction.
- Figure 62 shows Mo Ru— HO 1-CNT— C 1, Mo Ru_H0 1— CNT— C 2 and Mo Ru— H02— CN T 1 C 1, which are Ru— Mo— S synthesized by hydrothermal reaction. The results of RDE evaluation of Mo Ru—H02—CNT—C 2 are shown.
- Figure 63 shows the Ru-Mo-S synthesized by solvothermal reaction, Mo Ru, SOI-CNT-CI, Mo Ru-SOI-CNT-C2, and Mo Ru-S02-CNT-CI. The results of RDE evaluation of Mo Ru—SO 2—CNT—C 2 are shown. BEST MODE FOR CARRYING OUT THE INVENTION ''' 6937
- the purpose of this example is synthesis of a fine particle composite containing fine particles of Mo S 2 , Ru S 2 , Rh 2 S 3 , Re S 2 and conductive fine particles by hydrothermal reaction or solvothermal reaction.
- FIG. 1 is a flowchart showing the synthesis method of the present invention by hydrothermal reaction or solvothermal reaction. Teflon-lined autoclaves were used for reactions at low temperatures, and Hastelloy C-lined autoclaves were used for reactions at high temperatures. In both cases, they were reacted to i n- s i t u. Specific synthesis conditions are described below.
- the raw materials (Mo, Ru, Rh, Re and S) are introduced into the autoclave. Decide the type and quantity ratio of raw materials.
- Mo raw material Mo (CO) 6 , Mo Cl 5 , ( ⁇ 4 ) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 20 , (NH 4 ) 3 [P 0 4 Mo 12 0] ⁇ 3 H 2 0, S raw material And S (sulfur solid), thiourea ((NH 2 ) 2 CS), xylene or distilled water as a solvent, sorporothermic reaction or hydrothermal reaction, reaction conditions: 220 ° C or 3500 ° C, 10 Went for hours. Thereafter, calcination was performed at 350 ° C. to 750 ° C. for 5 hours in an Ar atmosphere.
- the crystallinity was improved by calcining at 350 ° C in an Ar atmosphere. Also, by synthesizing at a high temperature (350 ° C, 10 h), the crystallinity was improved as compared with the one synthesized at a low temperature.
- Figure 2 shows the XRD pattern of Mo S 2 synthesized by solvothermal reaction.
- hot metal xylene
- temperature 2 20 ° C
- time 10 h
- a Mo C
- Figure 3 shows a S EM photographs of Mo S 2 powder synthesized from Mo C 1 5 (calcined 400 ° C, 5 h).
- the starting material for io was S or thiourea, the synthesis temperature was 220 ° C, and the reaction time was 10 hours.
- the synthesis temperature was 220 ° C
- the reaction time was 10 hours.
- Mo S 2 powder with slightly higher crystallinity was obtained, and when thiourea was used as the raw material, the product strongly aggregated. Decided to use S as source.
- Figure 4 shows the XRD pattern of Mo S 2 synthesized from the Sorpozamar reaction.
- solvent xylene
- temperature 220 ° C
- time 10 h
- a is Mo (C
- Figure 5 shows a SEM image of Mo S 2 powder synthesized from thiourea (calcined 40
- Mo S 2 synthesized by a sorbothermal reaction with a reaction temperature of 20 ° C and a reaction time of 10 hours was calcined in an Ar stream from Mo (CO) 6 and S.
- Figure 6 shows the XRD patterns of Mo S 2 (a) synthesized by solvothermal reaction and its calcined product (b, c).
- b is 3 50 ° C, 2 hours
- ⁇ c is 600. C, 2 o'clock. 2008/066937
- the crystallinity increased by calcining at 350 ° C, and even when calcined at 600 ° C, the crystallinity did not change much from that at 350 ° C. Therefore, the calcining conditions will be 400 ° C or higher for 5 hours in the future experiments.
- the raw material S / Mo ratio was changed when Mo S 2 was synthesized from Mo (CO) 6 and S by a sorbothermal reaction with a reaction temperature of 220 ° C and a reaction time of 10 hours.
