JP2010089031A - Metal-particle supporting catalyst, and method of producing the same - Google Patents
Metal-particle supporting catalyst, and method of producing the same Download PDFInfo
- Publication number
- JP2010089031A JP2010089031A JP2008262771A JP2008262771A JP2010089031A JP 2010089031 A JP2010089031 A JP 2010089031A JP 2008262771 A JP2008262771 A JP 2008262771A JP 2008262771 A JP2008262771 A JP 2008262771A JP 2010089031 A JP2010089031 A JP 2010089031A
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- Prior art keywords
- metal
- particle
- supported catalyst
- particles
- carrier
- 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.)
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- 239000002923 metal particle Substances 0.000 title claims abstract description 141
- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 105
- 239000002184 metal Substances 0.000 claims abstract description 102
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 41
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 23
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000006722 reduction reaction Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims description 72
- 238000004519 manufacturing process Methods 0.000 claims description 53
- 229910021645 metal ion Inorganic materials 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 28
- -1 sodium halide Chemical class 0.000 claims description 22
- 239000010931 gold Substances 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 14
- 230000000737 periodic effect Effects 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 239000002612 dispersion medium Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052713 technetium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 89
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 35
- 150000002500 ions Chemical class 0.000 description 29
- 239000007787 solid Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 17
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 15
- 150000002736 metal compounds Chemical class 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 5
- 239000011246 composite particle Substances 0.000 description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910002668 Pd-Cu Inorganic materials 0.000 description 4
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910018885 Pt—Au Inorganic materials 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
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- 230000001678 irradiating effect Effects 0.000 description 3
- 239000011817 metal compound particle Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
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- 239000004584 polyacrylic acid Substances 0.000 description 3
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
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- 229910001111 Fine metal Inorganic materials 0.000 description 1
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- 238000003917 TEM image Methods 0.000 description 1
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- ZGIMJFKTMVSZAG-UHFFFAOYSA-J [Na][Pt](Cl)(Cl)(Cl)Cl Chemical compound [Na][Pt](Cl)(Cl)(Cl)Cl ZGIMJFKTMVSZAG-UHFFFAOYSA-J 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
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- 238000010908 decantation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
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- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- VZORGPCQYCYZLZ-UHFFFAOYSA-E nonasodium;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VZORGPCQYCYZLZ-UHFFFAOYSA-E 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- DJXYWDRBAAVVSG-UHFFFAOYSA-J potassium;tetrachloroplatinum Chemical compound [K].Cl[Pt](Cl)(Cl)Cl DJXYWDRBAAVVSG-UHFFFAOYSA-J 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000008096 xylene Substances 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
Abstract
Description
本発明は、金属粒子が担持された金属粒子担持触媒の製造方法およびその製造方法により得られる金属粒子担持触媒に関する。 The present invention relates to a method for producing a metal particle-supported catalyst in which metal particles are supported, and a metal particle-supported catalyst obtained by the method.
触媒は、燃料電池における反応促進の他、有機物質合成、自動車排ガスの浄化等、各種の分野で使用されている。この様な触媒としては、アルミナ、シリカ等の酸化物やカーボンなどの多孔質体を担体とし、これに白金、ロジウム等が担持された触媒や、複数の金属が担持された多元系触媒が知られている。また、担体物質については、シリカ、ゼオライト、シリカーアルミナ複合体、セリアなどが用いられている。 Catalysts are used in various fields such as organic substance synthesis and purification of automobile exhaust gas, in addition to promoting reaction in fuel cells. As such a catalyst, there are known a catalyst in which a porous body such as an oxide such as alumina or silica or carbon and a carrier such as platinum and rhodium are supported, and a multi-component catalyst in which a plurality of metals are supported. It has been. As the carrier material, silica, zeolite, silica-alumina composite, ceria and the like are used.
従来の、担体物質に金属を含むコロイド粒子が担持されてなる触媒の代表的な製造方法のひとつとして、多孔質の金属酸化物からなる担体にジニトロジアンミン白金や塩化白金酸、硝酸ロジウムといった金属塩溶液を含浸させ、還元雰囲気中で焼成する方法が知られている。また、前記多元系触媒についても、担持する複数の金属塩の溶液を調製し、これに担体を混合して複数のＰｄイオンを担体上に吸着させ、ついで乾燥、焼成する製造方法が知られている。 As one of the typical methods for producing a conventional catalyst in which colloidal particles containing a metal are supported on a support material, a metal salt such as dinitrodiammine platinum, chloroplatinic acid or rhodium nitrate is used on a support made of a porous metal oxide. A method of impregnating a solution and baking in a reducing atmosphere is known. Also for the multi-component catalyst, a manufacturing method is known in which a solution of a plurality of metal salts to be supported is prepared, a support is mixed with the solution, a plurality of Pd ions are adsorbed on the support, and then dried and calcined. Yes.
上記の製造方法も含めた担体物質に金属を含むコロイド粒子が担持されてなる触媒の製造方法としては、特許文献１には、金属酸化物などからなる微小な担体粒子の表面に、触媒活性をもつ微小な金属粒子を析出させる方法において、前記担体を合成する少なくとも一つの原料の吸収バンドに合致する波長を含む光を、前記原料に照射し前記担体粒子を析出させる工程と、析出した前記担体粒子と触媒活性をもつ前記金属粒子を析出するための前記原料とに、同時に、前記原料の吸収バンドに合致する波長を含む光を照射し、前記金属粒子を前記担体粒子の表面に析出させる工程と、析出した前記金属粒子を選別補収する工程とからなることを特徴とする触媒の製造方法が開示されている。 As a method for producing a catalyst in which colloidal particles containing a metal are supported on a carrier material, including the production method described above, Patent Document 1 discloses catalytic activity on the surface of fine carrier particles made of a metal oxide or the like. And depositing the carrier particles by irradiating the raw material with light having a wavelength matching an absorption band of at least one raw material for synthesizing the carrier, and depositing the carrier particles. A step of irradiating particles and the raw material for depositing the metal particles having catalytic activity simultaneously with light having a wavelength matching the absorption band of the raw material to deposit the metal particles on the surface of the carrier particles And a process for selectively collecting the deposited metal particles. A method for producing a catalyst is disclosed.
特許文献２には、金属粒子及び／又は金属化合物粒子が該粒子を実質的に個々に且つ別々に保護する数平均分子量が3,000〜300,000の有機高分子化合物と共に固体担体に吸着担持されてなり、該高分子化合物及び該固体担体の少くとも一方が、共有結合を形成して両者間に化学結合を作るべく作用し得る官能基を有さないことを特徴とする金属粒子及び／又は金属化合物粒子担持複合体およびその製造方法として、分散媒、金属粒子及び／又は金属化合物粒子及び保護コロイド粒子作用を持つ数平均分子量が3,000〜300,000の有機高分子化合物を含み、該粒子が該分散媒中に分散してコロイド粒子を形成し、且つ該高分子が該粒子に吸着して保護コロイド粒子として該粒子を実質的に個々に且つ別々に保護してなるコロイド粒子分散液を提供し、該コロイド粒子分散液と固体担体とを接触させ、該高分子化合物および該固体担体の少なくとも一方が、共有結合を形成して両者間に化学結合を作るべく作用し得る官能基を有さず、かくして、該高分子化合物で保護された該粒子が該固体担体に吸着されてなる粒子担持複合体を形成し、そして得られた複合体を該分散媒から単離することを特徴とする金属粒子及び／又は金属化合物粒子担持複合体の製造方法が開示されている。 In Patent Document 2, metal particles and / or metal compound particles are adsorbed and supported on a solid support together with an organic polymer compound having a number average molecular weight of 3,000 to 300,000 which protects the particles substantially individually and separately. Metal particles and / or metal compound particles, wherein at least one of the polymer compound and the solid support does not have a functional group capable of forming a covalent bond and forming a chemical bond therebetween. The supported composite and the method for producing the same include a dispersion medium, metal particles and / or metal compound particles, and an organic polymer compound having a number average molecular weight of 3,000 to 300,000 having a protective colloid particle action, and the particles are contained in the dispersion medium. Dispersing to form colloidal particles, and providing a colloidal particle dispersion comprising the polymer adsorbed on the particles and protecting the particles substantially individually and separately as protective colloidal particles. At least one of the polymer compound and the solid support does not have a functional group that can act to form a covalent bond and form a chemical bond therebetween, thus Metal particles characterized by forming a particle-supported complex formed by adsorbing the particles protected by the polymer compound to the solid support, and isolating the obtained complex from the dispersion medium, and A method for producing a metal compound particle-supported composite is disclosed.
特許文献３には、金属含有イオン及び該金属含有イオンの還元により生成する金属粒子が担持される担体を含む溶液中にプロパルギルアルコールを加え、該金属含有イオンとプロパルギルアルコールとの反応物を該担体上に担持した後、該担体を水素ガスを含有する還元性ガス中で熱処理して、該担体上の金属含有イオンとプロパルギルアルコールとの反応物を金属含有コロイド粒子に還元することを特徴とする高分散金属含有コロイド粒子担
持触媒の製造方法が開示されている。
In Patent Document 3, propargyl alcohol is added to a solution containing a carrier on which metal-containing ions and metal particles generated by reduction of the metal-containing ions are supported, and a reaction product of the metal-containing ions and propargyl alcohol is added to the carrier. After being supported on the substrate, the support is heat-treated in a reducing gas containing hydrogen gas to reduce a reaction product of metal-containing ions and propargyl alcohol on the support to metal-containing colloidal particles. A method for producing a highly dispersed metal-containing colloidal particle supported catalyst is disclosed.
特許文献４には、担体となる固体物質の存在下、金属の化合物またはイオンを含有した、還元能を有する液体または還元物質を溶解した液体に、マイクロ波を照射させるか、或いは、金属の化合物またはイオンを含有した、還元能を有する液体または還元物質を溶解した液体に、マイクロ波を照射させた後に、担体となる固体物質を存在させることを特徴とする、金属含有コロイド粒子を表面に付着させた金属含有コロイド粒子付着担体の製造方法が開示されている。 In Patent Document 4, in the presence of a solid substance serving as a carrier, a liquid having a reducing ability or a liquid in which a reducing substance is dissolved, containing a metal compound or ions, is irradiated with microwaves, or a metal compound. Alternatively, a metal-containing colloidal particle is attached to the surface, characterized by having a solid substance serving as a carrier present after irradiating a microwave to a liquid containing a reducing ability or containing a reducing substance containing ions. A method for producing a metal-containing colloidal particle adhesion carrier is disclosed.
特許文献５には、周期表第４周期から第６周期の２Ｂ族、３Ｂ族、４Ｂ族、５Ｂ族、６Ｂ族及び第４周期８族の少なくとも１種の第二元素と金とを含有する金属粒子が担体上に担持された金属粒子担持体と、その製造方法として金及びその化合物の少なくとも１種ならびに第二元素及びその化合物の少なくとも１種を含む担体を熱処理することを特徴とする製造方法が開示されている。 Patent Document 5 contains at least one second element of Group 2B, Group 3B, Group 4B, Group 5B, Group 6B, and Group 8 of the Period 4 to Period 6 of the periodic table and gold. A metal particle carrier in which metal particles are supported on a carrier, and a production method comprising heat treating a carrier containing at least one of gold and its compound and at least one of a second element and its compound as a production method thereof A method is disclosed.
特許文献６には、窒化アルミニウム粒子を空気又は酸素存在下で焼成させ、当該窒化アルミニウム粒子の表面に酸化アルミニウム層を形成する酸化アルミニウム層形成工程と、該酸化アルミニウム層形成工程により得られた窒化アルミニウム粒子を、Ｐｄイオン又は金属粒子を含む水溶液に含浸させた後、乾燥させることにより、窒化アルミニウム担体に金属触媒を保持させる保持工程と、該保持工程で得られた窒化アルミニウム担体を空気又は酸素存在下で焼成する焼成工程とを含むことを特徴とする金属又は金属酸化物から成る金属触媒が窒化アルミニウムから成る担体に保持された触媒の製造方法が開示されている。 In Patent Document 6, aluminum nitride particles are fired in the presence of air or oxygen to form an aluminum oxide layer on the surface of the aluminum nitride particles, and the nitride obtained by the aluminum oxide layer formation step. The aluminum particles are impregnated with an aqueous solution containing Pd ions or metal particles, and then dried to hold the metal catalyst on the aluminum nitride carrier, and the aluminum nitride carrier obtained in the holding step is air or oxygen A method for producing a catalyst in which a metal catalyst composed of a metal or a metal oxide is held on a carrier composed of aluminum nitride, which comprises a calcination step of calcination in the presence of the catalyst.
