JP5290599B2 - Method for dispersing and immobilizing gold fine particles on a carrier - Google Patents
Method for dispersing and immobilizing gold fine particles on a carrier Download PDFInfo
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- JP5290599B2 JP5290599B2 JP2008067090A JP2008067090A JP5290599B2 JP 5290599 B2 JP5290599 B2 JP 5290599B2 JP 2008067090 A JP2008067090 A JP 2008067090A JP 2008067090 A JP2008067090 A JP 2008067090A JP 5290599 B2 JP5290599 B2 JP 5290599B2
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- JP
- Japan
- Prior art keywords
- gold
- fine particles
- polymer material
- reducing agent
- polymer
- Prior art date
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- 239000010931 gold Substances 0.000 title claims description 172
- 229910052737 gold Inorganic materials 0.000 title claims description 170
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims description 168
- 239000010419 fine particle Substances 0.000 title claims description 90
- 238000000034 method Methods 0.000 title claims description 47
- 230000003100 immobilizing effect Effects 0.000 title claims description 15
- 239000002245 particle Substances 0.000 claims description 81
- 239000003638 chemical reducing agent Substances 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 57
- 239000002861 polymer material Substances 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 30
- 150000002344 gold compounds Chemical class 0.000 claims description 29
- -1 positive Rishiran Polymers 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 10
- 229910010272 inorganic material Inorganic materials 0.000 claims description 8
- 239000011147 inorganic material Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 229910003767 Gold(III) bromide Inorganic materials 0.000 claims description 3
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000000412 dendrimer Substances 0.000 claims description 3
- 229920000736 dendritic polymer Polymers 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- OVWPJGBVJCTEBJ-UHFFFAOYSA-K gold tribromide Chemical compound Br[Au](Br)Br OVWPJGBVJCTEBJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940014053 gold tribromide Drugs 0.000 claims description 3
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 3
- 229940076131 gold trichloride Drugs 0.000 claims description 3
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims description 3
- 229920005615 natural polymer Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229940071240 tetrachloroaurate Drugs 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 2
- ZWXNIIPEHHCEKA-UHFFFAOYSA-N CC[Au]CC Chemical compound CC[Au]CC ZWXNIIPEHHCEKA-UHFFFAOYSA-N 0.000 claims description 2
- AUFHQOUHGKXFEM-UHFFFAOYSA-N C[Au]C Chemical compound C[Au]C AUFHQOUHGKXFEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 description 46
- 239000003054 catalyst Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000012876 carrier material Substances 0.000 description 21
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 14
- 239000004926 polymethyl methacrylate Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000002082 metal nanoparticle Substances 0.000 description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 12
- 239000008103 glucose Substances 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000006911 nucleation Effects 0.000 description 9
- 238000010899 nucleation Methods 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- MIQUYXUHGQNVDN-UHFFFAOYSA-N ethane-1,2-diamine;gold Chemical compound [Au].NCCN MIQUYXUHGQNVDN-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000011859 microparticle Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910001111 Fine metal Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000001768 cations Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000002116 nanohorn Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004337 magnesium citrate Substances 0.000 description 2
- 229960005336 magnesium citrate Drugs 0.000 description 2
- 235000002538 magnesium citrate Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- CIWXFRVOSDNDJZ-UHFFFAOYSA-L ferroin Chemical compound [Fe+2].[O-]S([O-])(=O)=O.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 CIWXFRVOSDNDJZ-UHFFFAOYSA-L 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- GKYQBMNOFTZZSX-UHFFFAOYSA-K n-ethylethanamine;trichlorogold Chemical compound Cl[Au](Cl)Cl.CCNCC GKYQBMNOFTZZSX-UHFFFAOYSA-K 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Description
本発明は、金微粒子を高分子材料表面に分散・固定化する方法に関する。より詳細には、還元剤で金前駆体を還元して高分子材料表面に分散・固定化する際に、従来法に比べより小さく且つ金微粒子の凝集がなく、粒度のそろったより均一な大きさの金微粒子を高分子材料表面に分散・固定化する方法に関する。
The present invention relates to gold fine particles how dispersing and immobilizing a polymer material surface. More specifically, when the gold precursor is reduced and dispersed and immobilized on the surface of the polymer material with a reducing agent, it is smaller than the conventional method and there is no aggregation of gold fine particles, and the particle size is more uniform and uniform. concerning the gold microparticles how dispersing and immobilizing a polymer material surface.
貴金属は、種々の装飾材料、歯科用材料、電子回路材料、触媒材料、例えば有機物の酸化あるいは還元反応触媒、自動車排気ガスの浄化触媒や、燃料電池用の触媒などとして広く用いられている。触媒として用いる場合、貴金属は高価なことと、その性能を最大限引き出すため、ナノ粒子（例えば、２〜１０ｎｍ）として露出表面積を大きくする工夫がなされている。具体的には、比表面積が大きく、熱的、化学的安定性の高いシリカやアルミナ、チタニアなどの金属酸化物、あるいは活性炭、カーボンブラックなどの炭素材料を担体に用い、その表面に貴金属がナノ粒子として分散・固定された状態とされて用いられている。 Precious metals are widely used as various decorative materials, dental materials, electronic circuit materials, catalyst materials, for example, organic matter oxidation or reduction reaction catalysts, automobile exhaust gas purification catalysts, and fuel cell catalysts. When used as a catalyst, the precious metal is expensive and has been devised to increase the exposed surface area as nanoparticles (eg, 2 to 10 nm) in order to maximize its performance. Specifically, metal oxides such as silica, alumina, and titania with high specific surface area and high thermal and chemical stability, or carbon materials such as activated carbon and carbon black are used as a support, and noble metal is nano-sized on the surface. It is used in a dispersed and fixed state as particles.