- Fig. 7 shows the XRD pattern of Mo S 2 product synthesized from Mo (CO) 6 and S by solvothermal reaction at 220 ° C for 10 hours with varying S / Mo ratio.
- Fig. 8 shows that the S / Mo ratio was changed from Mo (CO) 6 and S to 220 ° C, 10 hours of Sopothermal reaction of Mo S 2 at 400 ° C for 5 hours.
- the XRD pattern of the calcined product is shown. In each figure, a is the S / Mo ratio of 1.6, b is 2.0, c is 2.4, and d is 3.0.
- Fig. 9A shows a scanning electron micrograph of the product Mo S 2 produced by the sopothermal reaction
- Fig. 9B shows the calcined product at 400 ° C for 5 hours
- Fig. 10 shows a transmission electron micrograph of the calcined product at 400 ° C for 5 hours of the product Mo S 2 produced by the solvothermal reaction.
- the obtained Mo S 2 can be observed to be composed of fine particles of about 100 nm, has high dispersibility, and is synthesized from different Mo raw materials shown in Figs. 3A, B, and 5A, B. properties were significantly different from S 2. Even when the calcination was carried out, no particularly strong aggregation was observed. From the transmission electron microscope observation, a fine structure in which the fibrous layers of the product overlapped was observed. The reason why the diffraction intensity differs from the XRD pattern described on the JC PD S card is thought to be due to this structure. 2008/066937
- the shape of the product was the same as that at low temperature, and it was found to be composed of fine particles. From the transmission electron microscope observation, it was found that the contrast had two parts where a strong fibrous layer and a lattice image with relatively high crystallinity were observed. The spacing of each lattice is 6.2 A and 2.7 A, which is considered to correspond to ⁇ 0 02> and ⁇ 1 00> of Mo S 2 .
- Mo C 15 As Mo raw materials, Mo C 15 , (NH 4 ) 6 Mo 7 0 24 ⁇ 4 H 2 0, (NH 4 ) 3 [P 0 4 Mo 12 0] ⁇ 3 H 2 0, as S raw materials, thiourea ( (NH 2) 2 CS) with attempts to synthesis of Mo S 2 by hydrothermal reaction, high Mo S 2 crystalline than Soruposamaru reaction was obtained. If the addition of hydroxide Natoriumu to Mo C 1 5, and (N ⁇ 4) 6 ⁇ 7 0 24 ⁇ 4H 2 0, (NH 4) 3 [P0 4 Mo 12 ⁇ ] - Using 3H 2 0 in raw material In some cases, Mo S 2 composed of fine particles with relatively high dispersibility was produced. 1. 2. 1 Reaction of Mo C 15 with thiourea with addition of ammonia
- FIG. 16 shows the hydrothermal synthesis (2 20 ° C) with sodium hydroxide added with S / Mo ratio of 2.2. shows an 0 hour) were Mo S 2 and it calcined (400 ° C, 5 hours in a stream of argon) was Mo S 2 XRD pattern.
- a is a Na OH aqueous solution concentration of 0.6M
- b is a Na OH aqueous solution concentration of 0.9M
- c is a Na OH aqueous solution concentration of 1.2M
- d is a Na OH aqueous solution concentration of 1.8M.
- Mo S 2 synthesized by adding sodium hydroxide was composed of fine spherical particles with relatively high crystallinity and high dispersibility.
- the sample consisted of fine particles with relatively high dispersibility.
- the FT IR spectrum did not absorb due to organic matter.
- FIG. 21 shows the XRD pattern of the product obtained by hydrothermal reaction of ( ⁇ 4 ) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 2 0 with thiourea and its calcined product.
- FIG. 22 A in B, submitted a ( ⁇ 4) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 2 0 to the product obtained by the hydrothermal reaction between thiourea and a resultant of precalcination thereof Hashi ⁇ electron microscope photograph of.
- Fig. 22A shows the hydrothermal composition (220 ° C, 10 hours)
- Fig. 22B shows the calcined product (in argon, 400 ° C, 5 hours).
- Figure 2 3 shows a ( ⁇ 4) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 2 0 and thiourea and the product obtained by the hydrothermal reaction precalcination thereof of FT IR spectra.
