JP2007111635A - Metal catalyst and method for manufacturing the same - Google Patents
Metal catalyst and method for manufacturing the same Download PDFInfo
- Publication number
- JP2007111635A JP2007111635A JP2005306068A JP2005306068A JP2007111635A JP 2007111635 A JP2007111635 A JP 2007111635A JP 2005306068 A JP2005306068 A JP 2005306068A JP 2005306068 A JP2005306068 A JP 2005306068A JP 2007111635 A JP2007111635 A JP 2007111635A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- metal
- fine particles
- metal catalyst
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 114
- 239000002184 metal Substances 0.000 title claims abstract description 113
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title abstract description 29
- 239000006229 carbon black Substances 0.000 claims abstract description 91
- 239000010419 fine particle Substances 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 64
- 239000007791 liquid phase Substances 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 57
- 238000011282 treatment Methods 0.000 claims description 30
- 229910052697 platinum Inorganic materials 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 11
- -1 peroxide carbonate Chemical class 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 239000002923 metal particle Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229910001111 Fine metal Inorganic materials 0.000 claims description 7
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical group 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
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- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 5
- 235000019241 carbon black Nutrition 0.000 description 79
- 230000003647 oxidation Effects 0.000 description 22
- 238000007254 oxidation reaction Methods 0.000 description 22
- VODGJKZAAVKBAL-UHFFFAOYSA-L diazanium;manganese(2+);disulfate Chemical compound [NH4+].[NH4+].[Mn+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VODGJKZAAVKBAL-UHFFFAOYSA-L 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
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- 238000003756 stirring Methods 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
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- 241000282320 Panthera leo Species 0.000 description 5
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- 238000001179 sorption measurement Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000013626 chemical specie Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 150000004685 tetrahydrates Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229930091371 Fructose Natural products 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004688 heptahydrates Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
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- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
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- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
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- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZPRATGFHKWAKR-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O BZPRATGFHKWAKR-UHFFFAOYSA-N 0.000 description 1
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- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- AMWUFXLSROXQFP-UHFFFAOYSA-N iron(3+);pentane-2,4-dione Chemical compound [Fe+3].CC(=O)CC(C)=O AMWUFXLSROXQFP-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- RXSBEASMBJFZCL-UHFFFAOYSA-N nickel(2+);pentane-2,4-dione Chemical compound [Ni+2].CC(=O)CC(C)=O RXSBEASMBJFZCL-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910000487 osmium oxide Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 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
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- UQZIYBXSHAGNOE-XNSRJBNMSA-N stachyose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO[C@@H]3[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O3)O)O2)O)O1 UQZIYBXSHAGNOE-XNSRJBNMSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
Description
本発明は、特に、燃料電池用触媒等として好適に用いることができる金属触媒と、その製造方法とに関するものである。 The present invention particularly relates to a metal catalyst that can be suitably used as a fuel cell catalyst and the like, and a method for producing the same.
燃料電池用触媒等としては、金属、特に、貴金属を用いた金属触媒が使用されるが、貴金属元素は地球上に限られた量しか存在しないことから、その使用量を極力減らし、しかも、触媒としての作用はできるだけ向上させることが求められる。そこで、金属触媒としては、例えば、カーボンブラックや無機化合物等からなる担体粒子の表面に、金属の微粒子を担持させた構造を有するものが用いられる。 As a catalyst for a fuel cell, a metal, particularly a metal catalyst using a noble metal is used. However, since noble metal elements exist in a limited amount on the earth, the amount used is reduced as much as possible. It is required to improve the action as much as possible. Thus, as the metal catalyst, for example, a catalyst having a structure in which metal fine particles are supported on the surface of carrier particles made of carbon black, an inorganic compound, or the like is used.
触媒作用は、主に、金属の表面において発揮されることから、上記構造の金属触媒において、良好な触媒作用を維持しつつ、金属の使用量をできるだけ少なくするためには、担体粒子の表面に担持させる金属微粒子を、できるだけ小粒径で、比表面積の大きいものとすることが有効である。 Since the catalytic action is mainly exerted on the surface of the metal, in the metal catalyst having the above structure, in order to minimize the amount of the metal used while maintaining good catalytic action, the surface of the carrier particle is used. It is effective that the metal fine particles to be supported have as small a particle size as possible and a large specific surface area.
担体粒子の表面に、金属微粒子を担持させる方法としては、含浸法と呼ばれる高温処理法や、液相還元法、気相法等があり、特に、近年、製造設備の簡易化が容易な液相還元法、すなわち、担体粒子を分散させた液相の反応系中で、析出対象である金属のイオンを、還元剤の作用によって還元することで、担体粒子の表面に、微粒子状に析出させる方法が、広く普及しつつある。 As a method for supporting the metal fine particles on the surface of the carrier particles, there are a high temperature treatment method called an impregnation method, a liquid phase reduction method, a gas phase method, and the like. Reduction method, that is, a method in which metal ions to be deposited are reduced by the action of a reducing agent in a liquid phase reaction system in which carrier particles are dispersed to deposit on the surface of carrier particles in the form of fine particles. However, it is becoming widespread.
液相還元法によって形成する金属微粒子の粒径を小さくするためには、担体粒子の比表面積を大きくすることが有効であると考えられている。例えば、特許文献１には、担体粒子として、比表面積が２５０〜３５０ｍ2／ｇ、粒径が１５０〜３５０Åである難黒鉛化性カーボンブラックや、比表面積が９００〜１５００ｍ2／ｇ、粒径が２００〜４００Åである易黒鉛化性カーボンブラックを使用することが記載されている。 In order to reduce the particle size of the metal fine particles formed by the liquid phase reduction method, it is considered effective to increase the specific surface area of the carrier particles. For example, Patent Document 1, as the carrier particles, specific surface area of 250 to 350 2 / g, particle size and non-graphitizable carbon black is 150～350A, specific surface area of 900~1500m 2 / g, particle size Describes the use of graphitizable carbon black having a particle diameter of 200 to 400 mm.
また、特許文献２には、担体粒子として、比表面積が７０〜８００ｍ2／ｇ、[００２]面の平均格子面間隔ｄ002が０．３３７〜０．３４８ｎｍ、結晶子の大きさＬｃ(002)が３〜１８ｎｍであるカーボン担体を用いることが記載されている。さらに、特許文献３には、担体粒子として、比表面積が６００〜１２００ｍ2／ｇである炭素粉末を用いることが記載されている。 Further, Patent Document 2 discloses that carrier particles have a specific surface area of 70 to 800 m 2 / g, an average lattice spacing d 002 of [002] plane of 0.337 to 0.348 nm, and a crystallite size Lc (002 ) Is 3 to 18 nm. Furthermore, Patent Document 3 describes that carbon powder having a specific surface area of 600 to 1200 m 2 / g is used as carrier particles.
また、金属微粒子の粒径を小さくするためには、液相還元法による金属微粒子の析出時に、液相の反応系中に、ホウ素、ケイ素、リン、硫黄、窒素等の不純物元素を含有させておき、これらを、金属元素と共析させる方法も有効であり、例えば、非特許文献１においては、金属元素としての白金とルテニウムとを、不純物元素としてのリンと共析させることで、金属微粒子の粒径を２ｎｍまで小さくできたことが報告されている。
しかしながら、これらの方法によって金属微粒子の粒径を小さくする効果には限界があり、この限界よりもさらに金属微粒子の粒径を小さくして、触媒効率を向上させることで、例えば、燃料電池の電池特性を、現状よりもさらに良好なものとするためには、新たな対策を講じることが求められる。本発明の目的は、担体粒子の表面に、現状よりもさらに粒径の小さい金属微粒子が担持された金属触媒と、その製造方法とを提供することにある。 However, there is a limit to the effect of reducing the particle size of the metal fine particles by these methods, and by reducing the particle size of the metal fine particles further than this limit and improving the catalyst efficiency, for example, a battery of a fuel cell In order to make the characteristics even better than the current situation, it is necessary to take new measures. An object of the present invention is to provide a metal catalyst in which metal fine particles having a smaller particle size than the current state are supported on the surface of carrier particles, and a method for producing the same.
