JP2011149042A - Method for producing platinum-cobalt alloy fine particle - Google Patents
Method for producing platinum-cobalt alloy fine particle Download PDFInfo
- Publication number
- JP2011149042A JP2011149042A JP2010010144A JP2010010144A JP2011149042A JP 2011149042 A JP2011149042 A JP 2011149042A JP 2010010144 A JP2010010144 A JP 2010010144A JP 2010010144 A JP2010010144 A JP 2010010144A JP 2011149042 A JP2011149042 A JP 2011149042A
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- JP
- Japan
- Prior art keywords
- platinum
- cobalt
- fine particles
- alloy fine
- cobalt alloy
- 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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- 239000010419 fine particle Substances 0.000 title claims abstract description 76
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910000531 Co alloy Inorganic materials 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 239000003446 ligand Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 31
- 239000010941 cobalt Substances 0.000 claims abstract description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000001681 protective effect Effects 0.000 claims abstract description 31
- 239000000446 fuel Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 49
- 238000009826 distribution Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 29
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 17
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 15
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical group CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 9
- 239000005642 Oleic acid Substances 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 21
- 239000005518 polymer electrolyte Substances 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000012528 membrane Substances 0.000 description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 5
- -1 aliphatic amines Chemical class 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 229910003472 fullerene Inorganic materials 0.000 description 5
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 4
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 4
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 4
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- 235000021342 arachidonic acid Nutrition 0.000 description 2
- 229940114079 arachidonic acid Drugs 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 2
- 229940043264 dodecyl sulfate Drugs 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
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- 238000000790 scattering method Methods 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
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- BITHHVVYSMSWAG-KTKRTIGZSA-N (11Z)-icos-11-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCC(O)=O BITHHVVYSMSWAG-KTKRTIGZSA-N 0.000 description 1
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- JPZYXGPCHFZBHO-UHFFFAOYSA-N 1-aminopentadecane Chemical compound CCCCCCCCCCCCCCCN JPZYXGPCHFZBHO-UHFFFAOYSA-N 0.000 description 1
- UNSRRHDPHVZAHH-UHFFFAOYSA-N 6beta,11alpha-Dihydroxy-3alpha,5alpha-cyclopregnan-20-on Natural products CCCCCCCCC=CCC=CCC=CCCCC(O)=O UNSRRHDPHVZAHH-UHFFFAOYSA-N 0.000 description 1
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- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- HXQHFNIKBKZGRP-UHFFFAOYSA-N Ranuncelin-saeure-methylester Natural products CCCCCC=CCC=CCCC=CCCCC(O)=O HXQHFNIKBKZGRP-UHFFFAOYSA-N 0.000 description 1
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- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- GWHCXVQVJPWHRF-UHFFFAOYSA-N cis-tetracosenoic acid Natural products CCCCCCCCC=CCCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
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- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
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- UYXRCZUOJAYSQR-UHFFFAOYSA-N nitric acid;platinum Chemical compound [Pt].O[N+]([O-])=O UYXRCZUOJAYSQR-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
本発明は燃料電池の製造技術に関し、特に白金−コバルト合金微粒子を製造する方法、該方法により得られる白金−コバルト合金微粒子、該合金微粒子を担持した燃料電池用担持触媒、ならびに該担持触媒を含む電極を備えた燃料電池に関する。 The present invention relates to a fuel cell manufacturing technique, and in particular, a method for producing platinum-cobalt alloy fine particles, platinum-cobalt alloy fine particles obtained by the method, a supported catalyst for fuel cells carrying the alloy fine particles, and the supported catalyst. The present invention relates to a fuel cell including an electrode.
近年、環境問題や資源問題への対策の一つとして、燃料電池に対する関心が高まっている。燃料電池は、電気的に接続された２つの電極に燃料と酸化剤を供給し、電気化学的に燃料の酸化を起こさせることで化学エネルギーを直接電気エネルギーに変換する装置である。電気化学的にエネルギーを取り出す燃料電池は、火力発電などとは異なってカルノーサイクルの制約を受けないため、高いエネルギー変換効率を示す。現在知られている燃料電池の種類としては、固体高分子型燃料電池（ＰＥＦＣ）、アルカリ電解質形燃料電池（ＡＦＣ)およびリン酸型燃料電池（ＰＡＦＣ）などがある。これらの中でも固体高分子型燃料電池は作動温度が低く、出力密度が高く、かつ小型化が可能なため、車載用電源などとして有望視されている。 In recent years, interest in fuel cells has increased as one of countermeasures against environmental problems and resource problems. A fuel cell is a device that directly converts chemical energy into electrical energy by supplying fuel and an oxidant to two electrically connected electrodes and causing the fuel to be oxidized electrochemically. A fuel cell that extracts energy electrochemically is not subject to the Carnot cycle, unlike thermal power generation, and thus exhibits high energy conversion efficiency. Currently known types of fuel cells include polymer electrolyte fuel cells (PEFC), alkaline electrolyte fuel cells (AFC), and phosphoric acid fuel cells (PAFC). Among these, the polymer electrolyte fuel cell is considered promising as an in-vehicle power source because it has a low operating temperature, a high output density, and can be miniaturized.
固体高分子型燃料電池は一般的に、白金や白金−ルテニウムなどの白金系合金をカーボンに担持させた担持触媒を電極の触媒層に用いる。しかし白金は非常に高価な材料であるため、白金使用量を減らすことがコスト低減のための課題となっている。この課題を解決するための一つの手段として、可能な限り微粒子化して表面積を大きくした白金あるいは白金系合金をカーボンに担持させた担持触媒を製造することにより白金使用量を減らすことが挙げられる。 In general, a polymer electrolyte fuel cell uses a supported catalyst in which a platinum-based alloy such as platinum or platinum-ruthenium is supported on carbon as a catalyst layer of an electrode. However, since platinum is a very expensive material, reducing the amount of platinum used is an issue for cost reduction. One means for solving this problem is to reduce the amount of platinum used by producing a supported catalyst in which platinum or a platinum-based alloy having a surface area made as fine as possible and having a large surface area is supported on carbon.