- a is a hydrothermal compound (220 ° C, 10 hours)
- b is a calcined product (in argon, 400 ° C, 5 hours).
- Ru (CO) 12 as Rti raw material
- S (sulfur solid) as S raw material
- xylene or distilled water as solvent
- solvosamal reaction or hydrothermal reaction reaction condition: 220 ° C
- reaction condition: 220 ° C It went for 10 hours. Thereafter, calcination was performed at 400 ° C for 5 hours in an Ar atmosphere.
- Figure 24 shows the XRD pattern of Ru S 2 synthesized by solvothermal reaction (220 ° C, 10 hours) with varying S / Ru ratio.
- the product was low crystalline regardless of the S / Ru ratio.
- Figure 2
- Fig. 25 shows the XRD pattern of the Ru S 2 calcined material (Ar flow, 400 ° C, 5 hours) synthesized by the sopothermal reaction (220 ° C, 10 hours).
- e SZRu-4.
- a is a hydrothermal composition and b is a calcined product.
- Fig. 29 shows the XRD pattern of the product RuS 2 (220 ° C, 10 hours) produced by the hydrothermal reaction.
- Fig. 30 shows the XRD pattern of the calcined product (400 ° C, 5 hours) of the product Ru S 2 (220 ° C, 10 hours) produced by the hydrothermal reaction.
- a is S
- Figs. 3 1 A and B show scanning electron microscope photographs of Ru S 2 and its calcined material.
- Fig. 3 1 B is the calcined product (400 ° C, 5 hours).
- the amorphous phase obtained with an S / Ru ratio of 4.4 was also crystallized to RUS 2 by calcination.
- SZRu ratio was 2.8, unidentified phases were mixed in the calcined product.
- the formation of Ru metal was also confirmed at an S / Ru ratio of 2.0.
- Rh 6 (CO) 16 as Rh raw material
- S sulfur solid
- xylene or distilled water as solvent
- solvothermal reaction or hydrothermal reaction reaction conditions: 220 ° C, 1 0 hours went.
- calcination was performed in an Ar atmosphere at 400 ° C for 5 hours (partially 750 ° C).
- Figure 32 shows the XRD pattern of Rh 2 S 3 synthesized by solvothermal reaction (220 ° C, 10 hours).
- Figure 33 shows the XRD pattern of the Rh 2 S 3 calcined product (Ar flow, 400 ° C, 5 hours) synthesized by solvothermal reaction (220 ° C, 10 hours).
- c is SZRh-S.0.
- a is the product of the solvothermal reaction R h 2 S 3
- b is the calcined product (Ar flow, 400 ° C, 5 hours)
- c is the calcined product (Ar flow, 750 ° C, 5 hours) Time).
- the product R h 2 S 3 resulting from the Sorpozamar reaction had low crystallinity, but when it was calcined, crystallization progressed significantly. Crystallization by calcination depends on the SR h ratio, and crystallization occurred at an S / Rh ratio of 3.6 or less, but no crystallization occurred at 5.0. However, by raising the calcining temperature to 750 ° C, even a sample with an S / Rli ratio of 5 crystallized.
- Figures 3A, B, C, and D show scanning electron micrographs of the Rh 2 S 3 product and its calcined product produced by the solvothermal reaction.
- D is SZRh ratio
- Figure 36 shows the XRD pattern of the product Rh 2 S 3 and its calcined product from the hydrothermal reaction.
- the hydrothermal reaction product Rh 2 S 3 had low crystallinity regardless of the S / Rh ratio, but the crystallization progressed significantly by calcination. When the 3/1 11 ratio was 1.5, impurities were present in the calcined product, and the target phase was obtained when the S-Rh ratio was 3.0.
- FIGS. 3A and B show electron micrographs of the hydrothermal reaction product Rh 2 S 3 and its calcined product.
- the hydrothermal compound was partially self-shaped and grew into large crystals. It is a strange phenomenon that the XRD pattern has an amorphous nature, but the crystal is surely growing.