貴金属中、金は他の貴金属に比べれば安価であるものの、触媒活性が極めて乏しいと従来考えられていた。これに対し、発明者は、金を好ましくは直径１０ｎｍ以下の超微粒子として種々の金属酸化物担体上に分散・固定することにより、高い触媒活性が発現されること、さらに金ナノ粒子触媒は、低温ＣＯ酸化、プロピレンの気相一段エポキシ化、低温水性ガスシフト反応、酸素と水素からの直接過酸化水素合成、炭化水素類の部分酸化など、多くの反応に対して、他の貴金属より優れた触媒活性を発現することを見出している（例えば、特許文献１および非特許文献１参照）。また、その他にも、金ナノ粒子について、不飽和化合物の水添、アルコールの酸化、ＮＯxの除去、エポキシ化合物、脂肪族アミンのカルボニル化などの触媒活性についての報告もなされている。さらに、本発明者は、金の粒子径が２ｎｍ以下、原子数で３００個以内のクラスターになると、触媒特性がさらに激変する場合があることも見出した。これら金属酸化物や炭素材料上に金ナノ粒子を分散・固定化する方法としては、従来、共沈法、析出沈殿法、コロイド混合法、気相グラフティング法、液相グラフティング法などの方法が採られている。 Among noble metals, gold has been conventionally considered to have very poor catalytic activity, although it is cheaper than other noble metals. In contrast, the inventor preferably exhibits high catalytic activity by dispersing and fixing gold on various metal oxide supports as ultrafine particles having a diameter of 10 nm or less. Catalyst superior to other precious metals for many reactions such as low temperature CO oxidation, gas phase one-stage epoxidation of propylene, low temperature water gas shift reaction, direct hydrogen peroxide synthesis from oxygen and hydrogen, partial oxidation of hydrocarbons It has been found that the activity is expressed (for example, see Patent Document 1 and Non-Patent Document 1). In addition, there have been reports on the catalytic activity of gold nanoparticles, such as hydrogenation of unsaturated compounds, oxidation of alcohols, removal of NOx, carbonylation of epoxy compounds and aliphatic amines. Furthermore, the present inventor has also found that when the gold particle diameter is 2 nm or less and the number of atoms is within 300 clusters, the catalyst characteristics may be further drastically changed. Methods for dispersing and immobilizing gold nanoparticles on these metal oxides and carbon materials include conventional methods such as coprecipitation, precipitation and precipitation, colloid mixing, gas phase grafting, and liquid phase grafting. Has been adopted.
これに対し、高分子材料を担体とし、その表面に貴金属、例えば白金やパラジウムなど白金族金属をナノ粒子として分散・固定化したものは、これまで材料としてほとんど注目されておらず、関連するものとして高分子電解質膜用白金電極があった。白金は微粒子としてカーボンブラック上に分散・固定化されているが、その担持量が１０ｗｔ％以上であるので、多くは凝集体となっており、必ずしも金属微粒子が独立分散した構造でない。高分子材料を担体として用いる触媒が実用化されていないのは、高分子材料の耐熱温度が２００℃以下と低く、基幹化成品を製造する工業反応プロセスの温度条件や自動車排ガスの温度域では使用できない上に、高分子材料の比表面積が小さく、しかも高分子材料は無機材料に比し高価であることに起因している。これに対し、精密化成品の合成では一般に溶液に溶解した状態で触媒が使用され（均一系触媒）、２００℃以下での反応が多く、分子レベルで触媒の設計が可能である反面、反応物と生成物から触媒を分離するプロセスにエネルギーが要せられることが課題となっている。このため、均一系触媒を高分子担体などに固定化することが試みられている。このことは、金ナノ粒子においても同様である。前記したとおり、金は貴金属の中でも寸法によって最も著しく特性が変動することが分かっており、また粒径がナノレベルとなっても空気中で安定であることから、低温反応用触媒などの用途として、高分子材料を担体とし、種々の寸法・形状で分散・固定化された材料が望まれている。 On the other hand, materials that use a polymer material as a carrier and have dispersed or immobilized noble metals such as platinum or palladium as nanoparticles on the surface have received little attention as materials so far. There was a platinum electrode for polymer electrolyte membrane. Platinum is dispersed and fixed as fine particles on carbon black. Since the supported amount is 10 wt% or more, most of them are aggregates, and the metal fine particles are not necessarily dispersed independently. Catalysts that use polymeric materials as carriers have not been put to practical use because they have a low heat-resistant temperature of 200 ° C or lower and are used in the temperature conditions of industrial reaction processes for manufacturing basic chemical products and in the temperature range of automobile exhaust gas. In addition, the specific surface area of the polymer material is small, and the polymer material is more expensive than the inorganic material. On the other hand, in the synthesis of precision chemical products, the catalyst is generally used in the state of being dissolved in a solution (homogeneous catalyst), and there are many reactions at 200 ° C. or lower, and the catalyst can be designed at the molecular level. And the process of separating the catalyst from the product requires energy. For this reason, attempts have been made to immobilize a homogeneous catalyst on a polymer carrier or the like. The same applies to gold nanoparticles. As described above, it is known that gold has the most significant fluctuation in characteristics among noble metals, and because it is stable in the air even when the particle size becomes nano level, it can be used as a catalyst for low temperature reaction. A material dispersed and fixed in various dimensions and shapes using a polymer material as a carrier is desired.
