JP6709557B2 - Supported catalyst - Google Patents
Supported catalyst Download PDFInfo
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- JP6709557B2 JP6709557B2 JP2018223118A JP2018223118A JP6709557B2 JP 6709557 B2 JP6709557 B2 JP 6709557B2 JP 2018223118 A JP2018223118 A JP 2018223118A JP 2018223118 A JP2018223118 A JP 2018223118A JP 6709557 B2 JP6709557 B2 JP 6709557B2
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- Prior art keywords
- supported catalyst
- protective material
- nanoparticles
- carbon
- polymer protective
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- 239000003054 catalyst Substances 0.000 title claims description 54
- 239000002245 particle Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 32
- 230000001681 protective effect Effects 0.000 claims description 32
- 239000002105 nanoparticle Substances 0.000 claims description 30
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910000929 Ru alloy Inorganic materials 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000006104 solid solution Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 241000255925 Diptera Species 0.000 claims description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 24
- 239000000203 mixture Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 241000003832 Lantana Species 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000002116 nanohorn Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- HYLLZXPMJRMUHH-UHFFFAOYSA-N 1-[2-(2-methoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOC HYLLZXPMJRMUHH-UHFFFAOYSA-N 0.000 description 1
- SNAQINZKMQFYFV-UHFFFAOYSA-N 1-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOC SNAQINZKMQFYFV-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- RERATEUBWLKDFE-UHFFFAOYSA-N 1-methoxy-2-[2-(2-methoxypropoxy)propoxy]propane Chemical compound COCC(C)OCC(C)OCC(C)OC RERATEUBWLKDFE-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
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- RJBIZCOYFBKBIM-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]propane Chemical compound COCCOCCOC(C)C RJBIZCOYFBKBIM-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
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- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical group [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- -1 perovskite Chemical compound 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
本発明は、高分子保護材フリーの担持触媒に関する。 TECHNICAL FIELD The present invention relates to a supported catalyst free of a polymeric protective material.
従来、化学反応触媒又は燃料電池などでは、カーボン系の担体にナノ粒子を担持した不均一系触媒が用いられている。また、ボイラー又は排ガスの浄化などでは、セラミックス系の担体にナノ粒子を担持した不均一系触媒が用いられている。不均一系触媒に用いるナノ粒子としてＰｄ−Ｒｕ合金ナノ粒子が開示されている（例えば、特許文献１、非特許文献１を参照。）。非特許文献１では、Ｐｄ−Ｒｕ合金ナノ粒子を担体に担持して不均一系触媒として使用する場合、ポリビニルピロリドンなどの高分子保護材を用いてナノ粒子を合成・精製した後に、得られたナノ粒子を担体に担持している。 Conventionally, in a chemical reaction catalyst or a fuel cell, a heterogeneous catalyst in which nanoparticles are supported on a carbon-based carrier has been used. Further, in purification of a boiler or exhaust gas, a heterogeneous catalyst in which nanoparticles are supported on a ceramic-based carrier is used. Pd-Ru alloy nanoparticles have been disclosed as nanoparticles used for a heterogeneous catalyst (see, for example, Patent Document 1 and Non-Patent Document 1). In Non-Patent Document 1, when Pd-Ru alloy nanoparticles are supported on a carrier and used as a heterogeneous catalyst, the nanoparticles were obtained after synthesizing and purifying the nanoparticles using a polymer protective material such as polyvinylpyrrolidone. The nanoparticles are carried on a carrier.
しかし、ナノ粒子の合成時に用いた高分子保護材が触媒中に残っていると、触媒の効果が十分に発揮されない場合がある。高分子保護材の除去を目的としてナノ粒子の精製を繰り返すと、精製回数が増加するにつれて得られるナノ粒子の収量が少なくなるという問題である。 However, if the polymer protective material used during the synthesis of nanoparticles remains in the catalyst, the effect of the catalyst may not be sufficiently exhibited. If the purification of nanoparticles is repeated for the purpose of removing the polymer protective material, the yield of nanoparticles obtained decreases as the number of purification increases.
本発明の目的は、触媒の性能を低下させる高分子保護材を用いず、触媒の効果を十分に発揮できる担持触媒を提供することである。 An object of the present invention is to provide a supported catalyst that can sufficiently exhibit the effect of the catalyst without using a polymer protective material that deteriorates the performance of the catalyst.
