JP2007123108A - Platinum colloid carried carbon and its manufacturing method - Google Patents
Platinum colloid carried carbon and its manufacturing method Download PDFInfo
- Publication number
- JP2007123108A JP2007123108A JP2005314933A JP2005314933A JP2007123108A JP 2007123108 A JP2007123108 A JP 2007123108A JP 2005314933 A JP2005314933 A JP 2005314933A JP 2005314933 A JP2005314933 A JP 2005314933A JP 2007123108 A JP2007123108 A JP 2007123108A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- platinum
- platinum colloid
- colloid
- ions
- 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.)
- Granted
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 460
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 220
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 186
- 239000000084 colloidal system Substances 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 77
- 150000002500 ions Chemical class 0.000 claims abstract description 75
- 239000000446 fuel Substances 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 40
- 239000010931 gold Substances 0.000 claims description 38
- 239000000725 suspension Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 15
- 230000008093 supporting effect Effects 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- 150000002344 gold compounds Chemical class 0.000 claims description 11
- 150000003058 platinum compounds Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229940045985 antineoplastic platinum compound Drugs 0.000 claims description 3
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 claims description 3
- VMDSWYDTKFSTQH-UHFFFAOYSA-N sodium;gold(1+);dicyanide Chemical compound [Na+].[Au+].N#[C-].N#[C-] VMDSWYDTKFSTQH-UHFFFAOYSA-N 0.000 claims description 3
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 claims description 3
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 claims description 2
- KYHBHUGWTQLYOZ-UHFFFAOYSA-N [N+](=O)([O-])[Pt]([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-].[K] Chemical compound [N+](=O)([O-])[Pt]([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-].[K] KYHBHUGWTQLYOZ-UHFFFAOYSA-N 0.000 claims description 2
- XKUTVNLXHINPAP-UHFFFAOYSA-N azane platinum Chemical compound N.[Pt] XKUTVNLXHINPAP-UHFFFAOYSA-N 0.000 claims description 2
- ACDVNLCTXBOVNW-UHFFFAOYSA-L platinum(2+);dichloride;hydrate Chemical compound O.Cl[Pt]Cl ACDVNLCTXBOVNW-UHFFFAOYSA-L 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 150000003057 platinum Chemical class 0.000 description 20
- 239000006229 carbon black Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 9
- 239000011164 primary particle Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- -1 hydrogen ions Chemical class 0.000 description 8
- 239000005518 polymer electrolyte Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000009841 combustion method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910002845 Pt–Ni Inorganic materials 0.000 description 2
- 229910002848 Pt–Ru Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 238000010248 power generation Methods 0.000 description 2
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- 239000002002 slurry Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
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- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 description 1
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- 229910002839 Pt-Mo Inorganic materials 0.000 description 1
- 229910018883 Pt—Cu Inorganic materials 0.000 description 1
- RKSYBNRHLACADA-UHFFFAOYSA-M [K].Cl[Pt] Chemical compound [K].Cl[Pt] RKSYBNRHLACADA-UHFFFAOYSA-M 0.000 description 1
- ZSWXBIJLMOBGSP-UHFFFAOYSA-M [Na].Cl[Pt] Chemical compound [Na].Cl[Pt] ZSWXBIJLMOBGSP-UHFFFAOYSA-M 0.000 description 1
- ZGIMJFKTMVSZAG-UHFFFAOYSA-J [Na][Pt](Cl)(Cl)(Cl)Cl Chemical compound [Na][Pt](Cl)(Cl)(Cl)Cl ZGIMJFKTMVSZAG-UHFFFAOYSA-J 0.000 description 1
- OKPZIQOBDZDBRW-UHFFFAOYSA-N [Pt].[K] Chemical compound [Pt].[K] OKPZIQOBDZDBRW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- DJXYWDRBAAVVSG-UHFFFAOYSA-J potassium;tetrachloroplatinum Chemical compound [K].Cl[Pt](Cl)(Cl)Cl DJXYWDRBAAVVSG-UHFFFAOYSA-J 0.000 description 1
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- 239000012279 sodium borohydride Substances 0.000 description 1
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- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Fuel Cell (AREA)
- Catalysts (AREA)
- Powder Metallurgy (AREA)
- Inert Electrodes (AREA)
Abstract
Description
本発明は、白金コロイドが担持されたカーボンの製造方法およびその製造方法により得られる新規の白金コロイド担持カーボンに関する。 The present invention relates to a method for producing carbon carrying platinum colloid and a novel platinum colloid carrying carbon obtained by the production method.
近年、エネルギー、環境問題に関連して、クリーンな水素をエネルギー源とする、高効率かつ無公害でＣＯ2等の温暖化ガスを発生しない発電システムとして燃料電池が注目さ
れている。この燃料電池について、家庭や事業所などの固定設備、自動車や携帯電話のバッテリーなどの移動設備などでの使用を目的に本格的な開発研究が行われている。
In recent years, in relation to energy and environmental problems, fuel cells have attracted attention as power generation systems that use clean hydrogen as an energy source and do not generate greenhouse gases such as CO 2 with high efficiency and pollution. This fuel cell has been fully developed and researched for use in fixed equipment such as homes and offices, and mobile equipment such as batteries for automobiles and mobile phones.
燃料電池は、電気化学反応を利用して、使用する燃料の有する化学エネルギーを電気エネルギーに変換する装置であり、この電気化学反応を有効に利用するために触媒が必要とされる。燃料電池は使用する電解質によって分類され、アルカリ電解質型、固体高分子電解質型、リン酸型、溶融炭酸塩型、固体電解質型に分けられる。これらのうち、固体高分子電解質型およびリン酸型は電荷移動体がプロトンであり、プロトン型燃料電池ともいわれる。 A fuel cell is a device that converts the chemical energy of a fuel to be used into electric energy by using an electrochemical reaction, and a catalyst is required to effectively use this electrochemical reaction. Fuel cells are classified according to the electrolyte used, and are classified into alkaline electrolyte type, solid polymer electrolyte type, phosphoric acid type, molten carbonate type, and solid electrolyte type. Among these, the solid polymer electrolyte type and the phosphoric acid type have proton charge transfer bodies and are also called proton type fuel cells.
このような燃料電池に用いる燃料としては、天然ガス、ＬＰガス、都市ガス、アルコール、ガソリン、灯油、軽油などの炭化水素系燃料が挙げられる。
このような燃料電池の発電メカニズムは以下の通りである。上記炭化水素系燃料が、まず、水蒸気改質や部分酸化などの反応により、水素ガスおよびＣＯガスに変換され、ＣＯガスを除去して水素ガスを得る。この水素ガスは、アノードに供給され、アノードの金属触媒によってプロトン（水素イオン）と電子に解離される。この電子は回路を通じて仕事をしながらカソードに流れ、プロトン（水素イオン）は電解質膜を拡散してカソードに流れ、カソードにてこの電子と水素イオンとカソードに供給される酸素とから水が形成されて電解質膜に拡散する。すなわち、酸素と燃料に由来する水素とを供給して水を生成する過程で電流を取り出すメカニズムである。
Examples of the fuel used in such a fuel cell include hydrocarbon fuels such as natural gas, LP gas, city gas, alcohol, gasoline, kerosene, and light oil.
The power generation mechanism of such a fuel cell is as follows. The hydrocarbon fuel is first converted into hydrogen gas and CO gas by a reaction such as steam reforming or partial oxidation, and the CO gas is removed to obtain hydrogen gas. This hydrogen gas is supplied to the anode and dissociated into protons (hydrogen ions) and electrons by the metal catalyst of the anode. The electrons flow to the cathode while working through the circuit, and protons (hydrogen ions) diffuse through the electrolyte membrane and flow to the cathode. At the cathode, water is formed from the electrons, hydrogen ions, and oxygen supplied to the cathode. Diffuses into the electrolyte membrane. That is, it is a mechanism for taking out an electric current in the process of supplying water with oxygen and hydrogen derived from fuel.
このような燃料電池に用いられるカソード電極としては、Ｐｔ、Ｐｔ−Ｎｉ、Ｐｔ−Ｃｏ、Ｐｔ−Ｃｕ等の金属成分からなる触媒層（薄膜）をスパッタ法により多孔質支持層上に形成したものが検討され、アノード電極としては、耐ＣＯ被毒性の高いＰｔ−Ｒｕ、Ｐｔ−Ｆｅ、Ｐｔ−Ｎｉ、Ｐｔ−Ｃｏ、Ｐｔ−Ｍｏ等の金属成分からなる触媒層（薄膜）をスパッタ法により多孔質支持層上に形成したものが検討されている。 As a cathode electrode used in such a fuel cell, a catalyst layer (thin film) made of a metal component such as Pt, Pt—Ni, Pt—Co, or Pt—Cu is formed on a porous support layer by sputtering. As the anode electrode, a catalyst layer (thin film) made of a metal component such as Pt—Ru, Pt—Fe, Pt—Ni, Pt—Co, and Pt—Mo, which has high CO poisoning resistance, is porous by sputtering. Those formed on a quality support layer are being studied.
しかしながら、スパッタ法で形成した触媒層は、金属微粒子の粒子径が不均一かつ大きくなりやすく、このため金属微粒子の表面積が低下するために充分な活性が得られないことがある。さらに、多孔質支持層表面に均一に金属微粒子層からなる薄膜を形成することは困難である。また、スパッタ法に用いる装置は高価であり、経済性に難点がある。 However, in the catalyst layer formed by the sputtering method, the particle diameter of the metal fine particles tends to be uneven and large, and therefore the surface area of the metal fine particles is reduced, so that sufficient activity may not be obtained. Furthermore, it is difficult to form a thin film consisting of a metal fine particle layer uniformly on the surface of the porous support layer. Moreover, the apparatus used for the sputtering method is expensive, and there is a difficulty in economy.