近年、高分子材料と金との複合材料に関する技術として、ＮａＡｕＣｌ4・２Ｈ2Ｏとピロールとを混合して、超音波をかけることにより、金粒子への還元とピロールの重合とを同時に行い、これにより金ナノ粒子を高分子内部に包み込んだ複合体を製造する方法（非特許文献２参照）、ＮａＯＨ水溶液で前処理した第四級アンモニウム基を官能基として有するイオン交換樹脂を加熱乾燥後金前駆体水溶液で処理し、１５０℃で６時間加熱することにより金ナノ粒子を担持させる、いわゆる含浸法によって、イオン交換樹脂に金を担持させる方法（非特許文献３参照）、乾燥した陽イオン交換樹脂にＨＡｕＣｌ4・４Ｈ2Ｏ水溶液を含浸させ、６０℃で３時間乾燥する方法（非特許文献４参照）、陽イオン交換樹脂に金微粒子を担持する方法（非特許文献５参照）が報告されている。 In recent years, as a technique related to a composite material of a polymer material and gold, NaAuCl 4 .2H 2 O and pyrrole are mixed and subjected to ultrasonication to simultaneously perform reduction to gold particles and polymerization of pyrrole, Thus, a method for producing a composite in which gold nanoparticles are encapsulated in a polymer (see Non-Patent Document 2), an ion exchange resin having a quaternary ammonium group pre-treated with an aqueous NaOH solution as a functional group, after heat drying A method of supporting gold on an ion exchange resin by a so-called impregnation method by treating with an aqueous precursor solution and heating at 150 ° C. for 6 hours (see Non-Patent Document 3), dried cation exchange A method in which a resin is impregnated with an aqueous solution of HAuCl 4 .4H 2 O and dried at 60 ° C. for 3 hours (see Non-Patent Document 4), a method in which gold fine particles are supported on a cation exchange resin ( Non-Patent Document 5) has been reported.
しかし、前記ＮａＡｕＣｌ4・２Ｈ2Ｏとピロールとを混合して、超音波をかけることにより、金粒子への還元とピロールの重合とを同時に行う方法は、金粒子がピロール重合体により包み込まれた状態となっており、触媒としての利用には適していない。また、イオン交換樹脂を用い、金ナノ粒子をイオン交換樹脂上に担持する方法では、長時間、高温での加熱が必要とされる。さらに、前記方法は、いずれも特殊な樹脂への金ナノ粒子の付着方法であり、しかも後者の方法においては瞬時に反応が終了しないことから、粒度が不揃いとなり、触媒活性の点で問題を有する。さらに、カチオン性の高分子電解質側鎖を高分子粒子表面に導入し、還元剤を徐々に加えることにより、得られる金ナノ粒子が小さくなること（非特許文献６参照）も報告されているが、この方法も側鎖部分に金ナノ粒子が固定化されており、コアの高分子粒子表面に直接担持されているわけではない。 However, the method of simultaneously performing the reduction to gold particles and the polymerization of pyrrole by mixing the NaAuCl 4 .2H 2 O and pyrrole and applying ultrasonic waves results in the gold particles being encapsulated by the pyrrole polymer. It is in a state and is not suitable for use as a catalyst. Moreover, in the method of using an ion exchange resin and supporting gold nanoparticles on the ion exchange resin, heating at a high temperature for a long time is required. Furthermore, all of the above methods are methods for attaching gold nanoparticles to a special resin, and in the latter method, since the reaction does not end instantaneously, the particle size becomes uneven and there is a problem in terms of catalytic activity. . Furthermore, it is also reported that the gold nanoparticles obtained can be reduced by introducing a cationic polyelectrolyte side chain onto the polymer particle surface and gradually adding a reducing agent (see Non-Patent Document 6). This method also has gold nanoparticles immobilized on the side chain portion, and is not directly supported on the surface of the core polymer particles.
一方、還元剤を用いて金属化合物を還元する際、ナノオーダーの金属微粒子を得るため、例えば還元剤としてクエン酸ナトリウムを用い６０℃以上で還元するとか、水素化ホウ素ナトリウムを用い０℃で還元するなど、還元剤の種類や還元温度について種々の検討がなされてきた。これら還元剤の選択および温度制御により金属ナノ粒子の形成は可能であるが、還元の際に使用する金属化合物、還元剤、添加剤など使用する材料や濃度などにより最適条件を決める必要があり条件設定が難しく、また温度制御のみでは粒径の制御が難しいのが現状である。 On the other hand, when reducing a metal compound using a reducing agent, in order to obtain nano-order fine metal particles, for example, reducing at 60 ° C. or higher using sodium citrate as the reducing agent, or reducing at 0 ° C. using sodium borohydride. Various studies have been made on the type of reducing agent and the reduction temperature. Metal nanoparticles can be formed by selecting these reducing agents and controlling the temperature, but it is necessary to determine the optimum conditions depending on the materials and concentrations used, such as the metal compounds, reducing agents, and additives used in the reduction. At present, it is difficult to set, and it is difficult to control the particle size only by temperature control.