本発明に係る担持触媒は、ナノ粒子としてＰｄ−Ｒｕ合金粒子が担持体に担持された担持触媒において、前記担持体は、カルシア、セリア、セリアジルコニア、ランタナ、ランタナアルミナ、酸化スズ、酸化タングステン、アルミノシリケート、アルミノホスフェート、ボロシリケート、リンタングステン酸、ヒドロキシアパタイト、ハイドロタルサイト、ペロブスカイト、コージェライト、ムライト、シリコンカーバイド、活性炭、カーボンナノチューブ及びカーボンナノホーンの中から選ばれる１種以上であり、前記担持触媒の外表面に高分子保護材が存在しないことを特徴とする。 Supported catalyst according to the present invention is a supported catalyst Pd-Ru alloy particles as nanoparticles supported on carrier, wherein the carrier is mosquitoes Resid A, Se Li A, ceria zirconia, lanthana, lanthana alumina, oxide One or more selected from tin, tungsten oxide, aluminosilicate, aluminophosphate, borosilicate, phosphotungstic acid, hydroxyapatite, hydrotalcite, perovskite, cordierite, mullite, silicon carbide, activated carbon, carbon nanotube and carbon nanohorn. And the polymer protective material is not present on the outer surface of the supported catalyst.
本発明に係る担持触媒は、高分子保護材を含有しないことが好ましい。触媒活性をより高めることができる。 The supported catalyst according to the present invention preferably contains no polymer protective material. The catalytic activity can be further enhanced.
本発明に係る担持触媒では、前記ナノ粒子と前記担持体との間に前記高分子保護材が介在しないことが好ましい。触媒活性をより高めることができる。 In the supported catalyst according to the present invention, it is preferable that the polymer protective material is not interposed between the nanoparticles and the support. The catalytic activity can be further enhanced.
本発明に係る担持触媒では、前記担持体は、カーボン若しくはセラミックスのいずれか一方又は両方である形態を包含する。 In the supported catalyst according to the present invention, the support includes a form in which either one or both of carbon and ceramics is used.
本発明に係る担持触媒では、前記Ｐｄ−Ｒｕ合金粒子は、固溶体を形成していることが好ましい。触媒活性をより高めることができる。 In the supported catalyst according to the present invention, the Pd-Ru alloy particles preferably form a solid solution. The catalytic activity can be further enhanced.
本発明は、触媒の性能を低下させる高分子保護材を用いず、触媒の効果を十分に発揮できる担持触媒を提供することができる。 INDUSTRIAL APPLICABILITY The present invention can provide a supported catalyst that can sufficiently exert the effect of the catalyst without using a polymer protective material that deteriorates the performance of the catalyst.
次に本発明について実施形態を示して詳細に説明するが本発明はこれらの記載に限定して解釈されない。本発明の効果を奏する限り、実施形態は種々の変形をしてもよい。 Next, the present invention will be described in detail by showing embodiments, but the present invention is not construed as being limited to these descriptions. The embodiments may be variously modified as long as the effects of the present invention are exhibited.
本実施形態に係る担持触媒は、ナノ粒子としてＰｄ−Ｒｕ合金粒子が担持体に担持された担持触媒において、担持触媒の外表面に高分子保護材が存在しない。高分子保護材が担持触媒の外表面に存在しないことで、触媒の作用を十分の発揮させることができる。高分子保護材は、例えば、ポリビニルピロリドン（ＰＶＰ）である。本実施形態に係る担持触媒では、高分子保護材がナノ粒子の外表面に付着していないことが好ましく、高分子保護材がナノ粒子の外表面及び担持体の外表面に付着していないことがより好ましい。 The supported catalyst according to the present embodiment is a supported catalyst in which Pd—Ru alloy particles as nanoparticles are supported on a support, and a polymer protective material does not exist on the outer surface of the supported catalyst. Since the polymer protective material does not exist on the outer surface of the supported catalyst, the function of the catalyst can be sufficiently exerted. The polymer protective material is, for example, polyvinylpyrrolidone (PVP). In the supported catalyst according to the present embodiment, it is preferable that the polymer protective material does not adhere to the outer surface of the nanoparticles, and the polymer protective material does not adhere to the outer surface of the nanoparticles and the outer surface of the carrier. Is more preferable.
本実施形態に係る担持触媒では、ナノ粒子と担持体との間に高分子保護材が介在しないことが好ましい。 In the supported catalyst according to the present embodiment, it is preferable that no polymer protective material is interposed between the nanoparticles and the carrier.
本実施形態に係る担持触媒は、高分子保護材を含有しないことが好ましい。担持触媒が高分子保護材を含有するか否かは、例えば、Ｘ線回折パターン（ＸＲＤパターン）によって確認できる。例えば高分子保護材がＰＶＰであるとき、室温でλ＝ＣｕＫαの測定条件で測定したＸＲＤパターンにおいて、１０°付近にＰＶＰ由来のパターンが確認されないことで、担持触媒が高分子保護材を含有しないことを確認することができる。 The supported catalyst according to this embodiment preferably does not contain a polymer protective material. Whether or not the supported catalyst contains the polymer protective material can be confirmed by, for example, an X-ray diffraction pattern (XRD pattern). For example, when the polymer protective material is PVP, in the XRD pattern measured at room temperature under the measurement condition of λ=CuKα, the PVP-derived pattern is not confirmed at around 10°, so that the supported catalyst does not contain the polymer protective material. You can check that.