請求項１記載の発明は、担体粒子としての、酸化処理されたカーボンブラックと、このカーボンブラックの表面に担持された多数の金属微粒子とを有することを特徴とする金属触媒である。 The invention described in claim 1 is a metal catalyst characterized by having oxidized carbon black as carrier particles and a large number of metal fine particles supported on the surface of the carbon black.
請求項２記載の発明は、金属微粒子の粒径が１．１ｎｍ以下で、かつ担持量が、金属触媒の総量の１５〜６０重量％である請求項１記載の金属触媒である。 The invention according to claim 2 is the metal catalyst according to claim 1, wherein the particle size of the metal fine particles is 1.1 nm or less and the supported amount is 15 to 60% by weight of the total amount of the metal catalyst.
請求項３記載の発明は、金属微粒子が、白金、パラジウム、金、銀、ロジウム、イリジウム、ルテニウム、オスミウム、コバルト、マンガン、ニッケル、鉄、クロム、モリブデン、およびチタンからなる群より選ばれる少なくとも１種の金属の微粒子である請求項１記載の金属触媒である。 The invention according to claim 3 is characterized in that the metal fine particles are at least one selected from the group consisting of platinum, palladium, gold, silver, rhodium, iridium, ruthenium, osmium, cobalt, manganese, nickel, iron, chromium, molybdenum, and titanium. 2. The metal catalyst according to claim 1, wherein the metal catalyst is a fine metal particle.
請求項４記載の発明は、カーボンブラックのＢＥＴ比表面積が、５００〜１５００ｍ2／ｇである請求項１記載の金属触媒である。 The invention according to claim 4 is the metal catalyst according to claim 1, wherein the carbon black has a BET specific surface area of 500 to 1500 m 2 / g.
請求項５記載の発明は、燃料電池用触媒として用いられる請求項１記載の金属触媒である。 The invention according to claim 5 is the metal catalyst according to claim 1, which is used as a catalyst for a fuel cell.
請求項６記載の発明は、担体粒子としてのカーボンブラックを酸化処理する工程と、酸化処理したカーボンブラックを、液相の反応系中に分散させた状態で、析出対象である金属のイオンを、還元剤の作用によって還元して、カーボンブラックの表面に微粒子状に析出させることで、多数の金属微粒子を、カーボンブラックの表面に担持させる工程とを含むことを特徴とする金属触媒の製造方法である。 The invention according to claim 6 is a process of oxidizing carbon black as carrier particles, and in a state where the oxidized carbon black is dispersed in a liquid phase reaction system, ions of metal to be deposited are A method for producing a metal catalyst, comprising a step of supporting a large number of fine metal particles on the surface of carbon black by reducing the fine particles on the surface of carbon black by reduction by the action of a reducing agent. is there.
請求項７記載の発明は、カーボンブラックを、硝酸、リン酸、フッ酸、および硫酸、からなる群より選ばれる少なくとも１種の酸を含む処理液中に分散して酸化処理する請求項６記載の金属触媒の製造方法である。 According to a seventh aspect of the invention, the carbon black is dispersed and oxidized in a treatment solution containing at least one acid selected from the group consisting of nitric acid, phosphoric acid, hydrofluoric acid, and sulfuric acid. This is a method for producing a metal catalyst.
請求項８記載の発明は、カーボンブラックを、過酸化水素、過酸化炭酸塩、過酸化硫酸、および過酸化リン酸からなる群より選ばれる少なくとも１種の過酸化物を含む処理液中に分散して酸化処理する請求項６記載の金属触媒の製造方法である。 The invention according to claim 8 is characterized in that carbon black is dispersed in a treatment liquid containing at least one peroxide selected from the group consisting of hydrogen peroxide, peroxide carbonate, sulfuric acid peroxide, and phosphoric acid peroxide. The method for producing a metal catalyst according to claim 6, wherein the oxidation treatment is performed.
発明者が検討したところ、担体粒子として、酸化処理したカーボンブラックを用いると、その表面に、例えば、液相還元法によって担持される金属微粒子の粒径を、現状よりも、さらに小さくできることが明らかとなった。その理由を、発明者は、下記のように考えている。 As a result of investigations by the inventors, it is clear that when oxidized carbon black is used as the carrier particles, the particle size of the metal fine particles supported on the surface thereof, for example, by the liquid phase reduction method can be made smaller than the current state. It became. The inventor considers the reason as follows.
すなわち、カーボンブラックを酸化処理すると、電気陰性度の高い元素（酸素、窒素、フッ素、硫黄、リン等）を含む、例えば、−ＣＯＯＨ、−Ｃ＝Ｏ、−Ｃ≡Ｎ、−ＣＦ3、−Ｃ−ＳＯ3、−Ｃ−ＰＯ3等の化学種が、カーボンブラックの表面に存在する割合が増大する。ところが、これらの化学種は、特に、液相還元法によって金属微粒子を析出させる際に、反応系中に含まれる金属のイオンを吸着する吸着サイトとして機能するため、その存在する割合が増加することで、吸着される金属のイオンを成長の核として、カーボンブラックの表面に析出される金属微粒子の数が増加し、それに伴って、個々の金属微粒子の粒径が小さくなるのである。 That is, when carbon black is oxidized, it contains elements having high electronegativity (oxygen, nitrogen, fluorine, sulfur, phosphorus, etc.), for example, —COOH, —C═O, —C≡N, —CF 3 , — The ratio of chemical species such as C—SO 3 and —C—PO 3 on the surface of carbon black increases. However, these chemical species function as adsorption sites for adsorbing metal ions contained in the reaction system, particularly when depositing fine metal particles by the liquid phase reduction method. Thus, the number of metal fine particles deposited on the surface of the carbon black increases with the ions of the metal adsorbed as the growth nucleus, and the particle diameter of each metal fine particle decreases accordingly.
したがって、請求項１記載の発明によれば、カーボンブラックの表面に担持される金属微粒子の粒径を、現状よりも小さくして、金属触媒の触媒効率を向上させることができる。また、そのため、例えば、当該金属触媒を燃料電池に使用した際には、その電池特性を、これまでよりも、さらに良好なものとすることが可能となる。 Therefore, according to the first aspect of the present invention, it is possible to improve the catalyst efficiency of the metal catalyst by reducing the particle size of the metal fine particles supported on the surface of the carbon black from the current level. For this reason, for example, when the metal catalyst is used in a fuel cell, the cell characteristics can be made better than before.
請求項２記載の発明によれば、金属微粒子の粒径を１．１ｎｍ以下、担持量を、金属触媒の総量の１５〜６０重量％とすることによって、金属触媒の触媒効率を、より一層、向上することができる。 According to the invention of claim 2, by making the particle size of the metal fine particles 1.1 nm or less and the supported amount 15 to 60% by weight of the total amount of the metal catalyst, the catalytic efficiency of the metal catalyst is further increased. Can be improved.
請求項３記載の発明によれば、金属微粒子として、良好な触媒活性を有する、白金、パラジウム、金、銀、ロジウム、イリジウム、ルテニウム、オスミウム、コバルト、マンガン、ニッケル、鉄、クロム、モリブデン、およびチタンからなる群より選ばれる少なくとも１種の金属の微粒子を用いることによって、金属触媒の触媒効率を、より一層、向上することができる。 According to the invention of claim 3, platinum, palladium, gold, silver, rhodium, iridium, ruthenium, osmium, cobalt, manganese, nickel, iron, chromium, molybdenum, and metal having fine catalytic activity, and By using fine particles of at least one metal selected from the group consisting of titanium, the catalytic efficiency of the metal catalyst can be further improved.