このような状況下、本発明者らは、金前駆体である金化合物が溶解した高分子材料粒子分散液に、還元剤を一気に加えることにより、金属ナノ粒子となる核を一度に多数生成させ、且つ核成長を抑えることにより、その表面に金属ナノ粒子を分散・固定化することが難しかった前記の如きアニオンあるいはカチオン基などの官能基を表面に有しない高分子材料表面に金微粒子を付着させることができることを見出した（特許文献２参照）。従来無機酸化物担体に金属イオンを吸着させた後、金属ナノ粒子を還元して担持する場合には還元剤を一気に加えていた。これは、還元剤を徐々に加えると、一度生成した金属ナノ粒子が核となって、核成長を引き起こし、得られる金属ナノ粒子が大きくなるため、一気に還元することによって小さな金属ナノ粒子の核を多数形成させるためである。 Under such circumstances, the present inventors added a reducing agent all at once to a polymer material particle dispersion in which a gold compound as a gold precursor was dissolved, thereby generating a large number of nuclei that become metal nanoparticles at a time. In addition, it was difficult to disperse and immobilize metal nanoparticles on the surface by suppressing nucleation, and gold fine particles were attached to the surface of a polymer material that does not have a functional group such as anion or cation group as described above. It was found that this can be achieved (see Patent Document 2). Conventionally, after metal ions are adsorbed on an inorganic oxide support, when reducing and supporting metal nanoparticles, a reducing agent is added all at once. This is because when the reducing agent is gradually added, the metal nanoparticles once generated become nuclei, causing nucleation and the resulting metal nanoparticles become larger, so the nuclei of small metal nanoparticles are reduced by reducing all at once. This is to form a large number.
このように、本発明者らの研究により、アニオンあるいはカチオン基など極性の高い官能基を有さない通常の高分子材料（樹脂）にナノオーダーの金微粒子を付着させる方法が見出されたが、上記のとおり金属ナノ粒子となる核を一度に多数生成させ、且つ核成長を抑える必要性から、還元剤を一気に加えることが必要である。しかし、還元剤を一気に加えて金前駆体の還元を行うことによると思われるが、微粒子の凝集体が形成されるという問題、および形成される粒径の大きさおよび均一性の制御が難しいという問題をも有している。さらに、この方法においては、形成される金微粒子の大きさも、１０〜１００ｎｍ程度の大きさのものが一般的で、より小さく、かつ凝集粒子の形成がない、粒径のそろった金微粒子を、樹脂をも含めた担体表面に簡便な方法で分散・固定化する方法が求められている。 As described above, the inventors' research has found a method of attaching nano-order gold fine particles to an ordinary polymer material (resin) having no highly polar functional group such as an anion or a cation group. As described above, it is necessary to add a reducing agent all at once because of the necessity of generating a large number of nuclei to be metal nanoparticles at a time and suppressing the growth of the nuclei. However, it seems to be due to the reduction of the gold precursor by adding a reducing agent all at once, but it is difficult to control the size and uniformity of the formed particle size, and the problem that fine particle aggregates are formed. It also has a problem. Furthermore, in this method, the size of the gold fine particles to be formed is generally about 10 to 100 nm, and the gold fine particles having a uniform particle size, which are smaller and have no formation of aggregated particles, There is a demand for a method of dispersing and immobilizing on a carrier surface including a resin by a simple method.
したがって、本発明の目的は、還元剤を用いてアニオンあるいはカチオン基などの極性の高い官能基を表面に有しない通常の高分子材料の担体材料表面に金ナノ粒子を分散・固定化する方法において、従来の還元法に比べ、より小さい粒径を有すると共に、金微粒子の凝集がない粒度のそろった金微粒子を担体材料上に簡便に形成する方法を提供することである。
Thus, the method object of the present invention, dispersing and immobilizing gold nanoparticles on a support material the surface of a conventional polymer materials having no the surface highly polar functional group such as anionic or cationic groups by using a reducing agent The present invention provides a method for easily forming, on a support material, gold fine particles having a smaller particle size and having no particle size aggregation compared to conventional reduction methods.
本発明者らは、鋭意研究を行ったところ、通常金微粒子の担体材料として用いられている無機酸化物については認められないが、担体材料が極性の高い官能基を表面に有さない高分子材料、または該高分子材料と無機物からなり無機物の含有量が５０重量％以下の有機・無機ハイブリッド材料あるいは炭素材料である場合、還元剤をゆっくり加えても核成長よりも核生成が優先して起こり、金属ナノ粒子の凝集・核成長が抑制されて、従来法よりも小さなナノオーダーの金微粒子を還元剤の種類を変えなくても還元剤の添加速度のみによって金属ナノ粒子のサイズをコントロールでき、これによって金微粒子の凝集もなくかつ一気に還元剤を投入する従来法よりも粒径の小さいナノオーダーの金属微粒子を、担体材料上に簡便に分散・固定化できることを見出し、この知見に基づいて本発明がなされたものである。なお、本発明において金微粒子、金ナノ粒子という場合、これらには金クラスターをも包含するものである。 As a result of intensive research, the present inventors have not found inorganic oxides that are normally used as carrier materials for gold fine particles, but the carrier materials do not have a highly polar functional group on the surface. In the case of a material, or an organic / inorganic hybrid material or carbon material composed of a polymer material and an inorganic material and containing 50% by weight or less of inorganic material, nucleation takes precedence over nucleation even if a reducing agent is added slowly. As a result, aggregation and nucleation of metal nanoparticles are suppressed, and the size of metal nanoparticles can be controlled only by the addition rate of the reducing agent without changing the type of reducing agent for nano-order gold fine particles smaller than conventional methods. This makes it easy to disperse and immobilize nano-sized metal microparticles with a smaller particle size than conventional methods that do not agglomerate gold microparticles and add a reducing agent all at once on a carrier material It found that that can, in which the present invention has been made based on this finding. In the present invention, when referred to as gold fine particles and gold nanoparticles, these include gold clusters.