金属微粒子を合成する方法としては、逆ミセル法、ポリオール法、ホットソープ法といった、金属塩または金属錯体を液中で還元する方法が知られている。例えば、特許文献１には、触媒前駆体を高級脂肪族カルボン酸および高級脂肪族アミンを加えた溶媒中に入れ、触媒前駆体を逆ミセル内部に閉じ込めた状態で還元反応させた後に担体に担持させることにより、粒径がそろったナノレベルの合金粒子が担持された担持触媒を得る方法が記載されている。特許文献２には、磁気記録媒体に用いる合金ナノパーティクルの製造方法が記載されており、該方法によれば直径の平均値が１〜３ｎｍの範囲内にある鉄−白金合金ナノパーティクルが得られるとされている。特許文献３には、各種の合金ナノ粒子の製造方法が記載されている。しかし、いずれの文献にも、平均粒径が２ｎｍ程度以下である白金−コバルト合金微粒子を製造する方法について具体的には開示されていない。
As a method for synthesizing metal fine particles, a method of reducing a metal salt or a metal complex in a liquid, such as a reverse micelle method, a polyol method, or a hot soap method is known. For example, in
固体高分子型燃料電池用電極触媒の技術分野における重要な課題の一つに、触媒材料が固体高分子電解質膜の劣化の原因とならないようにすることが挙げられる。この点において、例えば鉄やニッケルを触媒材料として用いた場合、鉄およびニッケルは酸性環境下では溶出してイオン化し、固体高分子電解質膜を劣化させることが知られている。一方、コバルトは、鉄やニッケルと比べるとそのような固体高分子電解質膜の劣化を引き起こしにくい材料であることが知られている。つまり、コバルトは電極触媒を製造するにあたって白金と合金化する金属として好適であり、平均粒径が非常に小さい白金−コバルト合金微粒子を製造する方法が求められていた。 One important issue in the technical field of electrode catalysts for polymer electrolyte fuel cells is to prevent the catalyst material from causing deterioration of the polymer electrolyte membrane. In this respect, for example, when iron or nickel is used as a catalyst material, it is known that iron and nickel are eluted and ionized in an acidic environment to deteriorate the solid polymer electrolyte membrane. On the other hand, cobalt is known to be a material that hardly causes deterioration of such a solid polymer electrolyte membrane as compared with iron or nickel. That is, cobalt is suitable as a metal to be alloyed with platinum in producing an electrode catalyst, and a method for producing platinum-cobalt alloy fine particles having an extremely small average particle diameter has been demanded.
本発明は、より小さい平均粒径を有し、特に燃料電池用担持触媒の製造に用いた場合に高い触媒性能を実現させることができる白金−コバルト合金微粒子を製造する方法を提供することを目的とする。 It is an object of the present invention to provide a method for producing platinum-cobalt alloy fine particles having a smaller average particle diameter and capable of realizing high catalyst performance particularly when used in the production of a supported catalyst for a fuel cell. And
本発明者は、白金−コバルト合金微粒子を製造する際に使用する保護配位子の量を最適化することにより、非常に小さい平均粒径を有する白金−コバルト合金微粒子が得られることを見出し、本発明を完成するに至った。本発明は以下の発明を包含する。 The present inventor has found that by optimizing the amount of protective ligand used when producing platinum-cobalt alloy fine particles, platinum-cobalt alloy fine particles having a very small average particle diameter can be obtained. The present invention has been completed. The present invention includes the following inventions.
（１）溶媒に、白金（Ｐｔ）の塩もしくは錯体およびコバルト（Ｃｏ）の塩もしくは錯体と保護配位子を、前記白金およびコバルトの塩もしくは錯体に含まれる金属の総量に対してモル比で１．０〜７．５の量で加えて加熱することを含む、白金−コバルト合金微粒子の製造方法。
（２）保護配位子がＣ６−２４脂肪族カルボン酸およびＣ６−２４脂肪族アミンを含む、（１）に記載の方法。
（３）Ｃ６−２４脂肪族カルボン酸がオレイン酸であり、Ｃ６−２４脂肪族アミンがオレイルアミンである、（２）に記載の方法。
（４）平均粒径２ｎｍ以下、粒径分布幅が１ｎｍ以下、かつコバルト組成分布幅が１０％以下である白金−コバルト合金微粒子。
（５）（１）〜（３）のいずれかに記載の方法により製造される、（４）に記載の白金−コバルト合金微粒子
（６）（４）または（５）に記載の白金−コバルト合金微粒子を担体に担持させた燃料電池用担持触媒。
（７）（６）に記載の担持触媒を含む電極を備えた燃料電池。
(1) A platinum (Pt) salt or complex and a cobalt (Co) salt or complex and a protective ligand in a solvent in a molar ratio to the total amount of metals contained in the platinum and cobalt salt or complex. A method for producing platinum-cobalt alloy fine particles, comprising adding and heating in an amount of 1.0 to 7.5.
(2) The method according to (1), wherein the protective ligand comprises a C 6-24 aliphatic carboxylic acid and a C 6-24 aliphatic amine.
(3) C 6-24 aliphatic carboxylic acid is oleic acid, a C 6-24 aliphatic amine is oleylamine, the method described in (2).
(4) Platinum-cobalt alloy fine particles having an average particle size of 2 nm or less, a particle size distribution width of 1 nm or less, and a cobalt composition distribution width of 10% or less.
(5) The platinum-cobalt alloy according to (4) or (5) produced by the method according to any one of (1) to (3) A fuel cell supported catalyst in which fine particles are supported on a carrier.
(7) A fuel cell comprising an electrode containing the supported catalyst according to (6).
本発明の方法によれば、平均粒径が非常に小さい白金−コバルト合金微粒子が得られる。そのような合金微粒子は、カーボンなどの担体に担持させて燃料電池の電極用触媒として用いることができる。該白金−コバルト合金微粒子の平均粒径が非常に小さいことから、それに比して表面積は大きくなり、活性も高くなる。また、触媒に用いる金属の量を減らすことができるため、燃料電池のコストダウンに貢献する。 According to the method of the present invention, platinum-cobalt alloy fine particles having an extremely small average particle diameter can be obtained. Such alloy fine particles can be supported on a carrier such as carbon and used as a catalyst for a fuel cell electrode. Since the average particle diameter of the platinum-cobalt alloy fine particles is very small, the surface area is increased and the activity is increased. In addition, since the amount of metal used for the catalyst can be reduced, it contributes to the cost reduction of the fuel cell.
本発明の第一の態様は、白金−コバルト合金微粒子を製造する方法に関する。本発明の方法は、まず溶媒に白金（Ｐｔ）の塩もしくは錯体およびコバルト（Ｃｏ）の塩もしくは錯体、ならびに保護配位子を加え、次に得られた溶液を加熱することにより上記の塩もしくは錯体を還元させて、白金−コバルト合金微粒子を析出させるものである。 A first aspect of the present invention relates to a method for producing platinum-cobalt alloy fine particles. In the method of the present invention, a salt or complex of platinum (Pt) and a salt or complex of cobalt (Co) and a protective ligand are first added to a solvent, and then the obtained solution is heated to obtain the above salt or complex. The complex is reduced to precipitate platinum-cobalt alloy fine particles.