請求項４記載の発明によれば、カーボンブラックのＢＥＴ比表面積を５００〜１５００ｍ2／ｇとすることによって、金属触媒の触媒効率を、より一層、向上することができる。 According to invention of Claim 4, the catalyst efficiency of a metal catalyst can be improved further by making the BET specific surface area of carbon black into 500-1500 m < 2 > / g.
請求項５記載の発明によれば、上記のように触媒効率に優れた金属触媒を用いることによって、燃料電池の電池特性を、現状よりもさらに良好なものとすることができる。 According to the fifth aspect of the present invention, by using the metal catalyst having excellent catalytic efficiency as described above, the cell characteristics of the fuel cell can be made even better than the current state.
請求項６記載の発明によれば、上記のように触媒効率に優れた金属触媒を、担体粒子としてのカーボンブラックを酸化処理する工程と、酸化処理したカーボンブラックの表面に、液相還元法によって、多数の金属微粒子を担持させる工程とを経ることで、効率よく製造することができる。 According to the sixth aspect of the present invention, the metal catalyst having excellent catalytic efficiency as described above is subjected to the oxidation treatment of the carbon black as the carrier particles, and the surface of the oxidation-treated carbon black is subjected to the liquid phase reduction method. And it can manufacture efficiently by passing through the process of carrying many metal microparticles.
請求項７、８記載の発明によれば、簡単な操作で、カーボンブラックを、効率よく酸化処理できるため、金属触媒の生産性を向上することができる。 According to the seventh and eighth aspects of the invention, the carbon black can be efficiently oxidized by a simple operation, so that the productivity of the metal catalyst can be improved.
《金属触媒》
本発明の金属触媒は、担体粒子としての、酸化処理したカーボンブラックの表面に、多数の金属微粒子が担持されたことを特徴とするものである。酸化処理して、担体粒子として用いるカーボンブラックとしては、金属触媒の担体として使用できる種々のカーボンブラックが、いずれも使用可能であるが、特に、そのＢＥＴ比表面積が５００〜１５００ｍ2／ｇであるカーボンブラックが好ましい。
《Metal catalyst》
The metal catalyst of the present invention is characterized in that a large number of metal fine particles are supported on the surface of oxidized carbon black as carrier particles. As the carbon black used as the carrier particles after the oxidation treatment, various carbon blacks that can be used as the carrier of the metal catalyst can be used, and in particular, the BET specific surface area is 500 to 1500 m 2 / g. Carbon black is preferred.
カーボンブラックのＢＥＴ比表面積が５００ｍ2／ｇ未満では、その表面に生成される多数の金属微粒子の、隣り合う間隔が近くなりすぎて、その成長過程で、隣り合う金属微粒子が融合して粒径が大きくなる機会が増加することから、たとえ酸化処理をしても、担持される金属微粒子の粒径を、現状よりも小さくできないおそれがある。そのため、金属触媒の触媒効率を向上させて、例えば、燃料電池の電池特性を、現状よりもさらに良好なものとすることができないおそれがある。 When the BET specific surface area of carbon black is less than 500 m 2 / g, the adjacent metal fine particles formed on the surface are too close to each other and the adjacent metal fine particles are fused in the growth process. Therefore, even if oxidation treatment is performed, the particle size of the supported metal fine particles may not be made smaller than the current state. Therefore, there is a possibility that the catalyst efficiency of the metal catalyst is improved, and for example, the cell characteristics of the fuel cell cannot be made even better than the current state.
一方、カーボンブラックのＢＥＴ比表面積が１５００ｍ2／ｇを超える場合には、多数の金属微粒子の、隣り合う間隔が拡がりすぎるため、金属触媒を、特に、燃料電池用として使用する際に、酸素ガスや水素ガスが金属微粒子間を拡散する過程が、触媒反応の律速段階となって、燃料電池の電池特性を、現状よりもさらに良好なものとすることができないおそれがある。なお、これらの問題点を併せ考慮すると、カーボンブラックのＢＥＴ比表面積は、上記の範囲内でも、特に、８００〜１３００ｍ2／ｇであるのが好ましい。 On the other hand, when the BET specific surface area of the carbon black exceeds 1500 m 2 / g, the interval between adjacent metal particles is too wide. Therefore, when the metal catalyst is used particularly for a fuel cell, oxygen gas is used. In addition, the process in which hydrogen gas diffuses between the metal fine particles becomes the rate-determining step of the catalytic reaction, and there is a possibility that the cell characteristics of the fuel cell cannot be made even better than the current state. In consideration of these problems, the BET specific surface area of carbon black is particularly preferably 800 to 1300 m 2 / g even within the above range.
酸化処理したカーボンブラックの表面に担持させる金属微粒子としては、白金、パラジウム、金、銀、ロジウム、イリジウム、ルテニウム、オスミウム、コバルト、マンガン、ニッケル、鉄、クロム、モリブデン、およびチタンからなる群より選ばれる少なくとも１種の金属の微粒子が挙げられる。 The fine metal particles supported on the surface of the oxidized carbon black are selected from the group consisting of platinum, palladium, gold, silver, rhodium, iridium, ruthenium, osmium, cobalt, manganese, nickel, iron, chromium, molybdenum, and titanium. And at least one kind of fine metal particles.
金属微粒子の粒径は、触媒効率を向上させることを考慮すると、現状、すなわち、前記非特許文献１に記載された２ｎｍよりも小さければよいが、特に、１．１ｎｍ以下であるのが好ましい。粒径が１．１ｎｍを超える場合には、金属微粒子の粒径を小さくすることによる、金属触媒の触媒効率を向上させる効果が十分に得られないおそれがある。なお、金属微粒子の粒径の下限値は、特に、限定されないが、実用上は、０．５ｎｍ以上であるのが好ましい。 In consideration of improving the catalyst efficiency, the particle size of the metal fine particles may be smaller than 2 nm described in the current situation, that is, Non-Patent Document 1, but is preferably 1.1 nm or less. When the particle size exceeds 1.1 nm, there is a possibility that the effect of improving the catalyst efficiency of the metal catalyst by reducing the particle size of the metal fine particles may not be sufficiently obtained. The lower limit of the particle size of the metal fine particles is not particularly limited, but is practically preferably 0.5 nm or more.
金属微粒子の担持量は、金属触媒の総量の１５〜６０重量％であるのが好ましい。担持量が１５重量％未満では、カーボンブラックの表面に生成される多数の金属微粒子の、隣り合う間隔が拡がりすぎ、一方、担持量が６０重量％を超える場合には、多数の金属微粒子の、隣り合う間隔が近くなりすぎて、その成長過程で、隣り合う金属微粒子が融合して粒径が大きくなる機会が増加するため、このいずれの場合にも、先に説明したように、燃料電池の電池特性を、現状よりもさらに良好なものとすることができないおそれがある。なお、これらの問題点を併せ考慮すると、金属微粒子の担持量は、上記の範囲内でも、特に、金属触媒の総量の２０〜５０重量％であるのが好ましい。 The supported amount of the metal fine particles is preferably 15 to 60% by weight of the total amount of the metal catalyst. When the supported amount is less than 15% by weight, the adjacent intervals of a large number of metal fine particles generated on the surface of the carbon black are too wide. On the other hand, when the supported amount exceeds 60% by weight, In this case, as described above, since the interval between adjacent portions becomes too close, and the chance that the adjacent metal fine particles are fused and the particle size is increased in the growth process, as described above. There is a possibility that the battery characteristics cannot be made even better than the current state. In consideration of these problems, the supported amount of the metal fine particles is preferably 20 to 50% by weight of the total amount of the metal catalyst, even within the above range.