本発明は、次の（１）〜（７）に記載の高分子材料表面に金微粒子を分散・固定化する方法に関する。
The present invention relates to how to disperse and immobilize the gold particles on the polymeric material surface according to the following (1) to (7).
（１）極性の高い官能基を表面に有さない高分子材料または該高分子材料と無機物からなり無機物の含有量が５０重量％以下の有機・無機ハイブリッド材料に接する金化合物水溶液に還元剤を徐々に添加することを特徴とする高分子材料上に金微粒子を分散・固定化する方法であって、前記高分子材料が、粉末、微粒子、薄膜、中空粒子、多孔体またはデンドリマー形態であるとともに、ビニル系ポリマー、ポリエーテル、ポリエステル、ポリカーボネート、ポリアミド、ポリウレタン、ジエン系ポリマー、メラミン・ベンゾグアナミン系ポリマー、芳香族系ポリマー、ポリイミド、ポリシラン、ポリシロキサン、ポリカプロラクトン、硫黄系ポリマーおよび天然高分子から選択される少なくとも１種の高分子材料であることを特徴とする、高分子材料上に金微粒子を分散・固定化する方法。
(1) A reducing agent is applied to an aqueous solution of a gold compound that is in contact with an organic / inorganic hybrid material that is composed of a polymer material that does not have a highly polar functional group on the surface, or is composed of the polymer material and an inorganic material, and the inorganic content is 50% by weight or less. A method of dispersing and immobilizing gold fine particles on a polymer material characterized by being gradually added, wherein the polymer material is in the form of powder, fine particles, thin film, hollow particles, porous material or dendrimer vinyl polymers, polyethers, polyesters, polycarbonates, polyamides, polyurethanes, diene polymers, melamine-benzoguanamine polymers, aromatic polymers, polyimides, Po Rishiran, polysiloxanes, polycaprolactone, sulfur-based polymers and natural polymers It is at least one polymer material selected, How dispersing and immobilizing gold particles on a molecular material.
（２）前記還元剤が、金イオンを還元することのできる無機または有機還元剤の少なくとも１種であることを特徴とする上記（１）に記載の高分子材料上に金微粒子を分散・固定化する方法。
(2) the reducing agent is dispersed and fixed fine gold particles on a high molecular material according to (1), wherein the at least one inorganic or organic reducing agent capable of reducing gold ions How to turn.
（３）前記金化合物が、四塩化金酸、四塩化金酸塩、三塩化金、三臭化金、シアン化金、シアン化金カリウム、三塩化ジエチルアミン金酸、エチレンジアミン金錯体、ジメチル金β−ジケトン誘導体金錯体、およびジエチル金β−ジケトン誘導体金錯体から選ばれた少なくとも１種であることを特徴とする上記（１）または（２）に記載の高分子材料上に金微粒子を分散・固定化する方法。
( 3 ) The gold compound is tetrachloroauric acid, tetrachloroaurate, gold trichloride, gold tribromide, gold cyanide, potassium gold cyanide, diethylamineauric acid trichloride, ethylenediamine gold complex, dimethylgold β - distributed diketone derivative gold complexes, and gold fine particles on a high molecular material according to above, wherein the at least one selected from diethyl gold β- diketone derivative gold complex (1) or (2) How to immobilize.
（４）前記還元剤は、前記金化合物水溶液に還元剤が加えられた際に、添加された還元剤により金錯イオンの一部が還元され、形成された金微粒子が高分子材料上に吸着される大きさとなって高分子材料上に移動したのち、さらに還元剤を加えることにより残余の金錯イオンの一部が還元されて上記と同様の移動を起こすという工程を繰り返す速度で添加されることを特徴とする上記（１）〜（３）のいずれかに記載の高分子材料上に金微粒子を分散・固定化する方法。
（５）前記還元剤の添加開始から添加終了までの時間が、１〜２０分であることを特徴とする上記（１）〜（４）のいずれかに記載の高分子材料上に金微粒子を分散・固定化する方法。
(4) When the reducing agent is added to the gold compound aqueous solution, a part of the gold complex ion is reduced by the added reducing agent, and the formed gold fine particles are adsorbed on the polymer material. It is added at a rate that repeats the process of moving the same amount as above after moving onto the polymer material and then reducing the remaining part of the complex metal ions by adding a reducing agent. A method for dispersing and immobilizing gold fine particles on the polymer material according to any one of (1) to (3) above.
(5) The time from the start of addition of the reducing agent to the end of addition is 1 to 20 minutes, and the gold fine particles are placed on the polymer material according to any one of (1) to (4) above A method of dispersion and immobilization.
（６）前記金化合物水溶液のイオン強度が、１×１０−５〜０．０５であることを特徴とする上記（１）〜（５）のいずれかに記載の高分子材料上に金微粒子を分散・固定化する方法。
(6) the ionic strength of the gold compound aqueous solution, a 1 × 10 -5 above characterized in that it is a 0.05 (1) to (5) the gold particles on the high molecular material according to any one of A method of dispersion and immobilization.