本実施形態に係る担持触媒は、従来の担持触媒の製造方法のように予め合成したナノ粒子を担持体に担持させる方法ではなく、ナノ粒子の合成とナノ粒子の担持体への担持とを同時に行う方法で製造することが好ましい。ナノ粒子の合成とナノ粒子の担持体への担持とを同時に行うことで、従来の製造方法と比較して製造工程を少なくすることができる。本明細書において、ナノ粒子とは、平均粒子径が１００ｎｍ以下の微細粒子をいう。ナノ粒子の平均粒子径は、透過型電子顕微鏡（ＴＥＭ）によって得られた粒子像から少なくとも１００個以上の粒子の粒子径を計測し、その平均を求めることによって算出した値である。ＴＥＭの観察倍率は、例えば、１２００００倍又は１５００００倍であることが好ましい。ナノ粒子の平均粒子径の下限は、特に限定されないが、１ｎｍ以上であることが好ましい。 The supported catalyst according to the present embodiment is not a method of supporting previously synthesized nanoparticles on a carrier like a conventional method for manufacturing a supported catalyst, but simultaneously synthesizing nanoparticles and supporting nanoparticles on a carrier at the same time. It is preferable to manufacture by the method of performing. By simultaneously synthesizing the nanoparticles and supporting the nanoparticles on the carrier, the number of manufacturing steps can be reduced as compared with the conventional manufacturing method. In the present specification, the nanoparticles mean fine particles having an average particle diameter of 100 nm or less. The average particle size of nanoparticles is a value calculated by measuring the particle size of at least 100 particles from a particle image obtained by a transmission electron microscope (TEM) and calculating the average. The observation magnification of TEM is preferably, for example, 120,000 times or 150,000 times. The lower limit of the average particle diameter of the nanoparticles is not particularly limited, but is preferably 1 nm or more.
本実施形態に係る担持触媒の製造方法は、Ｐｄ−Ｒｕ合金粒子を合成するとともに、Ｐｄ−Ｒｕ合金粒子を担持体に担持させる工程１を有し、工程１は、担持体と有機溶媒とを含有し、かつ、高分子保護材を含有しない混合物を加熱する工程１ａと、Ｐｄ化合物、Ｒｕ化合物及び純水を含有し、かつ、高分子保護材を含有しない混合物を作製する工程１ｂと、工程１ａの混合物と工程１ｂの混合物とを混合する工程１ｃとを有することが好ましい。 The method for producing a supported catalyst according to the present embodiment includes a step 1 of synthesizing Pd-Ru alloy particles and supporting Pd-Ru alloy particles on a support, and the step 1 includes a support and an organic solvent. A step 1a of heating a mixture containing and not containing a polymer protective material; a step 1b of producing a mixture containing a Pd compound, a Ru compound and pure water and containing no polymer protective material; It is preferable to have a step 1c of mixing the mixture of 1a and the mixture of step 1b.
次に、工程１で用いる各物質について説明する。 Next, each substance used in step 1 will be described.
（ナノ粒子の合成原料となる化合物）
Ｐｄ−Ｒｕ合金粒子の合成原料となる化合物はＲｕ化合物及びＰｄ化合物である。Ｒｕ化合物は、例えば、Ｒｕ塩化物、Ｒｕ窒化物である。Ｐｄ化合物は、例えば、Ｐｄ塩化物、Ｐｄ窒化物である。このうち、Ｒｕ化合物及びＰｄ化合物はＲｕ塩化物及びＰｄ塩化物であることが好ましい。担持触媒をより効率的に得ることができる。Ｒｕ塩化物は、例えば、塩化ルテニウム（ＩＩＩ）ｎ水和物、塩化ルテニウム（ＩＶ）ｎ水和物、ルテニウム酸ナトリウムである。Ｐｄ塩化物は、例えば、テトラクロロパラジウム酸カリウム（ＩＩ）、ジニトロジアンミンパラジウム（ＩＩ）である。
(Compounds used as raw materials for synthesizing nanoparticles)
The compounds that are raw materials for synthesizing Pd-Ru alloy particles are Ru compounds and Pd compounds. The Ru compound is, for example, Ru chloride or Ru nitride. The Pd compound is, for example, Pd chloride or Pd nitride. Among these, the Ru compound and the Pd compound are preferably Ru chloride and Pd chloride. The supported catalyst can be obtained more efficiently. Ru chloride is, for example, ruthenium (III) chloride n-hydrate, ruthenium (IV) chloride n-hydrate, and sodium ruthenate. Pd chlorides are, for example, potassium tetrachloropalladate (II) and dinitrodiamminepalladium (II).