特許文献７には、１種又は２種以上の遷移金属の金属塩を含む金属塩溶液を製造する工程と、前記金属塩溶液と、有機物と、１種又は２種以上の金属酸化物からなる多孔質担体とを溶媒に分散させ、原子数１０〜５００００の１種又は２種以上の遷移Ｐｄイオンと、前記遷移Ｐｄイオンに結合する有機物とからなる複合錯体を形成しつつ、該複合錯体を該多孔質担体上に担持させる工程と、前記複合錯体が担持された担体を焼成する工程とを含む触媒の製造方法が開示されている。 Patent Document 7 includes a step of producing a metal salt solution containing a metal salt of one or more transition metals, the metal salt solution, an organic substance, and one or more metal oxides. While dispersing a porous carrier in a solvent and forming a complex complex composed of one or more transition Pd ions having 10 to 50000 atoms and an organic substance bonded to the transition Pd ion, A method for producing a catalyst is disclosed which comprises a step of supporting on the porous support and a step of firing the support on which the composite complex is supported.
また、金属ナノ微粒子の形状はその機能とくに触媒特性に大きな影響があることが知られている。例えば、白金表面での一酸化窒素分子の解離反応は、白金表面の形態によって活性が異なり、特に(１００) 面の有効性が知られている。表面制御された白金粒子に関
しては、特許文献８に、白金化合物の水溶液に、感温性ポリマーを添加する第１の工程と、第１の工程の終了後１分以内にアルカリ水溶液の添加を開始して、所定のｐＨ値に調整する第２の工程と、第２の工程の終了後１分以内に不活性ガスの吹き込みを開始し、所定時間吹き込む第３の工程と、第３の工程の終了後１分以内に還元性ガスの吹き込みを開始し、所定時間吹き込んだ後に、外気と遮断する第４の工程と、所定温度で所定時間保持する第５の工程とを含む金属粒子の製造方法が開示されている。また、特許文献９には、白金粒子からなり、その５重量％以上が立方体形状または正四面体形状の白金粒子である燃料電池用電極触媒に関する発明が開示されている。白金以外の金属において多面体構造を有する微粒子が担体に担持してなる、触媒用の金属微粒子担持触媒が求められていた。
本発明は、面状領域を有する金属粒子が担体表面に担持されてなる金属粒子担持触媒であって、酸化反応や還元反応などの反応に有用な高活性で、高寿命である金属粒子担持触媒を提供することを目的とする。さらに、本発明は、この様な金属粒子担持触媒の製造方法を提供することを目的とする。 The present invention relates to a metal particle-supported catalyst in which metal particles having a planar region are supported on a support surface, and is a highly active and long-life metal particle-supported catalyst useful for reactions such as oxidation reactions and reduction reactions. The purpose is to provide. Furthermore, an object of the present invention is to provide a method for producing such a metal particle-supported catalyst.
前記目的を達成するための本発明は、第４周期遷移金属元素、第５周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも１種の金属からなる金属粒子が担体に担持されてなる金属粒子担持触媒であって、前記金属粒子の少なくとも一部が面状領域を有する金属粒子であることを特徴とする金属粒子担持触媒である。 In order to achieve the above object, according to the present invention, metal particles comprising at least one metal selected from the group consisting of a fourth periodic transition metal element, a fifth periodic transition metal element, platinum and gold are supported on a carrier. A metal particle-supported catalyst, wherein at least part of the metal particles are metal particles having a planar region.
前記金属粒子担持触媒の好適な態様として、前記金属粒子が、第４周期遷移金属元素、第５周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも２種の金属からなる複合金属粒子であり、
前記第４周期遷移金属元素が、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、ＮｉおよびＣｕからなる群より選ばれる元素であり、前記第５周期遷移金属元素が、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、ＰｄおよびＡｇからなる群より選ばれる元素であり、
前記面状領域を有する金属粒子の面状領域が、最大幅３〜１００ｎｍの範囲のものであり、
前記面状領域を有する金属粒子が、担体表面の１ｍ2あたり、１０2〜１０17個担持されており、
金属粒子の含有割合が０．１〜５０質量％であり、
前記担体がＳｉ、Ａｌ、Ｃ、Ｔｉ、ＺｒおよびＣｅからなる群より選ばれる少なくとも１種を含有し、
酸化反応または還元反応に使用できる。
As a preferred embodiment of the metal particle-supported catalyst, the metal particle is a composite metal composed of at least two metals selected from the group consisting of a fourth period transition metal element, a fifth period transition metal element metal element, platinum and gold. Particles,
The fourth period transition metal element is an element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, and Cu, and the fifth period transition metal element is Zr, Nb, Mo, Tc. And an element selected from the group consisting of Ru, Rh, Pd and Ag,
The planar region of the metal particles having the planar region is one having a maximum width of 3 to 100 nm,
10 2 to 10 17 metal particles having the planar region are supported per 1 m 2 of the carrier surface,
The content ratio of the metal particles is 0.1 to 50% by mass,
The carrier contains at least one selected from the group consisting of Si, Al, C, Ti, Zr and Ce;
It can be used for oxidation or reduction reactions.
また、他の発明は、以下の（I）〜（IV）工程を含むことを特徴とする金属粒子担持触
媒の製造方法である。
（I）担体の懸濁液に、ハロゲン化ナトリウム、ポリビニルアルコール、有機酸および
有機酸塩からなる群より選ばれる少なくとも１つの化合物を、前記担体１００質量部に対して０．1〜５０質量部添加する工程
（II）（I）工程で得られた前記化合物を吸着した担体を分離し、分散媒に再懸濁させ
る工程
（III）（II）工程で得られた懸濁液に、１５〜４０℃で、第４周期遷移金属元素、第
５周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも１種の金属のイオンを前記担体１００質量部に対して１〜１８０質量部添加し、さらに必要に応じて還元剤を添加し、混合する工程
（IV）（III）工程で得られた懸濁液を１５〜２００℃にて乾燥させる工程
前記金属粒子担持触媒の製造方法の好適な態様として、
前記乾燥を、不活性雰囲気下、水素雰囲気下または水素-不活性ガス混合雰囲気下で行
う。
Another invention is a method for producing a metal particle-supported catalyst, comprising the following steps (I) to (IV).
(I) 0.1 to 50 parts by mass of at least one compound selected from the group consisting of sodium halide, polyvinyl alcohol, organic acid and organic acid salt is added to 100 parts by mass of the carrier in the suspension of the carrier. Step of adding (II) Step of separating the carrier adsorbing the compound obtained in step (I) and resuspending it in a dispersion medium (III) Into the suspension obtained in step (II), 1 to 180 parts by mass of ions of at least one metal selected from the group consisting of a fourth period transition metal element, a fifth period transition metal element metal element, platinum and gold at 40 ° C. Step of adding and further adding and mixing a reducing agent as necessary (IV) Step of drying the suspension obtained in step (III) at 15 to 200 ° C. As a preferred embodiment,
The drying is performed under an inert atmosphere, a hydrogen atmosphere, or a hydrogen-inert gas mixed atmosphere.
本発明に係る金属粒子担持触媒においては、担持された金属粒子の少なくとも一部が、面状領域をとり、特に最大幅３〜１００ｎｍの面を有し、さらに、この面状領域を有する
金属粒子は、担体の単位面積（ｍ2）あたり、１０2〜１０17個存在する。このため、該金属粒子担持触媒は、優れた表面活性を示すことが可能であり、例えば、硝酸性窒素処理用の触媒として優れた効果を示すことができる。
In the metal particle-supported catalyst according to the present invention, at least a part of the supported metal particles has a planar region, in particular, a surface having a maximum width of 3 to 100 nm, and the metal particle having this planar region. Are 10 2 to 10 17 per unit area (m 2 ) of the carrier. For this reason, this metal particle carrying catalyst can show the outstanding surface activity, for example, can show the outstanding effect as a catalyst for nitrate nitrogen treatment.
以下、金属粒子担持触媒本およびその製造方法について詳細に説明する。
本発明に係る金属粒子担持触媒は、第４周期遷移金属元素、第５周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも１種の金属からなる金属粒子（または前記２種から選ばれる複合金属粒子）が担体に担持されてなる金属粒子担持触媒であって、前記金属粒子の少なくとも一部が面状領域を有する金属粒子であることを特徴とする。
Hereinafter, the metal particle-supported catalyst book and the production method thereof will be described in detail.
The metal particle-supported catalyst according to the present invention is a metal particle composed of at least one metal selected from the group consisting of a fourth period transition metal element, a fifth period transition metal element metal element, platinum and gold (or from the above two types). A metal particle-supported catalyst in which a selected composite metal particle) is supported on a carrier, wherein at least a part of the metal particle is a metal particle having a planar region.
これらの面状領域を有する金属粒子については、最大幅３〜１００ｎｍの面を含む面状領域をとるものが望ましい。このような面状領域を有する金属粒子は、表面活性に優れることが期待される。 About the metal particle which has these planar areas, what takes a planar area | region containing the surface of 3-100 nm of maximum widths is desirable. Metal particles having such a planar region are expected to be excellent in surface activity.
［金属粒子担持触媒］
担体
本発明に使用される担体については、金属粒子が担持可能な物質であれば、格別な制限はない。通常はＳｉ、Ａｌ、Ｃ、Ｔｉ、ＺｒまたはＣｅから選ばれる１種または２種以上を含有する無機系担体物質が使用される。この担体については、非晶質であっても、晶質であってもよく、合成物質、天然鉱物のいずれであっても構わない。通常、Si、Al、Ti、Zr、Ceが使用される場合は、その酸化物が使用され、Cが使用される場合は、カーボン単
体、活性炭が使用される。前記酸化物は、複合酸化物であってもよく、さらに、NaやK、Feなどの成分を含んでいても良い。このような無機系担体物質の具体例としては、シリカ
粒子（メソポーラスシリカ、シリカライト）、シリカーアルミナ粒子、アルミナ粒子、カーボン粒子、活性炭（ヤシガラ系、フェノール樹脂系、塩基性など）ゼオライト粒子（Y
型、Ａ型、モルデナイト型、ZSM-5型など、天然物でも合成物でもよい）、セリア（酸化
セリウム）粒子、カオリン粒子、スメクタイト粒子、バーミキュライト粒子、雲母片、チタニアおよびジルコニアなどを挙げることができるが、これらに限定されるものではない。
[Metal particle supported catalyst]
Carrier The carrier used in the present invention is not particularly limited as long as it is a substance that can carry metal particles. Usually, an inorganic carrier material containing one or more selected from Si, Al, C, Ti, Zr or Ce is used. The carrier may be amorphous or crystalline, and may be a synthetic substance or a natural mineral. Usually, when Si, Al, Ti, Zr, and Ce are used, the oxide is used, and when C is used, simple carbon and activated carbon are used. The oxide may be a complex oxide, and may further contain components such as Na, K, and Fe. Specific examples of such inorganic carrier materials include silica particles (mesoporous silica, silicalite), silica-alumina particles, alumina particles, carbon particles, activated carbon (coconut shell, phenol resin, basic, etc.) zeolite particles ( Y
Type, A type, mordenite type, ZSM-5 type, which may be natural or synthetic), ceria (cerium oxide) particles, kaolin particles, smectite particles, vermiculite particles, mica flakes, titania and zirconia. However, it is not limited to these.
また、担体の形状は特に限定されるものではなく、球状粒子であってもよく、不定形物質であってもよい。担体が球状粒子である場合、担体の平均粒子径は、担持される金属粒子の有する面状領域の最大幅と同等またはそれ以上であれば特に限定されるものではないが、リアクターとして装置化することを踏まえれば、担体の平均粒子径は好ましくは１００ｎｍ〜５００ｍｍ、より好ましくは１μｍ〜１００ｍｍの範囲が推奨される。 Further, the shape of the carrier is not particularly limited, and it may be a spherical particle or an amorphous substance. When the support is a spherical particle, the average particle diameter of the support is not particularly limited as long as it is equal to or greater than the maximum width of the planar region of the supported metal particles, but the apparatus is formed as a reactor. In view of this, the average particle diameter of the carrier is preferably 100 nm to 500 mm, more preferably 1 μm to 100 mm.