また、カーボンペーパー、カーボンクロス等のカーボン多孔体に白金微粒子等を担持した電極も知られている。この電極は、たとえば、カーボンペーパーに金属塩あるいは金属水酸化物を固着させ、還元雰囲気下で加熱処理することによって得ることができる。しかしながら、この方法では加熱処理する際に金属微粒子が凝集したり、粒子成長して、粒子径が不均一になるとともに、粒子径を所望の大きさに調整することが困難であり、加えて経時的に活性が低下する問題があった。 In addition, an electrode in which platinum fine particles or the like are supported on a carbon porous body such as carbon paper or carbon cloth is also known. This electrode can be obtained, for example, by fixing a metal salt or metal hydroxide to carbon paper and heat-treating in a reducing atmosphere. However, in this method, the metal fine particles agglomerate or grow during the heat treatment, the particle size becomes non-uniform, and it is difficult to adjust the particle size to a desired size. There was a problem that the activity decreased.
一方、白金コロイドを炭素粒子に担持させる方法としては、白金錯体の水溶液に蟻酸等
の還元剤を混合して白金コロイド粒子を生成させ、そこに炭素粒子を加えて炭素粒子表面に白金コロイド粒子を付着させる方法や、白金錯体の水浴液に炭素粒子を加えてから還元剤を添加し、炭素粒子表面に白金コロイド粒子を生成させる沈殿法が知られていた。上記担体である炭素粒子の粒径は、カーボンブラックで０．１〜０．０１μｍ、大きな粒子である粉末活性炭でも１００μｍ以下である。また、表面に付着する白金コロイド粒子の粒径は、大きくても０、０２μｍ、製造法によっては０．００３〜０．００５μｍである。
On the other hand, as a method for supporting platinum colloid on carbon particles, a reducing agent such as formic acid is mixed with an aqueous solution of a platinum complex to form platinum colloid particles, and carbon particles are added thereto to form platinum colloid particles on the carbon particle surface. There have been known a deposition method and a precipitation method in which carbon particles are added to a platinum complex water bath and then a reducing agent is added to produce platinum colloidal particles on the surface of the carbon particles. The particle size of carbon particles as the carrier is 0.1 to 0.01 μm for carbon black, and 100 μm or less for powdered activated carbon which is a large particle. Further, the particle size of the platinum colloid particles adhering to the surface is at most 0,02 μm, and depending on the production method, it is 0.003-0.005 μm.
白金コロイド粒子を担持した炭素粒子は、ガス拡散が行なわれる電極上で電解質の液体リン酸に包まれ、水素ガスまたは酸素含有ガスと接触している。そして、１００℃以上の燃料電池作動条件下では、長時間の使用によってその性能が低下する。これは、熱的運動によって白金コロイド粒子が炭素粒子表面上を移動し、コロイド粒子同士の接触が起って凝集し、遂には大きな一つの粒子へ粗大化し、触媒として有効な表面積が減少するためと考えられている。このコロイド粒子同士の接触、凝集を防ぐ方法として、炭素粒子表面に凹凸をつけて白金コロイド粒子を担持させる方法が提案された。例えば、炭素粒子に金属酸化物の触媒を担持し、次に加熱することによって炭素粒子表面の触媒近傍を酸化せしめて凹部を形成し、その後、この金属酸化物触媒を除いてから白金コロイド粒子を表面に生成付着させる方法が挙げられる。しかし、この方法では操作条件が複雑であるばかりでなく、加熱条件のコントロールが困難で、炭素粒子自身が発火してしまうことがあった。 The carbon particles carrying the colloidal platinum particles are encapsulated in the liquid phosphoric acid of the electrolyte on the electrode where gas diffusion is performed, and are in contact with hydrogen gas or oxygen-containing gas. And under the fuel cell operating condition of 100 ° C. or higher, the performance is deteriorated by long-time use. This is because the colloidal platinum particles move on the surface of the carbon particles due to thermal motion, and the colloidal particles come into contact with each other and agglomerate, eventually coarsening into one large particle, reducing the effective surface area as a catalyst. It is believed that. As a method of preventing contact and aggregation between the colloidal particles, a method of supporting platinum colloidal particles by providing irregularities on the carbon particle surface has been proposed. For example, a metal oxide catalyst is supported on carbon particles, and then heated to oxidize the vicinity of the catalyst on the surface of the carbon particles to form a recess, and after removing the metal oxide catalyst, the platinum colloid particles are removed. A method of generating and adhering to the surface is mentioned. However, in this method, not only the operating conditions are complicated, but also the heating conditions are difficult to control, and the carbon particles themselves may ignite.
カーボン担体に白金コロイドを担持させる技術としては、例えば、特許文献１には、炭素粒子表面に白金コロイド粒子を担持させ、次に懸濁状態または粉末浮遊状態でオゾンと接触させることを特徴とする燃料電池用触媒の製造方法が提案されている。この製造方法において、炭素粒子表面に白金コロイド粒子を担持させる方法として、白金錯体の水浴液に炭素粒子を加えた後、還元剤を添加して炭素粒子表面に白金コロイド粒子を生成させる沈殿法が採用されている。 As a technique for supporting platinum colloid on a carbon carrier, for example, Patent Document 1 is characterized in that platinum colloid particles are supported on the surface of carbon particles, and then contacted with ozone in a suspended state or a suspended powder state. A method for producing a fuel cell catalyst has been proposed. In this production method, as a method of supporting platinum colloid particles on the carbon particle surface, there is a precipitation method in which after adding carbon particles to a platinum complex water bath solution, a reducing agent is added to generate platinum colloid particles on the carbon particle surface. It has been adopted.
特許文献２には、第１工程、第２工程、第３工程、第４工程を有し、第１工程は親水処理をしたカーボン触媒担体を水に分散させて、白金塩を添加し加温する工程であり、第２工程は、前記工程で得られた系のｐＨをアルカリ性にする工程であり、第３工程は、アルカリ性にされた系に白金コロイド保護剤を添加する工程であり、第４工程は白金コロイド保護剤の加えられた系を粉砕機で混合しながらアルデヒド基を有する還元剤を徐々に添加する工程である、ことを特徴とする白金担持触媒の製造方法が提案されている。この製造方法は、系を混合しながら還元剤を添加すると、還元剤がすみやかに系全体に均一に混合され、粉砕機により担体が分散し、吸着サイトの数が増大する点に特徴がある。 Patent Document 2 has a first step, a second step, a third step, and a fourth step. In the first step, a hydrophilically treated carbon catalyst carrier is dispersed in water, a platinum salt is added, and heating is performed. The second step is a step of making the pH of the system obtained in the step alkaline, and the third step is a step of adding a platinum colloid protective agent to the alkalinized system. There is proposed a method for producing a platinum-supported catalyst characterized in that four steps are steps in which a reducing agent having an aldehyde group is gradually added while mixing a system in which a platinum colloid protective agent is added with a pulverizer. . This production method is characterized in that when a reducing agent is added while mixing the system, the reducing agent is promptly and uniformly mixed throughout the system, the carrier is dispersed by a pulverizer, and the number of adsorption sites is increased.
特許文献３には、白金又は白金合金がカーボン担体に担持された電極触媒の製造方法であって、白金錯イオンを含む溶液又は白金と合金化させる金属のイオン若しくは錯イオンと白金錯イオンとを含む溶液から、−ＳＯ3Ｙ又は−ＰＯ3Ｙ2を有する有機化合物（Ｙは
水素原子又はアルカリ金属原子を示す。）の存在下で白金コロイド粒子又は白金合金コロイド粒子のゾルを生成した後、該ゾルをカーボン担体と混合し、乾燥して溶媒を除去することを特徴とする固体高分子型燃料電池用電極触媒の製造方法が提案されており、この製造方法により得られる電極触媒は、白金又は白金合金触媒の分散性が高く、触媒、電解質及び燃料ガスの存在する三相界面が拡大されているので、初期の活性に優れるとともに長期にわたって安定して高い出力を得られる固体高分子電解質型燃料電池を提供できる旨の記載がある。この製造方法も基本的には、前記の沈殿法を利用したものである。
Patent Document 3 discloses a method for producing an electrode catalyst in which platinum or a platinum alloy is supported on a carbon carrier, and includes a solution containing platinum complex ions or a metal ion or complex ion alloyed with platinum and a platinum complex ion. from a solution comprising, after generating a -SO 3 Y or -PO 3 organic compound having Y 2 (Y is. represents a hydrogen atom or an alkali metal atom) sol colloidal platinum particles or platinum alloy colloid particles in the presence of, A method for producing an electrode catalyst for a polymer electrolyte fuel cell, which comprises mixing the sol with a carbon support and drying to remove the solvent, has been proposed. Alternatively, the dispersibility of the platinum alloy catalyst is high, and the three-phase interface in which the catalyst, electrolyte, and fuel gas are present has been expanded. It is described to the effect that can provide a solid polymer electrolyte fuel cell obtained by. This production method is also basically based on the precipitation method described above.
特許文献４には、固体高分子電解質膜の両側に電極を配してなる単位セル及びこの単位セルの両側をセパレータで挟持した固体高分子型燃料電池に使用される電極原料を製造する方法において、溶媒の中に貴金属コロイドを分散させる工程と、前記溶媒の中にイオン交換高分子を添加する工程と、前記溶媒の中にカーボンブラックを添加し、カーボンブラ
ックに貴金属を担持させる工程と、前記溶媒の中に還元剤を添加し、イオン交換高分子が付着した貴金属担持カーボンブラックを形成する工程とを具備することを特徴とする固体高分子型燃料電池用電極材料の製造方法が提案されている。この製造方法によると、貴金属の表面全体にイオン交換高分子が担持されたカーボンブラックが得られ、貴金属とイオン交換高分子との接触面積が従来と比べて大きくなり、これを反応層として燃料電池に用いた場合、貴金属とイオン交換高分子と酸素（又は水素）との３相界面増加による電池性能が向上する旨の記載がある。
Patent Document 4 discloses a method of manufacturing a unit cell in which electrodes are arranged on both sides of a solid polymer electrolyte membrane and an electrode material used in a polymer electrolyte fuel cell in which both sides of the unit cell are sandwiched by separators. A step of dispersing a noble metal colloid in a solvent, a step of adding an ion exchange polymer in the solvent, a step of adding carbon black in the solvent and supporting the noble metal on the carbon black, A method for producing an electrode material for a polymer electrolyte fuel cell comprising a step of adding a reducing agent in a solvent to form a noble metal-supported carbon black to which an ion exchange polymer is adhered. Yes. According to this manufacturing method, carbon black having an ion exchange polymer supported on the entire surface of the noble metal is obtained, and the contact area between the noble metal and the ion exchange polymer is increased compared to the conventional one, and this is used as a reaction layer for the fuel cell. Is used, the battery performance is improved by increasing the three-phase interface between the noble metal, the ion exchange polymer and oxygen (or hydrogen).