（担持体）
担持体は、カーボン若しくはセラミックスのいずれか一方又は両方である形態を包含する。セラミックスは、例えば、アルミナ、シリカ、シリカアルミナ、カルシア、マグネシア、チタニア、セリア、ジルコニア、セリアジルコニア、ランタナ、ランタナアルミナ、酸化スズ、酸化タングステン、アルミノシリケート、アルミノホスフェート、ボロシリケート、リンタングステン酸、ヒドロキシアパタイト、ハイドロタルサイト、ペロブスカイト、コージェライト、ムライト又はシリコンカーバイドである。カーボンは、例えば、活性炭、カーボンブラック、アセチレンブラック、カーボンナノチューブ又はカーボンナノホーンである。本実施形態では、これらの担持体の中から１種だけを使用するか、又は２種以上を併用してもよい。２種以上を併用する場合は、セラミックスから２種以上を組合せて用いるか、カーボンから２種以上を組合せて用いるか、又はセラミックスから１種以上及びカーボンから１種以上を組合せて用いてもよい。より好ましくは、アルミナ、シリカ、チタニア、セリア、ジルコニア、活性炭及びカーボンブラックの中から選ばれる１種以上を用いる。
(Support)
The carrier includes a form that is either or both of carbon and ceramics. Ceramics, for example, alumina, silica, silica-alumina, calcia, magnesia, titania, ceria, zirconia, ceria zirconia, lantana, lantana alumina, tin oxide, tungsten oxide, aluminosilicate, aluminophosphate, borosilicate, phosphotungstic acid, hydroxy. It is apatite, hydrotalcite, perovskite, cordierite, mullite or silicon carbide. The carbon is, for example, activated carbon, carbon black, acetylene black, carbon nanotube or carbon nanohorn. In the present embodiment, only one type of these carriers may be used, or two or more types may be used in combination. When two or more kinds are used in combination, two or more kinds of ceramics may be used in combination, two or more kinds of carbon may be used in combination, or one or more kinds of ceramics and one or more kinds of carbon may be used in combination. .. More preferably, at least one selected from alumina, silica, titania, ceria, zirconia, activated carbon and carbon black is used.
（有機溶媒）
有機溶媒は、炭素数が２以上であり、還元性をもつことが好ましい。有機溶媒の炭素数は、４以上であることがより好ましい。有機溶媒の炭素数の上限は、特に限定されないが、常温において液体であることが好ましい。
(Organic solvent)
The organic solvent preferably has 2 or more carbon atoms and has a reducing property. The carbon number of the organic solvent is more preferably 4 or more. The upper limit of the carbon number of the organic solvent is not particularly limited, but it is preferably liquid at room temperature.
有機溶媒の沸点は１００℃以上であることが好ましい。取り扱い性に優れる。また、担持触媒をより安全に得ることができる。有機溶媒の沸点は、１６０℃以上であることがより好ましい。有機溶媒の沸点の上限は、特に限定されないが、担持触媒から溶媒をより容易に除去できる点で、３００℃以下であることが好ましく、２９０℃以下であることがより好ましい。 The boiling point of the organic solvent is preferably 100° C. or higher. Excellent handleability. In addition, the supported catalyst can be obtained more safely. The boiling point of the organic solvent is more preferably 160° C. or higher. The upper limit of the boiling point of the organic solvent is not particularly limited, but is preferably 300° C. or lower, and more preferably 290° C. or lower, from the viewpoint of easily removing the solvent from the supported catalyst.
有機溶媒は、多価アルコール、ブタノール、イソブタノール、エトキシエタノール、ジメチルホルムアミド、キシレン、Ｎ−メチルピロリジノン、ジクロロベンゼン、トルエン、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチルラクテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールブチルメチルエーテル、トリプロピレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、リエチレングリコールモノメチルエーテル、ジエチレングリコールジブチルエーテル、トリエチレングリコールブチルメチルエーテル、ポリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル及びポリエチレングリコールモノメチルエーテルの中から選ばれる１種以上であることが好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。このうち、多価アルコールがより好ましい。 Organic solvents include polyhydric alcohols, butanol, isobutanol, ethoxyethanol, dimethylformamide, xylene, N-methylpyrrolidinone, dichlorobenzene, toluene, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethyl lactate, Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether At least one selected from ethylene glycol monophenyl ether, ethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and polyethylene glycol monomethyl ether is preferable. The supported catalyst can be obtained more safely and efficiently. Of these, polyhydric alcohols are more preferable.