粒子径が前記範囲の担体は、容易に得ることができ、また、本発明の製造方法により、容易に面状領域を有する金属粒子をその表面に均一に担持させることができる。なお、二次粒子径が上記範囲にあれば、担体は凝集した状態でも使用することができるが、できる限り単分散していることが好ましい。
前記担体の平均径としては、面状領域を有する金属粒子の面状領域の最大幅の５倍以上の長さであるものがより推奨される。
前記担体が球状粒子でない場合（不定形等）については、担体の最短径が、担持される金属粒子の有する面状領域の最大幅と同等またはそれ以上であれば特に限定されるものではないが、リアクターとして装置化することを踏まえれば、担体の最短径は好ましくは１００ｎｍ〜５００ｍｍ、より好ましくは１μｍ〜１００ｍｍの範囲が推奨される。担体の最長径については、１２０ｎｍ〜１０００ｍｍ、より好ましくは、１．２μｍ〜１２０ｍｍの範囲が推奨される。
前記最短径が前記範囲の担体は、容易に得ることができ、また、本発明の製造方法により、容易に面状領域を有する金属粒子をその表面に均一に担持させることができる。なお、二次粒子径が上記範囲にあれば、担体は凝集した状態でも使用することができるが、できる限り単分散していることが好ましい。
前記担体の最短径としては、面状領域を有する金属粒子の面状領域の最大幅の５倍以上の長さであるものがより推奨される。
金属粒子
本発明に係る金属粒子担持触媒においては、担体に面状領域を有する金属粒子が担持されていることを特徴としている。
ここで面状領域を有する金属粒子とは、粒子の一部が平面状となっている金属粒子または４個以上の平面状領域から構成される金属粒子を意味する。具体的には、次の１）または２）の金属粒子を挙げることができる。
１）面状の領域を少なくとも１箇所有し、それ以外の部分は球状または不定形の金属粒子２）四面体状構造、五面体状構造、六面体状構造またはそれ以上の面状の領域で囲まれてなる多面体状構造からなる金属粒子
前記面状の領域については、電子顕微鏡写真などで平面または略平面状であることが確認できるものであれば構わない。この様な面の形状としては、例えば、円形状の面、略楕円形状の面、三角形状の面、四角形状の面、多角形状の面、不定形状であるものの一部に直線状部分（辺）を有する面などを挙げることができる。
A carrier having a particle size in the above range can be easily obtained, and metal particles having a planar region can be easily uniformly supported on the surface by the production method of the present invention. If the secondary particle diameter is in the above range, the carrier can be used even in an agglomerated state, but is preferably monodispersed as much as possible.
As the average diameter of the carrier, one having a length of 5 times or more the maximum width of the planar region of the metal particles having the planar region is more recommended.
When the carrier is not a spherical particle (such as indefinite shape), there is no particular limitation as long as the shortest diameter of the carrier is equal to or greater than the maximum width of the planar region of the metal particles to be carried. In view of the fact that it is realized as a reactor, the minimum diameter of the carrier is preferably 100 nm to 500 mm, more preferably 1 μm to 100 mm. About the longest diameter of a support | carrier, the range of 120 nm-1000 mm, More preferably, 1.2 micrometers-120 mm is recommended.
The carrier having the shortest diameter in the above range can be easily obtained, and metal particles having a planar region can be easily supported uniformly on the surface by the production method of the present invention. If the secondary particle diameter is in the above range, the carrier can be used even in an agglomerated state, but is preferably monodispersed as much as possible.
As the shortest diameter of the carrier, one having a length of 5 times or more the maximum width of the planar region of the metal particles having the planar region is more recommended.
Metal particles The metal particle-supported catalyst according to the present invention is characterized in that metal particles having a planar region are supported on a carrier.
Here, the metal particle having a planar region means a metal particle in which a part of the particle is planar or a metal particle composed of four or more planar regions. Specifically, the following metal particles 1) or 2) can be mentioned.
1) At least one planar region, and other portions are spherical or irregular metal particles 2) Surrounded by a tetrahedral structure, pentahedral structure, hexahedral structure or more planar regions The metal particles having a polyhedral structure are not particularly limited as long as the planar region can be confirmed to be planar or substantially planar by an electron micrograph or the like. As the shape of such a surface, for example, a circular surface, a substantially elliptical surface, a triangular surface, a quadrangular surface, a polygonal surface, a part of an indefinite shape, a linear portion (side ) And the like.
前記面状の領域については、その最大幅が３〜１００ｎｍの範囲にあるものが好ましい。最大幅が３ｎｍ未満の場合は、触媒活性が低い傾向がある。面状領域の最大幅が１００ｎｍを超える金属粒子を担体に担持させることは容易ではない。前記最大幅の範囲としては、好適には３〜５０ｎｍの範囲が推奨される。また、更に好適には、３〜４５ｎｍの範囲が推奨される。 The planar region preferably has a maximum width in the range of 3 to 100 nm. When the maximum width is less than 3 nm, the catalytic activity tends to be low. It is not easy to support metal particles having a maximum width of a planar region exceeding 100 nm on a carrier. The range of the maximum width is preferably 3 to 50 nm. More preferably, the range of 3 to 45 nm is recommended.
本発明においては、金属粒子担持触媒の電子顕微鏡写真（写真投影図）から、金属粒子の有する面状領域の最大幅を測定する。具体的には、電子顕微鏡により倍率３０万倍で写真撮影して得られる写真投影図において、５００ｎｍ四方に表れる面状領域のうち、最も大きい最大幅を測定し、同様の測定を写真投影図上の５０箇所について行って、その平均値を算定する。この平均値を金属粒子担持触媒に担持している面状領域を有する金属粒子の面状領域の最大幅とした。なお、ここで最大幅とは、面状領域の外縁上の２点を結ぶ線分のうち、最大の長さの意味である。 In the present invention, the maximum width of the planar region of the metal particles is measured from an electron micrograph (photo projection view) of the metal particle-supported catalyst. Specifically, in a photographic projection obtained by taking a picture with an electron microscope at a magnification of 300,000 times, the largest maximum width is measured in a planar region appearing in a 500 nm square, and the same measurement is performed on the photographic projection. The average value is calculated. This average value was defined as the maximum width of the planar region of the metal particles having the planar region supported on the metal particle-supported catalyst. Here, the maximum width means the maximum length of line segments connecting two points on the outer edge of the planar region.
前記面状領域を有する金属粒子は、担体の単位面積（１ｍ2）あたり、１０2〜１０17個／ｍ2、好ましくは、１０3〜１０15／ｍ2個担持されていることが望ましい。このような
範囲で担持されていることにより、金属粒子に基づく触媒効果などが安定して発現し易くなる。前記範囲の下限未満の場合、金属粒子に基づく効果が十分に発現せず、触媒効果または導電性効果が微弱なものとなる場合がある。また、前記範囲の上限を超える場合、金属粒子に基づく効果が飽和する傾向が強くなるので、その上限を超える個数の金属粒子は必要とはされない。
It is desirable that 10 2 to 10 17 particles / m 2 , preferably 10 3 to 10 15 / m 2 , of the metal particles having the planar regions are supported per unit area (1 m 2 ) of the carrier. By being carried in such a range, the catalytic effect based on the metal particles and the like can be stably and easily expressed. When the amount is less than the lower limit of the above range, the effect based on the metal particles may not be sufficiently exhibited, and the catalytic effect or the conductive effect may be weak. When the upper limit of the range is exceeded, the effect based on the metal particles tends to be saturated, so that the number of metal particles exceeding the upper limit is not required.
本発明においては、本発明に係る金属粒子担持触媒を、肉眼または読取装置にて、担体に担持した金属粒子の個数を測定できる程度まで拡大した電子顕微鏡写真に基づいて金属粒子の担持個数を測定する。 In the present invention, the number of supported metal particles is measured based on an electron micrograph enlarged to the extent that the number of metal particles supported on a carrier can be measured with the naked eye or a reading device. To do.
具体的測定方法については、実施例にて開示した。
前記金属粒子担持触媒に含まれる金属粒子の質量割合は、適用する用途の要請に応じて選択されるものであり、格別に限定されるものではないが、通常は、例えば、０．１〜５０質量％、好ましくは ０．５〜２０質量％の範囲にある。金属粒子がこの範囲で担持さ
れていると、例えば、金属粒子の作用による触媒作用などが実用的なレベルとなり易くなる。
Specific measurement methods are disclosed in the examples.
The mass ratio of the metal particles contained in the metal particle-supported catalyst is selected according to the demand of the application to be applied and is not particularly limited. % By mass, preferably in the range of 0.5-20% by mass. When the metal particles are supported in this range, for example, the catalytic action due to the action of the metal particles tends to be at a practical level.
面状領域を有する金属粒子としては、四面体状粒子（三角錐型）、六面体状粒子（立方体状または直方体状）、八面体状粒子等が挙げられ、好ましくは正四面体状粒子、正六面体状粒子、正八面体状粒子が推奨される。このうち、辺の長さが均一な多面体状粒子は、結晶面が均等に現れており、そのため反応形態への依存性もあるものの、酸化反応や還元反応に使用した際の活性が高くなり易いため特に好適である。 Examples of the metal particles having a planar region include tetrahedral particles (triangular pyramid), hexahedral particles (cubic or cuboid), octahedral particles, and the like, preferably tetrahedral particles, regular hexahedrons, and the like. Particles and regular octahedral particles are recommended. Among these, polyhedral particles having uniform side lengths have uniform crystal planes, and thus have a dependency on the reaction form, but are likely to have high activity when used in oxidation and reduction reactions. Therefore, it is particularly suitable.
なお、本発明においては、担体上に面状領域を有する金属粒子以外に、面状領域を有する金属粒子に該当しない粒子が含まれていても構わない。ここで、面状領域を有する金属粒子に該当しない金属粒子としては、例えば、球状金属粒子、平面を有さない不定形金属粒子などを挙げることができる。本発明の金属粒子担持触媒において面状領域を有する金属粒子は、担持している金属粒子全体（個数）の好ましくは２０〜１００％の範囲であることが推奨される。更に好ましくは３０〜１００％の範囲が推奨される。 In addition, in this invention, the particle | grains which do not correspond to the metal particle which has a planar area | region other than the metal particle which has a planar area | region on a support | carrier may be contained. Here, as a metal particle which does not correspond to the metal particle which has a planar area | region, a spherical metal particle, an amorphous metal particle which does not have a plane, etc. can be mentioned, for example. In the metal particle-supported catalyst of the present invention, it is recommended that the metal particles having a planar region be in the range of preferably 20 to 100% of the total (number) of metal particles supported. More preferably, the range of 30 to 100% is recommended.
前記金属粒子は、第４周期遷移金属元素、第５周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも１種の金属からなる。前記金属粒子は、第４周期遷移金属元素、第５周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも２種以上の金属からなる複合金属粒子であってもよい。金属粒子が複合金属粒子であると、化学的に安定であり、合金独自の特性が発現しやすいという利点がある。複合金属粒子としては、Au-Pt、Au-Ag、Au-Pd、Au-Pd、Au-Ru、Pt-Ｐｄ、Pt-Ru、Pt-Ag、Ag-Pd
、Ag-Pd-Sn、Pd-Cu、Pd-Cu-Sn、からなる複合金属粒子等がより好ましい。
The metal particles are made of at least one metal selected from the group consisting of a fourth period transition metal element, a fifth period transition metal element metal element, platinum, and gold. The metal particles may be composite metal particles made of at least two metals selected from the group consisting of a fourth period transition metal element, a fifth period transition metal element metal element, platinum and gold. When the metal particles are composite metal particles, there is an advantage that they are chemically stable and the characteristics unique to the alloy are easily developed. As composite metal particles, Au-Pt, Au-Ag, Au-Pd, Au-Pd, Au-Ru, Pt-Pd, Pt-Ru, Pt-Ag, Ag-Pd
More preferable are composite metal particles made of Ag-Pd-Sn, Pd-Cu, Pd-Cu-Sn, and the like.