- FIGS. 38A and B show an electron micrograph and an electron diffraction pattern of the product R h 2 S 3 of the hydrothermal reaction of SZRh 3.0.
- a is a hydrothermal composition
- b is a calcined product. From the IR spectrum in Fig. 40, it was found that organic substances were not incorporated into the hydrothermal reaction product.
- Re raw material is Re 2 (CO) 10
- S raw material is S (sulfur solid)
- xylene or distilled water is used as solvent, solvothermal reaction or hydrothermal reaction, reaction condition: 220 ° C , Went for 10 hours. Thereafter, calcination was performed at 400 ° C or 750 ° C for 5 hours in an Ar atmosphere.
- Figure 41 shows the XRD pattern of Re S 2 synthesized by the sopothermal reaction (220 ° C, 10 hours).
- Figure 42 shows the XRD pattern of the Re S 2 calcined product (in Ar stream, 400 ° C, 5 hours) synthesized by the sopothermal reaction (220 ° C, 10 hours).
- Figure 43 shows the XRD pattern of the product R e S 2 and calcined product obtained with an SZR e ratio of 4.
- a is the solvothermal reaction product R e S 2
- b is its 400 ° C calcined product
- c is its 750 ° C calcined product.
- FIG. 44 shows the XRD pattern of the product Re S 2 and calcined product obtained at an S / R e ratio of 9.
- a is the sorbothermal reaction product R e S 2
- b is its 400 ° C calcined product
- c is its 750 ° C calcined product. 7
- the product consisted of spherical particles, and when the S / R e ratio was 2, the size was uniform. When the S / R e ratio was 4, the particle size distribution became wider.
- a is a hydrothermal compound and b is a calcined product. 8066937
- Table 1 shows the E D X analysis results of the calcined product at 75 ° C.
- Figure 48 shows the XRD pattern of Re S 2 synthesized by hydrothermal reaction (220 ° C, 10 hours), and R synthesized by hydrothermal reaction (220 ° C, 10 hours).
- This shows the XRD pattern of e S 2 calcined product (A r in airflow, 400 ° C, 5 hours).
- Figures 49 A, B, C, and D show scanning electron micrographs of the hydrothermal reaction product Re S 2 and calcined product.
- Rh 6 (CO) 16 as the Rh raw material
- (NH 4 ) 6 Mo 7 0 2 4 ⁇ 4 ⁇ 20 as the Mo raw material
- S (sulfur solid) as the S raw material
- xylene as the solvent
- the thermal reaction was performed under reaction conditions: 400 ° C. for 10 hours. Thereafter, calcination was performed at 400 ° C. for 5 hours in an Ar atmosphere.
- Figure 50 shows the TEM observation results of R h— Mo— S synthesized by the solvothermal reaction (220 ° C., 10 hours).
- FIG. 50 shows the oxygen reduction current values of Rl ⁇ l 2 S 3 / C and Rl ⁇ l—Mo—S / C. In FIG. 50, an enlarged portion near the oxygen reduction starting potential is added.
- FIG. 52 shows the results of the oxygen reduction catalyst performance of a fine particle composite containing sulfides or composite sulfide fine particles of several elements and conductive fine particles according to the present invention. From the results shown in FIG. 52, it can be seen that the fine particle composite of the present invention containing sulfide or composite sulfide fine particles and conductive fine particles has excellent oxygen reduction catalyst performance.
- Synthetic powder is put into alcohol, and ultrasonically dispersed for about 5 minutes.
- the resulting slurry is dropped onto a Cu micro-dallide, and after natural drying, the field emission analytical electron microscope is used as an observation sample.
- ecnai "G2-F20-MAT type, acceleration voltage: 200 kV (maximum), resolution: 0.24 nm (on-axis irradiation), FE-TEM observation was performed.
- Rh 2 S 3 / C both Rh and S are dispersed at almost the same position, and it is judged as a composite. Also, C is widely dispersed so as to cover the detection positions of Rh and S. In Rh-Mo-S / C, Rh, Mo, and S are dispersed in almost the same position, and are judged to be composites. In addition, C is widely dispersed to wrap around the detection positions of Rh, Mo, and S.