多価アルコールは、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール及びブチレングリコールの中から選ばれる１種以上であることが好ましい。このうち、トリエチレングリコールがより好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。 The polyhydric alcohol is preferably one or more selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and butylene glycol. Of these, triethylene glycol is more preferable. The supported catalyst can be obtained more safely and efficiently.
次に、工程１について説明する。 Next, step 1 will be described.
工程１ａでは、まず、担持体と有機溶媒とを含有し、かつ、高分子保護材を含有しない混合物を作製する。混合物の作製にあたり、担持体を有機溶媒中に懸濁させた後、例えば超音波などの分散機を用いて分散させることが好ましい。 In step 1a, first, a mixture containing a support and an organic solvent and containing no polymer protective material is prepared. In preparing the mixture, it is preferable to suspend the carrier in an organic solvent and then disperse the carrier using a disperser such as ultrasonic waves.
次いで、混合物を加熱する。加熱方法は、特に限定されず、例えば、オイルバス、マントルヒーター、ブロックヒーター若しくは熱媒循環式ジャケットなどの外部加熱方式、又はマイクロ波照射方式である。加熱温度は、１００〜３００℃であることが好ましく、１８０〜２３０℃であることがより好ましい。 The mixture is then heated. The heating method is not particularly limited, and is, for example, an external heating method such as an oil bath, a mantle heater, a block heater or a heating medium circulating jacket, or a microwave irradiation method. The heating temperature is preferably 100 to 300°C, more preferably 180 to 230°C.
工程１ｂでは、Ｐｄ化合物、Ｒｕ化合物及び純水を含有し、かつ、高分子保護材を含有しない混合物を作製する。混合物は、Ｐｄ化合物及びＲｕ化合物が純水に溶解した溶液であるか、又はＰｄ化合物及びＲｕ化合物が純水に分散した分散液であってもよい。このうち、混合物は、Ｐｄ化合物及びＲｕ化合物が純水に溶解した溶液であることがより好ましい。Ｐｄ化合物とＲｕ化合物との割合は、得られるＰｄ−Ｒｕ合金粒子においてＲｕとＰｄとの原子比が所定の範囲となるように調整する。Ｒｕ：Ｐｄが原子比で０．１：０．９〜０．９：０．１の範囲であることが特に好ましい。合金の原子比は、例えば高周波誘導結合プラズマ発光分光分析、原子吸光分光光度法で測定することができる。 In step 1b, a mixture containing a Pd compound, a Ru compound, and pure water, but containing no polymer protective material is prepared. The mixture may be a solution in which Pd compound and Ru compound are dissolved in pure water, or a dispersion liquid in which Pd compound and Ru compound are dispersed in pure water. Of these, the mixture is more preferably a solution of Pd compound and Ru compound dissolved in pure water. The ratio between the Pd compound and the Ru compound is adjusted so that the atomic ratio of Ru and Pd in the obtained Pd-Ru alloy particles is within a predetermined range. It is particularly preferable that the atomic ratio of Ru:Pd is 0.1:0.9 to 0.9:0.1. The atomic ratio of the alloy can be measured by, for example, high frequency inductively coupled plasma emission spectroscopy or atomic absorption spectrophotometry.
工程１ｃでは、工程１ａの混合物を前記した加熱温度に保ちながら、工程１ａの混合物と工程１ｂの混合物とを混合する。混合方法は、特に限定されないが、工程１ａの混合物に、工程１ｂの混合物を噴霧する方法であることが好ましい。工程１ｃでは、工程１ａの混合物と工程１ｂの混合物とを混合後、加熱状態を保持することが好ましい。混合液の全量を混合後加熱状態を保持する時間は、５〜６０分であることが好ましく、１０〜３０分であることがより好ましい。 In step 1c, the mixture of step 1a and the mixture of step 1b are mixed while maintaining the mixture of step 1a at the above-mentioned heating temperature. The mixing method is not particularly limited, but a method of spraying the mixture of step 1b onto the mixture of step 1a is preferable. In step 1c, it is preferable to maintain the heated state after mixing the mixture of step 1a and the mixture of step 1b. The time for maintaining the heated state after mixing the entire amount of the mixed solution is preferably 5 to 60 minutes, and more preferably 10 to 30 minutes.