好ましくは、前記第４周期遷移金属元素は、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、ＮｉおよびＣｕからなる群より選ばれる元素であり、前記第５周期遷移金属元素が、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、ＰｄおよびＡｇからなる群より選ばれる元素である。 Preferably, the fourth periodic transition metal element is an element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, and Cu, and the fifth periodic transition metal element is Zr, Nb, It is an element selected from the group consisting of Mo, Tc, Ru, Rh, Pd and Ag.
また、本金属粒子担持触媒は、触媒活性を向上させるため種々の酸化物を微量添加しても構わない。この様な例としては、ＣｅＯ、ＢｉＯ、ＢａＯ、ＭｇＯ、ＺｒＯ、ＮｉＯ、ＩｒＯまたはＳｅＯなどの酸化物を挙げることができる。 In addition, the present metal particle-supported catalyst may be added with a small amount of various oxides in order to improve the catalytic activity. Examples of such include oxides such as CeO, BiO, BaO, MgO, ZrO, NiO, IrO, and SeO.
本発明の金属粒子担持触媒の大きさは実質的に、無機系担体物質の大きさによって決定される。本発明の金属粒子担持触媒は、必要に応じて、公知の方法で、ペレット、ハニカムなどの所望の形状に成形してもよい。 The size of the metal particle-supported catalyst of the present invention is substantially determined by the size of the inorganic support material. The metal particle-supported catalyst of the present invention may be formed into a desired shape such as a pellet or a honeycomb by a known method, if necessary.
本発明の金属粒子担持触媒は、酸化反応または還元反応等に使用することができる。
本発明の金属粒子担持触媒は、たとえば以下の金属粒子担持触媒の製造方法により製造することができる。
The metal particle-supported catalyst of the present invention can be used for an oxidation reaction or a reduction reaction.
The metal particle-supported catalyst of the present invention can be produced, for example, by the following method for producing a metal particle-supported catalyst.
本発明に係る金属粒子担持触媒の製造方法について、以下に述べる。
[金属粒子担持触媒の製造方法]
本発明に係る第１の金属粒子担持触媒の製造方法は、以下の（I）〜（IV）工程を含む
。
（I）担体の懸濁液に、ハロゲン化ナトリウム、ポリビニルアルコール、有機酸および有
機酸塩からなる群より選ばれる少なくとも１つの化合物を、前記担体１００質量部に対して０．1〜５０質量部添加する工程
（II）（I）工程で得られた前記化合物を吸着した担体を分離し、分散媒に再懸濁させる
工程
（III）（II）工程で得られた懸濁液に、１５〜４０℃で、第４周期遷移金属元素、第５
周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも１種の金属のイオンを前記担体１００質量部に対して１〜１８０質量部添加し、さらに必要に応じて還元剤を添加し、混合する工程
（IV）（III）工程で得られた懸濁液を１５〜２００℃にて乾燥させる工程
（I）工程
担体の懸濁液の調製
本発明に使用される担体については、前記した通りである。本発明では、上記担体は、通常、水に懸濁させた状態で使用される。担体の懸濁液は、上記担体に、例えば、脱イオン水を加えて、９５℃で１時間混合することにより得ることができる。水の使用量は、担体１００質量部に対して１００〜９９，９００質量部が好ましく、４００〜１９，９００質量部がより好ましい。このようにして得られた担体物質の懸濁液は、必要に応じて、さらに水で希釈してもよく、あるいはデカンテーションで濃縮してもよい。希釈水としては脱イオン水が好ましい。希釈後の担体の懸濁液の濃度は、０．１〜５０質量％が好ましく、０．５〜１０質量％がより好ましい。
The method for producing a metal particle-supported catalyst according to the present invention will be described below.
[Method for producing metal particle supported catalyst]
The first method for producing a metal particle-supported catalyst according to the present invention includes the following steps (I) to (IV).
(I) 0.1 to 50 parts by mass of at least one compound selected from the group consisting of sodium halide, polyvinyl alcohol, organic acid and organic acid salt is added to 100 parts by mass of the carrier in the suspension of the carrier. Step (II) The carrier obtained by adsorbing the compound obtained in the step (II) (I) is separated and resuspended in the dispersion medium (III) (II). At 40 ° C., the fourth period transition metal element, the fifth
Periodic transition metal element At least one metal ion selected from the group consisting of metal elements, platinum and gold is added in an amount of 1 to 180 parts by mass with respect to 100 parts by mass of the carrier, and a reducing agent is added if necessary. Step (I) Step of drying the suspension obtained in Step (IV) and Step (III) of mixing at 15 to 200 ° C.
Preparation of carrier suspension The carrier used in the present invention is as described above. In the present invention, the carrier is usually used in a state suspended in water. The carrier suspension can be obtained, for example, by adding deionized water to the carrier and mixing at 95 ° C. for 1 hour. The amount of water used is preferably 100 to 99,900 parts by weight, more preferably 400 to 19,900 parts by weight with respect to 100 parts by weight of the carrier. The carrier material suspension thus obtained may be further diluted with water, if necessary, or may be concentrated by decantation. As the dilution water, deionized water is preferred. The concentration of the carrier suspension after dilution is preferably 0.1 to 50% by mass, more preferably 0.5 to 10% by mass.
ハロゲン化ナトリウム、ポリビニルアルコール、有機酸、有機酸塩の添加
次に、上記担体の懸濁液に、ハロゲン化ナトリウム、ポリビニルアルコール、有機酸および有機酸塩からなる群より選ばれる少なくとも１つの化合物を添加する。この操作により、前記化合物が前記担体に吸着される。
Addition of sodium halide, polyvinyl alcohol, organic acid, organic acid salt Next, at least one compound selected from the group consisting of sodium halide, polyvinyl alcohol, organic acid and organic acid salt is added to the suspension of the carrier. Added. By this operation, the compound is adsorbed on the carrier.
前記ハロゲン化ナトリウム等の化合物は、金属イオンの形状制御剤として機能し、その種類および量によって、形成される金属粒子の形状を制御できる。
前記ハロゲン化ナトリウムとしては、たとえば、NaCl、NaBr、NaI、NaAt、NaF等を挙げることができる。
The compound such as sodium halide functions as a shape control agent for metal ions, and the shape and shape of the formed metal particles can be controlled by the type and amount thereof.
Examples of the sodium halide include NaCl, NaBr, NaI, NaAt, NaF, and the like.
前記有機酸としては、たとえばポリアクリル酸、シュウ酸、酢酸、蟻酸、クエン酸、セバシン酸、マレイン酸、フタル酸、酒石酸、エチレンジアミン4酢酸、グルコン酸、乳酸
、等を挙げることができる。
Examples of the organic acid include polyacrylic acid, oxalic acid, acetic acid, formic acid, citric acid, sebacic acid, maleic acid, phthalic acid, tartaric acid, ethylenediaminetetraacetic acid, gluconic acid, and lactic acid.
前記有機酸塩としては、上記有機酸のＮａ塩、Ｋ塩等を挙げることができる。
前記化合物の添加量としては、前記担体１００質量部に対して０．1〜５０質量部であ
ることが好ましく、０．５〜５０質量％であることがより好ましく、１〜５０質量％であることがさらに好ましい。前記化合物の添加量が前記範囲内であると、形成される金属粒子が面状領域を有するように制御することが容易になる。
Examples of the organic acid salt include Na salt and K salt of the organic acid.
The addition amount of the compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 50% by mass, and 1 to 50% by mass with respect to 100 parts by mass of the carrier. More preferably. When the addition amount of the compound is within the above range, it is easy to control the formed metal particles so as to have a planar region.
これらの形状制御剤は、直接、担体の懸濁液に添加しても良く、脱イオン水で希釈して添加しても良い。担体表面への吸着は、室温で攪拌するだけでもよく４０〜１００℃で加熱攪拌してもよい。
（II）工程
（I）工程で得られた前記化合物を吸着した担体を分離し、分散媒に再懸濁させる。
These shape control agents may be added directly to the carrier suspension or may be diluted with deionized water. Adsorption on the surface of the carrier may be merely stirred at room temperature or heated and stirred at 40 to 100 ° C.
(II) Step The carrier adsorbed with the compound obtained in the step (I) is separated and resuspended in a dispersion medium.
前記担体の分離の方法としては、特に制限はなく、たとえば吸引濾過等を挙げることができる。
分離された前記化合物を吸着した担体は、そのまま再懸濁させてもよく、乾燥後再懸濁させてもよい。乾燥は、たとえば１０〜２００℃で、１０分〜２４時間程度行うことができる。
The method for separating the carrier is not particularly limited, and examples thereof include suction filtration.
The carrier on which the separated compound is adsorbed may be resuspended as it is, or may be resuspended after drying. Drying can be performed, for example, at 10 to 200 ° C. for about 10 minutes to 24 hours.
前記分散媒としては、通常水が用いられる。
再懸濁によって得られた、前記化合物を吸着した担体の懸濁液の濃度は、０．１〜７０質量％が好ましく、１〜５０質量％がより好ましい。
（III）工程
（II）工程で得られた、前記化合物を吸着した担体の懸濁液に、金属イオンを添加する。金属イオンは、第４周期遷移金属元素、第５周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも１種の金属のイオンである。
As the dispersion medium, water is usually used.
The concentration of the suspension of the carrier adsorbed with the compound obtained by resuspension is preferably 0.1 to 70% by mass, and more preferably 1 to 50% by mass.
(III) Process A metal ion is added to the suspension of the support | carrier which adsorb | sucked the said compound obtained at the process (II). The metal ion is an ion of at least one metal selected from the group consisting of a fourth period transition metal element, a fifth period transition metal element metal element, platinum, and gold.
前記第４周期遷移金属元素は、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、ＮｉおよびＣｕからなる群より選ばれる元素であり、前記第５周期遷移金属元素は、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、ＰｄおよびＡｇからなる群より選ばれる元素である。 The fourth periodic transition metal element is an element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, and Cu, and the fifth periodic transition metal element is Zr, Nb, Mo, Tc. , Ru, Rh, Pd and Ag.
金属イオンの添加量は、前記化合物を吸着した担体の懸濁液に含まれる前記担体１００質量部に対して金属元素換算で１〜１８０質量部が好ましく、２〜８０質量部がより好ましい。なお、金属イオンの添加量が多い程、面状領域を有する金属粒子が生成しやすくなる。 The amount of metal ions added is preferably 1 to 180 parts by mass, more preferably 2 to 80 parts by mass in terms of metal element, relative to 100 parts by mass of the carrier contained in the carrier suspension adsorbing the compound. In addition, it becomes easy to produce | generate the metal particle which has a planar area | region, so that there is much addition amount of a metal ion.
上記範囲の量の金属イオンを前記懸濁液に添加する方法としては、１）金属元素換算で上記範囲の量の金属イオンを含む所定の溶液を前記懸濁液に添加する方法、および２）金属元素換算で上記割合の金属イオンを形成し得る量の金属化合物を前記懸濁液に添加して、この懸濁液中で金属イオンを発生させる方法を挙げることができる。 As a method of adding the amount of metal ions in the above range to the suspension, 1) a method of adding a predetermined solution containing the amount of metal ions in the above range in terms of metal element to the suspension, and 2) An example is a method in which an amount of a metal compound capable of forming the above-mentioned ratio of metal ions in terms of metal element is added to the suspension, and metal ions are generated in the suspension.
前記１）の方法において、金属イオンを含む溶液は、金属イオンを形成し得る金属化合物を溶媒に溶解することにより調製できる。上記金属イオンの価数については、特に限定されるものではない。 In the method 1), a solution containing metal ions can be prepared by dissolving a metal compound capable of forming metal ions in a solvent. The valence of the metal ion is not particularly limited.
金属イオンを生成可能な上記化合物としては、上記懸濁液中で金属イオンを形成するものであれば特に制限されず、例えば、Pdイオンを形成する化合物としては、塩化パラジウム、硝酸パラジウム、硫酸パラジウム、クエン酸パラジウム、酢酸パラジウムなどが挙げられる。これらのパラジウム化合物は１種単独で、または２種以上を混合して用いることができる。 The compound capable of generating a metal ion is not particularly limited as long as it forms a metal ion in the suspension. Examples of the compound that forms a Pd ion include palladium chloride, palladium nitrate, palladium sulfate. , Palladium citrate, palladium acetate and the like. These palladium compounds can be used alone or in combination of two or more.