特許文献５には、ＰｔX：ＭｏY（但し、それぞれＸは０．５〜０．９そしてＹは０．５〜０．１である）の原子組成を有し、ガス拡散電極に用いるためのカーボンブラックに支持された触媒を調製する方法であって、最初に白金コロイド分散液をカーボンブラックに吸収させ、次いでモリブデンコロイド分散液をカーボンブラックに吸収させ、そして最後に上記２つの元素を還元及び／又は不活性雰囲気中において３００℃を越える温度で合金化することを含む製造方法が提案されている。 Patent Document 5 discloses an atomic composition of Pt X : Mo Y (where X is 0.5 to 0.9 and Y is 0.5 to 0.1, respectively), and is used for a gas diffusion electrode. Of a catalyst supported on carbon black, first the platinum colloidal dispersion is absorbed into carbon black, then the molybdenum colloidal dispersion is absorbed into carbon black, and finally the two elements are reduced. And / or a production method has been proposed which comprises alloying at a temperature above 300 ° C. in an inert atmosphere.
特許文献６には、導電性炭素材料並びにこれに担持された白金および金を含む粒子からなり、前記粒子の内部が金に富み、粒子の外表面が白金に富むことを特徴とする燃料電池用電極触媒とその製造方法として、白金錯体および金錯体の混合溶液を還元してコロイドを調製する工程、および前記コロイドを導電性炭素材料に担持する工程を有する燃料電池用電極触媒の製造方法が提案されている。この触媒は、反応に関与しない白金を低減させるため、白金と金を含む粒子が導電性炭素材料に担持されており、前記粒子の内部が金に富み、前記粒子の外表面が白金に富んでいる点に特徴があり、白金錯体および金錯体の混合溶液を還元してコロイドを調製し、そのコロイドを導電性炭素材料に担持させることにより製造される点に特徴がある。 Patent Document 6 includes a conductive carbon material and particles containing platinum and gold supported thereon, the inside of the particles being rich in gold, and the outer surface of the particles being rich in platinum. A method for producing an electrode catalyst for a fuel cell having a step of preparing a colloid by reducing a mixed solution of a platinum complex and a gold complex, and a step of supporting the colloid on a conductive carbon material is proposed as an electrode catalyst and a production method thereof. Has been. In this catalyst, in order to reduce platinum that does not participate in the reaction, particles containing platinum and gold are supported on a conductive carbon material, the inside of the particles is rich in gold, and the outer surface of the particles is rich in platinum. It is characterized in that it is produced by reducing a mixed solution of a platinum complex and a gold complex to prepare a colloid, and supporting the colloid on a conductive carbon material.
特許文献７には、陽イオン交換性高分子により安定化された白金コロイドとカーボンとを含んでなるスラリー状の触媒を製造するステップと、該スラリー状の触媒を湿式塗布して触媒反応層を形成するステップとを含む固体高分子型燃料電池用電極の製造方法が提案されている。この製造方法によれば、微粒子化した白金を高度に分散化し、かつ当該白金と陽イオン交換性高分子とが接触しているスラリー状の触媒を湿式塗布して触媒反応層を形成するため、プロトン導電性が確保されて、三相界面が拡大され、触媒利用の効率化を達成することができる旨の記載がある。また、この製造方法により、同じ白金量でより大きな出力を得ることができるため、高価な白金使用量を削減し、コストダウンが可能となり、更に、膜−電極接合体の製造工程を簡略化でき、経済的にも大きな効果を有する旨の記載がある。
本発明の目的は、従来のカーボン担体に白金コロイドを担持させる白金コロイド担持カーボンの製造方法に比べて簡易な操作により、担体上における白金コロイドの分散性が同等ないしはそれ以上に優れた白金コロイド担持カーボンを製造する方法およびこの方法により得られた白金コロイド担持カーボンを提供することにある。 An object of the present invention is to support a platinum colloid carrying the same or better dispersibility of the platinum colloid on the carrier by a simple operation as compared with a conventional method for producing a platinum colloid-carrying carbon in which a platinum colloid is carried on a carbon carrier. The object is to provide a method for producing carbon and platinum colloid-carrying carbon obtained by this method.
すなわち、本発明に係る白金コロイド担持カーボンの製造方法は、ＰｔイオンまたはＡｕイオンの存在下、平均粒子径１〜１００ｎｍの白金コロイドをカーボン担体に担持させることを特徴とする。 That is, the method for producing platinum colloid-supporting carbon according to the present invention is characterized in that platinum colloid having an average particle diameter of 1 to 100 nm is supported on a carbon carrier in the presence of Pt ions or Au ions.
本発明の白金コロイド担持カーボンの製造方法としては、カーボンの懸濁液に、ＰｔイオンまたはＡｕイオンをカーボン固形分１００重量部に対して金属元素換算で３〜１００重量部含有させ、このイオン含有懸濁液に、１５〜４０℃で、平均粒子径１〜１８０ｎｍの白金コロイドをカーボン固形分１００重量部に対して金属元素換算で１０〜１００重量部添加して混合することが好ましい。 As a method for producing platinum colloid-carrying carbon of the present invention, 3 to 100 parts by weight of Pt ions or Au ions in terms of metal elements are contained in a carbon suspension with respect to 100 parts by weight of carbon solid content. It is preferable to add and mix 10 to 100 parts by weight of a platinum colloid having an average particle diameter of 1 to 180 nm with respect to 100 parts by weight of carbon solids in terms of metal element at 15 to 40 ° C.
前記Ｐｔイオンは、塩化白金酸、塩化白金（IV）酸カリウム、塩化白金（IV）酸ナトリウム、テトラニトロ白金（II）カリウム、ヘキサヒドロキソ白金（IV）酸ナトリウム水和物、ジニトロジアンミン白金硝酸、ジニトロジアンミン白金アンモニアおよびテトラアンミンジクロロ白金水和物からなる群から選ばれる１種または２種以上の白金化合物、あるいは、前記Ａｕイオンが、塩化金酸、亜硫酸金ナトリウム、シアン化金カリウムおよびシアン化金ナトリウムからなる群から選ばれる１種または２種以上の金化合物から得られることが好ましい。 The Pt ions include chloroplatinic acid, potassium chloroplatinum (IV), sodium chloroplatinum (IV), potassium tetranitroplatinum (II), sodium hexahydroxoplatinate (IV), dinitrodiammine platinum nitrate, dinitro One or more platinum compounds selected from the group consisting of diammine platinum ammonia and tetraammine dichloroplatinum hydrate, or the Au ion is chloroauric acid, sodium gold sulfite, potassium gold cyanide and sodium gold cyanide. It is preferably obtained from one or more gold compounds selected from the group consisting of:
本発明に係る白金コロイド担持カーボンは、上記製造方法により製造されたものであることを特徴とする。
また、本発明に係る白金コロイド担持カーボンは、比表面積が１００〜１０００ｍ2／
ｇのカーボン担体に白金コロイドを担持させた白金コロイド担持カーボンであって、前記カーボン担体の比表面積に対する前記白金コロイド担持カーボンの比表面積の低下率が４８〜８０％であり、かつ、前記カーボン担体の平均細孔容積に対する前記白金コロイド担持カーボンの平均細孔容積の低下率が３５〜７０％であることを特徴とする。また、前記白金コロイド担持カーボンは、白金を２０〜５０重量％含有することが好ましい。このような白金コロイド担持カーボンは、上記製造方法により製造することができる。
The platinum colloid-supporting carbon according to the present invention is produced by the above production method.
The platinum colloid-supporting carbon according to the present invention has a specific surface area of 100 to 1000 m 2 /
g of a carbon support having a platinum colloid supported on a carbon support of g, a reduction rate of the specific surface area of the platinum colloid support carbon with respect to the specific surface area of the carbon support is 48 to 80%, and the carbon support The decrease rate of the average pore volume of the platinum colloid-supported carbon with respect to the average pore volume is 35 to 70%. The platinum colloid-supporting carbon preferably contains 20 to 50% by weight of platinum. Such platinum colloid-carrying carbon can be produced by the above production method.
本発明に係る燃料電池用触媒は、上記白金コロイド担持カーボンからなることを特徴とする。
また、本発明に係る燃料電池は、カソード電極及びアノード電極のうち少なくとも一方の電極が、上記燃料電池用触媒を含むことを特徴とする。
The fuel cell catalyst according to the present invention is characterized by comprising the platinum colloid-supported carbon.
The fuel cell according to the present invention is characterized in that at least one of the cathode electrode and the anode electrode includes the fuel cell catalyst.
本発明の白金コロイド担持カーボンは、従来の白金コロイド担持カーボンに比べて、担持された白金コロイドの分散状態が優れており、使用した白金コロイドはカーボン担体上で極めて有効に触媒機能を発揮することができる。また、本発明の製造方法によれば、このような白金コロイドが高分散した状態でカーボン担体に担持されている白金コロイド担持カーボンを簡易な操作により得ることができる。この白金コロイド担持カーボンは、例えば、燃料電池用の電極触媒用の材料として極めて有用である。 The platinum colloid-supported carbon of the present invention is superior in the dispersion state of the supported platinum colloid compared to the conventional platinum colloid-supported carbon, and the platinum colloid used exhibits a catalytic function very effectively on the carbon support. Can do. Further, according to the production method of the present invention, platinum colloid-supporting carbon supported on a carbon carrier in a state where such a platinum colloid is highly dispersed can be obtained by a simple operation. This platinum colloid-carrying carbon is extremely useful as a material for an electrode catalyst for a fuel cell, for example.