Ｒｕ化合物及びＰｄ化合物の合計量と担持体の量との割合は、担持触媒中のＰｄ−Ｒｕ合金粒子の担持量が所定の範囲となるように調整する。担持触媒中のＰｄ−Ｒｕ合金粒子の担持量は、０．００１〜６０質量％であることが好ましい。ここで、担持量は、乾燥状態の担持触媒の質量に対するナノ粒子の質量の割合であり、例えば高周波誘導結合プラズマ発光分光分析、原子吸光分光光度分析で測定することができる。 The ratio between the total amount of the Ru compound and the Pd compound and the amount of the support is adjusted so that the amount of Pd-Ru alloy particles supported in the supported catalyst falls within a predetermined range. The supported amount of Pd-Ru alloy particles in the supported catalyst is preferably 0.001 to 60 mass %. Here, the supported amount is the ratio of the mass of the nanoparticles to the mass of the supported catalyst in a dry state, and can be measured by, for example, high frequency inductively coupled plasma emission spectrometry or atomic absorption spectrophotometry.
工程１では、Ｒｕ化合物及びＰｄ化合物が有機溶媒によって還元され、担持体の表面でＰｄ−Ｒｕ合金粒子の核生成及び粒成長が起こる。そして、Ｐｄ−Ｒｕ合金粒子が担持体に担持された担持触媒が得られる。溶解法ではＰｄ−Ｒｕ合金粒子中のＲｕ含有量が１０〜９０原子％ではＰｄ−Ｒｕ合金の固溶体を形成しないが、本実施形態ではＰｄ−Ｒｕ合金の固溶体を形成することができる。Ｐｄ−Ｒｕ合金粒子が固溶体を形成していることで、触媒活性がより高まる。より好ましくは、Ｐｄ−Ｒｕ合金粒子が固溶体の単相を形成している。Ｐｄ−Ｒｕ合金粒子の状態は、例えば、走査透過電子顕微鏡法（ＳＴＥＭ）を用いたエネルギー分散型蛍光Ｘ線分析法（ＥＤＳ）の元素マッピングによって確認できる。Ｐｄ−Ｒｕ合金粒子の平均粒子径は、３０ｎｍ以下であることが好ましく、２０ｎｍ以下であることがより好ましい。Ｐｄ−Ｒｕ合金粒子の平均粒子径の下限は、特に限定されないが、１ｎｍ以上であることが好ましい。 In step 1, the Ru compound and the Pd compound are reduced by the organic solvent, and nucleation and grain growth of Pd-Ru alloy particles occur on the surface of the support. Then, a supported catalyst in which the Pd-Ru alloy particles are supported on the support is obtained. In the melting method, when the Ru content in the Pd-Ru alloy particles is 10 to 90 atomic %, the solid solution of the Pd-Ru alloy is not formed, but in the present embodiment, the solid solution of the Pd-Ru alloy can be formed. Since the Pd-Ru alloy particles form a solid solution, the catalytic activity is further enhanced. More preferably, the Pd-Ru alloy particles form a single phase of solid solution. The state of the Pd-Ru alloy particles can be confirmed by, for example, elemental mapping of energy dispersive X-ray fluorescence analysis (EDS) using scanning transmission electron microscopy (STEM). The average particle diameter of the Pd-Ru alloy particles is preferably 30 nm or less, more preferably 20 nm or less. The lower limit of the average particle diameter of the Pd-Ru alloy particles is not particularly limited, but is preferably 1 nm or more.
工程１ｃの後、担持触媒を溶媒から分離精製することが好ましい。担持触媒を分離精製する方法は、特に限定されないが、例えば、温度が下がった混合物をろ過し、洗浄・乾燥する方法である。 After step 1c, it is preferable to separate and purify the supported catalyst from the solvent. The method of separating and purifying the supported catalyst is not particularly limited, but is, for example, a method of filtering a mixture whose temperature has decreased, washing and drying.
以降、実施例を示しながら本発明についてさらに詳細に説明するが、本発明は実施例に限定して解釈されない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.
（実施例１Ｂ）
フラスコに純水を５０ｍＬ投入した。塩化ルテニウム（ＩＩＩ）ｎ水和物（以下、ＲｕＣｌ３・ｎＨ２Ｏ）を０．１１７７ｇとテトラクロロパラジウム酸カリウム（ＩＩ）（以下、Ｋ２ＰｄＣｌ４）を０．１６３５ｇとを秤とり前記純水に添加して溶解した水溶液を作製した。水溶液に高分子保護材は添加しなかった。また、活性炭（ＦＡＭ−５０、日本エンバイロケミカルズ社製）を１．１５ｇ秤とりトリエチレングリコール（以下、ＴＥＧ）１００ｍＬ中に添加し、超音波で分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を２０５℃に加熱し、混合液の温度が２００℃以上を保持した条件で前記水溶液を霧状に添加した。水溶液の全量を添加終了後１５ｍｉｎ加熱保持し、その後冷却した。冷却後の混合液を減圧濾過し、固体成分（濾物）をＨ２Ｏ及びエタノールを用いて十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 1B)
50 mL of pure water was added to the flask. Ruthenium (III) chloride n hydrate (hereinafter RuCl 3 .nH 2 O) 0.1177 g and potassium tetrachloropalladate (II) (hereinafter K 2 PdCl 4 ) 0.1635 g were weighed and the above pure An aqueous solution which was added to water and dissolved was prepared. No polymeric protective material was added to the aqueous solution. In addition, 1.15 g of activated carbon (FAM-50, manufactured by Nippon EnviroChemicals) was weighed and added to 100 mL of triethylene glycol (hereinafter, TEG), and ultrasonically dispersed to prepare a mixed solution. No polymer protective material was added to the mixed solution. The mixed solution was heated to 205° C., and the aqueous solution was added in a mist state under the condition that the temperature of the mixed solution was kept at 200° C. or higher. The entire amount of the aqueous solution was heated and held for 15 minutes after the addition was completed, and then cooled. The cooled mixed liquid was filtered under reduced pressure, the solid component (filtrate) was sufficiently washed with H 2 O and ethanol, and then dried under reduced pressure to obtain a supported catalyst.