その他の金属イオンを生成可能な化合物の一例を以下に記す。
銅イオン：塩化銅、硫酸銅、硝酸銅
白金イオン：塩化白金酸、塩化白金（IV）酸カリウム、塩化白金（IV）酸ナトリウム、テトラニトロ白金（II）カリウム、ヘキサヒドロキソ白金（IV）酸ナトリウム水和物、ジニトロジアンミン白金硝酸、ジニトロジアンミン白金アンモニアおよびテトラアンミンジクロロ白金水和物
金イオン：塩化金酸、亜硫酸金ナトリウム、シアン化金カリウムおよびシアン化金ナトリウム
銀イオン：硝酸銀、硫酸銀、
鉄イオン：硫酸第二鉄、酢酸第一鉄
前記１）の方法において、金属イオンを含む溶液は、金属イオンを形成し得る金属化合物を溶媒に溶解することにより調製できる。上記金属イオンの価数については、特に限定されるものではない。
An example of a compound capable of generating other metal ions is described below.
Copper ions: Copper chloride, copper sulfate, copper nitrate Platinum ions: Chloroplatinic acid, potassium platinum (IV) chloride, sodium platinum (IV) chloride, potassium tetranitroplatinum (II), sodium hexahydroxoplatinum (IV) Japanese, dinitrodiammine platinum nitrate, dinitrodiammine platinum ammonia and tetraamminedichloroplatinum hydrate gold ions: chloroauric acid, sodium gold sulfite, potassium gold cyanide and sodium gold cyanide silver ions: silver nitrate, silver sulfate,
Iron ion: ferric sulfate, ferrous acetate In the above method 1), a solution containing metal ions can be prepared by dissolving a metal compound capable of forming metal ions in a solvent. The valence of the metal ion is not particularly limited.
金属イオンを生成する金属化合物は、溶媒に溶解して、前記懸濁液に添加される。
金属イオンを含む溶液に用いられる溶媒は、該金属との反応性を示さず、該金属化合物を溶解できるものでは特に限定されるものではない。
The metal compound that generates metal ions is dissolved in a solvent and added to the suspension.
The solvent used for the solution containing a metal ion is not particularly limited as long as it does not show reactivity with the metal and can dissolve the metal compound.
このような溶媒としては、
水；
メタノール、エタノール、イソプロパノール、ｎ−ブタノール、メチルイソカルビノール
などのアルコール類；
アセトン、２−ブタノン、エチルアミルケトン、ジアセトンアルコール、イソホロン、シクロヘキサノンなどのケトン類；
Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドなどのアミド類；
ジエチルエーテル、イソプロピルエーテル、テトラヒドロフラン、１，４−ジオキサン、３，４−ジヒドロ−２Ｈ−ピランなどのエーテル類；
２−メトキシエタノール、２−エトキシエタノール、２−ブトキシエタノール、エチレングリコールジメチルエーテルなどのグリコールエーテル類；
２−メトキシエチルアセテート、２−エトキシエチルアセテート、２−ブトキシエチルアセテートなどのグリコールエーテルアセテート類；
酢酸メチル、酢酸エチル、酢酸イソブチル、酢酸アミル、乳酸エチル、エチレンカーボネートなどのエステル類；
ベンゼン、トルエン、キシレンなどの芳香族炭化水素類；
ヘキサン、ヘプタン、ｉｓｏ−オクタン、シクロヘキサンなどの脂肪族炭化水素類；
塩化メチレン、１，２−ジクロルエタン、ジクロロプロパン、クロルベンゼンなどのハロゲン化炭化水素類；
ジメチルスルホキシドなどのスルホキシド類；
Ｎ−メチル−２−ピロリドン、Ｎ−オクチル−２−ピロリドンなどのピロリドン類などを挙げることができる。
Such solvents include
water;
Alcohols such as methanol, ethanol, isopropanol, n-butanol, methyl isocarbinol;
Ketones such as acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone, cyclohexanone;
Amides such as N, N-dimethylformamide and N, N-dimethylacetamide;
Ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H-pyran;
Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether;
Glycol ether acetates such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate;
Esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethylene carbonate;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Aliphatic hydrocarbons such as hexane, heptane, iso-octane, cyclohexane;
Halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene;
Sulfoxides such as dimethyl sulfoxide;
Examples thereof include pyrrolidones such as N-methyl-2-pyrrolidone and N-octyl-2-pyrrolidone.
前記２）の方法は、前記１）の方法で述べた金属化合物をそのまま前記懸濁液に添加する方法である。
金属粒子が複合金属粒子である金属粒子担持触媒を製造する場合には、前記１）の方法においては、２種以上の金属化合物を溶媒に溶解して得られた溶液を前記懸濁液に添加すればよく、前記２）の方法においては、２種以上の金属化合物を前記懸濁液に添加すればよい。
The method 2) is a method in which the metal compound described in the method 1) is added to the suspension as it is.
When producing a metal particle-supported catalyst in which the metal particles are composite metal particles, in the method 1), a solution obtained by dissolving two or more metal compounds in a solvent is added to the suspension. In the method 2), two or more kinds of metal compounds may be added to the suspension.
上記担体物質懸濁液に、金属イオンを含む溶液あるいは金属化合物を添加する際の温度は、特に限定されないが、１５〜４０℃が好ましい。添加温度が前記範囲より低いと、十分に金属イオンを担持できないことがあり、添加温度が前記範囲より高いと、担持効率のさらなる向上が見られないため、経済的に好ましくない。 Although the temperature at the time of adding the solution or metal compound containing a metal ion to the said support substance suspension is not specifically limited, 15-40 degreeC is preferable. If the addition temperature is lower than the above range, the metal ions may not be sufficiently supported, and if the addition temperature is higher than the above range, further improvement in the support efficiency will not be seen, which is economically undesirable.
また、上記添加後、上記範囲の温度に保持しながら懸濁液を攪拌して充分に混合することが好ましい。攪拌は１５〜４０℃で、通常５分以上、好ましくは１０分以上行なうことが望ましく、必要に応じて、３時間程度まで、好ましくは１時間程度まで攪拌してもよい。特に、固体状の金属化合物を添加した場合には、金属化合物が充分に溶解して金属イオンが生成するまで攪拌などの操作を充分に行なう必要がある。 Further, after the addition, it is preferable that the suspension is stirred and sufficiently mixed while maintaining the temperature within the above range. Stirring is preferably carried out at 15 to 40 ° C. for usually 5 minutes or longer, preferably 10 minutes or longer. If necessary, stirring may be performed for up to about 3 hours, preferably up to about 1 hour. In particular, when a solid metal compound is added, it is necessary to sufficiently perform operations such as stirring until the metal compound is sufficiently dissolved and metal ions are generated.
また、イオン化傾向の高い金属イオンを用いる場合は、金属イオンを吸着させた後に還元剤を添加することもできる。還元剤としては、アルコール、ヒドラジン、蟻酸、ホルムアルデヒド、ヒドロキノン、過塩素酸、硫酸第一鉄、水素化ホウ素ナトリウム、過酸化水素、過マンガン酸カリウムなどが挙げられる。 Moreover, when using a metal ion with a high ionization tendency, a reducing agent can also be added after adsorbing a metal ion. Examples of the reducing agent include alcohol, hydrazine, formic acid, formaldehyde, hydroquinone, perchloric acid, ferrous sulfate, sodium borohydride, hydrogen peroxide, potassium permanganate and the like.
本発明では、形状制御剤存在下で前記懸濁液に金属イオンを混合することにより、上記形状制御剤が存在しない場合に比べて、担体に面状領域を有する金属粒子を良好に担持させることができる。このように面状領域を有する金属粒子が良好に形成されるのは、担体に吸着された形状制御剤と金属イオンとが選択的に錯形成した状態で金属イオンが担体に吸着されるので、金属として析出する際に粒子成長が選択的に生じ、その結果密着性の高い面状領域を有する金属粒子が得られやすくなるからであると推測される。
（IV）工程
上記混合操作後、必要に応じて、金属粒子担持触媒を含む懸濁液を水で希釈してもよい。通常、金属粒子担持触媒１００質量部に対して、最大で２５０,０００質量部程度の水で
希釈することができる。
この金属粒子担持触媒を、通常１５〜２００℃、好ましくは５０〜２００℃で１〜２０時間乾燥する。乾燥温度が１５℃より低いと面状領域を有する金属粒子が形成されない場合があり、２００℃より高いと粒子のシンタリングや酸化が進行するといった問題がある。前記乾燥工程は、不活性雰囲気下、水素雰囲気下または水素-不活性ガス混合雰囲気下で
行うことが好ましい。不活性雰囲気としては、窒素、アルゴン、およびヘリウム雰囲気等を挙げることができる。これらの雰囲気下で乾燥を行うと、面状領域を有する金属粒子を担持させ易いという利点がある。
In the present invention, by mixing metal ions in the suspension in the presence of a shape control agent, the carrier can be more favorably loaded with metal particles having planar regions than in the case where the shape control agent is not present. Can do. The reason why the metal particles having the planar region are formed well is that the metal ions are adsorbed on the carrier in a state where the shape control agent adsorbed on the carrier and the metal ions are selectively complexed. It is presumed that this is because particle growth occurs selectively when precipitated as a metal, and as a result, metal particles having a planar region with high adhesion are easily obtained.
(IV) Step After the above mixing operation, the suspension containing the metal particle-supported catalyst may be diluted with water as necessary. Usually, it can be diluted with up to about 250,000 parts by mass of water with respect to 100 parts by mass of the metal particle supported catalyst.
The metal particle-supported catalyst is usually dried at 15 to 200 ° C., preferably 50 to 200 ° C. for 1 to 20 hours. When the drying temperature is lower than 15 ° C., metal particles having a planar region may not be formed. When the drying temperature is higher than 200 ° C., there is a problem in that particle sintering and oxidation progress. The drying step is preferably performed in an inert atmosphere, a hydrogen atmosphere, or a hydrogen-inert gas mixed atmosphere. Examples of the inert atmosphere include nitrogen, argon, and helium atmospheres. When drying is performed in these atmospheres, there is an advantage that metal particles having a planar region can be easily supported.
本発明の製造方法により、金属粒子担持量が、金属粒子担持触媒全体に対して、０．１〜５０質量％であり、かつ金属粒子が担体物質表面に極めて良好に分散し、さらにその金属粒子の少なくとも一部が面状領域を有する金属粒子である金属粒子担持触媒を得ることができる。なお、この金属粒子担持量は、金属イオンを添加する際の温度、金属イオンの含有量、金属粒子混合時の温度、金属粒子の混合量、還元剤の有無などの製造条件を適宜調整することによりコントロールすることができる。 According to the production method of the present invention, the amount of metal particles supported is 0.1 to 50% by mass with respect to the entire metal particle-supported catalyst, and the metal particles are very well dispersed on the surface of the support material. It is possible to obtain a metal particle-supported catalyst in which at least a part of is a metal particle having a planar region. In addition, this metal particle carrying amount adjusts manufacturing conditions, such as the temperature at the time of adding metal ion, the content of metal ion, the temperature at the time of metal particle mixing, the amount of metal particle mixing, the presence or absence of a reducing agent, as appropriate. Can be controlled.