以下、本発明の白金コロイド担持カーボンの製造方法について詳細に説明する。
本発明の白金コロイド担持カーボンは、ＰｔイオンまたはＡｕイオンの存在下、平均粒子径１〜１００ｎｍの白金コロイドをカーボン担体に担持させることにより製造することができる。
Hereinafter, the method for producing the platinum colloid-supporting carbon of the present invention will be described in detail.
The platinum colloid-supporting carbon of the present invention can be produced by supporting a platinum colloid having an average particle diameter of 1 to 100 nm on a carbon carrier in the presence of Pt ions or Au ions.
上記カーボン担体は特に限定されるものではなく、通常吸着剤、触媒、触媒担体等として用いられるカーボンを使用することができる。
また、上記カーボン担体の形状は特に限定されるものではない。カーボン担体の平均粒子径は担持される白金コロイドの平均粒子径と同等またはそれ以上であれば特に限定されないが、たとえば、０．０１〜１０μｍが好ましく、０．０１〜０．１μｍがより好ましい。また、カーボン担体の平均粒子径は白金コロイドの平均粒子径の１０倍以上が好ましい。粒子径が前記範囲のカーボン担体は容易に得ることができ、また、本発明の製造方法により、容易に白金コロイドを表面に均一に担持させることができる。なお、二次粒子径が上記範囲にあれば、カーボン担体は凝集した状態でも使用することができるが、できる限り単分散していることが好ましい。
The carbon carrier is not particularly limited, and carbon that is usually used as an adsorbent, a catalyst, a catalyst carrier and the like can be used.
Further, the shape of the carbon support is not particularly limited. The average particle diameter of the carbon support is not particularly limited as long as it is equal to or larger than the average particle diameter of the supported platinum colloid, but is preferably 0.01 to 10 μm, and more preferably 0.01 to 0.1 μm. The average particle size of the carbon support is preferably 10 times or more the average particle size of the platinum colloid. A carbon support having a particle size in the above range can be easily obtained, and platinum colloid can be easily supported uniformly on the surface by the production method of the present invention. If the secondary particle diameter is in the above range, the carbon support can be used even in an aggregated state, but it is preferable that the carbon support is monodispersed as much as possible.
上記カーボン担体の比表面積は１００〜１０００ｍ2／ｇが好ましく、１８０〜９００
ｍ2／ｇがより好ましい。また、細孔容積は０．１〜１．５ｃｍ3／ｇが好ましく、０．２〜１．２ｃｍ3／ｇがより好ましい。カーボン担体の比表面積および細孔容積が上記範囲
にあると、優れた触媒活性を有する白金コロイド担持カーボンを得ることができる。
The specific surface area of the carbon support is preferably 100 to 1000 m 2 / g, 180 to 900.
m 2 / g is more preferable. Further, the pore volume is preferably 0.1~1.5cm 3 / g, 0.2~1.2cm 3 / g is more preferable. When the specific surface area and pore volume of the carbon support are within the above ranges, platinum colloid-supporting carbon having excellent catalytic activity can be obtained.
上記カーボン担体は、通常、水に懸濁させた状態で使用される。カーボン懸濁液は、上記カーボン担体に、例えば、脱イオン水を加えて、９５℃で１時間煮沸することにより得ることができる。水の使用量は、カーボン担体１００重量部に対して９００〜９９，９００重量部が好ましく、１，９００〜１９，９００重量部がより好ましい。このようにして得られたカーボン懸濁液は、必要に応じて、さらに水で希釈してもよく、あるいはデカンテーションで濃縮してもよい。希釈水としては脱イオン水が好ましい。希釈後の懸濁液のカーボン濃度は、０．１〜１０重量％が好ましく、０．５〜５重量％がより好ましい。 The carbon carrier is usually used in a state suspended in water. The carbon suspension can be obtained, for example, by adding deionized water to the carbon carrier and boiling at 95 ° C. for 1 hour. The amount of water used is preferably 900 to 99,900 parts by weight and more preferably 1,900 to 19,900 parts by weight with respect to 100 parts by weight of the carbon support. The carbon suspension thus obtained may be further diluted with water as necessary, or may be concentrated by decantation. As the dilution water, deionized water is preferred. The carbon concentration of the suspension after dilution is preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight.
次に、上記カーボン懸濁液にＰｔイオンまたはＡｕイオンを含有させる。ＰｔイオンまたはＡｕイオンの含有量はカーボン懸濁液中のカーボン固形分１００重量部に対して金属元素換算で３〜１００重量部が好ましく、５〜８０重量部がより好ましい。ＰｔイオンまたはＡｕイオンの含有量が３重量部未満になると、白金コロイドを添加してもカーボン担体に対する充分な担持効果が得られず、また１００重量部を超えると前記担持効果のさらなる向上が得られず、経済的に好ましくない。 Next, Pt ions or Au ions are contained in the carbon suspension. The content of Pt ions or Au ions is preferably 3 to 100 parts by weight, and more preferably 5 to 80 parts by weight, in terms of metal element, with respect to 100 parts by weight of the carbon solid content in the carbon suspension. When the content of Pt ions or Au ions is less than 3 parts by weight, a sufficient supporting effect on the carbon support cannot be obtained even if platinum colloid is added, and when the content exceeds 100 parts by weight, the above supporting effect is further improved. This is not economically preferable.
上記範囲の量のＰｔイオンまたはＡｕイオンを含有させるためには、金属元素換算で上記範囲の量のＰｔイオンまたはＡｕイオンを含む溶液を上記カーボン懸濁液に添加してもよいし、あるいは、金属元素換算で上記割合のＰｔイオンを形成し得る量の白金化合物または金属元素換算で上記割合のＡｕイオンを形成し得る量の金化合物を上記カーボン懸濁液に添加して懸濁液中でＰｔイオンまたはＡｕイオンを発生させてもよい。 In order to contain Pt ions or Au ions in the above range, a solution containing Pt ions or Au ions in the above range in terms of metal element may be added to the carbon suspension, or An amount of platinum compound capable of forming the above-mentioned proportion of Pt ions in terms of metal element or an amount of gold compound capable of forming the above-mentioned proportion of Au ions in terms of metal element is added to the carbon suspension. Pt ions or Au ions may be generated.
ＰｔイオンまたはＡｕイオンを含む溶液はＰｔイオンを形成し得る白金化合物またはＡｕイオンを形成し得る金化合物を溶媒に溶解することにより調製できる。
上記Ｐｔイオンは、その価数が特に限定されず、Ｐｔ2+、Ｐｔ4+、Ｐｔ6+のいずれでもよい。
A solution containing Pt ions or Au ions can be prepared by dissolving a platinum compound capable of forming Pt ions or a gold compound capable of forming Au ions in a solvent.
The valence of the Pt ion is not particularly limited, and may be any of Pt 2+ , Pt 4+ and Pt 6+ .
上記白金化合物としては、上記カーボン懸濁液中でＰｔイオンを形成するものであれば特に制限されず、例えば、塩化白金酸、塩化白金（IV）酸カリウム、塩化白金（IV）酸ナトリウム、テトラニトロ白金（II）カリウム、ヘキサヒドロキソ白金（IV）酸ナトリウム水和物、ジニトロジアンミン白金硝酸、ジニトロジアンミン白金アンモニアおよびテトラアンミンジクロロ白金水和物が挙げられる。これらの白金化合物は１種単独で、または２種以上を混合して用いることができる。また、上記金化合物としては、上記カーボン懸濁液中でＡｕイオンを形成するものであれば特に制限されず、例えば、亜硫酸金ナトリウム、シアン化金カリウムおよびシアン化金ナトリウムが挙げられる。これらの金化合物は１種単独で、または２種以上を混合して用いることができる。 The platinum compound is not particularly limited as long as it forms Pt ions in the carbon suspension. For example, chloroplatinic acid, potassium platinum (IV) chloride, sodium platinum (IV) chloride, tetranitro Examples include potassium platinum (II), sodium hexahydroxoplatinate (IV) hydrate, dinitrodiammine platinum nitrate, dinitrodiammine platinum ammonia and tetraamminedichloroplatinum hydrate. These platinum compounds can be used individually by 1 type or in mixture of 2 or more types. The gold compound is not particularly limited as long as it forms Au ions in the carbon suspension, and examples thereof include sodium gold sulfite, potassium gold cyanide, and sodium gold cyanide. These gold compounds can be used alone or in combination of two or more.
ＰｔイオンまたはＡｕイオンを含む溶液に用いられる溶媒は、白金化合物または金化合物との反応性を示さず、白金化合物または金化合物を溶解できるものでは特に限定されるものではない。このような溶媒としては、
水；
メタノール、エタノール、イソプロパノール、ｎ−ブタノール、メチルイソカルビノールなどのアルコール類；
アセトン、２−ブタノン、エチルアミルケトン、ジアセトンアルコール、イソホロン、シクロヘキサノンなどのケトン類；
Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドなどのアミド類；
ジエチルエーテル、イソプロピルエーテル、テトラヒドロフラン、１，４−ジオキサン、３，４−ジヒドロ−２Ｈ−ピランなどのエーテル類；
２−メトキシエタノール、２−エトキシエタノール、２−ブトキシエタノール、エチレングリコールジメチルエーテルなどのグリコールエーテル類；
２−メトキシエチルアセテート、２−エトキシエチルアセテート、２−ブトキシエチルアセテートなどのグリコールエーテルアセテート類；
酢酸メチル、酢酸エチル、酢酸イソブチル、酢酸アミル、乳酸エチル、エチレンカーボネートなどのエステル類；
ベンゼン、トルエン、キシレンなどの芳香族炭化水素類；
ヘキサン、ヘプタン、ｉｓｏ−オクタン、シクロヘキサンなどの脂肪族炭化水素類；
塩化メチレン、１，２−ジクロルエタン、ジクロロプロパン、クロルベンゼンなどのハロゲン化炭化水素類；
ジメチルスルホキシドなどのスルホキシド類；
Ｎ−メチル−２−ピロリドン、Ｎ−オクチル−２−ピロリドンなどのピロリドン類
などを挙げることができる。
The solvent used for the solution containing Pt ions or Au ions is not particularly limited as long as it does not show reactivity with the platinum compound or gold compound and can dissolve the platinum compound or gold compound. Such solvents include
water;
Alcohols such as methanol, ethanol, isopropanol, n-butanol, methyl isocarbinol;
Ketones such as acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone, cyclohexanone;
Amides such as N, N-dimethylformamide and N, N-dimethylacetamide;
Ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H-pyran;
Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether;
Glycol ether acetates such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate;
Esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethylene carbonate;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Aliphatic hydrocarbons such as hexane, heptane, iso-octane, cyclohexane;
Halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene;
Sulfoxides such as dimethyl sulfoxide;
Examples thereof include pyrrolidones such as N-methyl-2-pyrrolidone and N-octyl-2-pyrrolidone.