本発明の金属触媒は、酸化処理したカーボンブラックの表面に担持させることで、これまでよりも、さらに粒径が小さく、比表面積が大きい金属微粒子を有しており、特に、燃料電池用として使用した際に、その電池特性を、現状よりもさらに良好なものとすることができる。なお、本発明の金属触媒は、ガス浄化用触媒等としても、好適に使用することができる。 The metal catalyst of the present invention has metal fine particles having a smaller particle diameter and a larger specific surface area than those used in the past by being supported on the surface of oxidized carbon black, and is particularly used for fuel cells. In this case, the battery characteristics can be made better than the current state. In addition, the metal catalyst of this invention can be used conveniently also as a catalyst for gas purifications.
《金属触媒の製造方法》
本発明の金属触媒の製造方法は、担体粒子としてのカーボンブラックを酸化処理する工程と、酸化処理したカーボンブラックを、液相の反応系中に分散させた状態で、析出対象である金属のイオンを、還元剤の作用によって還元して、カーボンブラックの表面に微粒子状に析出させることで、多数の金属微粒子を、カーボンブラックの表面に担持させる工程とを含むことを特徴とするものである。
<< Production Method of Metal Catalyst >>
The method for producing a metal catalyst of the present invention comprises a step of oxidizing carbon black as support particles, and an ion of a metal to be deposited in a state where the oxidized carbon black is dispersed in a liquid phase reaction system. Is reduced by the action of a reducing agent and deposited in the form of fine particles on the surface of the carbon black, thereby supporting a large number of metal fine particles on the surface of the carbon black.
上記のように、本発明においては、まず、カーボンブラックを酸化処理する。そのためには、種々の酸化方法が採用できるが、特に、下記(1)(2)のいずれかの方法が、操作が簡単で、カーボンブラックを効率よく酸化処理できることから、好適に採用される。
(1) カーボンブラックを、酸を含む処理液中に分散して酸化処理する。
(2) カーボンブラックを、過酸化物を含む処理液中に分散する。
As described above, in the present invention, first, carbon black is oxidized. For this purpose, various oxidation methods can be employed. In particular, any one of the following methods (1) and (2) is preferably employed because it is easy to operate and can efficiently oxidize carbon black.
(1) Carbon black is dispersed in an acid-containing treatment solution and oxidized.
(2) Disperse carbon black in the treatment liquid containing peroxide.
このうち、(1)の酸化処理に使用する酸としては、例えば、硝酸、リン酸、フッ酸、および硫酸、からなる群より選ばれる少なくとも１種が挙げられる。(1)の酸化処理は、例えば、酸を含む、水溶液等の処理液中に、カーボンブラックを分散させて、かく拌することによって実施される。また、(2)の酸化処理に使用する過酸化物としては、例えば、過酸化水素（Ｈ2Ｏ2）、過酸化炭酸塩〔過酸化硫酸ナトリウム（Ｎａ2Ｃ2Ｏ6）〕、過酸化硫酸〔一過硫酸（Ｈ2ＳＯ5）、二過硫酸（Ｈ2Ｓ2Ｏ8）〕、および過酸化リン酸〔ペルオクソリン一酸（Ｈ3ＰＯ5）、ペルオクソ二リン酸（Ｈ4Ｐ2Ｏ8）〕からなる群より選ばれる少なくとも１種が挙げられる。(2)の酸化処理は、(1)の酸化処理と同様に、過酸化物を含む、水溶液等の処理液中に、カーボンブラックを分散させて、かく拌することによって実施される。 Among these, examples of the acid used for the oxidation treatment (1) include at least one selected from the group consisting of nitric acid, phosphoric acid, hydrofluoric acid, and sulfuric acid. The oxidation treatment (1) is performed, for example, by dispersing carbon black in a treatment solution such as an aqueous solution containing an acid and stirring the solution. Examples of the peroxide used in the oxidation treatment (2) include hydrogen peroxide (H 2 O 2 ), peroxide carbonate [sodium peroxide sulfate (Na 2 C 2 O 6 )], and peroxide. Sulfuric acid [monopersulfuric acid (H 2 SO 5 ), dipersulfuric acid (H 2 S 2 O 8 )], and peroxyphosphoric acid [peroxoline monoacid (H 3 PO 5 ), peroxodiphosphate (H 4 P 2) And at least one selected from the group consisting of O 8 )]. The oxidation treatment (2) is carried out by dispersing carbon black in a treatment solution such as an aqueous solution containing a peroxide and stirring the same as in the oxidation treatment (1).
これらの酸化処理を行うと、先に説明したように、カーボンブラックの表面に、液相還元法によって金属微粒子を析出させる際に、反応系中に含まれる金属のイオンを吸着する吸着サイトとして機能する、電気陰性度の高い元素（酸素、窒素、フッ素、硫黄、リン等）を含む、例えば、−ＣＯＯＨ、−Ｃ＝Ｏ、−Ｃ≡Ｎ、−ＣＦ3、−Ｃ−ＳＯ3、−Ｃ−ＰＯ3等の化学種が導入されて、その存在する割合が増加する。そのため、これらの化学種に吸着される金属のイオンを成長の核として、カーボンブラックの表面に析出される金属微粒子の数を増加させて、個々の金属微粒子の粒径を、これまでよりも小さくすることができる。 When these oxidation treatments are performed, as described above, when metal fine particles are deposited on the surface of carbon black by the liquid phase reduction method, it functions as an adsorption site for adsorbing metal ions contained in the reaction system. Including elements having high electronegativity (oxygen, nitrogen, fluorine, sulfur, phosphorus, etc.), for example, —COOH, —C═O, —C≡N, —CF 3 , —C—SO 3 , —C The introduction of chemical species such as -PO 3 increases the proportion present. Therefore, by using the metal ions adsorbed by these chemical species as the growth nucleus, the number of metal fine particles deposited on the surface of carbon black is increased, and the particle diameter of each metal fine particle is made smaller than before. can do.
カーボンブラックを、どの程度まで酸化処理するかは、特に限定されないが、カーボンブラックのｐＨが７以下、特に、３以下となるまで酸化処理するのが好ましい。なお、カーボンブラックのｐＨは、測定対象であるカーボンブラックを、ｐＨ７の超純水に０．１ｇ／リットルの割合で混合し、大気遮断下で、還流しながら１００℃で１５分間、加熱した後、室温まで冷却した液について、ｐＨメータを用いて測定したｐＨでもって表すこととする。 To what extent the carbon black is oxidized is not particularly limited, but it is preferable to oxidize the carbon black until the pH of the carbon black is 7 or less, particularly 3 or less. The pH of carbon black was measured by mixing carbon black to be measured with ultrapure water having a pH of 7 at a rate of 0.1 g / liter and heating at 100 ° C. for 15 minutes while refluxing under air shut-off. The liquid cooled to room temperature is represented by the pH measured using a pH meter.
なお、酸化処理されたカーボンブラックに代えて、ｐＨが７以下である酸性カーボンブラックを使用することも考えられるが、前記酸性カーボンブラックを使用したのでは、比較例の結果からも明らかなように、本発明と同じ作用効果は得られない。その理由は明らかではないが、本発明においては、酸性カーボンブラック以外のカーボンブラック、特に、ｐＨが７を超えるカーボンブラックを酸化処理して、そのｐＨを前記の範囲内に調整した状態で、使用することが肝要である。 In addition, it is conceivable to use acidic carbon black having a pH of 7 or less in place of the oxidized carbon black. However, when the acidic carbon black is used, it is clear from the results of the comparative example. The same effect as the present invention cannot be obtained. The reason is not clear, but in the present invention, carbon black other than acidic carbon black, in particular, carbon black having a pH of more than 7, is oxidized and used in a state where the pH is adjusted within the above range. It is important to do.