本発明の金属粒子担持触媒は、面状領域を有する金属粒子が担体表面に担持されてなる金属粒子担持触媒であって、高活性で、高寿命である。本発明の金属粒子担持触媒は、酸化反応や還元反応などの反応の触媒として広く使用することができ、たとえば硝酸性窒素を還元して窒素を生成する処理や種々の酸化物合成に用いる場合に高い触媒活性を示し、高寿命であり、触媒性能の再現性もよい。また、触媒以外の用途として、金属粒子を担体上に良好に分散した材料として、電気特性または磁気特性を利用する用途に適用可能である。
本願発明の好適な態様を以下に列挙する。
［好適な態様１］
第４周期遷移金属元素、第５周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも１種の金属からなる金属粒子が担体に担持されてなる金属粒子担持触媒であって、前記金属粒子の少なくとも一部が面状領域を一箇所のみ有する金属粒子であることを特徴とする金属粒子担持触媒。
［好適な態様２］
前記金属粒子が、第４周期遷移金属元素、第５周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも２種の金属からなる複合金属粒子であることを特徴とする前記金属粒子担持触媒。
［好適な態様３］
前記第４周期遷移金属元素が、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、ＮｉおよびＣｕからなる群より選ばれる元素であり、前記第５周期遷移金属元素が、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、ＰｄおよびＡｇからなる群より選ばれる元素であることを特徴とする前記金属粒子担持触媒。
［好適な態様４］
前記面状領域を一箇所のみ有する金属粒子の面状領域が、最大幅３〜１００ｎｍの範囲のものであることを特徴とする前記金属粒子担持触媒。
［好適な態様５］
前記面状領域を一箇所のみ有する金属粒子が、担体表面の１ｍ2あたり、１０2〜１０17個担持されていることを特徴とする前記金属粒子担持触媒。
［好適な態様６］
金属粒子の含有割合が０．１〜５０質量％であることを特徴とする前記金属粒子担持触媒。
［好適な態様７］
前記担体がＳｉ、Ａｌ、Ｃ、Ｔｉ、ＺｒおよびＣｅからなる群より選ばれる少なくとも１種を含有することを特徴とする前記金属粒子担持触媒。
［好適な態様８］
酸化反応または還元反応に使用できることを特徴とする前記金属粒子担持触媒。
［好適な態様９］
以下の（I）〜（IV）工程を含むことを特徴とする面状領域を一箇所のみ有する金属粒
子担持触媒の製造方法。
（I）担体の懸濁液に、ハロゲン化ナトリウム、ポリビニルアルコール、有機酸および有
機酸塩からなる群より選ばれる少なくとも１つの化合物を、前記担体１００質量部に対して０．1〜５０質量部添加する工程
（II）（I）工程で得られた前記化合物を吸着した担体を分離し、分散媒に再懸濁させる
工程
（III）（II）工程で得られた懸濁液に、１５〜４０℃で、第４周期遷移金属元素、第５
周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも１種の金属のイオンを前記担体１００質量部に対して１〜１８０質量部添加し、さらに必要に応じて還元剤を添加し、混合する工程
（IV）（III）工程で得られた懸濁液を１５〜２００℃にて乾燥させる工程
［好適な態様１０］
前記乾燥を、不活性雰囲気下、水素雰囲気下または水素-不活性ガス混合雰囲気下で行
うことを特徴とする前記金属粒子担持触媒の製造方法。
The metal particle-supported catalyst of the present invention is a metal particle-supported catalyst in which metal particles having a planar region are supported on a support surface, and has a high activity and a long life. The metal particle-supported catalyst of the present invention can be widely used as a catalyst for reactions such as an oxidation reaction and a reduction reaction. For example, when it is used for a process for reducing nitrate nitrogen to generate nitrogen and various oxide syntheses. It exhibits high catalytic activity, long life, and good reproducibility of catalyst performance. Further, as a use other than the catalyst, the present invention can be applied as a material in which metal particles are well dispersed on a support, in an application utilizing electric characteristics or magnetic characteristics.
Preferred embodiments of the present invention are listed below.
[Preferred embodiment 1]
A metal particle-supported catalyst in which metal particles comprising at least one metal selected from the group consisting of a fourth period transition metal element, a fifth period transition metal element, platinum and gold are supported on a carrier, A metal particle-supported catalyst, wherein at least a part of the metal particles is a metal particle having only one planar region.
[Preferred embodiment 2]
The metal particle is a composite metal particle comprising at least two kinds of metals selected from the group consisting of a fourth periodic transition metal element, a fifth periodic transition metal element metal element, platinum and gold. Supported catalyst.
[Preferred Aspect 3]
The fourth period transition metal element is an element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, and Cu, and the fifth period transition metal element is Zr, Nb, Mo, Tc. The metal particle-supported catalyst, which is an element selected from the group consisting of Ru, Rh, Pd, and Ag.
[Preferred aspect 4]
The metal particle-supported catalyst, wherein a planar region of the metal particles having only one planar region has a maximum width of 3 to 100 nm.
[Preferred Aspect 5]
The metal particle-supported catalyst, wherein 10 2 to 10 17 metal particles having only one planar region are supported per 1 m 2 of the support surface.
[Preferred Aspect 6]
The metal particle-supported catalyst, wherein the content ratio of the metal particles is 0.1 to 50% by mass.
[Preferred embodiment 7]
The metal particle-supported catalyst, wherein the carrier contains at least one selected from the group consisting of Si, Al, C, Ti, Zr and Ce.
[Preferred Aspect 8]
The metal particle-supported catalyst, which can be used in an oxidation reaction or a reduction reaction.
[Preferred embodiment 9]
The manufacturing method of the metal particle supported catalyst which has the planar area | region characterized by including the following (I)-(IV) processes only.
(I) At least one compound selected from the group consisting of sodium halide, polyvinyl alcohol, organic acid and organic acid salt is added to the suspension of the carrier in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass of the carrier. Step (II) The carrier obtained by adsorbing the compound obtained in the step (II) (I) is separated and resuspended in the dispersion medium (III) (II). At 40 ° C., the fourth period transition metal element, the fifth
Periodic transition metal element At least one metal ion selected from the group consisting of metal elements, platinum and gold is added in an amount of 1 to 180 parts by mass with respect to 100 parts by mass of the carrier, and a reducing agent is added if necessary. Step of mixing (IV) Step of drying the suspension obtained in step (III) at 15 to 200 ° C. [Preferred embodiment 10]
The method for producing a metal particle-supported catalyst, wherein the drying is performed in an inert atmosphere, a hydrogen atmosphere, or a hydrogen-inert gas mixed atmosphere.
［実施例］
以下、本発明を実施例により説明するが、本発明はこれらの実施例に何ら限定されるものではない。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all.
比表面積測定装置（ユアサアイオニクス製、型番マルチソーブ１２）を用いて窒素吸着法（ＢＥＴ法）を用いて、窒素の吸着量から、ＢＥＴ１点法により比表面積を測定した。［１］単位面積当たりの金属粒子存在個数測定
透過型電子顕微鏡（株式会社日立製作所製、Ｈ−８００）により、試料（金属粒子担持触媒）を倍率３０万倍で写真撮影して得られる写真投影図における、同一の担体について５００ｎｍ四方の表面に担持されている金属粒子の個数［Ｎ］とそのうち面状領域を有する金属粒子の個数［ｎ］をそれぞれ測定した。更に、この測定を５０箇所の５００ｎｍ四方について行い、それぞれの平均値（［ＮA］と［ｎA］）を算定した。そして、全金属粒子中の面状領域を有する金属粒子の存在割合（（nA／NA）×１００）［％］、およびそれいつ以外の金属粒子の存在割合（（NA−nA）／NA）×１００）［％］を求めた。
The specific surface area was measured by the BET 1-point method from the nitrogen adsorption amount using the nitrogen adsorption method (BET method) using a specific surface area measuring device (manufactured by Yuasa Ionics, model number Multisorb 12). [1] Measurement of the number of metal particles per unit area Photographic projection obtained by photographing a sample (metal particle supported catalyst) at a magnification of 300,000 times with a transmission electron microscope (H-800, manufactured by Hitachi, Ltd.) In the figure, the number [N] of metal particles supported on the surface of 500 nm square and the number [n] of metal particles having a planar region were measured for the same carrier. Furthermore, this measurement was performed on 50 nm squares at 50 locations, and the average values ([N A ] and [n A ]) were calculated. The existence ratio of the metal particles having a surface area in the total metal particle existence ratio of ((n A / N A) × 100) [%], and it always other metal particles ((N A -n A) / N A ) × 100) [%].
なお、前記写真投影図上の５００ｎｍ四方に複数の担体が存在する場合は、最低１００ｎｍ四方まで適宜測定範囲を調整して、同一の担体に担持した金属粒子数を測定する。
［２］金属粒子担持担体の組成分析
試料（金属粒子担持担体）を６００℃にて焼成し、残渣をアルカリ溶融剤にて溶融した後、２８（質量）％塩酸水溶液にて溶解し、溶解液を純水で希釈した後、ＩＣＰ誘導結合プラズマ発光分光分析装置ＳＰＳ１２００Ａ（セイコー電子株式会社製）にて測定し、金属粒子担持触媒の質量に占める金属粒子の割合［質量％］を求めた。
When there are a plurality of carriers in the 500 nm square on the photographic projection diagram, the measurement range is appropriately adjusted to a minimum of 100 nm square, and the number of metal particles carried on the same carrier is measured.
[2] Composition analysis sample of metal particle-supported carrier (metal particle-supported carrier) was baked at 600 ° C., the residue was melted with an alkali melting agent, and then dissolved in 28% (mass)% hydrochloric acid aqueous solution. Was diluted with pure water, and then measured with an ICP inductively coupled plasma emission spectrometer SPS1200A (manufactured by Seiko Electronics Co., Ltd.) to determine the ratio [mass%] of metal particles to the mass of the metal particle-supported catalyst.
［３］画像解析による形状の確認と面状領域の最大幅の測定方法
面状領域を有する金属粒子が有する面の最大幅については、次の方法により測定した。透過型電子顕微鏡（株式会社日立製作所製、Ｈ−８００）により、倍率３０万倍で写真撮影して得られる写真投影図により面状領域の有無および全体形状を確認し、写真投影図上の５００ｎｍ四方に存在する面状領域を有する金属粒子の中で、面状領域の最大幅が最も
大きい値を測定し、同様の測定を写真投影図上の５０箇所について行って、その平均値を該金属粒子が有する面状領域の最大幅とした。
[3] Method of confirming shape by image analysis and measuring method of maximum width of planar region The maximum width of the surface of the metal particles having the planar region was measured by the following method. With a transmission electron microscope (H-800, manufactured by Hitachi, Ltd.), the presence or absence of a planar region and the overall shape are confirmed from a photograph projection obtained by taking a photograph at a magnification of 300,000, and 500 nm on the photograph projection is obtained. Among metal particles having planar regions present in all directions, the maximum value of the planar region is measured, the same measurement is performed at 50 locations on the photographic projection, and the average value is calculated for the metal particles. It was set as the maximum width of the planar area | region which particle | grains have.
以下の実施例は、いずれも前記特許請求の範囲の要件を満たすものである。 Each of the following examples satisfies the requirements of the claims.
活性炭懸濁液の調製
活性炭（味の素ファインテクノ株式会社製、商品名：ＣＬ−Ｋ、粒度：０．５ｍｍ〜１．７ｍｍ、ヨウ素吸着量１，５５０ｍｇ／ｇ）を純水に分散させ、活性炭濃度が１０質量％の活性炭懸濁液（C-1）を調製した。
金属粒子担持触媒の製造
活性炭懸濁液（C-1）１００ｇにNaIを１ｇ添加して、２０℃で４０分間攪拌し、混合懸濁液を調製した。その後1Lの水を用いて混合液を洗浄して吸着していないNaIを除去し、
４４μｍフィルターを用いて吸引濾過、１１０℃にて乾燥させた。得られた乾燥物を 再度固形分 10質量％に成るように純水に懸濁し、懸濁液１００ｇにＰｄイオン濃度が３．０質量％の塩化パラジウム水溶液を１０ｇ添加して、２０℃で４０分間攪拌した。この液を空気中、１８０℃で１０時間乾燥させることにより、平均値が１５ｎｍの面状領域を有するＰｄ粒子（面状領域の最大幅：１５ｎｍ）が担持した活性炭（Ｐｄ粒子担持触媒）を得た。製造条件およびＰｄ粒子担持触媒の測定（分析）結果を表１に示した。
Preparation of activated carbon suspension Activated carbon (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name: CL-K, particle size: 0.5 mm to 1.7 mm, iodine adsorption amount 1,550 mg / g) is dispersed in pure water, and activated carbon concentration A 10% by mass activated carbon suspension (C-1) was prepared.
Production of metal particle supported catalyst 1 g of NaI was added to 100 g of activated carbon suspension (C-1) and stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. Then wash the mixture with 1 L of water to remove unadsorbed NaI,
Suction filtration using a 44 μm filter was carried out at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass, and 10 g of palladium chloride aqueous solution having a Pd ion concentration of 3.0% by mass was added to 100 g of the suspension. Stir for minutes. By drying this liquid in air at 180 ° C. for 10 hours, activated carbon (Pd particle-supported catalyst) supported by Pd particles having a planar region with an average value of 15 nm (maximum width of the planar region: 15 nm) is obtained. It was. Table 1 shows the production conditions and the measurement (analysis) results of the Pd particle-supported catalyst.