白金またはコバルトの塩もしくは錯体とは、還元されることによりそれぞれ白金またはコバルトを析出するような塩もしくは錯体を意味し、具体例としては白金またはコバルトの塩化物、硝酸塩、酢酸塩、あるいは白金またはコバルトのアセチルアセトナート錯体、アンミン錯体、エチレンジアミン錯体が挙げられる。これらの中でも、白金アセチルアセトナート錯体およびコバルトアセチルアセトナート錯体を用いることが好ましい。 A platinum or cobalt salt or complex means a salt or complex that, upon reduction, precipitates platinum or cobalt, respectively. Specific examples include platinum or cobalt chloride, nitrate, acetate, platinum or Examples include cobalt acetylacetonate complex, ammine complex, and ethylenediamine complex. Among these, it is preferable to use a platinum acetylacetonate complex and a cobalt acetylacetonate complex.
白金の塩もしくは錯体とコバルトの塩もしくは錯体との比は、白金−コバルト合金微粒子における所望の組成比に応じて適宜調節することができる。例えば、本発明の方法において、白金の塩もしくは錯体とコバルトの塩もしくは錯体との比をモル比で１：１とした場合、得られる白金−コバルト合金微粒子の組成は、白金：コバルトのモル比で７０：３０〜８０：２０の範囲内、典型的には７５：２５となる。 The ratio of the platinum salt or complex to the cobalt salt or complex can be appropriately adjusted according to the desired composition ratio of the platinum-cobalt alloy fine particles. For example, in the method of the present invention, when the ratio of the platinum salt or complex to the cobalt salt or complex is 1: 1, the composition of the resulting platinum-cobalt alloy fine particles is platinum: cobalt molar ratio. In the range of 70:30 to 80:20, typically 75:25.
本明細書において、用語「保護配位子」とは、析出した金属（白金またはコバルト）の微粒子に配位することにより、それらの微粒子が凝集することを防ぐ（金属微粒子を有機溶媒中で分散安定化させる）ための化合物を意味する。本発明の方法において、保護配位子としてはＣ６−２４脂肪族カルボン酸およびＣ６−２４脂肪族アミン、特にＣ６−２４脂肪族カルボン酸およびＣ６−２４脂肪族アミンの組み合わせを含むものが挙げられる。そのような６〜２４程度、特に１０〜２４程度の炭素鎖長を有するカルボン酸および脂肪族アミンであれば、金属微粒子に配位した際に、金属微粒子の凝集を防ぐ役割を十分果たすことが可能となる。Ｃ６−２４脂肪族カルボン酸およびＣ６−２４脂肪族アミンは飽和および不飽和のいずれであってもよい。なお、その他に利用可能な保護配位子としては、例えばＴＯＡ（トリオクチルアミン）やＰＶＰ（ポリビニルピロリドン）といった高分子化合物、ＣＴＡＢ（臭化ヘキサデシルトリメチルアンモニウム）、ＣＴＡＣ（塩化セチルトリメチルアンモニウム）、ＳＤＳ（ドデシル硫酸）およびＡＯＴ（ジ（２−エチルヘキシル）スルホコハク酸ナトリウム）など、ならびにこれらの中の、あるいはこれらとＣ６−２４脂肪族カルボン酸およびＣ６−２４脂肪族アミンとの任意の組み合わせも挙げることができる。 In this specification, the term “protective ligand” means that the fine particles of the deposited metal (platinum or cobalt) are coordinated to prevent the fine particles from aggregating (dispersing the fine metal particles in an organic solvent). Means a compound to be stabilized). In the method of the present invention, the protecting ligand comprises a combination of C 6-24 aliphatic carboxylic acids and C 6-24 aliphatic amine, especially C 6-24 aliphatic carboxylic acids and C 6-24 aliphatic amine Things. Such carboxylic acids and aliphatic amines having a carbon chain length of about 6 to 24, particularly about 10 to 24, can sufficiently fulfill the role of preventing aggregation of the metal fine particles when coordinated to the metal fine particles. It becomes possible. The C 6-24 aliphatic carboxylic acid and the C 6-24 aliphatic amine may be either saturated or unsaturated. Other protective ligands that can be used include, for example, polymer compounds such as TOA (trioctylamine) and PVP (polyvinylpyrrolidone), CTAB (hexadecyltrimethylammonium bromide), CTAC (cetyltrimethylammonium chloride), SDS (dodecyl sulfate) and AOT (sodium di (2-ethylhexyl) sulfosuccinate) and the like, and any combination thereof in or with C 6-24 aliphatic carboxylic acid and C 6-24 aliphatic amine Can also be mentioned.
保護配位子として用いることができるＣ６−２４脂肪族カルボン酸としては、例えばカプリン酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、マルガリン酸、ステアリン酸、アラキジン酸、アラキドン酸、ベヘン酸、リグノセリン酸、ミリストレイン酸、パルミトレイン酸、オレイン酸、エライジン酸、バクセン酸、ガドレイン酸、エイコセン酸、エルカ酸、ネルボン酸、リノール酸、エイコサジエン酸、ドコサジエン酸、リノレン酸、ピノレン酸、エレオステアリン酸、ミード酸、エイコサトリエン酸およびアラキドン酸などが挙げられる。これらの中でも、オレイン酸が最も好ましい。Ｃ６−２４脂肪族カルボン酸は複数混合して用いることもできる。また、Ｃ６−２４脂肪族カルボン酸は、モノカルボン酸に限らず、ジカルボン酸などの多官能性カルボン酸であってもよい。 Examples of the C 6-24 aliphatic carboxylic acid that can be used as a protective ligand include capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, arachidonic acid, and behenic acid. , Lignoceric acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid Acid, mead acid, eicosatrienoic acid, arachidonic acid and the like. Of these, oleic acid is most preferred. A plurality of C 6-24 aliphatic carboxylic acids may be used in combination. Further, the C 6-24 aliphatic carboxylic acid is not limited to a monocarboxylic acid, and may be a polyfunctional carboxylic acid such as a dicarboxylic acid.