上記カーボン懸濁液に、ＰｔイオンまたはＡｕイオンを含む溶液あるいは白金化合物または金化合物を添加する際の温度は、１５〜４０℃が好ましい。１５℃未満では十分に白金コロイドを担持できないことがあり、４０℃を超えても担持効率のさらなる向上が見られないため、経済的に好ましくない。また、上記添加後、上記範囲の温度に保持しながら懸濁液を攪拌して充分に混合することが好ましい。特に、固体状の白金化合物または金化合物を添加した場合には、白金化合物または金化合物が充分に溶解してイオンが生成するまで攪拌などの操作を充分に行なう必要がある。 The temperature at which a solution containing Pt ions or Au ions or a platinum compound or gold compound is added to the carbon suspension is preferably 15 to 40 ° C. If it is less than 15 ° C., the platinum colloid may not be sufficiently supported, and if it exceeds 40 ° C., no further improvement in the loading efficiency is observed, which is economically undesirable. Further, after the addition, it is preferable that the suspension is stirred and sufficiently mixed while maintaining the temperature within the above range. In particular, when a solid platinum compound or gold compound is added, it is necessary to sufficiently perform an operation such as stirring until the platinum compound or gold compound is sufficiently dissolved and ions are generated.
上記のようにして、カーボン懸濁液にＰｔイオンまたはＡｕイオンを含有させ、充分に分散させた後、白金コロイドを添加する。前記白金コロイドの製造方法は特に制限されず、燃焼法や沈殿法（金属塩還元反応法）など公知の方法が適用できる。 As described above, Pt ions or Au ions are contained in the carbon suspension and sufficiently dispersed, and then a platinum colloid is added. The method for producing the platinum colloid is not particularly limited, and a known method such as a combustion method or a precipitation method (metal salt reduction reaction method) can be applied.
燃焼法は、金属イオン溶液を水素ガス中またはリンなどへ投じて還元反応させ、その後、燃焼により加熱して反応を促進させ、生成した金属微粒子を液体分散媒中に注入し、還元終了後、界面活性剤を用いて金属コロイドを安定化処理する方法である。具体的には、特開昭６１−２７１０２６号公報に開示されているように、白金の王水溶液と低級アルコ−ルとの混合溶液及び水素ガスをそれぞれ別の供給系より送出し、燃焼させた水素ガス炎の直前において前記混合溶液を合流させて、白金を８３０〜８７０℃で燃焼させ、燃焼火炎を、コロイド生成槽中において槽底近くに達する渦流を生じさせた液体分散媒中に吹込むことにより白金コロイドを製造することができる。 In the combustion method, a metal ion solution is poured into hydrogen gas or phosphorus to cause a reduction reaction, and then heated by combustion to accelerate the reaction. The generated metal fine particles are injected into a liquid dispersion medium, and after the reduction is completed, This is a method of stabilizing a metal colloid using a surfactant. Specifically, as disclosed in Japanese Patent Laid-Open No. 61-271026, a mixed solution of platinum aqua solution and lower alcohol and hydrogen gas were sent from separate supply systems and burned. Immediately before the hydrogen gas flame, the mixed solution is combined to burn platinum at 830 to 870 ° C., and the combustion flame is blown into a liquid dispersion medium in which a vortex reaching the bottom of the tank is generated in the colloid production tank. Thus, a colloidal platinum can be produced.
沈殿法（金属塩還元反応法）は、燃焼法に比べて高濃度、高活性の白金コロイドを得ることが可能な製造方法といわれている。この方法では、白金イオン溶液に還元剤を添加し、温度およびｐＨを制御しながら還元処理して液中に白金微粒子を析出させることにより、高活性微粒子を得ることができる。反応中、液の温度を２０〜８０℃の範囲で低温より
高温に制御し、ｐＨを４〜１１の範囲に保持する。還元処理は、界面活性剤（保護コロイド）を用いずにコロイド状態を保持するために行い、金属イオンを還元する。
The precipitation method (metal salt reduction reaction method) is said to be a production method capable of obtaining a platinum colloid having a higher concentration and higher activity than the combustion method. In this method, highly active fine particles can be obtained by adding a reducing agent to a platinum ion solution, and performing a reduction treatment while controlling the temperature and pH to precipitate platinum fine particles in the liquid. During the reaction, the temperature of the liquid is controlled to be higher than the lower temperature in the range of 20 to 80 ° C., and the pH is maintained in the range of 4 to 11. The reduction treatment is performed to maintain a colloidal state without using a surfactant (protective colloid), and reduces metal ions.
本発明に用いる白金コロイドの平均粒子径は１〜１００ｎｍである。白金コロイドの平均粒子径が上記範囲にあると白金コロイドが充分に分散した状態でカーボン担体に担持することができる。一方、平均粒子径が１ｎｍ未満の白金コロイドは容易に製造することが困難なため好ましくなく、１００ｎｍを超えると、カーボン担体に充分に分散して容易に担持させることができないことがあり、また、触媒反応などに寄与できない白金の量が増大することがあるため望ましくない。 The average particle diameter of the platinum colloid used in the present invention is 1 to 100 nm. When the average particle diameter of the platinum colloid is in the above range, the platinum colloid can be supported on the carbon carrier in a sufficiently dispersed state. On the other hand, a platinum colloid having an average particle diameter of less than 1 nm is not preferable because it is difficult to produce easily, and if it exceeds 100 nm, it may not be sufficiently dispersed and easily supported on a carbon support, This is undesirable because the amount of platinum that cannot contribute to the catalytic reaction may increase.
白金コロイドは、通常、水または有機溶媒に分散した状態の白金コロイド溶液として使用される。白金コロイド溶液中の白金金属の固形分濃度は特に限定されないが、たとえば０．０１重量％以上が好ましい。 The platinum colloid is usually used as a platinum colloid solution dispersed in water or an organic solvent. The solid content concentration of platinum metal in the platinum colloid solution is not particularly limited, but is preferably 0.01% by weight or more, for example.
白金コロイドの添加量は、カーボン固形分１００重量部に対して金属元素換算で１０〜１８０重量部が好ましく、３０〜１６０重量部がより好ましい。白金コロイドの添加量が上記範囲にあると白金コロイドが充分に分散した状態でカーボン担体に担持することができる。一方、添加量が１０重量部未満になると、白金コロイドの担持は問題ないが、白金コロイドの担持量が少なくなり、白金コロイドによる触媒作用など、充分な効果が得られないことがある。また、添加量が１８０重量部を超えても担持量は増加しにくく、経済的に好ましくない。 The amount of platinum colloid added is preferably 10 to 180 parts by weight, more preferably 30 to 160 parts by weight, in terms of metal element, with respect to 100 parts by weight of carbon solid content. When the added amount of the platinum colloid is within the above range, the platinum colloid can be supported on the carbon carrier in a sufficiently dispersed state. On the other hand, when the addition amount is less than 10 parts by weight, there is no problem with the support of platinum colloid, but the support amount of platinum colloid decreases and sufficient effects such as catalysis by platinum colloid may not be obtained. Moreover, even if the addition amount exceeds 180 parts by weight, the loading amount is hardly increased, which is economically undesirable.
白金コロイドを添加して混合する際の温度は、特に限定されないが、１５〜４０℃が好ましい。１５℃未満では、十分に白金コロイドを担持できないことがあり、実用性が低下することがある。４０℃を超えると担持効果の更なる向上は認められず、経済的に好ましくない。 Although the temperature at the time of adding and mixing a platinum colloid is not specifically limited, 15-40 degreeC is preferable. If it is less than 15 degreeC, a platinum colloid may not fully be supported, and practicality may fall. If it exceeds 40 ° C., further improvement of the supporting effect is not recognized, which is economically undesirable.
上記混合の際、通常５分以上、好ましくは１０以上の攪拌を行なうことが望ましく、必要に応じて、通常３時間程度まで、好ましくは１時間程度まで攪拌してもよい。
上記混合操作後、必要に応じて、白金コロイド担持カーボンを含む懸濁液を水で希釈してもよい。通常、白金コロイド担持カーボン１００重量部に対して、最大で２５０,００
０重量部程度の水で希釈することができる。
During the above mixing, it is desirable to stir usually for 5 minutes or more, preferably 10 or more, and if necessary, the stirring may be usually for about 3 hours, preferably for about 1 hour.
After the mixing operation, the suspension containing the platinum colloid-supporting carbon may be diluted with water as necessary. Usually up to 250,000 per 100 parts by weight of platinum colloid-supported carbon
It can be diluted with about 0 parts by weight of water.
さらに、通常、水で希釈した白金コロイド担持カーボンを遠心分離し、望ましくは洗浄を３回以上繰り返して、残存するイオンを除去し、白金コロイド担持カーボンを分離精製する。その後、分離した白金コロイド担持カーボンを、通常、８０〜１００℃で１〜２０時間乾燥することが望ましい。 Further, platinum colloid-carrying carbon diluted with water is usually centrifuged, and washing is preferably repeated three or more times to remove remaining ions, and platinum colloid-carrying carbon is separated and purified. Thereafter, the separated platinum colloid-carrying carbon is usually preferably dried at 80 to 100 ° C. for 1 to 20 hours.