また、このＰｄ粒子担持触媒の電子顕微鏡写真（倍率３０万倍）を図１に示した。 An electron micrograph (magnification of 300,000 times) of this Pd particle-supported catalyst is shown in FIG.
金属粒子担持触媒の製造
実施例1で調製した活性炭懸濁液（C-1）１００ｇにNaIを１ｇおよびクエン酸3ナトリウム1ｇ添加して、２０℃で４０分間攪拌し、混合懸濁液を調製した。その後1Lの水を用い
て混合液を洗浄して吸着していないNaIを除去し、４４μｍフィルターを用いて吸引濾過
、１１０℃にて乾燥させた。得られた乾燥物を 再度固形分１０質量％に成るように純水に懸濁し、懸濁液１００ｇにＰｄイオン濃度が４．０質量％の塩化パラジウム水溶液を１０ｇ添加して、ついで６．０質量％の硫酸第一鉄水溶液１０ｇを添加し２０℃で４０分間攪拌した。この液を窒素雰囲気下、１１０℃で１０時間乾燥させることにより、面状領域を有するＰｄ粒子（面状領域の最大幅：１５ｎｍ）が担持した活性炭（Ｐｄ粒子担持触媒）を得た。製造条件およびＰｄ粒子担持触媒の測定（分析）結果を表１に示した。
Production of metal particle supported catalyst 1 g of NaI and 1 g of trisodium citrate were added to 100 g of the activated carbon suspension (C-1) prepared in Example 1 and stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. did. Thereafter, the mixed solution was washed with 1 L of water to remove unadsorbed NaI, suction filtered using a 44 μm filter, and dried at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass. To 100 g of the suspension, 10 g of palladium chloride aqueous solution having a Pd ion concentration of 4.0% by mass was added, and then 6.0%. 10 g of a mass% ferrous sulfate aqueous solution was added and stirred at 20 ° C. for 40 minutes. This liquid was dried at 110 ° C. for 10 hours in a nitrogen atmosphere to obtain activated carbon (Pd particle-supported catalyst) supported by Pd particles having a planar region (maximum width of the planar region: 15 nm). Table 1 shows the production conditions and the measurement (analysis) results of the Pd particle-supported catalyst.
製造条件およびＰｄ粒子担持触媒の評価を表１に示した。 The production conditions and the evaluation of the Pd particle supported catalyst are shown in Table 1.
金属粒子担持触媒の製造
実施例1で調製した活性炭懸濁液（C-1）１００ｇにNaBrを１ｇ添加して、２０℃で４０分間攪拌し、混合懸濁液を調製した。その後1Lの水を用いて混合液を洗浄して吸着していないNaBrを除去し、４４μｍフィルターを用いて吸引濾過、１１０℃にて乾燥させた。得られた乾燥物を再度固形分１０質量％に成るように純水に懸濁し、懸濁液１００ｇにＰｔイオン濃度が６．０質量％のジニトロジアンミン白金水溶液を１０ｇ添加して、ついで10.0質量％の水素化ホウ素ナトリウム水溶液10ｇを添加し２０℃で４０分間攪拌した。この液をアルゴン雰囲気下、１１０℃で１０時間乾燥させることにより、面状領域を有するＰｄ粒子（面状領域の最大幅：２０ｎｍ）が担持した活性炭（Ｐｄ粒子担持触媒）を得た。製造条件およびＰｄ粒子担持触媒の測定（分析）結果を表１に示した。
Production of metal particle supported catalyst 1 g of NaBr was added to 100 g of the activated carbon suspension (C-1) prepared in Example 1 and stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. Thereafter, the mixed solution was washed with 1 L of water to remove unadsorbed NaBr, and suction filtered using a 44 μm filter and dried at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass, 10 g of a dinitrodiammine platinum aqueous solution having a Pt ion concentration of 6.0% by mass was added to 100 g of the suspension, and then 10.0% by mass. A 10% aqueous solution of sodium borohydride was added and stirred at 20 ° C. for 40 minutes. This liquid was dried at 110 ° C. for 10 hours in an argon atmosphere to obtain activated carbon (Pd particle-supported catalyst) supported by Pd particles having a planar region (maximum width of the planar region: 20 nm). Table 1 shows the production conditions and the measurement (analysis) results of the Pd particle-supported catalyst.
製造条件およびＰｔ粒子担持触媒の評価を表１に示した。 The production conditions and the evaluation of the Pt particle supported catalyst are shown in Table 1.
ZSM-5（ゼオライト）懸濁液の調製
ZSM-5（日揮触媒化成株製、アルミナ濃度２０％）を純水に分散させ、濃度が１０質量
％の ZSM-5懸濁液（C-2）を調製した。
金属粒子担持触媒の製造
ZSM-5懸濁液（C-2）１００ｇにNaIを１ｇ添加して、２０℃で４０分間攪拌し、混合懸
濁液を調製した。その後1Lの水を用いて混合液を洗浄して吸着していないNaIを除去し、
４４μｍフィルターを用いて吸引濾過、１１０℃にて乾燥させた。得られた乾燥物を 再度固形分１００質量％に成るように純水に懸濁し、懸濁液１００ｇにＰｄイオン濃度が２．０質量％の塩化パラジウム水溶液を１０ｇおよびCuイオン濃度が２．０質量％の塩化銅水溶液を１０ｇ添加して、２０℃で４０分間攪拌した。この液を水素雰囲気下、５０℃で１０時間乾燥させることにより、面状領域を有するＰｄ-Cu複合粒子（面状領域の最大幅
：２０ｎｍ）が担持したゼオライト（Ｐｄ-Ｃｕ複合粒子担持触媒）を得た。
Preparation of ZSM-5 (zeolite) suspension
ZSM-5 (manufactured by JGC Catalysts & Chemicals, alumina concentration 20%) was dispersed in pure water to prepare a ZSM-5 suspension (C-2) having a concentration of 10% by mass.
Production of metal particle supported catalyst
1 g of NaI was added to 100 g of ZSM-5 suspension (C-2) and stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. Then wash the mixture with 1 L of water to remove unadsorbed NaI,
Suction filtration using a 44 μm filter was carried out at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 100% by mass, and 10 g of palladium chloride aqueous solution having a Pd ion concentration of 2.0% by mass and a Cu ion concentration of 2.0% were added to 100 g of the suspension. 10 g of a mass% aqueous copper chloride solution was added and stirred at 20 ° C. for 40 minutes. This liquid is dried in a hydrogen atmosphere at 50 ° C. for 10 hours to support a zeolite supported by Pd—Cu composite particles having a planar region (maximum width of the planar region: 20 nm) (Pd—Cu composite particle supported catalyst). Got.
製造条件およびＰｄ粒子担持触媒の測定（分析）結果を表１に示した。 Table 1 shows the production conditions and the measurement (analysis) results of the Pd particle-supported catalyst.
金属粒子担持触媒の製造
実施例４で調製したZSM-5懸濁液（C-2）１００ｇにポリアクリル酸（Ardrich製 濃度
６３％ Mw3000）を３．１９ｇ添加して、２０℃で４０分間攪拌し、混合懸濁液を調製し
た。その後1Lの水を用いて混合液を洗浄して吸着していないポリアクリル酸を除去し、４４μｍフィルターを用いて吸引濾過、１１０℃にて乾燥させた。得られた乾燥物を 再度固形分１０質量％に成るように純水に懸濁し、懸濁液１００ｇにFeイオン濃度が４．０質量％の硫酸第二鉄水溶液を１０ｇを添加して、２０℃で４０分間攪拌した。この液を水素雰囲気下、１８０℃で１０時間乾燥させることにより、面状領域を有するＦｅ粒子（面状領域の最大幅：４０ｎｍ）が担持したゼオライト（Ｆｅ粒子担持触媒）を得た。
Production of metal particle supported catalyst 3.19 g of polyacrylic acid (Ardrich concentration 63% Mw3000) was added to 100 g of the ZSM-5 suspension (C-2) prepared in Example 4 and stirred at 20 ° C. for 40 minutes. To prepare a mixed suspension. Thereafter, the mixed solution was washed with 1 L of water to remove unadsorbed polyacrylic acid, and suction filtered using a 44 μm filter and dried at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass, and 10 g of an aqueous ferric sulfate solution having an Fe ion concentration of 4.0% by mass was added to 100 g of the suspension. Stir at 40 ° C. for 40 minutes. This liquid was dried at 180 ° C. for 10 hours under a hydrogen atmosphere to obtain zeolite (Fe particle-supported catalyst) supported by Fe particles having a planar region (maximum width of the planar region: 40 nm).
製造条件およびFe粒子担持触媒の評価を表１に示した。 The production conditions and the evaluation of the Fe particle supported catalyst are shown in Table 1.
金属粒子担持触媒の製造
実施例4で調製したZSM-5懸濁液（C-2）１００ｇにポリビニルアルコール（関東化学製
Mw5000）を２ｇ添加して、２０℃で４０分間攪拌し、混合懸濁液を調製した。その後1Lの水を用いて混合液を洗浄して吸着していないポリビニルアルコールを除去し、４４μｍフィルターを用いて吸引濾過、１１０℃にて乾燥させた。得られた乾燥物を 再度固形分
１０質量％に成るように純水に懸濁し、懸濁液１００ｇにPdイオン濃度が２．０質量％の酢酸パラジウムアセトン溶液を２０ｇおよびAｇイオン濃度が２質量％添の硝酸銀水溶
液１０ｇを添加して、２０℃で４０分間攪拌した。この液を空気中、１１０℃で１０時間乾燥させることにより、面状領域を有するＡｇ-Ｐｄ複合粒子（面状領域の最大幅：１５
ｎｍ）が担持したゼオライト（Ｐｄ-Ｃｕ複合粒子担持触媒）を得た。
Production of metal particle supported catalyst Polyvinyl alcohol (manufactured by Kanto Chemical Co., Ltd.) was added to 100 g of the ZSM-5 suspension (C-2) prepared in Example 4.
2 g of Mw5000) was added and stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. Thereafter, the mixed liquid was washed with 1 L of water to remove unadsorbed polyvinyl alcohol, and suction filtration was performed using a 44 μm filter, followed by drying at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass. 20 g of palladium acetate / acetone solution having a Pd ion concentration of 2.0% by mass and 2% of Ag ion concentration were added to 100 g of the suspension. A 10% aqueous silver nitrate solution was added, and the mixture was stirred at 20 ° C. for 40 minutes. By drying this liquid in air at 110 ° C. for 10 hours, Ag—Pd composite particles having a planar region (maximum width of the planar region: 15
nm) supported zeolite (Pd—Cu composite particle supported catalyst) was obtained.
製造条件およびAg-Pd合金粒子担持触媒の評価を表１に示した。 The production conditions and evaluation of the Ag—Pd alloy particle supported catalyst are shown in Table 1.
シリカ粒子懸濁液の調製
シリカ粒子として日揮触媒化成株製、シリカマイクロビードP-1500（平均粒子径５μｍ
固形分100％）を純水に分散させ、シリカ濃度が１０質量％のシリカ粒子懸濁液（C-3）を調製した。
金属粒子担持触媒の製造
シリカ粒子懸濁液（C-3）１００ｇにNaClを１ｇおよびクエン酸3ナトリウム１ｇ添加し
て、２０℃で４０分間攪拌し、混合懸濁液を調製した。その後１Lの水を用いて混合液を
洗浄して吸着していないNaCl及びクエン酸3ナトリウムを除去し、４４μｍフィルターを
用いて吸引濾過、１１０℃にて乾燥させた。得られた乾燥物を再度固形分１０質量％に成るように純水に懸濁し、懸濁液１００ｇにＰｔイオン濃度が４．０質量％の塩化白金酸水溶液を１０ｇおよびAuイオン濃度が２．０質量％の塩化金酸水溶液を１０ｇ添加して、ついで還元剤として蟻酸1ｇ添加し、２０℃で４０分間攪拌した。この液を空気中、１１０
℃で１０時間乾燥させることにより、面状領域を有するＰｔ-Ａu複合粒子（面状領域の最大幅：１０ｎｍ）が担持したシリカ（Ｐｔ-Ａｕ複合粒子担持触媒）を得た。
Preparation of silica particle suspension Silica microbead P-1500 (average particle size 5 μm, manufactured by JGC Catalysts & Chemicals Co., Ltd.)