（７）高分子材料上に分散・固定化された金微粒子の平均粒子径が１０ｎｍ以下であり、金が高分子材料に対し、０．０１重量％〜５０重量％担持されることを特徴とする上記（１）〜（６）のいずれかに記載の高分子材料上に金微粒子を分散・固定化する方法。
(7) The average particle diameter of the gold fine particles dispersed and fixed on the polymer material is 10 nm or less, and gold is supported by 0.01% to 50% by weight with respect to the polymer material. A method of dispersing and fixing gold fine particles on the polymer material according to any one of the above (1) to (6).
従来の還元剤を用いて金前駆体である金化合物を一気に還元し通常の高分子材料などからなる担体材料上に金微粒子を分散・固定化する方法においては、金微粒子の凝集が見られると共に、形成される金微粒子の粒径およびその均一性に問題を有するものであったが、本発明においては、金微粒子担体材料としてアニオンまたはカチオン基などの官能基を有さない高分子材料を選択し、還元剤の添加速度を制御するという簡単な方法により、金属微粒子の核成長と凝集を抑制することができ、従来法に比べより小さい、粒径のそろった、また凝集粒子のないナノオーダーの金属微粒子を担持する高分子−金ナノ粒子複合材料が提供できる。これにより、例えばグルコース酸化触媒など触媒活性に富んだ金微粒子担持触媒を形成することができるとともに、さらに新しい反応を可能とする固体触媒などとしての用途が期待できる。また、金微粒子の粒径により金微粒子を担持する高分子材料の色調を制御することができることから、本発明の方法で得られた金微粒子が表面に分散・固定された材料は、触媒の他にも塗料用、化粧品用など種々の材料の着色剤としての用途も期待できる。さらに、これらの他、がん治療用マーカー、高感度ＤＮＡ検出素子、柔軟性のある導電性材料、燃料電池用や化学センサー用の電極、赤外線センサーなどの用途への材料としても期待できる。
In a method in which a gold compound as a gold precursor is reduced at once using a conventional reducing agent and gold fine particles are dispersed and immobilized on a carrier material made of a normal polymer material, the gold fine particles are aggregated. , but those in which was having problems with particle size and its uniformity of the gold fine particles to be formed, in the present invention, as gold particulate support material having no functional group such as anionic or cationic groups polymeric materials a By selecting and controlling the rate of addition of the reducing agent, it is possible to suppress nucleation and agglomeration of fine metal particles, which is smaller than that of the conventional method. high molecular you carrying the order of the fine metal particles - gold nanoparticle composite can be provided. This makes it possible to form a gold fine particle-supported catalyst rich in catalytic activity, such as a glucose oxidation catalyst, and can be expected to be used as a solid catalyst that enables a new reaction. In addition, since the color tone of the polymer material supporting the gold fine particles can be controlled by the particle size of the gold fine particles, the material in which the gold fine particles obtained by the method of the present invention are dispersed and fixed on the surface is used in addition to the catalyst. In addition, it can be expected to be used as a colorant for various materials such as paints and cosmetics. In addition to these, it can also be expected as a material for uses such as cancer treatment markers, highly sensitive DNA detection elements, flexible conductive materials, electrodes for fuel cells and chemical sensors, and infrared sensors.
本発明の高分子材料または有機・無機ハイブリッド材料上に金微粒子を分散・固定化する方法においては、高分子材料または有機・無機ハイブリッド材料が金前駆体である金化合物水溶液と接する状態、好ましくは前記材料を分散した状態で、還元剤を一気に加えるのではなく、徐々に加えることを特徴としている。従来無機酸化物に小さな金属ナノ粒子を担持させるには、核生成を瞬時に引き起こし、小さな核をより多く作ることが重要であると考えられてきた。これは、生成する核が少ないと、還元反応が更に進行しても生成した核が成長するのみで、新たな核生成が起こらないためである。事実、金触媒としての担体として通常用いられているシリカ、アルミナ、チタニアなどの金属酸化物においてはこのような現象が起こり、貴金属水溶液に還元剤を徐々に加えた場合には、生成した核が成長するのみで、新たな核生成が起こらない。このため、従来金属ナノ粒子の粒径を制御するには還元剤の種類や温度、濃度などの条件について種々検討されてきたのであり、貴金属ナノ粒子を形成させるためには、還元剤を一気に加えることが常識となっていたのである。
In the method for dispersing and immobilizing gold particles on a high molecular material or an organic-inorganic hybrid material of the present invention, the state where the high molecular material or an organic-inorganic hybrid material is in contact with the gold compound solution is gold precursor, preferably It is characterized in that the reducing agent is gradually added instead of all at once while the material is dispersed. Conventionally, in order to support small metal nanoparticles on an inorganic oxide, it has been considered important to cause nucleation instantaneously and create more small nuclei. This is because if the number of nuclei produced is small, the produced nuclei will only grow and no new nucleation will occur even if the reduction reaction proceeds further. In fact, this phenomenon occurs in metal oxides such as silica, alumina, and titania that are commonly used as carriers for gold catalysts, and when a reducing agent is gradually added to a noble metal aqueous solution, the produced nuclei It only grows and no new nucleation occurs. For this reason, in order to control the particle size of metal nanoparticles, various studies have been made on conditions such as the type, temperature, and concentration of the reducing agent. In order to form noble metal nanoparticles, the reducing agent is added all at once. That was common sense.