保護配位子として用いることができるＣ６−２４脂肪族アミンとしては、例えばデシルアミン、ウンデシルアミン、ラウリルアミン（ドデシルアミン）、トリデシルアミン、ミリスチルアミン（テトラデシルアミン）、ペンタデシルアミン、パルミチルアミン（セチルアミン）、ステアリルアミン（オクタデシルアミン）およびオレイルアミンなどが挙げられる。これらの中でもオレイルアミンが最も好ましい。Ｃ６−２４脂肪族アミンは複数混合して用いることもできる。また、Ｃ６−２４脂肪族アミンは、モノアミンに限らず、ジアミンなどの多官能性アミンであってもよい。なお、Ｃ６−２４脂肪族アミンは、保護配位子としてのみならず、白金またはコバルトの塩もしくは錯体を還元する還元剤としても機能する。Ｃ６−２４脂肪族アミンを保護配位子兼還元剤として使用することにより、他の還元剤を用いた場合にみられていたＣｏのみから構成される粗大粒子が生じないという効果を奏する。 Examples of the C 6-24 aliphatic amine that can be used as a protective ligand include decylamine, undecylamine, laurylamine (dodecylamine), tridecylamine, myristylamine (tetradecylamine), pentadecylamine, pal Examples include mytylamine (cetylamine), stearylamine (octadecylamine), and oleylamine. Of these, oleylamine is most preferred. A plurality of C 6-24 aliphatic amines may be used in combination. The C 6-24 aliphatic amine is not limited to a monoamine, and may be a polyfunctional amine such as diamine. The C 6-24 aliphatic amine functions not only as a protective ligand but also as a reducing agent for reducing a platinum or cobalt salt or complex. By using C 6-24 aliphatic amine as a protective ligand and reducing agent, there is an effect that coarse particles composed only of Co, which has been observed when other reducing agents are used, are not produced.
本発明の方法で用いるＣ６−２４脂肪族カルボン酸とＣ６−２４脂肪族アミンを組み合わせた保護配位子において、Ｃ６−２４脂肪族カルボン酸とＣ６−２４脂肪族アミンのモル比は１：２〜２：１の範囲内であることが好ましい。Ｃ６−２４脂肪族カルボン酸は、上述したように保護配位子として金属微粒子に配位することにより金属微粒子の凝集を抑制する機能を有するが、一方でＣ６−２４脂肪族カルボン酸はＣ６−２４脂肪族アミンによる還元をも抑制すると考えられる。Ｃ６−２４脂肪族カルボン酸とＣ６−２４脂肪族アミンのモル比は、より好ましくは１：１．５〜１．５：１の範囲内、最も好ましくは１：１である。 In C 6-24 protecting ligand in combination an aliphatic carboxylic acid and a C 6-24 aliphatic amines used in the methods of the present invention, the molar ratio of C 6-24 aliphatic carboxylic acid and a C 6-24 aliphatic amine Is preferably in the range of 1: 2 to 2: 1. As described above, C 6-24 aliphatic carboxylic acid has a function of suppressing aggregation of metal fine particles by coordinating to metal fine particles as a protective ligand, while C 6-24 aliphatic carboxylic acid is It is thought that the reduction | restoration by C6-24 aliphatic amine is also suppressed. The molar ratio of C 6-24 aliphatic carboxylic acid and a C 6-24 aliphatic amines, more preferably 1: 1.5 to 1.5: 1 range, and most preferably 1: 1.
本発明の方法で用いる保護配位子の量は、原料として用いる白金およびコバルトの塩もしくは錯体に含まれる金属の総量に対してモル比で１．０〜７．５、より好ましくは１．０〜７．０の範囲内である。保護配位子は還元により析出した金属微粒子に配位することにより金属微粒子が凝集するのを抑制する一方、保護配位子を過剰に加えることは、還元を抑制することにより金属微粒子の粒径を大きくしてしまうと考えられるため好ましくない。それに対し、保護配位子を上述の範囲の量で用いると、平均粒径が非常に小さい白金−コバルト合金微粒子が得られる。保護配位子の白金およびコバルトの塩もしくは錯体に含まれる金属の総量に対するモル比は、特に１．０〜６．７の範囲内であると、得られる白金−コバルト合金微粒子の平均粒径が２ｎｍ以下となり、より好ましい。 The amount of the protective ligand used in the method of the present invention is 1.0 to 7.5, more preferably 1.0, in molar ratio to the total amount of metal contained in the platinum or cobalt salt or complex used as a raw material. Within the range of -7.0. The protective ligand suppresses the aggregation of the metal fine particles by coordinating with the metal fine particles precipitated by reduction, while the excessive addition of the protective ligand reduces the particle size of the metal fine particles by suppressing the reduction. It is not preferable because it is considered that the value of the value will be increased. On the other hand, when the protective ligand is used in an amount in the above range, platinum-cobalt alloy fine particles having a very small average particle diameter can be obtained. When the molar ratio of the protective ligand to the total amount of metals contained in the platinum or cobalt salt or complex is in the range of 1.0 to 6.7, the average particle diameter of the obtained platinum-cobalt alloy fine particles is 2 nm or less, which is more preferable.
本発明の方法で用いる溶媒は特に限定されるものではないが、具体例としては、例えば炭化水素類（ヘキサン、トリメチルペンタン、オクタンなどの脂肪族炭化水素類；シクロヘキサンなどの脂環式炭化水素類；トルエン、キシレンなどの芳香族炭化水素類；ジクロロメタン、トリクロロエタンなどのハロゲン化炭化水素類など）、エステル類（酢酸メチル、酢酸エチルなど）、ケトン類（メチルエチルケトン、メチルイソブチルケトンなど）、エーテル類（ジエチルエーテル、ジプロピルエーテル、ジオクチルエーテルなど）などが挙げられる。これらの中でもエーテル類が好ましく、特にジオクチルエーテルが最も好ましい。 Although the solvent used in the method of the present invention is not particularly limited, specific examples thereof include hydrocarbons (aliphatic hydrocarbons such as hexane, trimethylpentane, and octane; alicyclic hydrocarbons such as cyclohexane). Aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and trichloroethane), esters (such as methyl acetate and ethyl acetate), ketones (such as methyl ethyl ketone and methyl isobutyl ketone), ethers ( Diethyl ether, dipropyl ether, dioctyl ether, etc.). Among these, ethers are preferable, and dioctyl ether is most preferable.