本発明の製造方法により、白金コロイド担持量が、白金コロイド担持カーボン全体に対して２０〜５０重量％であり、かつ白金コロイドがカーボン担体表面に極めて良好に分散した白金コロイド担持カーボンを得ることができる。この白金コロイド担持量は、ＰｔイオンまたはＡｕイオンを含有させる際の温度、ＰｔイオンまたはＡｕイオンの含有量、白金コロイド混合時の温度、白金コロイド混合量などの製造条件を適宜調整することによりコントロールすることができる。 By the production method of the present invention, it is possible to obtain platinum colloid-carrying carbon in which the amount of platinum colloid carried is 20 to 50% by weight with respect to the whole platinum colloid-carrying carbon and the platinum colloid is dispersed very well on the surface of the carbon carrier. it can. The amount of platinum colloid supported is controlled by appropriately adjusting manufacturing conditions such as the temperature at which Pt ions or Au ions are contained, the content of Pt ions or Au ions, the temperature at which platinum colloids are mixed, and the amount of platinum colloids mixed. can do.
担持前のカーボン担体の比表面積に対する上記白金コロイド担持カーボンの比表面積の低下率は、４８〜８０％が好ましく、５０〜７５％がより好ましい。また、担持前のカーボン担体の細孔容積に対する白金コロイド担持カーボンの細孔容積の低下率は、３５〜７０％が好ましく、３８〜６０％がより好ましい。担持による比表面積の減少は、白金コロイドがカーボン担体の表面に担持された度合いを表し、細孔容積の減少は、白金コロイド
が良好に分散して、カーボン担体表面の細孔中に担持されていることを表す。本発明の製造方法によると、上記のような白金コロイドが多量かつ高分散で担持された白金コロイド担持カーボンを得ることができる。
The reduction rate of the specific surface area of the platinum colloid-supporting carbon with respect to the specific surface area of the carbon support before supporting is preferably 48 to 80%, and more preferably 50 to 75%. Further, the reduction rate of the pore volume of the platinum colloid-supported carbon with respect to the pore volume of the carbon support before supporting is preferably 35 to 70%, more preferably 38 to 60%. The decrease in the specific surface area due to the loading represents the degree to which the platinum colloid was supported on the surface of the carbon support, and the decrease in the pore volume means that the platinum colloid was well dispersed and supported in the pores on the surface of the carbon support. Represents that According to the production method of the present invention, it is possible to obtain platinum colloid-carrying carbon in which a large amount of platinum colloid as described above is carried in a highly dispersed state.
本発明の白金コロイド担持カーボンとしては、例えば、比表面積が２０〜５２０ｍ2／
ｇ、平均細孔容積が０．０３０〜０．９７５ｃｍ3／ｇ、白金含有量が２０〜５０重量％
、平均粒子径が０．０１〜１０μｍ、白金コロイドの平均粒子径が２〜５０ｎｍ（但し、カーボン担体の平均粒子径の１０分の１以下が好ましい。）であって、本発明で規定する白金コロイド分散性の評価が３〜５の範囲にある白金コロイド担持カーボンが好ましい。
The platinum colloid-supporting carbon of the present invention has, for example, a specific surface area of 20 to 520 m 2 /
g, average pore volume of 0.030 to 0.975 cm 3 / g, platinum content of 20 to 50% by weight
Platinum having an average particle diameter of 0.01 to 10 μm and an average particle diameter of platinum colloid of 2 to 50 nm (however, preferably not more than one-tenth of the average particle diameter of the carbon support). Platinum colloid-supported carbon having an evaluation of colloidal dispersibility in the range of 3 to 5 is preferred.
また、本発明の白金コロイド担持カーボンとしては、比表面積が２５〜５００ｍ2／ｇ
、平均細孔容積が０．０４０〜０．６５ｃｍ3／ｇ、白金含有量が２０〜４０重量％、平
均粒子径が０．０１〜０．１μｍ、白金コロイドの平均粒子径が２〜５０ｎｍ（但し、カーボン担体の平均粒子径の１０分の１以下が好ましい。）であって、本発明で規定する白金コロイド分散性の評価が３〜５の範囲にある白金コロイド担持カーボンがさらに好ましい。
The platinum colloid-carrying carbon of the present invention has a specific surface area of 25 to 500 m 2 / g.
The average pore volume is 0.040 to 0.65 cm 3 / g, the platinum content is 20 to 40% by weight, the average particle size is 0.01 to 0.1 μm, and the average particle size of the platinum colloid is 2 to 50 nm ( However, it is preferably 1/10 or less of the average particle diameter of the carbon support.), And platinum colloid-supported carbon whose evaluation of platinum colloid dispersibility defined in the present invention is in the range of 3 to 5 is more preferable.
本発明の製造方法、すなわち、ＰｔイオンまたはＡｕイオンの存在下で、カーボン懸濁液に白金コロイドを混合することにより、上記イオンが存在しない場合に比べて白金コロイドが良好に担持することができる。これは、カーボン担体を構成する成分、特にカーボン担体表面に存在するシリカまたはアルミナに、ＰｔイオンまたはＡｕイオンが吸着して、カーボン担体表面に一種のプライマー層が形成され、そのプライマー層の作用、すなわち、白金コロイドとＰｔイオン間あるいは白金コロイドとＡｕイオン間で吸着反応が起こることによると推定される。 In the production method of the present invention, that is, by mixing platinum colloid with carbon suspension in the presence of Pt ions or Au ions, the platinum colloid can be supported better than the case where the above ions are not present. . This is because Pt ions or Au ions are adsorbed on the components constituting the carbon support, particularly silica or alumina present on the surface of the carbon support, and a kind of primer layer is formed on the surface of the carbon support. That is, it is estimated that an adsorption reaction occurs between the platinum colloid and the Pt ion or between the platinum colloid and the Au ion.
本発明の製造方法においては、既に金属状態にある白金コロイドを使用するので、カーボン担体に担持するだけで白金コロイド担持カーボンを得ることができる。例えば、イオン吸着還元法では、カーボン担体上にＰｔイオンを存在させ、これを焼成還元して白金金属を形成する必要があるが、これに比べて本発明の製造方法は、より簡便である。 In the production method of the present invention, platinum colloid already in a metallic state is used, so that platinum colloid-supported carbon can be obtained simply by supporting it on a carbon carrier. For example, in the ion adsorption reduction method, it is necessary to make Pt ions exist on a carbon support and calcinate and reduce them to form platinum metal, but the production method of the present invention is simpler than this.
本発明の白金コロイド担持カーボンは、燃料電池のカソード電極やアノード電極に含まれる燃料電池用触媒として利用することができる。上記白金コロイド担持カーボンを用いた燃料電池は、従来の燃料電池に比べて高出力である。 The platinum colloid-carrying carbon of the present invention can be used as a fuel cell catalyst contained in a cathode electrode or an anode electrode of a fuel cell. The fuel cell using the platinum colloid-carrying carbon has a higher output than the conventional fuel cell.
［実施例］
以下、本発明を実施例により説明するが、本発明は、この実施例により何ら限定されるものではない。なお、実施例中の「％」は、特に断りのない限り、「重量％」を意味する。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the examples, “%” means “% by weight” unless otherwise specified.
＜白金コロイドの調製＞
［調製例１］
塩化白金酸六水和物２５ｇ（白金金属換算で９ｇ）を純水１６,０００ｇに溶解して得
た金属塩水溶液に、錯化安定剤として濃度１．０重量％のクエン酸３ナトリウム水溶液１,６６０ｇと還元剤として濃度０．１重量％の水素化ホウ素ナトリウム水溶液１４０ｇと
を加え、窒素雰囲気下、２０℃で攪拌混合して、水に白金微粒子が分散してなる白金コロイド溶液を得た。この白金コロイド溶液を限外濾過膜法洗浄により精製した後、濃度を調整し、白金金属換算で濃度０．４２重量％の白金コロイド溶液を得た。この白金コロイドの平均粒子径は３ｎｍであった。
<Preparation of platinum colloid>
[Preparation Example 1]
A metal salt aqueous solution obtained by dissolving 25 g of chloroplatinic acid hexahydrate (9 g in terms of platinum metal) in 16,000 g of pure water was added to an aqueous solution of trisodium citrate having a concentration of 1.0% by weight as a complexing stabilizer. , 660 g and a sodium borohydride aqueous solution 140 g having a concentration of 0.1% by weight as a reducing agent were added and stirred and mixed at 20 ° C. in a nitrogen atmosphere to obtain a platinum colloid solution in which platinum fine particles were dispersed in water. . This platinum colloid solution was purified by ultrafiltration membrane washing and then the concentration was adjusted to obtain a platinum colloid solution having a concentration of 0.42% by weight in terms of platinum metal. The average particle diameter of this platinum colloid was 3 nm.
＜比表面積および細孔容積の測定方法＞
１１０℃で２０時間乾燥した試料をガラスセルに所定量採取し、脱気装置（カウンタークローム社製ＡＵＴＯＳＯＲＢ６）にて１１０℃で真空脱気を行ない、吸着等温線を求めた。この吸着等温線から比表面積および細孔容積を求めた。
<Method for measuring specific surface area and pore volume>
A predetermined amount of a sample dried at 110 ° C. for 20 hours was collected in a glass cell, and vacuum deaeration was performed at 110 ° C. with a deaerator (AUTOSORB6 manufactured by Counterchrome) to obtain an adsorption isotherm. The specific surface area and pore volume were determined from this adsorption isotherm.
＜イオンの分析方法＞
Ｐｔ：白金コロイド担持カーボン中の白金含有量を誘導結合プラズマ発光分光分析装置
（セイコー（株）製、ＳＰＳ １２００Ａ）により測定した。
<Ion analysis method>
Pt: The platinum content in the colloidal platinum-supported carbon was measured with an inductively coupled plasma emission spectrophotometer (Seiko Co., Ltd., SPS 1200A).