- Ru raw material Ru 3 (CO) 16 as Mo raw material, Mo CO 6 as S raw material, S (sulfur solid) as carbon black, Ketjen black EC 3 00 J (trade name) as carbon black as solvent
- xylene a sopothermal reaction was carried out under reaction conditions: 220 ° C. for 10 hours. Then, calcination was performed at 600 ° C for 5 hours in an Ar atmosphere.
- Figure 53 shows the results of RDE evaluation of Mo Ru S / C-1 and Mo Ru S / C-2, which are Ru Ru-Mo-S synthesized by solvothermal reaction.
- Figure 54 shows the TE of Mo Ru S / C-1 synthesized by solvothermal reaction. 6937
- Ru raw material Ru 3 (CO) 16 Mo raw material Mo C0 6 S raw material S (sulfur solid) Ketjen black EC 3 00 J (trade name) as car pump rack Solvent As xylene, MoZRh 0.2 / 0.8, and the solvothermal reaction was performed at 220 ° C for 10 hours. Thereafter, calcination was performed at 600 ° C. for 5 hours in an Ar atmosphere.
- Figure 55 shows the results of the RDE evaluation of Mo Ru SZC-1, Mo Ru S / C-4, and Mo Ru SZC-5, which are Ru-Mo-I S synthesized by the sopothermal reaction.
- carbon black referred to as Mo R u SZC-5
- carbon napup (CNT) paper referred to as P ap er
- Figure 56 shows the results of RDE evaluation of Mo RuS / C_5 and Paper, which are Ru-Mo-S, synthesized by a sorporotherm reaction.
- Ru material the Ru 3 (CO) 16, as Mo material, a Mo C_ ⁇ 6, as the S material, S (solid sulfur) and Ketjen Black EC 3 00 J carbon black (trade name)),
- Mo / Rh 0.2 1
- the solvothermal reaction was carried out at 79 under reaction conditions: 220 ° C. for 10 hours. Thereafter, calcination was performed in an Ar atmosphere at 350 ° C for 5 hours or 450 ° C for 5 hours.
- Figure 57 shows the results of R D E evaluation of Mo Ru S / C-1 1 1 C 2 and Mo Ru SZC-1 1 1 C 4, which are Ru—Mo—S synthesized by solvothermal reaction. 6.5 Baking time
- Figure 58 shows the results of R D E evaluation of Mo Ru S / C-12 and Mo Ru SZC-14, which are Ru—Mo—S synthesized by solvothermal reaction.
- Ru 3 (CO) 16 as Mo raw material, Mo C0 6 as Mo raw material, S (sulfur solid) as S raw material, carbon nanotube (CNT) 0.05 g water dispersion and water as solvent Mo / Rh 0.1 7 / 0.83, and hydrothermal reaction was performed under the reaction conditions: 140 ° C for 10 hours or 220 ° C for 10 hours. After that, calcination was performed at 350 ° C. for 2 hours in an Ar atmosphere.
- Fig. 5 9 shows Mo Ru—H 1— C, which is Ru— Mo— S synthesized by hydrothermal reaction.
- Fig. 60 shows the TEM observation results of Mo Ru-HI-CNT-C1, which is Ru-Mo-S synthesized by hydrothermal reaction. From the results in FIG. 60, it can be seen that Mo RuS is dispersed in nano size on the carbon nano tube. 66937
- Figure 61 shows the results of the R D E evaluation of Mo Ru — HI — CB — C I and Mo Ru — H2 — CB — C I, which are Ru— Mo— S synthesized by solvothermal reaction. 6, 8 Carbon nanotubes (CNT) Using aqueous dispersion, S amount and firing temperature are changed
- Ru material the Ru 3 (CO) 16, as Mo material, a Mo C_ ⁇ 6, as the S material, S (solid sulfur), carbon nanotubes (CNT) 0. 2 g aqueous dispersion, water as a solvent
- Mo / Rh 0.2 / 2 / 0.9 and under the reaction conditions of 220 ° C. for 10 hours. Then, under Ar atmosphere, 350 ° C, 2 hours or 5
- Figure 62 shows Mo Ru— H0 1— which is Ru— Mo— S synthesized by hydrothermal reaction.