本発明の方法において、溶媒は、白金およびコバルトの塩もしくは錯体のそれぞれの濃度の合計が２０〜４０ｍｍｏｌ／Ｌの濃度となる量、特に２５〜３５ｍｍｏｌ／Ｌの濃度となる量を用いるのが好ましい。例えば、白金およびコバルトの塩もしくは錯体をそれぞれ１．５ｍｍｏｌずつ用いる場合、溶媒の量は７５〜１５０ｍＬの範囲の量、特に８５〜１２０ｍＬとするのが好ましい。一方、溶媒は、例えば保護配位子の濃度が２０〜３００ｍｍｏｌ／Ｌ、好ましくは２０〜２８０ｍｍｏｌ／Ｌ、より好ましくは２０〜２６７ｍｍｏｌ／Ｌ、特に３０〜２１０ｍｍｏｌ／Ｌ、とりわけ３０〜２００ｍｍｏｌ／Ｌとなる量で用いるのが好適である。 In the method of the present invention, the solvent is preferably used in such an amount that the total concentration of platinum and cobalt salts or complexes is 20 to 40 mmol / L, particularly 25 to 35 mmol / L. . For example, when 1.5 mmol each of platinum or cobalt salts or complexes are used, the amount of the solvent is preferably in the range of 75 to 150 mL, particularly 85 to 120 mL. On the other hand, for example, the concentration of the protective ligand is 20 to 300 mmol / L, preferably 20 to 280 mmol / L, more preferably 20 to 267 mmol / L, particularly 30 to 210 mmol / L, especially 30 to 200 mmol / L. Is preferably used in an amount of
本発明の方法において、白金およびコバルトの塩もしくは錯体と保護配位子とを含む溶液を加熱する際の加熱温度および加熱時間は、当業者であれば適宜調節することができるが、典型的には１８０℃〜２８０℃の範囲で１〜５時間、例えば２１０〜２５０℃で２〜３時間である。 In the method of the present invention, a heating temperature and a heating time for heating a solution containing a platinum or cobalt salt or complex and a protective ligand can be appropriately adjusted by those skilled in the art. Is 180 to 280 ° C. for 1 to 5 hours, for example, 210 to 250 ° C. for 2 to 3 hours.
本発明の第二の態様は、上記の方法により得られる白金−コバルト合金微粒子に関する。本発明の白金−コバルト合金微粒子は平均粒径が２ｎｍ以下であり、さらにその粒径分布幅が１ｎｍ以下（より好ましくは０．７ｎｍ以下）、かつコバルト組成分布幅が１０％以下（より好ましくは７％以下）であることを特徴とする。粒径分布幅が１ｎｍ以下と非常に小さいことは、本発明の白金−コバルト合金微粒子は、各微粒子の粒径がほぼ均一であることを意味する。また、コバルト組成分布幅が１０％以下と非常に小さいことは、本発明の白金−コバルト合金微粒子は、各微粒子の組成にバラつきがほとんど無いことを意味する。すなわち、本発明の白金−コバルト合金微粒子は、粒径が非常に小さく、かつ粒径および組成の両面において均一なものである。なお、平均粒径は小さいほど好ましいが、本発明の方法により得られる白金−コバルト合金微粒子の粒径の下限は、およそ０．５ｎｍである。また、粒径分布幅やコバルト組成分布幅も小さいほど好ましいが、本発明により得られる白金−コバルト合金微粒子の粒径分布幅およびコバルト組成分布幅の下限は、およそ１％である。 The second aspect of the present invention relates to platinum-cobalt alloy fine particles obtained by the above method. The platinum-cobalt alloy fine particles of the present invention have an average particle size of 2 nm or less, a particle size distribution width of 1 nm or less (more preferably 0.7 nm or less), and a cobalt composition distribution width of 10% or less (more preferably). 7% or less). The very small particle size distribution width of 1 nm or less means that the fine particle of the platinum-cobalt alloy of the present invention has a substantially uniform particle size. In addition, the fact that the cobalt composition distribution width is as small as 10% or less means that the platinum-cobalt alloy fine particles of the present invention have almost no variation in the composition of each fine particle. That is, the platinum-cobalt alloy fine particles of the present invention have a very small particle size and are uniform in both particle size and composition. The average particle size is preferably as small as possible, but the lower limit of the particle size of the platinum-cobalt alloy fine particles obtained by the method of the present invention is about 0.5 nm. The smaller the particle size distribution width and the cobalt composition distribution width, the better. However, the lower limit of the particle size distribution width and cobalt composition distribution width of the platinum-cobalt alloy fine particles obtained by the present invention is about 1%.
なお、本明細書において言及する合金微粒子の平均粒径および粒径分布幅は、Ｘ線小角散乱法を用いて得られた粒径分布から求めたものである。Ｘ線小角散乱法により求められる粒径分布曲線において、平均粒径はピークトップの半値幅の平均値とし、粒径分布幅はピークトップの半値幅とする。また、本明細書において言及する白金−コバルト合金微粒子の組成は、ＳＴＥＭ−ＥＤＸ（Scanning Transmission Electron Microscope - Energy Dispersive X-ray Analysis）により複数点測定した結果に基づくものである。ＳＴＥＭ−ＥＤＸ測定に基づいて求められるコバルト組成分布曲線において、平均コバルト組成はピークトップの半値幅の平均値とし、粒径分布幅はピークトップの半値幅とする。 The average particle size and the particle size distribution width of the alloy fine particles referred to in this specification are obtained from the particle size distribution obtained using the X-ray small angle scattering method. In the particle size distribution curve obtained by the X-ray small angle scattering method, the average particle size is the average value of the half width of the peak top, and the particle size distribution width is the half width of the peak top. Further, the composition of the platinum-cobalt alloy fine particles referred to in this specification is based on the result of measuring a plurality of points by STEM-EDX (Scanning Transmission Electron Microscope-Energy Dispersive X-ray Analysis). In the cobalt composition distribution curve obtained on the basis of STEM-EDX measurement, the average cobalt composition is the average value of the half-width of the peak top, and the particle size distribution width is the half-width of the peak top.