（実施例２Ｂ）
フラスコに純水を５０ｍＬ投入した。ＲｕＣｌ３・ｎＨ２Ｏを０．０５８２ｇとＫ２ＰｄＣｌ４を０．０７７９ｇとを秤とり前記純水に添加して溶解した水溶液を作製した。水溶液に高分子保護材は添加しなかった。また、活性炭（ＦＡＭ−５０）を０．９５９ｇ秤とりＴＥＧ１００ｍＬ中に添加し、超音波で分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を２０５℃に加熱し、混合液の温度が２００℃以上を保持した条件で前記水溶液を霧状に添加した。水溶液の全量を添加終了後１５ｍｉｎ加熱保持し、その後冷却した。遠心分離を用いて冷却後の混合液から固体成分を沈降させ上澄みを除去し、固体成分をＨ２Ｏ及びエタノールを用いて十分に洗浄した後減圧乾燥を実施し、目的のＰｄ−Ｒｕ担持触媒を得た。
(Example 2B)
50 mL of pure water was added to the flask. An aqueous solution was prepared in which 0.0582 g of RuCl 3 .nH 2 O and 0.0779 g of K 2 PdCl 4 were weighed and added to the pure water to dissolve it. No polymeric protective material was added to the aqueous solution. Further, 0.959 g of activated carbon (FAM-50) was weighed and added to 100 mL of TEG, and ultrasonically dispersed to prepare a mixed liquid. No polymer protective material was added to the mixed solution. The mixed solution was heated to 205° C., and the aqueous solution was added in a mist state under the condition that the temperature of the mixed solution was kept at 200° C. or higher. After the completion of addition, the whole amount of the aqueous solution was heated and held for 15 minutes, and then cooled. The solid component was allowed to settle from the mixed liquid after cooling using centrifugation, the supernatant was removed, and the solid component was thoroughly washed with H 2 O and ethanol and then dried under reduced pressure to obtain the desired Pd-Ru supported catalyst. Got
（実施例３Ｂ）
フラスコに純水を５０ｍＬ投入した。ＲｕＣｌ３・ｎＨ２Ｏを０．３５３５ｇとＫ２ＰｄＣｌ４を０．４９１７ｇとを秤とり前記純水に添加して溶解した水溶液を作製した。水溶液に高分子保護材は添加しなかった。また、ケッチェンブラック（ＥＣ３００Ｊ、ライオン社製）を０．７０２３ｇ秤とりＴＥＧ１００ｍＬ中に添加し、超音波で分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を２０５℃に加熱し、混合液の温度が２００℃以上を保持した条件で前記水溶液を霧状に添加した。水溶液の全量を添加終了後１５ｍｉｎ加熱保持し、その後冷却した。遠心分離を用いて冷却後の混合液から固体成分を沈降させ上澄みを除去し、固体成分をＨ２Ｏ及びエタノールを用いて十分に洗浄した後減圧乾燥を実施し、目的のＰｄ−Ｒｕ担持触媒を得た。
(Example 3B)
50 mL of pure water was added to the flask. An aqueous solution in which 0.3535 g of RuCl 3 .nH 2 O and 0.4917 g of K 2 PdCl 4 were weighed and added to the pure water and dissolved was prepared. No polymeric protective material was added to the aqueous solution. Further, 0.7023 g of Ketjen Black (EC300J, manufactured by Lion) was weighed and added to 100 mL of TEG, and ultrasonically dispersed to prepare a mixed solution. No polymer protective material was added to the mixed solution. The mixed solution was heated to 205° C., and the aqueous solution was added in a mist state under the condition that the temperature of the mixed solution was kept at 200° C. or higher. The entire amount of the aqueous solution was heated and held for 15 minutes after the addition was completed, and then cooled. The solid component was allowed to settle from the mixed liquid after cooling using centrifugation, the supernatant was removed, and the solid component was thoroughly washed with H 2 O and ethanol, and then dried under reduced pressure to obtain the desired Pd-Ru-supported catalyst. Got
（Ｐｄ−Ｒｕ合金粒子の平均粒子径）
実施例１Ｂの担持触媒をＴＥＭで倍率１５００００倍で観察し、得られた粒子像から１００個の粒子の粒子径を計測し、その平均を求め、図１に実施例１ＢのＴＥＭ像を示す。実施例１Ｂの平均粒子径は、６．７１ｎｍであった。また、図１から、凝集した粒子の存在は確認されなかった。
(Average particle diameter of Pd-Ru alloy particles)
The supported catalyst of Example 1B was observed with a TEM at a magnification of 150,000 times, the particle size of 100 particles was measured from the obtained particle image, and the average thereof was calculated. The TEM image of Example 1B is shown in FIG. The average particle size of Example 1B was 6.71 nm. Moreover, the presence of aggregated particles was not confirmed from FIG.