次に、本発明では、液相還元法によって、カーボンブラックの表面に、金属微粒子を担持させる。すなわち、所定量の、酸化処理したカーボンブラックを分散させると共に、還元剤と、金属のイオン源となる金属化合物とを、それぞれ、所定の濃度で含む液相の反応系を調製し、この反応系を、所定の温度条件下で一定時間、反応させることにより、液相中に分散した担体粒子の表面に、還元された金属を、微粒子状に析出させて、担持させることができる。 Next, in the present invention, metal fine particles are supported on the surface of carbon black by a liquid phase reduction method. That is, a predetermined amount of oxidized carbon black is dispersed and a liquid phase reaction system containing a reducing agent and a metal compound serving as a metal ion source in a predetermined concentration is prepared. Is allowed to react for a predetermined time under a predetermined temperature condition, whereby the reduced metal can be deposited in the form of fine particles on the surface of the carrier particles dispersed in the liquid phase.
この際、液の温度や粘度、かく拌の有無、かく拌する場合は、かく拌速度等を変更することにより、形成される金属微粒子の粒径を調整することができる。すなわち、液の温度が低いほど、また粘度が高いほど、さらに、かく拌する場合は、かく拌速度が低いほど、形成される金属微粒子の粒径が小さくなる傾向がある。したがって、形成する金属微粒子の種類や粒径、使用する還元剤の種類、その他の条件を考慮しながら、液の温度、粘度、かく拌条件等を設定するのが好ましい。 At this time, the temperature and viscosity of the liquid, the presence or absence of stirring, and when stirring, the particle diameter of the formed metal fine particles can be adjusted by changing the stirring speed and the like. That is, as the temperature of the liquid is lower and the viscosity is higher, and when stirring is performed, the particle size of the formed metal fine particles tends to be smaller as the stirring speed is lower. Therefore, it is preferable to set the liquid temperature, viscosity, stirring conditions, and the like while considering the type and particle size of the metal fine particles to be formed, the type of reducing agent to be used, and other conditions.
金属微粒子のもとになる金属のイオン源としては、金属元素を含む種々の、液相の反応系に可溶の金属化合物が、いずれも使用可能である。また、金属化合物は、可能であれば、核成長の起点となって異常な核成長を生じさせるおそれのある、ハロゲン元素等の不純物元素を含まないのが好ましい。ただし、不純物元素を含む金属化合物を使用する場合でも、反応条件等を調整することにより、異常な核成長を抑えて、担体粒子の表面に、小粒径の金属微粒子を担持させることは可能である。 As the metal ion source that is the basis of the metal fine particles, any of various metal compounds containing a metal element and soluble in a liquid phase reaction system can be used. Moreover, it is preferable that the metal compound does not contain an impurity element such as a halogen element, which may cause abnormal nucleus growth as a starting point of nucleus growth, if possible. However, even when using a metal compound containing an impurity element, by adjusting the reaction conditions, etc., it is possible to suppress abnormal nuclei growth and to support small particles of metal particles on the surface of the carrier particles. is there.
金属のイオン源として好適な金属化合物としては、これに限定されないが、例えば、白金の場合、ジニトロジアンミン白金(II)（Ｐｔ（ＮＯ2）2（ＮＨ3）2）、ヘキサクロロ白金(IV)酸六水和物（Ｈ2〔ＰｔＣｌ6〕・６Ｈ2Ｏ）等が挙げられ、特に、ジニトロジアンミン白金(II)が好ましい。 Examples of metal compounds suitable as a metal ion source include, but are not limited to, for example, in the case of platinum, dinitrodiammine platinum (II) (Pt (NO 2 ) 2 (NH 3 ) 2 ), hexachloroplatinum (IV) acid Hexahydrate (H 2 [PtCl 6 ] · 6H 2 O) and the like, and dinitrodiammine platinum (II) is particularly preferable.
パラジウムの場合は、塩化パラジウム(II)溶液（ＰｄＣｌ2）、金の場合は、テトラクロロ金(III)酸四水和物（ＨＡｕＣｌ4・４Ｈ2Ｏ）等が挙げられる。銀の場合は、硝酸銀(I)（ＡｇＮＯ3）、メタンスルホン酸銀（ＣＨ3ＳＯ3Ａｇ）等が挙げられ、特に、硝酸銀(I)が好ましい。ロジウムの場合は、塩化ロジウム(III)溶液（ＲｈＣｌ3・３Ｈ2Ｏ）、イリジウムの場合は、ヘキサクロロイリジウム(III)酸六水和物（２(ＩｒＣｌ6)・６Ｈ2Ｏ）、ルテニウムの場合は、硝酸ルテニウム（III）溶液（Ｒｕ(ＮＯ3)3）、オスミウムの場合は、酸化オスミウム(VIII)（ＯｓＯ4）等が挙げられる。 In the case of palladium, palladium chloride (II) solution (PdCl 2 ), and in the case of gold, tetrachloroauric (III) acid tetrahydrate (HAuCl 4 .4H 2 O) and the like can be mentioned. In the case of silver, silver nitrate (I) (AgNO 3 ), silver methanesulfonate (CH 3 SO 3 Ag) and the like can be mentioned, and silver (I) nitrate is particularly preferable. For rhodium, rhodium (III) chloride solution (RhCl 3 .3H 2 O), for iridium, hexachloroiridium (III) hexahydrate (2 (IrCl 6 ) · 6H 2 O), for ruthenium These include ruthenium (III) nitrate solution (Ru (NO 3 ) 3 ) and, in the case of osmium, osmium oxide (VIII) (OsO 4 ).
コバルトの場合は、硝酸コバルト(II)六水和物（Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ）、硫酸コバルト(II)七水和物（ＣｏＳＯ4・７Ｈ2Ｏ）、塩基性炭酸コバルト(II)（ｘＣｏＣＯ3・ｙＣｏ（ＯＨ）2・ｚＨ2Ｏ、ｘ、ｙ、ｚは製法により異なる、通常はｘ＝２、ｙ＝３、ｚ＝１）、塩化コバルト(II)六水和物（ＣｏＣｌ2・６Ｈ2Ｏ）、アセチルアセトンコバルト(II)（Ｃｏ〔ＣＨ（ＣＯＣＨ3）2〕2）、酢酸コバルト(II)四水和物（Ｃｏ（ＣＨ3ＣＯＯ）2・４Ｈ2Ｏ）等が挙げられる。マンガンの場合は、硝酸マンガン(II)水和物（Ｍｎ（ＮＯ3）2・ｎＨ2Ｏ、ｎ＝４〜６）、塩化マンガン(II)四水和物（ＭｎＣｌ2・４Ｈ2Ｏ）、硫酸アンモニウムマンガン(II)六水和物（Ｍｎ（ＮＨ4）2（ＳＯ4）2・６Ｈ2Ｏ）等が挙げられる。 In the case of cobalt, cobalt nitrate (II) hexahydrate (Co (NO 3 ) 2 .6H 2 O), cobalt sulfate (II) heptahydrate (CoSO 4 .7H 2 O), basic cobalt carbonate ( II) (xCoCO 3 · yCo (OH) 2 · zH 2 O, x, y, and z vary depending on the production method, usually x = 2, y = 3, z = 1), cobalt chloride (II) hexahydrate (CoCl 2 · 6H 2 O), acetylacetone cobalt (II) (Co [CH (COCH 3 ) 2 ] 2 ), cobalt acetate (II) tetrahydrate (Co (CH 3 COO) 2 · 4H 2 O), etc. Is mentioned. In the case of manganese, manganese nitrate (II) hydrate (Mn (NO 3 ) 2 .nH 2 O, n = 4 to 6), manganese chloride (II) tetrahydrate (MnCl 2 .4H 2 O), And ammonium manganese sulfate (II) hexahydrate (Mn (NH 4 ) 2 (SO 4 ) 2 .6H 2 O).