＜白金コロイド分散性の評価＞
白金コロイド担持カーボン中の白金コロイドの分散性は、透過型電子顕微鏡により観察し、下記基準で評価した。
５：白金コロイドの凝集は見られず、一次粒子径相当の大きさの白金コロイド粒子がカ
ーボン担体表面全体に高分散で担持された状態。
４：カーボン担体表面の一部で一次粒子が最大２個結合した大きさに相当する白金コロ
イド粒子が見られたが、カーボン担体表面の大部分では、一次粒子径相当の大きさ
の白金コロイド粒子が高分散で担持された状態。
３：カーボン担体表面の一部で一次粒子が最大３個結合した大きさに相当する白金コロ
イド粒子が見られたが、カーボン担体表面の大部分では、一次粒子径相当の大きさ
の白金コロイド粒子が高分散で担持された状態
２：カーボン担体表面の一部で一次粒子が最大４個結合した大きさに相当する白金コロ
イド粒子が見られたが、カーボン担体表面の大部分では、一次粒子径相当の大きさ
の白金コロイド粒子が高分散で担持された状態。
１：カーボン担体表面に白金コロイド粒子が全く担持されていない状態、または一次粒
子径相当の大きさの白金コロイド粒子が見当たらず、一次粒子が２個以上結合した
大きさに相当する白金コロイド粒子のみがカーボン担体表面に担持された状態。
<Evaluation of dispersibility of platinum colloid>
The dispersibility of the platinum colloid in the platinum colloid-supporting carbon was observed with a transmission electron microscope and evaluated according to the following criteria.
5: Aggregation of platinum colloid was not observed, and platinum colloidal particles having a size corresponding to the primary particle diameter were supported in a highly dispersed state on the entire carbon support surface.
4: Platinum colloid particles corresponding to the size of a maximum of two primary particles bonded to a part of the surface of the carbon support were observed. On the most part of the surface of the carbon support, a platinum colloid having a size corresponding to the primary particle size was observed. A state in which particles are supported with high dispersion.
3: Platinum colloidal particles corresponding to the size of up to three primary particles bonded to a part of the surface of the carbon support were observed, but most of the surface of the carbon support was a colloidal platinum with a size corresponding to the primary particle size. Particles supported in a highly dispersed state 2: Platinum colloidal particles corresponding to a size in which a maximum of four primary particles were bonded to a part of the surface of the carbon support were observed. A state in which platinum colloidal particles of a size equivalent to the particle diameter are supported in a highly dispersed state.
1: Platinum colloidal particles corresponding to a size in which no platinum colloidal particles are supported on the surface of the carbon support, or in which no platinum colloidal particles with a size equivalent to the primary particle size are found and two or more primary particles are bonded. Only the carbon carrier is supported on the surface.
固形分重量で０．２ｇのカーボンブラック（ライオン（株）製、商品名：ケッチェンブラックＥＣ、ＤＢＰ吸油量：３６０ｃｍ3／１００ｇ、比表面積：８５０ｍ2／ｇ、一次粒子径：３９．５ｎｍ）を９５℃に煮沸した水に分散させ、カーボンブラック２％（固形分）の分散液を得た。この分散液を脱イオン水で希釈し、攪拌することにより、カーボンブラック懸濁液（カーボンブラック固形分０．２％）を調製した。 Solids weight in 0.2g of carbon black (Lion Co., Ltd., trade name: Ketchen black EC, DBP oil absorption: 360cm 3 / 100g, specific surface area: 850m 2 / g, primary particle diameter: 39.5nm) Was dispersed in water boiled at 95 ° C. to obtain a dispersion of 2% (solid content) of carbon black. This dispersion was diluted with deionized water and stirred to prepare a carbon black suspension (carbon black solid content 0.2%).
このカーボンブラック懸濁液１００ｇにＡｕイオン濃度が１％の塩化金酸水溶液を１４ｇ添加して２０℃で５分間攪拌した。この混合懸濁液に、調製例１で得た白金コロイド溶液（白金コロイド平均粒子径：３ｎｍ）７１ｇ（白金固形分で０．２ｇ）を添加した。白金コロイド添加後の混合懸濁液のｐＨは２．３であった。この混合懸濁液を２０℃で４０分間攪拌した後、遠心分離機で固液分離し、更に水を５００ｇ加えて３分間洗浄した。遠心分離および洗浄操作を３回繰り返して懸濁液中に残存している白金コロイド、Ｃｌイオン、Ａｕイオン等を除去した後、得られた固形物を９０℃で１０時間乾燥させて白金コロイド担持カーボンを得た。この白金コロイド担持カーボンの分析結果等を表１および表２に示す。 To 100 g of this carbon black suspension, 14 g of an aqueous chloroauric acid solution with an Au ion concentration of 1% was added and stirred at 20 ° C. for 5 minutes. To this mixed suspension, 71 g of platinum colloid solution (platinum colloid average particle size: 3 nm) obtained in Preparation Example 1 (0.2 g in terms of platinum solid content) was added. The pH of the mixed suspension after adding the platinum colloid was 2.3. The mixed suspension was stirred at 20 ° C. for 40 minutes, then solid-liquid separated with a centrifuge, and further 500 g of water was added and washed for 3 minutes. Centrifugation and washing are repeated three times to remove platinum colloid, Cl ions, Au ions, etc. remaining in the suspension, and then the resulting solid is dried at 90 ° C. for 10 hours to carry platinum colloid. Carbon was obtained. Tables 1 and 2 show the analysis results and the like of this platinum colloid-supporting carbon.
得られた白金コロイド担持カーボンを触媒として、電解質膜溶液である５重量％ナフイオン溶液および溶媒の酢酸ブチルと混合し、室温で１時間攪拌して触媒ペーストを調製した。混合比（重量比）は、触媒：酢酸ブチル：ナフイオン溶液＝１：１．２：４．７とした。この触媒ペーストを直径８ｍｍ、面積０．５ｃｍ2のカーボンペーパー上にスクリー
ン印刷法により塗布した後、自然乾燥させて触媒層を形成し、電極（空気極）を作製した。
Using the obtained platinum colloid-supported carbon as a catalyst, a 5 wt% naphthion solution as an electrolyte membrane solution and a solvent butyl acetate were mixed and stirred at room temperature for 1 hour to prepare a catalyst paste. The mixing ratio (weight ratio) was catalyst: butyl acetate: naphthoion solution = 1: 1.2: 4.7. This catalyst paste was applied on carbon paper having a diameter of 8 mm and an area of 0.5 cm 2 by a screen printing method, and then naturally dried to form a catalyst layer, thereby producing an electrode (air electrode).
また、上記白金コロイド担持カーボンの代わりに、触媒としてＰｔ−Ｒｕ／Ｃ（田中貴金属工業（株）製）を用いた以外は、上記と同様にして対極触媒電極（燃料極）を作製した。 Further, a counter electrode catalyst electrode (fuel electrode) was produced in the same manner as described above except that Pt-Ru / C (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) was used instead of the platinum colloid-supported carbon.
上記空気極と燃料極とで固体高分子膜（デュポン社製、品番：Ｎ−１１７）を挟み、ホットプレスにて１３０℃、４ＭＰａで３分間圧着して膜／電極接合体（ＭＥＡ）を作製した。 A membrane / electrode assembly (MEA) is fabricated by sandwiching a solid polymer membrane (manufactured by DuPont, product number: N-117) between the air electrode and the fuel electrode, and pressing with a hot press at 130 ° C. and 4 MPa for 3 minutes. did.
この膜／電極接合体を用いて燃料電池用セルを作製した。セルの性能を評価するために、負荷電流を変えながら負荷電流（Ｉ）とセル電圧（Ｖ）の関係を、電流電圧計（ケースレーインスツルメンツ社製、品番：デジタルマルチメータ２０００／２０００−ＳＣＡＮ）およびガルバノポテンンシオスタット（北斗電工株式会社製、品番：ＨＣ−１１１）を用いて測定し、Ｉ−Ｖ曲線を得た。Ｉ−Ｖの積から最大出力密度を求め、後述する比較例１で求めた最大出力密度に対する比率として表２に示した。 A fuel cell was produced using this membrane / electrode assembly. In order to evaluate the performance of the cell, while changing the load current, the relationship between the load current (I) and the cell voltage (V) was measured using a current voltmeter (manufactured by Keithley Instruments, product number: Digital Multimeter 2000 / 2000-SCAN) and Measurement was performed using a galvano potentiostat (Hokuto Denko, product number: HC-111) to obtain an IV curve. The maximum output density was determined from the product of IV and is shown in Table 2 as a ratio to the maximum output density determined in Comparative Example 1 described later.
Ａｕイオン濃度が１％の塩化金酸水溶液の添加量を１０ｇに変更した以外は実施例１と同様にして白金コロイド担持カーボンを得た。この白金コロイド担持カーボンの透過型電子顕微鏡写真撮影による表面写真（倍率：２５０，０００倍）を図１に示す。また、この白金コロイド担持カーボンの分析結果等を表１および表２に示す。 A platinum colloid-carrying carbon was obtained in the same manner as in Example 1 except that the addition amount of the chloroauric acid aqueous solution having an Au ion concentration of 1% was changed to 10 g. FIG. 1 shows a surface photograph (magnification: 250,000 times) of the platinum colloid-supported carbon taken by transmission electron micrograph. Tables 1 and 2 show the results of analysis of the platinum colloid-supported carbon.
また、この白金コロイド担持カーボンを用いた以外は実施例１と同様にして燃料電池用セルを作製して最大出力密度を求め、後述する比較例１で求めた最大出力密度に対する比率として表２に示した。 Further, a fuel cell was prepared in the same manner as in Example 1 except that this platinum colloid-supported carbon was used, and the maximum output density was determined. The ratio to the maximum output density determined in Comparative Example 1 described later is shown in Table 2. Indicated.
