JP6609758B2 - 担体担持パラジウムコア白金シェル微粒子およびその製造方法 - Google Patents
担体担持パラジウムコア白金シェル微粒子およびその製造方法 Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims description 259
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 143
- 229910052697 platinum Inorganic materials 0.000 title claims description 130
- 239000010419 fine particle Substances 0.000 title claims description 103
- 238000004519 manufacturing process Methods 0.000 title claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 113
- 239000003054 catalyst Substances 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 239000002994 raw material Substances 0.000 claims description 64
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- 229910052799 carbon Inorganic materials 0.000 claims description 45
- 239000007771 core particle Substances 0.000 claims description 32
- 229910052763 palladium Inorganic materials 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- -1 hydroxide ions Chemical class 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 12
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 11
- 239000002612 dispersion medium Substances 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000012696 Pd precursors Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- QFJIELFEXWAVLU-UHFFFAOYSA-H tetrachloroplatinum(2+) dichloride Chemical compound Cl[Pt](Cl)(Cl)(Cl)(Cl)Cl QFJIELFEXWAVLU-UHFFFAOYSA-H 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002609 medium Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 description 34
- 229910052751 metal Inorganic materials 0.000 description 34
- 239000002184 metal Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 29
- 238000012360 testing method Methods 0.000 description 28
- 239000011258 core-shell material Substances 0.000 description 26
- 239000010410 layer Substances 0.000 description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 25
- 239000001301 oxygen Substances 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 25
- 238000006722 reduction reaction Methods 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000005755 formation reaction Methods 0.000 description 21
- 239000000446 fuel Substances 0.000 description 20
- 230000009467 reduction Effects 0.000 description 18
- 239000012295 chemical reaction liquid Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 13
- 229920000554 ionomer Polymers 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000002082 metal nanoparticle Substances 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000002923 metal particle Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910021397 glassy carbon Inorganic materials 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000010757 Reduction Activity Effects 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 239000011859 microparticle Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010420 shell particle Substances 0.000 description 4
- 229910021126 PdPt Inorganic materials 0.000 description 3
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 3