（合金の状態）
実施例１Ｂの担持触媒について、ＸＲＤ測定及び昇温ＸＲＤ測定を行った。ＸＲＤ測定条件は、室温でλ＝ＣｕＫαである。昇温ＸＲＤ測定条件は、室温、１００℃、２００℃、３００℃、４００℃、５００℃で、λ＝０．５８Åである。図２に実施例１ＢのＸＲＤパターンを示す。図３に実施例１Ｂの昇温ＸＲＤパターンを示す。図２及び図３からＰｄ−Ｒｕ合金ナノ粒子が合成されたことが確認できた。また、実施例１Ｂの担持触媒について、ＳＴＥＭ測定を行った。図４に実施例１ＢのＳＴＥＭ像を、図５に実施例１ＢのＥＤＳマッピングを示す。図４からＰｄ−Ｒｕ合金粒子が担持体上に形成されていることが確認できた。また、図５はＰｄとＲｕとの固溶限界を超えた混合比でＰｄとＲｕとが混合した粒子を形成していることを示しており、Ｐｄ−Ｒｕ合金が固溶体を形成していることが確認できた。図５では、元素マッピングをグレー階調に処理した画像を示したが、元素マッピングはグレー調に処理する前のカラー画像によって、より正確に表現される。
(State of alloy)
The supported catalyst of Example 1B was subjected to XRD measurement and temperature rising XRD measurement. The XRD measurement condition is λ=CuKα at room temperature. The temperature rising XRD measurement conditions are room temperature, 100° C., 200° C., 300° C., 400° C. and 500° C., and λ=0.58Å. FIG. 2 shows the XRD pattern of Example 1B. FIG. 3 shows the temperature rising XRD pattern of Example 1B. It was confirmed from FIGS. 2 and 3 that Pd-Ru alloy nanoparticles were synthesized. Also, STEM measurement was performed on the supported catalyst of Example 1B. FIG. 4 shows the STEM image of Example 1B, and FIG. 5 shows the EDS mapping of Example 1B. From FIG. 4, it was confirmed that Pd-Ru alloy particles were formed on the carrier. Further, FIG. 5 shows that particles of Pd and Ru are mixed at a mixing ratio exceeding the solid solution limit of Pd and Ru, and that the Pd-Ru alloy forms a solid solution. Was confirmed. Although FIG. 5 shows an image in which the element mapping is processed in gray gradation, the element mapping is more accurately represented by a color image before being processed in gray.
Claims (5)
前記担持体は、カルシア、セリア、セリアジルコニア、ランタナ、ランタナアルミナ、酸化スズ、酸化タングステン、アルミノシリケート、アルミノホスフェート、ボロシリケート、リンタングステン酸、ヒドロキシアパタイト、ハイドロタルサイト、ペロブスカイト、コージェライト、ムライト、シリコンカーバイド、活性炭、カーボンナノチューブ及びカーボンナノホーンの中から選ばれる１種以上であり、
前記担持触媒の外表面に高分子保護材が存在しないことを特徴とする担持触媒。 In a supported catalyst in which Pd-Ru alloy particles as nanoparticles are supported on a support,
The bearing member, mosquitoes Resid A, Se Li A, ceria zirconia, lanthana, lanthana alumina, tin oxide, tungsten oxide, aluminosilicates, aluminophosphates, borosilicates, phosphotungstic acid, hydroxyapatite, hydrotalcite, perovskite, One or more selected from cordierite, mullite, silicon carbide, activated carbon, carbon nanotubes and carbon nanohorns,
A supported catalyst characterized in that no polymeric protective material is present on the outer surface of the supported catalyst.
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