- Carbon nanotubes (CNT) Using xylene dispersion and changing S content and firing temperature
- the thermal reaction was performed under reaction conditions: 220 ° C. for 10 hours. Thereafter, calcination was performed at 350 ° C. for 2 hours or 550 ° C. for 2 hours in an Ar atmosphere.
- Figure 63 shows the Ru-Mo-S synthesized by the solvothermal reaction, Mo Ru 1 S 01—CNT—CI, Mo Ru—S 0 1—CNT—C 2, and Mo Ru_S 02—CNT—C 1 and the results of RDE evaluation of Mo Ru—S 02—CNT—C 2 are shown.
- fine particles of sulfide or composite sulfide of one or more elements selected from molypden (Mo), rhodium (Rh), ruthenium (Ru), and rhenium (R e), and conductive fine particles, A fine particle composite can be obtained.
- These fine particle composites containing sulfides or composite sulfide fine particles of specific elements and conductive fine particles are used for known applications and can be expected to be developed for various applications by utilizing their characteristics. For example, it can be used as a fuel cell catalyst capable of reducing the cost.
- various physical properties can be exhibited by selecting a dopant element to be doped.
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- Nanotechnology (AREA)
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Abstract
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CA2698823A CA2698823C (en) | 2007-09-14 | 2008-09-12 | Fine particle composite, method for producing the same, catalyst used for solid polymer fuel cell, and solid polymer fuel cell |
EP08830969.5A EP2198961B1 (en) | 2007-09-14 | 2008-09-12 | Process for producing the fine-particle composite |
US12/677,576 US9193604B2 (en) | 2007-09-14 | 2008-09-12 | Fine particle composite, method for producing the same, catalyst used for solid polymer fuel cell, and solid polymer fuel cell |
CN200880106866A CN101801526A (zh) | 2007-09-14 | 2008-09-12 | 微粒子复合材料、其制造方法、固体高分子型燃料电池用催化剂和固体高分子型燃料电池 |
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JP2008233905A JP2009082910A (ja) | 2007-09-14 | 2008-09-11 | 微粒子コンポジット、その製造方法、固体高分子型燃料電池用触媒、及び固体高分子型燃料電池 |
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US (1) | US9193604B2 (ja) |
EP (1) | EP2198961B1 (ja) |
JP (1) | JP2009082910A (ja) |
KR (1) | KR101264475B1 (ja) |
CN (2) | CN105047954A (ja) |
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CN111185201A (zh) * | 2020-02-25 | 2020-05-22 | 辽宁大学 | 铼掺杂硫化钼纳米片/碳布复合材料及其制备方法和在电催化水制氢中的应用 |
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Cited By (5)
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US20120112134A1 (en) * | 2009-06-30 | 2012-05-10 | Hanwha Chemical Corporation | Blending Improvement Carbon-Composite having Carbon-Nanotube and its Continuous Manufacturing Method and Apparatus |
US9567222B2 (en) * | 2009-06-30 | 2017-02-14 | Hanwha Chemical Corporation | Blending improvement carbon-composite having carbon-nanotube and its continuous manufacturing method and apparatus |
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CN111185201A (zh) * | 2020-02-25 | 2020-05-22 | 辽宁大学 | 铼掺杂硫化钼纳米片/碳布复合材料及其制备方法和在电催化水制氢中的应用 |
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CA2698823A1 (en) | 2010-03-08 |
CA2698823C (en) | 2012-12-18 |
US20100213420A1 (en) | 2010-08-26 |
KR101264475B1 (ko) | 2013-05-14 |
CN105047954A (zh) | 2015-11-11 |
CN101801526A (zh) | 2010-08-11 |
JP2009082910A (ja) | 2009-04-23 |
US9193604B2 (en) | 2015-11-24 |
KR20100051877A (ko) | 2010-05-18 |
EP2198961A4 (en) | 2012-08-01 |
EP2198961A1 (en) | 2010-06-23 |
EP2198961B1 (en) | 2017-07-05 |
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