100% solid content) was dispersed in pure water to prepare a silica particle suspension (C-3) having a silica concentration of 10% by mass.
Production of metal particle supported catalyst 1 g of NaCl and 1 g of sodium tricitrate were added to 100 g of silica particle suspension (C-3), and the mixture was stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. Thereafter, the mixed solution was washed with 1 L of water to remove unadsorbed NaCl and trisodium citrate, suction filtered using a 44 μm filter, and dried at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass. 10 g of a chloroplatinic acid aqueous solution having a Pt ion concentration of 4.0% by mass and an Au ion concentration of 2. 10 g of 0 mass% chloroauric acid aqueous solution was added, then 1 g of formic acid was added as a reducing agent, and the mixture was stirred at 20 ° C. for 40 minutes. This liquid is 110 in the air.
By drying at 10 ° C. for 10 hours, silica (Pt—Au composite particle-supported catalyst) supported by Pt—Au composite particles having a planar region (maximum width of the planar region: 10 nm) was obtained.
製造条件およびＰｔ-Au合金粒子担持触媒の評価を表１に示した。 The production conditions and evaluation of the Pt—Au alloy particle supported catalyst are shown in Table 1.
金属粒子担持触媒の製造
実施例7で調製したシリカ粒子懸濁液（C-3）１００ｇに３３％酢酸を９．１ｇ添加して、２０℃で４０分間攪拌し、混合懸濁液を調製した。その後１Lの水を用いて混合液を洗
浄して吸着していない酢酸を除去し、４４μｍフィルターを用いて吸引濾過、１１０℃にて乾燥させた。得られた乾燥物を 再度固形分１０質量％に成るように純水に懸濁し、懸濁液１００ｇにCuイオン濃度が４．０質量％の硫酸銅水溶液を１０ｇを添加して、２０℃で４０分間攪拌した。この液を水素雰囲気下、１１０℃で１０時間乾燥させることにより、面状領域を有するＣｕ粒子（面状領域の最大幅：２０ｎｍ）が担持したシリカ（Ｃｕ粒子担持触媒）を得た。
Production of Metal Particle-Supported Catalyst 9.1 g of 33% acetic acid was added to 100 g of the silica particle suspension (C-3) prepared in Example 7, and stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. . Thereafter, the mixed solution was washed with 1 L of water to remove the unadsorbed acetic acid, filtered with suction using a 44 μm filter, and dried at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass, and 10 g of an aqueous copper sulfate solution having a Cu ion concentration of 4.0% by mass was added to 100 g of the suspension. Stir for 40 minutes. This liquid was dried at 110 ° C. for 10 hours in a hydrogen atmosphere to obtain silica (Cu particle-supported catalyst) supported by Cu particles having a planar region (maximum width of the planar region: 20 nm).
製造条件およびCu粒子担持触媒の評価を表１に示した。 The production conditions and the evaluation of the Cu particle supported catalyst are shown in Table 1.
金属粒子担持触媒の製造
実施例7で調製したシリカ粒子懸濁液（C-3）１００ｇにシュウ酸を２．０ｇ添加して、２０℃で４０分間攪拌し、混合懸濁液を調製した。その後1Lの水を用いて混合液を洗浄して吸着していないシュウ酸を除去し、４４μｍフィルターを用いて吸引濾過、１１０℃にて乾燥させた。得られた乾燥物を再度固形分１０質量％に成るように純水に懸濁し、懸濁液10０ｇにAuイオン濃度が４．０質量％の塩化金酸溶液を１０ｇを添加して、２０℃で４０分間攪拌した。この液を空気中、１１０℃で１０時間乾燥させることにより、面状領域を有するＡｕ粒子（面状領域の最大幅：５ｎｍ）が担持したシリカ（Ａｕ粒子担持触媒）を得た。
Production of metal particle supported catalyst To 100 g of the silica particle suspension (C-3) prepared in Example 7, 2.0 g of oxalic acid was added and stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. Thereafter, the mixed solution was washed with 1 L of water to remove unadsorbed oxalic acid, suction filtered using a 44 μm filter, and dried at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass, 10 g of a chloroauric acid solution having an Au ion concentration of 4.0% by mass was added to 100 g of the suspension, and 20 ° C. For 40 minutes. This liquid was dried in air at 110 ° C. for 10 hours to obtain silica (Au particle-supported catalyst) supported by Au particles having a planar region (maximum width of the planar region: 5 nm).
製造条件およびAu粒子担持触媒の評価を表１に示した。
[比較例１]
The production conditions and the evaluation of the Au particle supported catalyst are shown in Table 1.
[Comparative Example 1]
実施例7で調製したシリカ粒子懸濁液（C-3）１００ｇにＰｄイオン濃度が３．０質量％の塩化パラジウム水溶液を１０ｇ添加して、２０℃で４０分間攪拌した。この液を空気中、１８０℃で１０時間乾燥させることにより、平均粒子径３ｎｍの球状Ｐｄ粒子が担持した活性炭（Ｐｄ粒子担持触媒）を得た。 10 g of an aqueous palladium chloride solution having a Pd ion concentration of 3.0% by mass was added to 100 g of the silica particle suspension (C-3) prepared in Example 7, and the mixture was stirred at 20 ° C. for 40 minutes. This liquid was dried in air at 180 ° C. for 10 hours to obtain activated carbon (Pd particle-supported catalyst) supported by spherical Pd particles having an average particle diameter of 3 nm.
製造条件およびＰｄ粒子担持触媒の評価を表１に示した。
[比較例2]
The production conditions and the evaluation of the Pd particle supported catalyst are shown in Table 1.
[Comparative Example 2]
実施例7で調製したシリカ粒子懸濁液（C-3）１００ｇにNaIを１ｇ添加して、２０℃で
４０分間攪拌し、混合懸濁液を調製した。その後１Lの水を用いて混合液を洗浄して吸着
していないNaIを除去し、４４μｍフィルターを用いて吸引濾過、１１０℃にて乾燥させ
た。得られた乾燥物を再度固形分１０質量％に成るように純水に懸濁し、懸濁液１００ｇ
にＰｄイオン濃度が１．０質量％の塩化パラジウム水溶液を５ｇ添加して、２０℃で４０分間攪拌した。この液を空気中、１１０℃で１０時間乾燥させることにより、平均粒子径３ｎｍの球状Ｐｄ粒子が担持した活性炭（Ｐｄ粒子担持触媒）を得た。
1 g of NaI was added to 100 g of the silica particle suspension (C-3) prepared in Example 7, and the mixture was stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. Thereafter, the mixed solution was washed with 1 L of water to remove unadsorbed NaI, suction filtered using a 44 μm filter, and dried at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass.
5 g of an aqueous palladium chloride solution having a Pd ion concentration of 1.0 mass% was added thereto, followed by stirring at 20 ° C. for 40 minutes. This liquid was dried in air at 110 ° C. for 10 hours to obtain activated carbon (Pd particle supported catalyst) supported by spherical Pd particles having an average particle diameter of 3 nm.
製造条件およびＰｄ粒子担持触媒の評価を表１に示した。
[比較例3]
The production conditions and the evaluation of the Pd particle supported catalyst are shown in Table 1.
[Comparative Example 3]
実施例7で調製したシリカ粒子懸濁液（C-3）１００ｇにNaIを６ｇ添加して、２０℃で
４０分間攪拌し、混合懸濁液を調製した。その後1Lの水を用いて混合液を洗浄して吸着していないNaIを除去し、４４μｍフィルターを用いて吸引濾過、１１０℃にて乾燥させた
。得られた乾燥物を再度固形分１０質量％に成るように純水に懸濁し、懸濁液１００ｇにＰｄイオン濃度が３．０質量％の塩化パラジウム水溶液を１０ｇ添加して、２０℃で４０分間攪拌した。この液を空気中、１１０℃で１０時間乾燥させることにより、平均粒子径3nmの球状Ｐｄ粒子が担持した活性炭（Ｐｄ粒子担持触媒）を得た。
6 g of NaI was added to 100 g of the silica particle suspension (C-3) prepared in Example 7, and the mixture was stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. Thereafter, the mixed solution was washed with 1 L of water to remove unadsorbed NaI, suction filtered using a 44 μm filter, and dried at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass, and 10 g of a palladium chloride aqueous solution having a Pd ion concentration of 3.0% by mass was added to 100 g of the suspension. Stir for minutes. This liquid was dried in air at 110 ° C. for 10 hours to obtain activated carbon (Pd particle-supported catalyst) on which spherical Pd particles having an average particle diameter of 3 nm were supported.
製造条件およびＰｄ粒子担持触媒の評価を表１に示した。
[比較例4]
The production conditions and the evaluation of the Pd particle supported catalyst are shown in Table 1.
[Comparative Example 4]
実施例7で調製したシリカ粒子懸濁液（C-3）１００ｇにNaIを１ｇ添加して、２０℃で
４０分間攪拌し、混合懸濁液を調製した。その後１Lの水を用いて混合液を洗浄して吸着
していないNaIを除去し、４４μｍフィルターを用いて吸引濾過、１１０℃にて乾燥させ
た。得られた乾燥物を再度固形分１０質量％に成るように純水に懸濁し、懸濁液１００ｇにＰｄイオン濃度が３．０質量％の塩化パラジウム水溶液を１０ｇ添加して、２０℃で４０分間攪拌した。この液を空気中、５００℃で１０時間乾燥させることにより、平均粒子径３ｎｍの球状Ｐｄ粒子が担持した活性炭（Ｐｄ粒子担持触媒）を得た。
1 g of NaI was added to 100 g of the silica particle suspension (C-3) prepared in Example 7, and the mixture was stirred at 20 ° C. for 40 minutes to prepare a mixed suspension. Thereafter, the mixed solution was washed with 1 L of water to remove unadsorbed NaI, suction filtered using a 44 μm filter, and dried at 110 ° C. The obtained dried product was again suspended in pure water so as to have a solid content of 10% by mass, and 10 g of a palladium chloride aqueous solution having a Pd ion concentration of 3.0% by mass was added to 100 g of the suspension. Stir for minutes. This liquid was dried in air at 500 ° C. for 10 hours to obtain activated carbon (Pd particle supported catalyst) supported by spherical Pd particles having an average particle diameter of 3 nm.
製造条件およびＰｄ粒子担持触媒の評価を表１に示した。 The production conditions and the evaluation of the Pd particle supported catalyst are shown in Table 1.
Claims (10)
（I）担体の懸濁液に、ハロゲン化ナトリウム、ポリビニルアルコール、有機酸および有
機酸塩からなる群より選ばれる少なくとも１つの化合物を、前記担体１００質量部に対して０．1〜５０質量部添加する工程
（II）（I）工程で得られた前記化合物を吸着した担体を分離し、分散媒に再懸濁させる
工程
（III）（II）工程で得られた懸濁液に、１５〜４０℃で、第４周期遷移金属元素、第５
周期遷移金属元素金属元素、白金および金からなる群より選ばれる少なくとも１種の金属のイオンを前記担体１００質量部に対して１〜１８０質量部添加し、さらに必要に応じて還元剤を添加し、混合する工程
（IV）（III）工程で得られた懸濁液を１５〜２００℃にて乾燥させる工程 The manufacturing method of the metal particle supported catalyst characterized by including the following (I)-(IV) processes.
(I) 0.1 to 50 parts by mass of at least one compound selected from the group consisting of sodium halide, polyvinyl alcohol, organic acid and organic acid salt is added to 100 parts by mass of the carrier in the suspension of the carrier. Step (II) The carrier obtained by adsorbing the compound obtained in the step (II) (I) is separated and resuspended in the dispersion medium (III) (II). At 40 ° C., the fourth period transition metal element, the fifth
Periodic transition metal element At least one metal ion selected from the group consisting of metal elements, platinum and gold is added in an amount of 1 to 180 parts by mass with respect to 100 parts by mass of the carrier, and a reducing agent is added if necessary. Step of mixing (IV) Step of drying the suspension obtained in step (III) at 15 to 200 ° C.
うことを特徴とする請求項９に記載の金属粒子担持触媒の製造方法。 The method for producing a metal particle-supported catalyst according to claim 9, wherein the drying is performed in an inert atmosphere, a hydrogen atmosphere, or a hydrogen-inert gas mixed atmosphere.
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