本発明の第三の態様は、上記の白金−コバルト合金微粒子を担体に担持させた燃料電池用担持触媒に関する。本発明の担持触媒は、上述した方法により調製される、溶媒に白金およびコバルトの塩もしくは錯体と保護配位子とを加えて加熱することにより得られる白金−コバルト合金微粒子が析出した溶液に、触媒担体を加えて合金微粒子を担持させ、固形物を濾別し、熱処理（例えば酸素１％雰囲気で１６０℃、３時間）することにより得られるものである。触媒担体としては、特に限定されるものではないが、例えばカーボンなどの導電体を好適に用いることができる。具体的には、活性炭、カーボンブラック、カーボン繊維、カーボンナノチューブ、カーボンナノホーン、グラファイト、グラファイトナノファイバー、フラーレン、フラーレンナノウィスカー、フラーレンナノファイバー、グラファイト化処理を施したフラーレンナノウィスカーおよびフラーレンナノファイバーなどを好適に用いることができる。特にカーボンブラックが好ましい。
A third aspect of the present invention relates to a supported catalyst for a fuel cell in which the above platinum-cobalt alloy fine particles are supported on a carrier. The supported catalyst of the present invention is prepared by the above-described method in a solution in which platinum-cobalt alloy fine particles obtained by adding a platinum or cobalt salt or complex and a protective ligand to a solvent and heating are precipitated. A catalyst carrier is added to support the alloy fine particles, the solid matter is filtered, and heat treatment (for example, 160 ° C. in an
本発明の担持触媒は、平均粒径が非常に小さい白金−コバルト合金微粒子を担持したものであるため、金属使用量に対する金属表面積が大きく、その結果高い触媒活性を有する。また、該白金−コバルト合金微粒子が粒径および組成の両面において均一であることも、本発明の担持触媒の高い活性に貢献する。 Since the supported catalyst of the present invention supports platinum-cobalt alloy fine particles having an extremely small average particle diameter, the metal surface area relative to the amount of metal used is large, and as a result, the catalyst has high catalytic activity. Further, the fact that the platinum-cobalt alloy fine particles are uniform in both particle size and composition also contributes to the high activity of the supported catalyst of the present invention.
本発明の第四の態様は、上記の担持触媒を含む電極を備えた燃料電池に関する。本発明の燃料電池は、固体高分子型燃料電池であることが好ましい。金属微粒子を担体に担持させた触媒を電極に用いた燃料電池の構造およびその製造方法は、当業者に広く知られている。例えば、固体高分子型燃料電池は、膜電極接合体（ＭＥＡ）が１対のセパレータで挟まれた構造を有し、膜電極接合体は固体高分子電解質膜が触媒層とガス拡散層の二層構造を有する１対のガス拡散電極によって挟まれた構成を有する。固体高分子型燃料電池の電極における触媒層は、例えば、金属微粒子を担持させた導電性のカーボンブラック粉末とパーフルオロカーボン系イオン交換樹脂などの高分子電解質膜前駆体とを混合し均一な分散液を得て、該分散液を、パーフルオロカーボン系イオン交換樹脂などからなる高分子電解質膜の両面に塗布して乾燥させた後に、両面を２枚のカーボンクロスまたはカーボンペーパーで密着させるか、あるいは該分散液を２枚のカーボンクロスまたはカーボンペーパー上に塗布して乾燥させた後に分散液が塗布された面が高分子電解質膜と密着するように高分子電解質膜の両面から挟みこむことなどにより形成することができる。 A fourth aspect of the present invention relates to a fuel cell provided with an electrode including the above supported catalyst. The fuel cell of the present invention is preferably a solid polymer fuel cell. The structure of a fuel cell using a catalyst in which metal fine particles are supported on a carrier as an electrode and a method for producing the same are well known to those skilled in the art. For example, a polymer electrolyte fuel cell has a structure in which a membrane electrode assembly (MEA) is sandwiched between a pair of separators. The membrane electrode assembly has a solid polymer electrolyte membrane consisting of a catalyst layer and a gas diffusion layer. The structure is sandwiched between a pair of gas diffusion electrodes having a layer structure. The catalyst layer in the electrode of the polymer electrolyte fuel cell is prepared by, for example, mixing a conductive carbon black powder carrying metal fine particles and a polymer electrolyte membrane precursor such as a perfluorocarbon-based ion exchange resin to form a uniform dispersion. The dispersion is applied to both sides of a polymer electrolyte membrane made of a perfluorocarbon-based ion exchange resin and dried, and then both sides are adhered with two carbon cloths or carbon paper, or Formed by applying the dispersion onto two carbon cloths or carbon paper and drying it, and sandwiching it from both sides of the polymer electrolyte membrane so that the surface on which the dispersion is applied is in close contact with the polymer electrolyte membrane. can do.
以下、実施例を用いて本発明をより詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these Examples.
１．白金−コバルト合金微粒子担持カーボン触媒の製造
［実施例１］
ジオクチルエーテル１００ｍｌ中に、白金１．５ｍｍｏｌを含む白金アセチルアセトナートと、コバルト１．５ｍｍｏｌを含むコバルトアセチルアセトナートを添加し、これにオレイン酸１．５ｍｍｏｌ（０．５ｍｌ）、オレイルアミン１．５ｍｍｏｌ（０．５ｍｌ）を加え十分に攪拌した。２３０℃で１時間加熱して還元し、白金−コバルト合金微粒子を析出させた。還元終了後、冷却し、カーボンブラック（Ｋｅｔｊｅｎ ＥＣ、ケッチェンブラックインターナショナル製）１ｇを添加した。十分に撹拌し、白金−コバルト合金微粒子をカーボン上に担持させた。液体と固形物を濾別し、白金−コバルト合金微粒子担持カーボン触媒を取り出した。この触媒を酸素１％で１６０℃、３時間で熱処理した。
1. Production of platinum-cobalt alloy fine particle supported carbon catalyst [Example 1]
To 100 ml of dioctyl ether, platinum acetylacetonate containing 1.5 mmol of platinum and cobalt acetylacetonate containing 1.5 mmol of cobalt were added, and 1.5 mmol (0.5 ml) of oleic acid and 1.5 mmol of oleylamine ( 0.5 ml) was added and stirred thoroughly. It reduced by heating at 230 degreeC for 1 hour, and platinum-cobalt alloy fine particles were deposited. After the reduction, the mixture was cooled and 1 g of carbon black (Ketjen EC, manufactured by Ketjen Black International) was added. The mixture was sufficiently stirred, and platinum-cobalt alloy fine particles were supported on carbon. The liquid and the solid were separated by filtration, and the platinum-cobalt alloy fine particle supported carbon catalyst was taken out. This catalyst was heat-treated at 160 ° C. for 3 hours with 1% oxygen.
［実施例２］
オレイン酸を４．０ｍｍｏｌ（１．３ｍｌ）、オレイルアミンを４．０ｍｍｏｌ（１．３ｍｌ）用いた以外は実施例１と同様にした。
[Example 2]
Example 1 was repeated except that 4.0 mmol (1.3 ml) of oleic acid and 4.0 mmol (1.3 ml) of oleylamine were used.
［実施例３］
オレイン酸を１０．０ｍｍｏｌ（３．２ｍｌ）、オレイルアミンを１０．０ｍｍｏｌ（３．３ｍｌ）用いた以外は実施例１と同様にした。
[Example 3]
Example 1 was repeated except that 10.0 mmol (3.2 ml) of oleic acid and 10.0 mmol (3.3 ml) of oleylamine were used.
