JP5534394B2 - フェニルアゾメチンデンドリマーに内包された白金−異種金属複合ナノ微粒子を用いた燃料電池用触媒 - Google Patents
フェニルアゾメチンデンドリマーに内包された白金−異種金属複合ナノ微粒子を用いた燃料電池用触媒 Download PDFInfo
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- 229920000736 dendritic polymer Polymers 0.000 title claims description 78
- 239000000412 dendrimer Substances 0.000 title claims description 64
- 239000003054 catalyst Substances 0.000 title claims description 35
- 239000002105 nanoparticle Substances 0.000 title claims description 33
- 239000000446 fuel Substances 0.000 title claims description 28
- 239000002905 metal composite material Substances 0.000 title claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 115
- 229910052697 platinum Inorganic materials 0.000 claims description 42
- 229910052751 metal Chemical group 0.000 claims description 18
- 239000002184 metal Chemical group 0.000 claims description 18
- 150000002466 imines Chemical class 0.000 claims description 16
- 150000004696 coordination complex Chemical class 0.000 claims description 15
- 150000002736 metal compounds Chemical class 0.000 claims description 14
- 150000003058 platinum compounds Chemical class 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 10
- 230000001603 reducing effect Effects 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004032 porphyrins Chemical group 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- -1 platinum ion Chemical class 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229910021397 glassy carbon Inorganic materials 0.000 description 8
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 5
- 238000001075 voltammogram Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004545 rotated electrode voltammetry Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- WGHCVSYNPVNMID-UHFFFAOYSA-N alumane;sodium Chemical compound [Na].[AlH3].[AlH3] WGHCVSYNPVNMID-UHFFFAOYSA-N 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000012679 convergent method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AASUFOVSZUIILF-UHFFFAOYSA-N diphenylmethanone;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 AASUFOVSZUIILF-UHFFFAOYSA-N 0.000 description 1
- 238000012678 divergent method Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000002259 gallium compounds Chemical class 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Description
式(I)の符号R2は、置換基を1つ以上有していてもよいフェニル基であり、全てが同一のものであっても互いに異なっていてもよい。置換基を有するフェニル基R2の具体例としては、ハロゲン原子、アルキル基、アルコキシ基、フェニル基、アミノ基、シアノ基またはジメチルアミノ基などの置換基がo位、m位、p位のいずれか1ヶ所または2ヶ所以上に置換した置換フェニル基が挙げられる。
<実施例1>
3.3μMのTPM-DPA G4 dendrimer(クロロホルム:アセトニトリル=1:1)溶液2mlに、塩化錫(II)アセトニトリル溶液を、dendrimer:Sn=1:4の比率となるように加え、さらに塩化白金(IV)アセトニトリル溶液をdendrimer:Pt=1:24の比率となるように加えて十分に錯形成させた。
<実施例2>
実施例1において合成したPt24Sn4@dendrimer、および同様の方法で合成した異なる組成の金属複合ナノ粒子(PtnSn28-n@dendrimer)について、燃料電池用触媒としての活性を評価した。撹拌終了後のナノ微粒子を分散させた溶液を、炭素基板(グラッシーカーボン)上に少量(1μL〜5μL)滴下し、溶媒を揮発させることによって微粒子修飾電極を作成した。
対極:白金
参照極:Ag/AgCl 3M NaCl
作用極:GCE(Φ=6mm)にPt24Sn4@dendrimerを担持
電解質:1 N H2SO4 (O2飽和)
スキャンレート:5 mV/s
同様の手法によって得た白金単独からなる微粒子(Pt28@dendrimer)で観測される酸素還元の開始電位は0.40 Vであるが、これと比較してPt24Sn4@dendrimerでは開始電位が0.41 Vに向上し、Pt16Sn12@dendrimerでは0.44 Vとさらに向上した。この開始電位の向上は、酸素還元反応に必要な過電圧の低下に対応しており、燃料電池触媒として用いた場合には起電力の向上に寄与する。
<実施例3>
上記において得られた金属複合ナノ微粒子について、メタノールの酸化反応に対する触媒活性を評価した(図4)。図4の試験条件は次のとおりである。
対極:白金
参照極:Ag/AgCl 3M NaCl
作用極:GCE(Φ=6mm) にPt24Sn4@dendrimer等を担持
電解質:1 N H2SO4 + 1.5 M ethanol
スキャンレート:5 mV/s
図4より、上記において得られた金属複合ナノ微粒子は、メタノールの酸化反応に対しても高い触媒活性を示した。即ち、実施例2の結果と併せて、本発明の金属複合ナノ微粒子は、燃料電池において、酸素還元反応が生起する空気極、酸化反応が生起する燃料極のいずれにおいても高い触媒活性を発揮することが示された。
<実施例4>
Pt16M12(Mはバナジウム、鉄、銅、ガリウム、スズいずれかの金属元素を示す。)の組成を有する白金-異種金属複合ナノ微粒子を調製した。
<実施例5>
実施例4において得られた白金-異種金属複合ナノ微粒子の評価を行った。市販の電気化学測定用グラッシーカーボン電極(φ=6mm)に、各異種金属(M)を含む複合ナノ微粒子の分散溶液を均等に載せ、乾燥させた。この際の分散溶液積載量は、均一分散した複合ナノ微粒子の質量のうち、白金相当量がそれぞれ17.1, 25.7, 34.3ngとなるように設定した。
作用極:白金触媒を担持したグラッシーカーボンディスク電極(φ=6mm)
参照電極:Ag/AgCl (3molL-1NaCl)
対極:Ptコイル
電解質溶液:0.5molL-1硫酸水溶液 (O2ガスパージによる酸素飽和)
電極回転数ω=120, 180, 300rpm
それぞれの異種金属種(M)、白金積載量、電極回転数におけるボルタモグラムより、参照電極(Ag/AgCl)基準で0.0V, 0.35Vのそれぞれにおける電流値を読み取り、図5(0.0V)、図6(0.35V)にそれぞれ得られたデータをもとに以下の手順で速度論的限界電流値(jK)を算出し、プロットした。
<実施例6>
バイメタリッククラスター(Pt16Sn12)と、ホモクラスター(Pt28)の触媒活性の比較検証実験を行った。実施例4と同様に、二塩化スズおよび四塩化白金のアセトニトリル溶液を3mmolL-1の濃度となるように調製した。
Claims (3)
- 次式(I)
- 前記式(I)のR 1 は、次式:
(式中のMは2つの水素原子または任意の金属原子を示し、Dはデンドロン結合部位を示す。)のいずれかで表わされる請求項1に記載の燃料電池用触媒。 - 前記還元を行う前のフェニルアゾメチンデンドリマー金属錯体は、デンドリマーの第1世代から第m世代未満までのイミン部位に異種金属化合物が配位しており、その外側のイミン部位に白金化合物が配位している請求項1又は2に記載の燃料電池用触媒。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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