ニッケルの場合は、硝酸ニッケル(II)六水和物（Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ）、塩化ニッケル(II)六水和物（ＮｉＣｌ2・６Ｈ2Ｏ）、硫酸ニッケル(II)七水和物（ＮｉＳＯ4・７Ｈ2Ｏ）、アセチルアセトンニッケル(II)（Ｎｉ〔ＣＨ（ＣＯＣＨ3）2〕2）、塩基性炭酸ニッケル(II)（ａＮｉＣＯ3・ｂＮｉ（ＯＨ）2・ｃＨ2Ｏ、ａ、ｂ、ｃは製法により異なる、通常はａ＝２、ｂ＝３、ｃ＝４）、酢酸ニッケル(II)四水和物（Ｎｉ（ＣＨ3ＣＯＯ）2・４Ｈ2Ｏ）等が挙げられる。鉄の場合は、硝酸鉄(III)六水和物、九水和物（Ｆｅ（ＮＯ3）3・６Ｈ2Ｏ、９Ｈ2Ｏ）、塩化鉄(II)四水和物（ＦｅＣｌ2・４Ｈ2Ｏ）、硫酸鉄(II)七水和物（ＦｅＳＯ4・７Ｈ2Ｏ）、アセチルアセトン鉄(III)（Ｆｅ〔ＣＨ（ＣＯＣＨ3）2〕3）等が挙げられる。 In the case of nickel, nickel nitrate (II) hexahydrate (Ni (NO 3 ) 2 .6H 2 O), nickel chloride (II) hexahydrate (NiCl 2 .6H 2 O), nickel sulfate (II) Heptahydrate (NiSO 4 .7H 2 O), acetylacetone nickel (II) (Ni [CH (COCH 3 ) 2 ] 2 ), basic nickel carbonate (II) (aNiCO 3 · bNi (OH) 2 · cH 2 O, a, b and c differ depending on the production method, usually a = 2, b = 3, c = 4), nickel acetate (II) tetrahydrate (Ni (CH 3 COO) 2 .4H 2 O), etc. Is mentioned. In the case of iron, iron nitrate (III) hexahydrate, nonahydrate (Fe (NO 3 ) 3 · 6H 2 O, 9H 2 O), iron (II) chloride tetrahydrate (FeCl 2 · 4H) 2 O), iron sulfate (II) heptahydrate (FeSO 4 .7H 2 O), acetylacetone iron (III) (Fe [CH (COCH 3 ) 2 ] 3 ) and the like.
クロムの場合は、アセチルアセトンクロム(III)（Ｃｒ〔ＣＨ（ＣＯＣＨ3）2〕3）、塩化クロム(II)（ＣｒＣｌ2）、硝酸クロム(III)九水和物（Ｃｒ（ＮＯ3）3・９Ｈ2Ｏ）等が挙げられる。モリブデンの場合は、塩化モリブデン(V)（ＭｏＣｌ5）、チタンの場合は塩化チタン(IV)溶液（ＴｉＣｌ4）等が挙げられる。 In the case of chromium, acetylacetone chromium (III) (Cr [CH (COCH 3 ) 2 ] 3 ), chromium chloride (II) (CrCl 2 ), chromium nitrate (III) nonahydrate (Cr (NO 3 ) 3. 9H 2 O) and the like. In the case of molybdenum, molybdenum chloride (V) (MoCl 5 ), and in the case of titanium, titanium chloride (IV) solution (TiCl 4 ) and the like can be mentioned.
還元剤としては、金属微粒子の粒径を、極力、小さくすることを考慮すると、できるだけ還元力の弱い還元剤が、好適に使用される。還元力の弱い還元剤としては、例えば、メタノール、エタノール、イソプロピルアルコール等のアルコール類や、アスコルビン酸等を挙げることができる他、エチレングリコール、グルタチオン、有機酸類（クエン酸、リンゴ酸、酒石酸等）、還元性糖類（グルコース、ガラクトース、マンノース、フルクトース、スクロース、マルトース、ラフィノース、スタキオース等）、および糖アルコール類（ソルビトール等）等を挙げることができ、特に、還元性糖類や、その誘導体としての糖アルコール類、あるいは、アルコール類が好ましい。また、還元剤として、アルコール類と、その他の還元剤とを併用すると、担体粒子の表面に担持させる金属微粒子の担持量を増加させることができる。 As the reducing agent, considering that the particle size of the metal fine particles should be as small as possible, a reducing agent having a weakest reducing power is preferably used. Examples of the reducing agent having a weak reducing power include alcohols such as methanol, ethanol and isopropyl alcohol, ascorbic acid and the like, as well as ethylene glycol, glutathione and organic acids (citric acid, malic acid, tartaric acid, etc.). , Reducing sugars (glucose, galactose, mannose, fructose, sucrose, maltose, raffinose, stachyose, etc.) and sugar alcohols (sorbitol, etc.). Especially, reducing sugars and sugars as derivatives thereof Alcohols or alcohols are preferred. Further, when alcohols and other reducing agents are used in combination as the reducing agent, the amount of metal fine particles supported on the surface of the carrier particles can be increased.
また、液相の反応系中には、例えば、そのｐＨを、金属イオンの還元析出に適した範囲に調整するためのｐＨ調整剤、担体粒子を分散させるための分散剤、液相の粘度を調整するための粘度調整剤等の、各種の添加剤を添加してもよい。 Further, in the liquid phase reaction system, for example, a pH adjusting agent for adjusting the pH to a range suitable for reduction precipitation of metal ions, a dispersing agent for dispersing carrier particles, and a viscosity of the liquid phase. You may add various additives, such as a viscosity modifier for adjusting.
このうち、ｐＨ調整剤としては、各種の酸やアルカリが何れも使用可能であるが、特に、核成長の起点となって異常な核成長を生じさせるおそれのある不純物元素を含まない、酸やアルカリを使用するのが好ましい。かかる、不純物元素を含まない酸としては、硝酸等を挙げることができ、アルカリとしては、アンモニア水等を挙げることができる。 Among these, as the pH adjuster, any of various acids and alkalis can be used. In particular, an acid or an alkali that does not contain an impurity element that may cause abnormal nucleus growth as a starting point of nucleus growth. It is preferable to use an alkali. Nitric acid etc. can be mentioned as this acid which does not contain an impurity element, Ammonia water etc. can be mentioned as an alkali.
液相のｐＨの好適な範囲は、析出させる金属の種類や、そのもとになる金属のイオン源としての、金属化合物の種類等によって異なり、また、その好適な範囲内でｐＨを小さくするほど、形成される金属微粒子の粒径が小さくなる傾向がある。よって、形成する金属微粒子の種類や粒径、使用する還元剤の種類、その他の条件を考慮しながら、ｐＨ調整剤を添加するか否か、添加する場合は、どの程度の量を添加するか、を選択するのが好ましい。 The preferred range of the pH of the liquid phase varies depending on the type of metal to be deposited and the type of metal compound as the source of the metal ion, and the lower the pH within the preferred range. The particle diameter of the formed metal fine particles tends to be small. Therefore, whether or not to add a pH adjuster, taking into account the type and particle size of the fine metal particles to be formed, the type of reducing agent to be used, and other conditions, and how much should be added Are preferably selected.