このような従来の技術常識に反し、本発明において、担体材料がアニオンあるいはカチオン基のような極性の高い官能基を表面に有さない高分子材料あるいは該高分子材料と無機物からなり無機物の含有量が５０重量％以下の有機・無機ハイブリッド材料に限って、還元剤を徐々に加えることにより、従来の還元剤を一気に加える還元法による金微粒子の分散・固定化法に比べ、金微粒子の凝集がなく、またより小さい粒径で、粒度もよりそろった金微粒子が担体材料上に分散・固定化されるのか、その理由は定かではない。その理由について、本発明者らは次のように考えているが、この説明により本発明が限定されるものではない。図１を参照して説明すると、担体材料が水などの溶液に分散された状態においては、担体材料の周囲に電気二重層が形成される。この電気二重層は、担体材料が溶液に分散されればどの担体表面にも存在するものである。ここに、例えば金錯イオンが存在すると、担体材料が負に荷電されていることから、正に荷電されている金錯イオンが担体の二重層を取り囲むような状態に吸引される。極性の強い官能基を表面に有さない高分子材料においては担体と金錯イオンとの相互作用が弱く、このため金錯イオンが担体材料表面にまでは吸着されない。このとき従来のように還元剤（図中では、ＮａＢＨ４）を一気に加えるとこれら金錯イオンが同時に還元されるが、一度に大量の金ナノ粒子核ができ、凝集が起き易くなり、大きな金粒子ができるとともに、金微粒子の粒度の制御もできない。これに対し、本発明の方法においては、還元剤を滴下により徐々に加えると、電気二重層上の金錯イオンの一部が電気二重層内で金に還元され、ある程度大きくなった段階で担体に移動し、その後さらに還元剤が加えられると、電気二重層にある金錯イオンが新たに還元され、これもある程度大きくなった段階で担体に移動する。これを繰り返すことで、凝集がなく、粒度がそろい、従来の急速還元法に比べより小さい粒径の金微粒子が形成される。
一方、担体材料として金属酸化物を用いた場合には、高分子材料等に比べ担体と金錯イオンとの相互作用が強いために電気二重層ではなく担体表面に金錯イオンが直接吸着すると考えられる。さらに還元剤が加えられると金錯イオンは担体上の核の近傍にあることから核を基に成長し、粒径が小さく粒径のそろったナノ粒子を形成することができるものと考えられる。同様のことは、極性の高い官能基を有する重合体材料でも起こっていると考えられる。
前記電気二重層の厚みは、溶液中のイオン強度（イオン濃度×イオンの価数）によっても影響を受ける。このため、溶液中の電解質の濃度についても考慮することが必要である。なお、イオン強度は、溶液中に存在する全てのイオン種について、（イオンのモル濃度×イオンの価数の２乗）を足し合わせ、更にそれに１／２をかけたものをいう。
Contrary to such conventional technical common sense, in the present invention, the inorganic substance, a polymer material or polymeric material and inorganic material such no high polarity functional group on the surface as the carrier material there anion or cationic groups Only for organic / inorganic hybrid materials with a content of 50% by weight or less, by adding a reducing agent gradually, compared to the conventional method of dispersing and immobilizing gold fine particles by a reduction method in which a reducing agent is added all at once. The reason for whether or not gold fine particles having no agglomeration and having a smaller particle size and a uniform particle size are dispersed and immobilized on the carrier material is not clear. The present inventors consider the reason as follows, but the present invention is not limited by this explanation. Referring to FIG. 1, when the carrier material is dispersed in a solution such as water, an electric double layer is formed around the carrier material. This electric double layer is present on any carrier surface if the carrier material is dispersed in a solution. Here, for example, gold 錯I ON is present, since the support material is negatively charged, gold 錯I on which is positively charged is attracted to the state as to surround the double layer of the carrier. Weak interactions between the carrier and Kimu錯ions in the polymer material having no polar strong functional group on the surface, not adsorbed until Therefore gold 錯I-on to the support material surface. (In the figure, NaBH 4) In this case as in the prior art reducing agent is at once added when these gold 錯I on being reduced at the same time, it is a large amount of gold nanoparticles nuclei at a time, easily aggregation occurs, a large Gold particles are produced, and the particle size of the gold fine particles cannot be controlled. In contrast, in the method of the present invention, when added slowly dropwise a reducing agent, a part of the gold 錯I on on the electric double layer is reduced to gold in an electric double layer, at the stage it became somewhat larger When the reducing agent is added to the carrier after that, the gold complex ions in the electric double layer are newly reduced and moved to the carrier at a stage where this has increased to some extent. By repeating this, gold fine particles having a smaller particle size than that of the conventional rapid reduction method are formed without aggregation and with a uniform particle size.
On the other hand , when a metal oxide is used as the support material, the interaction between the support and the metal complex ion is stronger than that of the polymer material, etc., so it is considered that the metal complex ion is directly adsorbed on the support surface instead of the electric double layer It is done. Believed further reducing agent is added when the gold complex ions to grow based on nuclear since in the vicinity of the nucleus on the carrier, Ru can form nanoparticles particle size having uniform small particle size . The same may be true for polymeric materials with highly polar functional groups.
The thickness of the electric double layer is also affected by the ionic strength in the solution (ion concentration × ion valence). For this reason, it is necessary to consider the concentration of the electrolyte in the solution. The ionic strength is obtained by adding (the molar concentration of ions × the square of the valence of ions) for all ionic species present in the solution, and further multiplying that by ½.