- 150000003057 platinum Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- BZVCUDFTTWZWPF-UHFFFAOYSA-M potassium;ethane-1,2-diol;hydroxide Chemical compound [OH-].[K+].OCCO BZVCUDFTTWZWPF-UHFFFAOYSA-M 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000011172 small scale experimental method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004758 underpotential deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
Description
シェル:ある微粒子を下地として、下地の周囲に下地とは異なる物質が層状または部分的層状もしくは粒子の部分的集合の形に配置されているときシェル構造を形成しているという。下地のナノ粒子をコア粒子とし、コアシェル構造ということもある。
特に、パラジウムコア白金シェルナノ粒子は触媒用途として期待されているものの、均一なシェル層を安定な品質でコストを抑えて製造することは難しい。
課題を解決するためになされた第1の発明(以下、発明1という)は、アルコール類を分散媒とし、担体が分散している分散液にパラジウム前駆体(パラジウム原料)を加えて反応原料液とし、マイクロ波加熱することで前記パラジウム原料を還元して担体担持パラジウム微粒子を合成する担体担持パラジウム微粒子コロイドの製造方法であって、水酸化カリウムを除く水酸化物イオンを分散媒中に生成する機能を有する添加剤を添加することを特徴とする担体担持パラジウム微粒子コロイドの製造方法である。
温度25℃において、可逆水素電極を参照電極とした電位0.6Vを3秒間、1.0Vを3秒間の方形波を1サイクルとして電位サイクルを印加する耐久性試験を行ったとき、
0.1M過塩素酸水溶液を前記フラスコに加え、3L/分の酸素を30分間バブリングして窒素を追い出したものを電解液として使用し、
前記電極の回転速度1600[回転/分]、温度25℃、20[mV/秒]の高電位側への走査速度、の条件において、
可逆水素電極を参照電極とした電位0.9Vにおける酸素還元電流値をKoutecky−Levich式より導き、溶液抵抗を補償して算出する質量活性算出法を使用して、
10000電位サイクル後の酸素還元触媒としての白金質量活性、すなわち前記質量活性算出法における電流値を塗布した白金量0.96μgで除した値が耐久性試験前の質量活性の95%以上を維持できていることを特徴とするパラジウムコア白金シェル微粒子触媒である。
2:マイクロ波キャビティ反応系
3:白金シェル層形成液及びその送液ポンプ系
4:白金シェル層形成用原料液及び送液ポンプ系
5a,5b:ミキサーを用いる工程
6:白金シェル形成反応用タンク
7:カーボン担持パラジウムコア白金シェル触媒
7a:カーボン担体
7b:パラジウムコア白金シェル触媒
8a:負荷応答耐久性試験における初期活性を100%として表した点
8b:白金シェル形成反応用タンク
8c:負荷応答耐久性試験10000サイクル後の質量活性の維持率を表した点
8d:8aと8bを結んだ線
8e:8bと8cを結んだ線
M+(金属イオン)+ e-(還元剤から供給される電子) → M0(金属)・・・(1)
となる。
上記化学式の右項の0価の金属が数千個程度集まることで金属微粒子が構成される。
エチレングリコール → e- + エチレングリコール酸化産物+水素イオン・・・(2)
と表現される。
マイクロ波で金属原料塩を含んだエチレングリコールを急速に加熱することで、エチレングリコールから急速に電子が多量に供給され、原料金属塩が急速に還元されることによって粒子径の小さい微粒子が合成できる。一方、ゆるやかな加熱では金属粒子の核形成と結晶成長が穏やかになり、粒子径の大きいナノまたはミクロン粒子が生成される傾向がある。
Vulcan(登録商標)XC72が0.1重量パーセント、テトラクロロパラジウム(2)酸ナトリウムが2mMになるようにエチレングリコールに混合し、テトラクロロパラジウム(2)酸ナトリウムを完全に溶解させる。また、超音波をかけてVulcan(登録商標)XC72が均一な分散液になるようにする。さらに、5MNaOH水溶液をテトラクロロパラジウム(2)酸ナトリウムの物質量の4〜7倍になるように加えてよく混合し、これを反応原料液とした。この反応原料液をカーボン分散液を扱うことができるポンプで送液する。
比較例1として、市販の、カーボン担持白金触媒を用意し、酸素還元反応の触媒活性を比較した。
比較例2として、マイクロ波連続法でカーボン担持白金触媒を合成し、酸素還元反応の触媒活性を比較した。その作製法を以下に述べる。カーボン担体としてVulcan(登録商標)XC72、分散剤としてNafion(登録商標)(DE520CS)をエチレングリコールに混合し、超音波を十分に照射してカーボンをよく分散させた。その分散液にヘキサクロロ白金(4)酸エチレングリコール溶液と水酸化カリウムエチレングリコール溶液を加え、最終的にカーボンが0.1g/L、Nafion(登録商標)が0.03g/L、ヘキサクロロ白金(2)酸が2mM、水酸化カリウムが20mMの濃度になるようにして原料液とした。原料液は、実施例と同様に、マイクロ波キャビティの円筒中心軸に配置された内径2mmのPFA反応管を流速2ml/minで流し、原料液の温度が85℃になるように加熱した。
Claims (4)
- アルコール類を分散媒とし、担体が分散している分散液にパラジウム前駆体(パラジウム原料)を加えて反応原料液とし、マイクロ波加熱することで前記パラジウム原料を還元して担体担持パラジウム微粒子を合成する担体担持パラジウム微粒子コロイドの製造方法で、水酸化カリウムを除く水酸化物イオンを分散媒中に生成する機能を有する添加剤を添加することを特徴とする担体担持パラジウム微粒子コロイドの製造方法であって、
前記アルコール類がエチレングリコールであり、前記担体がカーボン微粒子であり、前記パラジウム前駆体がテトラクロロパラジウム(2)酸ナトリウムであり、前記添加剤として、前記パラジウム原料の物質量の4〜7倍の物質量の水酸化ナトリウムを添加し、カーボン担持パラジウム微粒子触媒をマイクロ波連続加熱法で製造する工程を含むことを特徴とする担体担持パラジウム微粒子コロイドの製造方法。 - 請求項1に記載の方法で製造したコロイドを原料とし、白金前駆体を含む溶液と、水酸化カリウムを除く水酸化物イオンを分散媒中に生成する機能を有する添加剤を加えて反応原料液とし常温で反応させることで担体担持パラジウムコア粒子に白金シェルを形成する担体担持パラジウムコア白金シェル微粒子触媒の製造方法であって、
前記白金前駆体溶液(白金原料)に前記添加剤を加えた後の、遊離、配位、吸着している水酸化物イオン濃度が前記白金原料の物質量の2〜6倍になることを特徴とする担体担持パラジウムコア白金シェル微粒子触媒の製造方法。 - 前記白金原料がヘキサクロロ白金(4)酸イオン含有溶液であり、前記添加剤が水酸化ナトリウムであり、該水酸化ナトリウム溶液を添加した後の、遊離、配位、吸着している水酸化物イオン濃度が前記白金原料の物質量の2〜6倍になることを特徴とする請求項2に記載の担体担持パラジウムコア白金シェル微粒子触媒の製造方法。
- 前記パラジウムコア白金シェル微粒子触媒を乾燥粉にした際、ナトリウム成分が該乾燥粉に残存していることを特徴とする請求項2または3に記載の担体担持パラジウムコア白金シェル微粒子触媒の製造方法。
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