また、分散剤や粘度調整剤としては、従来公知の種々の化合物を用いることができるが、この両者の機能を兼ね備えた高分子分散剤を使用するのが好ましい。かかる高分子分散剤としては、例えば、ポリエチレンイミン、ポリビニルピロリドン等のアミン系の高分子分散剤や、カルボキシメチルセルロース等の、分子中にカルボン酸基を有する炭化水素系の高分子分散剤、あるいは、１分子中にポリエチレンイミン部分とポリエチレンオキサイド部分とを有する共重合体（以下「ＰＥＩ−ＰＯ共重合体」とする）等を挙げることができる。 Moreover, as a dispersing agent and a viscosity modifier, conventionally well-known various compounds can be used, However, It is preferable to use the polymer dispersing agent which has both these functions. Examples of the polymer dispersant include amine-based polymer dispersants such as polyethyleneimine and polyvinylpyrrolidone, hydrocarbon-based polymer dispersants having a carboxylic acid group in the molecule such as carboxymethyl cellulose, or Examples thereof include a copolymer having a polyethyleneimine moiety and a polyethylene oxide moiety in one molecule (hereinafter referred to as “PEI-PO copolymer”).
高分子分散剤の添加量は、特に、限定されないが、添加量を多くするほど液相の粘度が上昇して、形成される金属微粒子の粒径が小さくなる傾向があることから、製造する金属微粒子の粒径や、使用する還元剤の種類、その他の条件を考慮しながら、好適な添加量の範囲を設定するのが好ましい。 The amount of addition of the polymer dispersant is not particularly limited, but as the addition amount increases, the viscosity of the liquid phase increases and the particle size of the formed metal fine particles tends to decrease, so the metal to be produced It is preferable to set a suitable addition amount range in consideration of the particle size of the fine particles, the type of reducing agent used, and other conditions.
〈実施例１〉
カーボンブラック〔ライオン(株)製のケッチェンブラックＥＣ、ＢＥＴ比表面積：約８００ｍ2／ｇ〕を、濃度９００ｇ／リットルの硝酸水溶液に、前記硝酸水溶液１リットルあたり、１０ｇの割合で配合し、５０℃で３時間、酸化処理した。酸化処理後のカーボンブラックのｐＨを、先に説明した測定方法で測定したところ２であった。
<Example 1>
Carbon black (Ketjen Black EC manufactured by Lion Co., Ltd., BET specific surface area: about 800 m 2 / g) was mixed with a nitric acid solution having a concentration of 900 g / liter at a rate of 10 g per liter of the nitric acid solution. Oxidation treatment was performed at 0 ° C. for 3 hours. The pH of the carbon black after the oxidation treatment was 2 as measured by the measurement method explained above.
次に、純水に、前記カーボンブラックと、エタノールと、フルクトースと、白金濃度５０ｇ／リットルのジニトロジアンミン硝酸白金溶液とを加えて液相の反応系を調製した。各成分の濃度は、カーボンブラック：２ｇ／リットル、エタノール：２００ｍｌ／リットル、フルクトース：０．１Ｍ、白金：０．０２Ｍとした。 Next, the carbon black, ethanol, fructose, and a dinitrodiammine platinum nitrate solution having a platinum concentration of 50 g / liter were added to pure water to prepare a liquid phase reaction system. The concentration of each component was carbon black: 2 g / liter, ethanol: 200 ml / liter, fructose: 0.1M, platinum: 0.02M.
次に、前記反応系を、マグネチックスターラを用いて、５００ｒｐｍの回転数でかく拌しながら、還流下、約９０℃で６時間、反応させることにより、液相中に分散した担体粒子の表面に、還元された白金を、微粒子状に析出させて、担持させることで、白金触媒を製造した。 Next, the reaction system is reacted at about 90 ° C. for 6 hours under reflux while stirring at a rotation speed of 500 rpm using a magnetic stirrer, so that the surface of the carrier particles dispersed in the liquid phase is applied. A platinum catalyst was produced by depositing the reduced platinum into fine particles and supporting them.
〈実施例２〉
カーボンブラック〔ライオン(株)製のケッチェンブラックＥＣＰ−６００ＪＤ、ＢＥＴ比表面積：約１４００ｍ2／ｇ〕を用いたこと以外は、実施例１と同様にして白金触媒を製造した。酸化処理後のカーボンブラックのｐＨは２であった。
<Example 2>
A platinum catalyst was produced in the same manner as in Example 1 except that carbon black (Ketjen Black ECP-600JD manufactured by Lion Corporation, BET specific surface area: about 1400 m 2 / g) was used. The pH of the carbon black after the oxidation treatment was 2.
〈実施例３〉
カーボンブラック〔ライオン(株)製のケッチェンブラックＥＣ、ＢＥＴ比表面積：約８００ｍ2／ｇ〕を、３％過酸化水素水に、前記過酸化水素水１リットルあたり１０ｇの割合で配合し、５０℃で３時間、酸化処理したこと以外は、実施例１と同様にして白金触媒を製造した。酸化処理後のカーボンブラックのｐＨは３であった。
<Example 3>
Carbon black (Ketjen Black EC, manufactured by Lion Corporation, BET specific surface area: about 800 m 2 / g) is mixed with 3% hydrogen peroxide solution at a rate of 10 g per liter of the hydrogen peroxide solution. A platinum catalyst was produced in the same manner as in Example 1 except that the oxidation treatment was carried out at 3 ° C. for 3 hours. The pH of the carbon black after the oxidation treatment was 3.
〈実施例４〉
カーボンブラック〔ライオン(株)製のケッチェンブラックＥＣ、ＢＥＴ比表面積：約８００ｍ2／ｇ〕を、リン酸に、前記リン酸１リットルあたり１０ｇの割合で配合し、５０℃で３時間、酸化処理したこと以外は、実施例１と同様にして白金触媒を製造した。酸化処理後のカーボンブラックのｐＨは２．５であった。
<Example 4>
Carbon black (Ketjen Black EC manufactured by Lion Co., Ltd., BET specific surface area: about 800 m 2 / g) is mixed with phosphoric acid at a rate of 10 g per liter of phosphoric acid and oxidized at 50 ° C. for 3 hours. A platinum catalyst was produced in the same manner as in Example 1 except that the treatment was performed. The pH of the carbon black after the oxidation treatment was 2.5.
〈実施例５〉
カーボンブラック〔ライオン(株)製のケッチェンブラックＥＣ、ＢＥＴ比表面積：約８００ｍ2／ｇ〕を、過酸化炭酸ナトリウムに、前記過酸化炭酸ナトリウム１リットルあたり１０ｇの割合で配合し、５０℃で３時間、酸化処理したこと以外は、実施例１と同様にして白金触媒を製造した。酸化処理後のカーボンブラックのｐＨは３であった。
<Example 5>
Carbon black [Ketjen Black EC, manufactured by Lion Corporation, BET specific surface area: about 800 m 2 / g] is blended with sodium peroxide at a rate of 10 g per liter of sodium peroxide, at 50 ° C. A platinum catalyst was produced in the same manner as in Example 1 except that the oxidation treatment was performed for 3 hours. The pH of the carbon black after the oxidation treatment was 3.
〈実施例６〉
カーボンブラック〔ライオン(株)製のケッチェンブラックＥＣ、ＢＥＴ比表面積：約８００ｍ2／ｇ〕を、濃度９００ｇ／リットルの硝酸水溶液に、前記硝酸水溶液１リットルあたり、１０ｇの割合で配合し、５０℃で３時間、酸化処理した後、ろ別し、アンモニア水に加えて中和処理して、先に説明した測定方法で測定したｐＨを７としたこと以外は、実施例１と同様にして白金触媒を製造した。
<Example 6>
Carbon black (Ketjen Black EC manufactured by Lion Co., Ltd., BET specific surface area: about 800 m 2 / g) was mixed with a nitric acid solution having a concentration of 900 g / liter at a rate of 10 g per liter of the nitric acid solution. After oxidizing at 3 ° C. for 3 hours, filtered, neutralized in addition to aqueous ammonia, and the same as in Example 1 except that the pH measured by the measuring method described above was set to 7. A platinum catalyst was produced.