［比較例１］
ジオクチルエーテル１００ｍｌ中に、白金１．５ｍｍｏｌを含む白金アセチルアセトナートと、コバルト１．５ｍｍｏｌを含むコバルトアセチルアセトナートを添加し、２３０℃で１時間加熱して還元し、白金−コバルト合金微粒子を析出させた。還元終了後、冷却し、カーボンブラック（Ｋｅｔｊｅｎ ＥＣ、ケッチェンブラックインターナショナル製）１ｇを添加した。十分に撹拌し、白金−コバルト合金微粒子をカーボン上に担持させた。液体と固形物を濾別し、白金−コバルト合金微粒子担持カーボン触媒を取り出した。この触媒を酸素１％で１６０℃、３時間で熱処理した。
[Comparative Example 1]
In 100 ml of dioctyl ether, platinum acetylacetonate containing 1.5 mmol of platinum and cobalt acetylacetonate containing 1.5 mmol of cobalt are added and reduced by heating at 230 ° C. for 1 hour to precipitate platinum-cobalt alloy fine particles. I let you. After the reduction, the mixture was cooled and 1 g of carbon black (Ketjen EC, manufactured by Ketjen Black International) was added. The mixture was sufficiently stirred, and platinum-cobalt alloy fine particles were supported on carbon. The liquid and the solid were separated by filtration, and the platinum-cobalt alloy fine particle supported carbon catalyst was taken out. This catalyst was heat-treated at 160 ° C. for 3 hours with 1% oxygen.
［比較例２］
オレイン酸を１５ｍｍｏｌ（４．８ｍｌ）、オレイルアミンを１５ｍｍｏｌ（５．０ｍｌ）用いた以外は実施例１と同様にした。
[Comparative Example 2]
Example 1 was repeated except that 15 mmol (4.8 ml) of oleic acid and 15 mmol (5.0 ml) of oleylamine were used.
［比較例３］
オレイン酸を４５ｍｍｏｌ（１４．３ｍｌ）、オレイルアミンを４５ｍｍｏｌ（１４．９ｍｌ）用いた以外は実施例１と同様にした。
[Comparative Example 3]
Example 1 was repeated except that 45 mmol (14.3 ml) of oleic acid and 45 mmol (14.9 ml) of oleylamine were used.
［比較例４］
市販品高比表面積カーボンブラックであるＫｅｔｊｅｎ ＥＣ（ケッチェンブラックインターナショナル製）５．０ｇを純水１．２Ｌに加え分散させた。この分散液に、白金０．５ｇを含むヘキサヒドロキソ白金硝酸溶液、コバルト０．５ｇを含む硝酸コバルト溶液を滴下し、十分にカーボンと攪拌した。これに０．１Ｎアンモニア約１００ｍＬを添加してｐＨを約１０とし、それぞれ水酸化物を形成させカーボン上に析出させた。さらにエタノールを用いて９０℃で還元し、分散液をろ過した。得られた粉末を８０℃で一晩乾燥させた後、この触媒を酸素１％で１６０℃、３時間で熱処理を行った。
[Comparative Example 4]
Commercially available high specific surface area carbon black Ketjen EC (Ketjen Black International) (5.0 g) was added to 1.2 L of pure water and dispersed. To this dispersion, a hexahydroxo platinum nitric acid solution containing 0.5 g of platinum and a cobalt nitrate solution containing 0.5 g of cobalt were dropped, and the mixture was sufficiently stirred with carbon. About 100 mL of 0.1N ammonia was added thereto to adjust the pH to about 10, and a hydroxide was formed and precipitated on carbon. Furthermore, it reduced at 90 degreeC using ethanol, and filtered the dispersion liquid. The obtained powder was dried at 80 ° C. overnight, and then the catalyst was heat-treated at 160 ° C. for 3 hours with 1% oxygen.
２．白金−コバルト合金微粒子の粒径測定
粒径測定はリガク製小角広角Ｘ線回折装置（ＲＩＮＴ２０００）を用い、解析にはリガク製“ＮＡＮＯ−Ｓｏｌｖｅｒ（ｖｅｒ．３．１）”を用い、平均粒径、粒径分布を求めた。測定は、析出した白金−コバルト合金微粒子をカーボン上に担持させる前に取り出し、エタノールを加えて分散させた後に乾燥させた試料について行った。図１は実施例３で得られた白金−コバルト合金微粒子を測定した結果得られた粒径分布を示したものである。図示したように、平均粒径はピークトップの半値幅の平均値とし、粒径分布幅はピークトップの半値幅とした。
2. Particle size measurement of platinum-cobalt alloy fine particles The particle size is measured using a small-angle wide-angle X-ray diffractometer (RINT2000) manufactured by Rigaku, and “NANO-Solver (ver. 3.1)” manufactured by Rigaku is used for analysis. The particle size distribution was determined. The measurement was performed on a sample which was taken out before the deposited platinum-cobalt alloy fine particles were supported on carbon, and was dispersed after adding ethanol and dried. FIG. 1 shows the particle size distribution obtained as a result of measuring the platinum-cobalt alloy fine particles obtained in Example 3. As shown in the figure, the average particle size was the average value of the half width of the peak top, and the particle size distribution width was the half width of the peak top.