Ａｕイオン濃度が１％の塩化金酸水溶液の添加量を６ｇに変更した以外は実施例１と同様にして白金コロイド担持カーボンを得た。この白金コロイド担持カーボンの分析結果等を表１および表２に示す。 A platinum colloid-carrying carbon was obtained in the same manner as in Example 1 except that the addition amount of the chloroauric acid aqueous solution having an Au ion concentration of 1% was changed to 6 g. Tables 1 and 2 show the analysis results and the like of this platinum colloid-supporting carbon.
また、この白金コロイド担持カーボンを用いた以外は実施例１と同様にして燃料電池用セルを作製して最大出力密度を求め、後述する比較例１で求めた最大出力密度に対する比率として表２に示した。 Further, a fuel cell was prepared in the same manner as in Example 1 except that this platinum colloid-supported carbon was used, and the maximum output density was determined. The ratio to the maximum output density determined in Comparative Example 1 described later is shown in Table 2. Indicated.
Ａｕイオン濃度が１％の塩化金酸水溶液の添加量を２ｇに変更した以外は実施例１と同様にして白金コロイド担持カーボンを得た。この白金コロイド担持カーボンの分析結果等を表１および表２に示す。 Platinum colloid-carrying carbon was obtained in the same manner as in Example 1 except that the addition amount of the chloroauric acid aqueous solution having an Au ion concentration of 1% was changed to 2 g. Tables 1 and 2 show the analysis results and the like of this platinum colloid-supporting carbon.
また、この白金コロイド担持カーボンを用いた以外は実施例１と同様にして燃料電池用セルを作製して最大出力密度を求め、後述する比較例１で求めた最大出力密度に対する比率として表２に示した。 Further, a fuel cell was prepared in the same manner as in Example 1 except that this platinum colloid-supported carbon was used, and the maximum output density was determined. The ratio to the maximum output density determined in Comparative Example 1 described later is shown in Table 2. Indicated.
塩化金酸水溶液の代わりにＰｔイオン濃度が１％の塩化白金酸水溶液を１４ｇ添加した以外は実施例１と同様にして白金コロイド担持カーボンを得た。この白金コロイド担持カーボンの分析結果等を表１および表２に示す。 A platinum colloid-supporting carbon was obtained in the same manner as in Example 1 except that 14 g of a chloroplatinic acid aqueous solution having a Pt ion concentration of 1% was added instead of the chloroauric acid aqueous solution. Tables 1 and 2 show the analysis results and the like of this platinum colloid-supporting carbon.
また、この白金コロイド担持カーボンを用いた以外は実施例１と同様にして燃料電池用セルを作製して最大出力密度を求め、後述する比較例１で求めた最大出力密度に対する比
率として表２に示した。
Further, a fuel cell was prepared in the same manner as in Example 1 except that this platinum colloid-supported carbon was used, and the maximum output density was determined. The ratio to the maximum output density determined in Comparative Example 1 described later is shown in Table 2. Indicated.
Ｐｔイオン濃度が１％の塩化白金酸水溶液の添加量を１０ｇに変更した以外は実施例６と同様にして白金コロイド担持カーボンを得た。この白金コロイド担持カーボンの分析結果等を表１および表２に示す。 A platinum colloid-carrying carbon was obtained in the same manner as in Example 6 except that the amount of the chloroplatinic acid aqueous solution having a Pt ion concentration of 1% was changed to 10 g. Tables 1 and 2 show the analysis results and the like of this platinum colloid-supporting carbon.
また、この白金コロイド担持カーボンを用いた以外は実施例１と同様にして燃料電池用セルを作製して最大出力密度を求め、後述する比較例１で求めた最大出力密度に対する比率として表２に示した。 Further, a fuel cell was prepared in the same manner as in Example 1 except that this platinum colloid-supported carbon was used, and the maximum output density was determined. The ratio to the maximum output density determined in Comparative Example 1 described later is shown in Table 2. Indicated.
Ｐｔイオン濃度が１％の塩化白金酸水溶液の添加量を６ｇに変更した以外は実施例６と同様にして白金コロイド担持カーボンを得た。この白金コロイド担持カーボンの分析結果等を表１および表２に示す。 Platinum colloid-carrying carbon was obtained in the same manner as in Example 6 except that the addition amount of the chloroplatinic acid aqueous solution having a Pt ion concentration of 1% was changed to 6 g. Tables 1 and 2 show the analysis results and the like of this platinum colloid-supporting carbon.
また、この白金コロイド担持カーボンを用いた以外は実施例１と同様にして燃料電池用セルを作製して最大出力密度を求め、後述する比較例１で求めた最大出力密度に対する比率として表２に示した。 Further, a fuel cell was prepared in the same manner as in Example 1 except that this platinum colloid-supported carbon was used, and the maximum output density was determined. The ratio to the maximum output density determined in Comparative Example 1 described later is shown in Table 2. Indicated.
Ｐｔイオン濃度が１％の塩化白金酸水溶液の添加量を２ｇに変更した以外は実施例６と同様にして白金コロイド担持カーボンを得た。この白金コロイド担持カーボンの分析結果等を表１および表２に示す。 A platinum colloid-carrying carbon was obtained in the same manner as in Example 6 except that the amount of the chloroplatinic acid aqueous solution having a Pt ion concentration of 1% was changed to 2 g. Tables 1 and 2 show the analysis results and the like of this platinum colloid-supporting carbon.
また、この白金コロイド担持カーボンを用いた以外は実施例１と同様にして燃料電池用セルを作製して最大出力密度を求め、後述する比較例１で求めた最大出力密度に対する比率として表２に示した。 Further, a fuel cell was prepared in the same manner as in Example 1 except that this platinum colloid-supported carbon was used, and the maximum output density was determined. The ratio to the maximum output density determined in Comparative Example 1 described later is shown in Table 2. Indicated.
［比較例１］
実施例１と同様にしてカーボンブラック懸濁液（Ａｕイオンを含まず）を調製した。このカーボンブラック懸濁液に、調製例１で得た白金コロイド溶液（白金コロイド平均粒子径：３ｎｍ）４７ｇ（白金固形分で０．２ｇ）を添加した。白金コロイド添加後の混合懸濁液のｐＨは２．３５であった。この混合懸濁液を２０℃で４０分間攪拌した後、遠心分離機で固液分離し、更に水を５００ｇ加えて３分間洗浄した。遠心分離および洗浄操作を３回繰り返して懸濁液中に残存している白金コロイド、Ｃｌイオン、Ａｕイオン等を除去した後、得られた固形物を９０℃で乾燥させて白金コロイド担持カーボンを得た。この白金コロイド担持カーボンの分析結果等を表１および表２に示す。
[Comparative Example 1]
A carbon black suspension (not including Au ions) was prepared in the same manner as in Example 1. To this carbon black suspension, 47 g of platinum colloid solution (platinum colloid average particle size: 3 nm) obtained in Preparation Example 1 (0.2 g in terms of platinum solid content) was added. The pH of the mixed suspension after adding the platinum colloid was 2.35. The mixed suspension was stirred at 20 ° C. for 40 minutes, then solid-liquid separated with a centrifuge, and further 500 g of water was added and washed for 3 minutes. Centrifugation and washing are repeated three times to remove platinum colloid, Cl ions, Au ions, etc. remaining in the suspension, and then the obtained solid is dried at 90 ° C. Obtained. Tables 1 and 2 show the analysis results and the like of this platinum colloid-supporting carbon.
また、この白金コロイド担持カーボンを用いた以外は実施例１と同様にして燃料電池用セルを作製して最大出力密度を求めた。 Further, a fuel cell was prepared in the same manner as in Example 1 except that this platinum colloid-supporting carbon was used, and the maximum output density was determined.
本発明の白金コロイド担持カーボンは、カーボン担体表面における白金コロイドの担持分散性に優れており、従来の白金コロイド担持カーボンに比べて、白金の作用を有効に利用することができ、たとえば燃料電池用触媒として燃料電池に適用することができる。 The platinum colloid-supported carbon of the present invention is excellent in the support and dispersibility of platinum colloid on the carbon support surface, and can effectively use the action of platinum as compared with conventional platinum colloid-supported carbon. It can be applied to a fuel cell as a catalyst.
Claims (8)
コロイド担持カーボンであって、
前記カーボン担体の比表面積に対する前記白金コロイド担持カーボンの比表面積の低下率が４８〜８０％であり、かつ、前記カーボン担体の平均細孔容積に対する前記白金コロイド担持カーボンの平均細孔容積の低下率が３５〜７０％であることを特徴とする白金コロイド担持カーボン。 A platinum colloid-supporting carbon in which a platinum colloid is supported on a carbon support having a specific surface area of 100 to 1000 m 2 / g,
The reduction rate of the specific surface area of the platinum colloid-supporting carbon with respect to the specific surface area of the carbon support is 48 to 80%, and the reduction rate of the average pore volume of the platinum colloid-supporting carbon with respect to the average pore volume of the carbon support Is a colloidal platinum-supporting carbon, characterized by being 35-70%.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010082443A1 (en) * | 2009-01-13 | 2010-07-22 | 株式会社フルヤ金属 | Platinum black powder, platinum black colloid, method for producing platinum black powder, and method for producing platinum black colloid |
| JP2010531226A (en) * | 2007-06-26 | 2010-09-24 | コミサリア ア レネルジー アトミック | Dispersion of composite materials, especially fuel cell composite materials |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003093874A (en) * | 2001-09-21 | 2003-04-02 | Mitsubishi Heavy Ind Ltd | Colloidal particle supporting method and manufacturing method for platinum supported carbon catalyst |
| JP2003320249A (en) * | 2002-05-01 | 2003-11-11 | Mitsubishi Heavy Ind Ltd | Metal-carrying catalyst and production of the same and solid polymer electrolyte type fuel cell using the same |
-
2005
- 2005-10-28 JP JP2005314933A patent/JP4954530B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003093874A (en) * | 2001-09-21 | 2003-04-02 | Mitsubishi Heavy Ind Ltd | Colloidal particle supporting method and manufacturing method for platinum supported carbon catalyst |
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