〈比較例１〉
酸化処理していないカーボンブラック〔ライオン(株)製のケッチェンブラックＥＣ、ＢＥＴ比表面積：約８００ｍ2／ｇ〕を使用したこと以外は、実施例１と同様にして白金触媒を製造した。カーボンブラックのｐＨは９であった。
<Comparative example 1>
A platinum catalyst was produced in the same manner as in Example 1, except that carbon black that had not been oxidized (Ketjen Black EC manufactured by Lion Corporation, BET specific surface area: about 800 m 2 / g) was used. The pH of carbon black was 9.
〈比較例２〉
酸化処理していないカーボンブラック〔ライオン(株)製のケッチェンブラックＥＣＰ−６００ＪＤ、ＢＥＴ比表面積：約１４００ｍ2／ｇ〕を使用したこと以外は、実施例１と同様にして白金触媒を製造した。カーボンブラックのｐＨは９であった。
<Comparative example 2>
A platinum catalyst was produced in the same manner as in Example 1 except that carbon black that had not been oxidized (Ketjen Black ECP-600JD manufactured by Lion Corporation, BET specific surface area: about 1400 m 2 / g) was used. . The pH of carbon black was 9.
〈比較例３〉
酸化処理していないカーボンブラック〔キャボット社製のＶｕｌｃａｎ ＸＣ−７２Ｒ、ＢＥＴ比表面積：約２２０ｍ2／ｇ〕を使用したこと以外は、実施例１と同様にして白金触媒を製造した。カーボンブラックのｐＨは９であった。
<Comparative Example 3>
A platinum catalyst was produced in the same manner as in Example 1 except that carbon black not subjected to oxidation treatment [Vulcan XC-72R manufactured by Cabot, BET specific surface area: about 220 m 2 / g] was used. The pH of carbon black was 9.
〈比較例４〉
ＢＥＴ比表面積が約２２００ｍ2／ｇの活性炭を使用したこと以外は、実施例１と同様にして白金触媒を製造した。活性炭のｐＨは９であった。
<Comparative example 4>
A platinum catalyst was produced in the same manner as in Example 1 except that activated carbon having a BET specific surface area of about 2200 m 2 / g was used. The pH of the activated carbon was 9.
〈比較例５〉
酸性カーボンブラック〔三菱化学(株)製の＃２３５０、ＢＥＴ比表面積：約３２０ｍ2／ｇ、ｐＨ２．５〕を使用したこと以外は、実施例１と同様にして白金触媒を製造した。
<Comparative Example 5>
A platinum catalyst was produced in the same manner as in Example 1 except that acidic carbon black (# 2350, BET specific surface area: about 320 m 2 / g, pH 2.5, manufactured by Mitsubishi Chemical Corporation) was used.
〈白金微粒子の担持量および粒径測定〉
白金微粒子の担持量および粒径は、下記の手順で求めた。すなわち、ＣＯ吸着法により、製造した白金触媒を前処理温度１２０℃、吸着温度５０℃の条件で処理してＣＯ吸着量を求め、その結果から、カーボンブラックの表面に担持された白金微粒子の表面積を算出した。また、製造した白金触媒における白金微粒子の担持量を、ＩＣＰ（Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌａｚｍａ、誘導結合プラズマ）分光分析法によって測定した。また、前記担持量と、先の表面積とから、カーボンブラックの表面に担持された白金微粒子の粒径を算出した。結果を表１に示す。
<Platinum fine particle loading and particle size measurement>
The supported amount and particle size of the platinum fine particles were obtained by the following procedure. That is, by the CO adsorption method, the produced platinum catalyst is treated under conditions of a pretreatment temperature of 120 ° C. and an adsorption temperature of 50 ° C. to determine the amount of CO adsorption. From the result, the surface area of the platinum fine particles supported on the surface of carbon black Was calculated. Further, the amount of platinum fine particles supported on the produced platinum catalyst was measured by ICP (Inductively Coupled Plasma) spectroscopy. Further, the particle size of the platinum fine particles supported on the surface of the carbon black was calculated from the supported amount and the surface area. The results are shown in Table 1.
表より、酸化処理したカーボンブラックを用いた実施例１〜６は、いずれも、比較例１〜５に比べて、白金微粒子の担持量を減少させることなしに、その粒径を、同等、またはそれ以上に小さくできることが判った。 From the table, Examples 1 to 6 using carbon black subjected to oxidation treatment all have the same particle size, without reducing the amount of platinum fine particles supported, compared to Comparative Examples 1 to 5, or It turned out that it can be made smaller than that.
Claims (8)
The carbon black is dispersed and oxidized in a treatment liquid containing at least one peroxide selected from the group consisting of hydrogen peroxide, peroxide carbonate, sulfuric acid peroxide, and phosphoric acid peroxide. The manufacturing method of the metal catalyst of description.
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|---|---|---|---|---|
| JP2008123810A (en) * | 2006-11-10 | 2008-05-29 | Hitachi Ltd | Electrode catalyst for fuel cell, its manufacturing method, and fuel cell |
| WO2009008389A1 (en) * | 2007-07-06 | 2009-01-15 | M.Technique Co., Ltd. | Method for production of metal-supporting carbon, method for production of crystal composed of fullerene molecule and fullerene nanowhisker/nanofiber nanotube, and apparatus for production of fullerene molecule and fullerene nanowhisker/nanofiber nanotube |
| CN112264017A (en) * | 2020-10-14 | 2021-01-26 | 扬州大学 | Transition metal iron-nickel nano powder catalyst modified by surface iron-nickel defect layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008123810A (en) * | 2006-11-10 | 2008-05-29 | Hitachi Ltd | Electrode catalyst for fuel cell, its manufacturing method, and fuel cell |
| WO2009008389A1 (en) * | 2007-07-06 | 2009-01-15 | M.Technique Co., Ltd. | Method for production of metal-supporting carbon, method for production of crystal composed of fullerene molecule and fullerene nanowhisker/nanofiber nanotube, and apparatus for production of fullerene molecule and fullerene nanowhisker/nanofiber nanotube |
| JPWO2009008389A1 (en) * | 2007-07-06 | 2010-09-09 | エム・テクニック株式会社 | Method for producing metal-supported carbon |
| US8974986B2 (en) | 2007-07-06 | 2015-03-10 | M. Technique Co., Ltd. | Method for producing metal-supported carbon, method for producing crystals consisting of fullerene molecules and fullerene nanowhisker/nanofiber nanotubes, and apparatus for producing the same |
| CN102847538B (en) * | 2007-07-06 | 2016-07-06 | M技术株式会社 | The manufacture method of the crystallization formed by fullerenes and manufacture device |
| EP3284540A1 (en) | 2007-07-06 | 2018-02-21 | M. Technique Co., Ltd. | Method for producing crystals consisting of fullerene molecules and fullerene nanowhisker/nanofiber nanotubes, and apparatus for producing the same |
| US9917308B2 (en) | 2007-07-06 | 2018-03-13 | M. Technique Co., Ltd. | Method for producing crystals comprising fullerene molecules and fullerene nanowhisker/nanofiber nanotubes |
| CN112264017A (en) * | 2020-10-14 | 2021-01-26 | 扬州大学 | Transition metal iron-nickel nano powder catalyst modified by surface iron-nickel defect layer |
| CN112264017B (en) * | 2020-10-14 | 2023-08-08 | 扬州大学 | Transition metal iron-nickel nano powder catalyst with surface modified by iron-nickel defect layer |
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