３．白金−コバルト合金微粒子の組成分布測定
粒子の組成はＳＴＥＭ−ＥＤＸで白金−コバルト合金微粒子を１点ずつ測定し、白金−コバルトの原子比を測定して求めた。測定は、析出した白金−コバルト合金微粒子をカーボン上に担持させる前に取り出し、エタノールを加えて分散させた後に乾燥させた試料について行った。粒子を１００点測定し、その分布から平均コバルト組成とコバルト組成分布幅を求めた。図２左は白金−コバルト合金微粒子のＳＴＥＭ像であり、図２右はＳＴＥＭ像上に示した分析位置３において得られたスペクトルである。図３は、実施例２で得られた白金−コバルト合金微粒子を測定した結果得られたコバルト組成分布を示したものである。図示したように、平均コバルト組成はピークトップの半値幅の平均値とし、粒径分布幅はピークトップの半値幅とした。
3. Composition distribution measurement of platinum-cobalt alloy fine particles The composition of the particles was determined by measuring the platinum-cobalt alloy fine particles one by one with STEM-EDX and measuring the atomic ratio of platinum-cobalt. The measurement was performed on a sample which was taken out before the deposited platinum-cobalt alloy fine particles were supported on carbon, and was dispersed after adding ethanol and dried. The particles were measured at 100 points, and the average cobalt composition and the cobalt composition distribution width were determined from the distribution. The left side of FIG. 2 is an STEM image of platinum-cobalt alloy fine particles, and the right side of FIG. 2 is a spectrum obtained at the
４．白金−コバルト合金微粒子担持カーボン触媒の活性評価
回転ディスク電極(ＲＤＥ）を用いて電流値を測定し、電流密度（Ａ／ｇ−Ｐｔ）を求めることにより触媒の活性評価を行った。回転ディスク電極を用いた酸素還元触媒評価方法は当業者に周知な方法である。この方法では、触媒を付着させた電極を卑方向（電位がマイナスになる方向）に掃印させて電極上で酸素還元反応を起こさせ、その際に流れる電流を測定する。酸素還元電流が大きいほど触媒活性が高いといえる。測定中電極は回転しており、電極の回転によって生じた流れにより電解液中の溶存酸素が電極表面の触媒付近に流入する。一般に回転数が大きくなるほど触媒付近の酸素濃度が高くなるため酸素還元電流が大きくなる。測定は以下の手順で行った。
4). Activity Evaluation of Platinum-Cobalt Alloy Fine Particle-Supported Carbon Catalyst The catalyst activity was evaluated by measuring the current value using a rotating disk electrode (RDE) and determining the current density (A / g-Pt). The oxygen reduction catalyst evaluation method using a rotating disk electrode is a method well known to those skilled in the art. In this method, the electrode to which the catalyst is attached is swept in the base direction (direction in which the potential becomes negative) to cause an oxygen reduction reaction on the electrode, and the current flowing at that time is measured. It can be said that the larger the oxygen reduction current, the higher the catalytic activity. The electrode is rotating during the measurement, and the dissolved oxygen in the electrolyte flows into the vicinity of the catalyst on the electrode surface due to the flow generated by the rotation of the electrode. In general, as the rotational speed increases, the oxygen concentration near the catalyst increases, so the oxygen reduction current increases. The measurement was performed according to the following procedure.
担持触媒粉末１０ｍｇを水１０ｍｌとエタノール１０ｍｌの混合溶液に分散させて触媒インクを得た。この触媒インクを２μｌとってグラッシーカーボン製電極（φ５ｍｍ）上に塗布し、乾燥させてサンプル電極を作成した。このサンプル電極を回転ディスク電極装置（北斗電工製）にセットし、作用極とした。参照極には水素電極（ＲＨＥ）、対極には白金電極をそれぞれ用いた。０．１Ｎの過塩素酸水溶液３００ｍｌに酸素を１００ｍｌ／分の流量で３０分間流して酸素を十分に飽和させたものを電解液として用いた。電極を１５００ｒｐｍで回転させ、電極の電圧を水素電極に対して５０ｍＶから１０００ｍＶまで２０ｍＶ／秒で掃印させて流れた電流値を測定した。８５０ｍＶにおける電流値から単位白金量あたりの電流密度を求めた。 A catalyst ink was obtained by dispersing 10 mg of the supported catalyst powder in a mixed solution of 10 ml of water and 10 ml of ethanol. 2 μl of this catalyst ink was applied onto a glassy carbon electrode (φ5 mm) and dried to prepare a sample electrode. This sample electrode was set on a rotating disk electrode device (manufactured by Hokuto Denko) and used as a working electrode. A hydrogen electrode (RHE) was used as the reference electrode, and a platinum electrode was used as the counter electrode. A solution obtained by allowing oxygen to flow through 300 ml of a 0.1 N perchloric acid aqueous solution at a flow rate of 100 ml / min for 30 minutes to sufficiently saturate oxygen was used as an electrolytic solution. The electrode was rotated at 1500 rpm, and the voltage value of the electrode was swept from 50 mV to 1000 mV with respect to the hydrogen electrode at a rate of 20 mV / second, and the current value flowing was measured. The current density per unit platinum amount was determined from the current value at 850 mV.
５．結果
各測定結果を表１にまとめた。
5. Results The measurement results are summarized in Table 1.
図４は、使用した保護配位子／金属比（モル比）に対して得られた白金−コバルト合金微粒子の平均粒径および粒径分布幅をプロットしたグラフである。グラフからも明らかなように、保護配位子／金属比が１．０〜７．５の範囲である実施例１〜３の白金−コバルト合金微粒子は平均粒径が２ｎｍ以下であり、かつ粒径分布幅が１ｎｍ以下であった。 FIG. 4 is a graph plotting the average particle size and particle size distribution width of the obtained platinum-cobalt alloy fine particles against the protective ligand / metal ratio (molar ratio) used. As is apparent from the graph, the platinum-cobalt alloy fine particles of Examples 1 to 3 having a protective ligand / metal ratio in the range of 1.0 to 7.5 have an average particle size of 2 nm or less, and The diameter distribution width was 1 nm or less.
図５は、使用した保護配位子／金属比に対してコバルト平均組成およびコバルト組成分布幅をプロットしたグラフである。グラフからも明らかなように、保護配位子／金属比が１．０〜７．５の範囲である実施例１〜３の白金−コバルト合金微粒子はコバルト平均組成にバラつきがなく、かつコバルト組成分布幅が１０％以下であった。 FIG. 5 is a graph plotting the average cobalt composition and the cobalt composition distribution width against the protective ligand / metal ratio used. As is apparent from the graph, the platinum-cobalt alloy fine particles of Examples 1 to 3 having a protective ligand / metal ratio in the range of 1.0 to 7.5 have no variation in the average cobalt composition, and the cobalt composition The distribution width was 10% or less.
図６は、実施例３と比較例２および４で得られた白金−コバルト合金微粒子担持カーボン触媒の電流密度比を表したグラフである。グラフからも明らかなように、保護配位子／金属比が１．０〜７．５の範囲内である実施例３の触媒は、保護配位子／金属比が１０である比較例２の触媒、および保護配位子を用いずに調製した比較例４の触媒に対して、顕著に高い電流密度値を示した。高い電流密度は、試験に供された触媒の活性が高いことを意味するものである。 FIG. 6 is a graph showing the current density ratio of the platinum-cobalt alloy fine particle-supported carbon catalysts obtained in Example 3 and Comparative Examples 2 and 4. As is apparent from the graph, the catalyst of Example 3 in which the protective ligand / metal ratio is in the range of 1.0 to 7.5 is the same as that of Comparative Example 2 in which the protective ligand / metal ratio is 10. The catalyst and the catalyst of Comparative Example 4 prepared without using a protective ligand showed significantly higher current density values. A high current density means that the activity of the catalyst subjected to the test is high.
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