以下、本発明の方法に使用される金前駆体である金化合物、還元剤、金微粒子を担持するために用いられる高分子材料、有機・無機ハイブリッド材料、反応溶液などについて説明し、次いでこれら材料を用いて金微粒子を担持した高分子材料の製造方法について説明する。
Hereinafter, the gold compound is a gold precursor used in the method of the present invention, the reducing agent, the gold particles a polymer material used for carrying, organic-inorganic hybrid materials, such as described for the reaction solution, followed by those a method for manufacturing the high-molecular material carrying gold particles using a material.
本発明において、金微粒子を形成するために用いられる金前駆体である金化合物は、反応溶液中に溶解されて用いられることから、反応溶液に溶解するものであればよく、これ以外に特に制限されるものではない。例えば、反応溶液として水が用いられる場合、金化合物は水溶性のものであればよい。水溶性金化合物としては、金の水酸化物、塩化物、臭化物、カルボン酸塩、および硝酸塩、塩化金酸およびその塩、金錯体化合物などが挙げられる。さらに具体的に例示すると、例えば、四塩化金酸（ＨＡｕＣｌ4）、四塩化金酸塩（例えば、ＮａＡｕＣｌ4）、三塩化金（ＡｕＣｌ3）、三臭化金（ＡｕＢｒ3）、シアン化金（ＡｕＣＮ）、シアン化金カリウム｛Ｋ〔Ａｕ（ＣＮ）2〕｝、三塩化ジエチルアミン金酸〔（Ｃ2Ｈ5）2ＮＨ・ＡｕＣｌ3〕、エチレンジアミン金錯体（例えば、塩化物錯体（Ａｕ［Ｃ2Ｈ4（ＮＨ2）2］Ｃｌ3））などを挙げることができるが、本発明で用いることができる金化合物がこれに限定されるものではない。これらの化合物は単独で用いられてもよいし、必要であれば２種以上を併用してもよい。また反応溶液は水溶性の有機溶剤、例えばエタノールなどであってもよいし、水と該水溶性の有機溶剤の混合液であってもよい。上記金化合物はいずれも水溶性有機溶媒に溶解可能であり、反応溶液として有機溶剤が用いられたとしても、金化合物は上記のごときものから選択されればよい。 In the present invention, the gold compound, which is a gold precursor used to form the gold fine particles, is used by being dissolved in the reaction solution. Is not to be done. For example, when water is used as the reaction solution, the gold compound may be water-soluble. Examples of the water-soluble gold compound include gold hydroxide, chloride, bromide, carboxylate, nitrate, chloroauric acid and its salt, gold complex compound and the like. More specifically, for example, tetrachloroauric acid (HAuCl 4 ), tetrachloroaurate (eg, NaAuCl 4 ), gold trichloride (AuCl 3 ), gold tribromide (AuBr 3 ), gold cyanide, for example. (AuCN), potassium gold cyanide {K [Au (CN) 2 ]}, diethylamine trichloride gold acid [(C 2 H 5 ) 2 NH · AuCl 3 ], ethylenediamine gold complex (for example, chloride complex (Au [ C 2 H 4 (NH 2 ) 2 ] Cl 3 )) and the like can be mentioned, but the gold compound that can be used in the present invention is not limited thereto. These compounds may be used alone or in combination of two or more if necessary. The reaction solution may be a water-soluble organic solvent such as ethanol, or a mixed solution of water and the water-soluble organic solvent. Any of the above gold compounds can be dissolved in a water-soluble organic solvent, and even if an organic solvent is used as the reaction solution, the gold compound may be selected from those described above.
一方、還元剤としては、従来、金属イオンの還元に用いられている還元剤のいずれをも用いることができる。このような還元剤は、無機系であっても、有機系であってもよい。無機系還元剤としては、例えば、水素化ホウ素ナトリウム（ＮａＢＨ4）、水素、二酸化硫黄（ＳＯ2）、亜硝酸ナトリウム（ＮａＮＯ2）などが挙げられ、有機系還元剤としては、ヒドラジン、ホルムアルデヒド、メタノール、クエン酸およびその塩（例えば、クエン酸ナトリウム、クエン酸マグネシウム）、シュウ酸およびその塩、グルコース、エチレングリコールなどが挙げられる。通常用いられる還元剤は、還元力の強い順に、水素化ホウ素ナトリウム（ＮａＢＨ4）、ホルムアルデヒド（ＨＣＨＯ）、クエン酸およびその塩（クエン酸ナトリウム、クエン酸マグネシウムなど）、グルコース（Ｃ6Ｈ12Ｏ6）などがあり、また、エチレングリコールも挙げられる。 On the other hand, as the reducing agent, any of the reducing agents conventionally used for reducing metal ions can be used. Such a reducing agent may be inorganic or organic. Examples of the inorganic reducing agent include sodium borohydride (NaBH 4 ), hydrogen, sulfur dioxide (SO 2 ), sodium nitrite (NaNO 2 ), and the like. Examples of the organic reducing agent include hydrazine, formaldehyde, Examples include methanol, citric acid and salts thereof (for example, sodium citrate and magnesium citrate), oxalic acid and salts thereof, glucose, ethylene glycol and the like. Commonly used reducing agents are sodium borohydride (NaBH 4 ), formaldehyde (HCHO), citric acid and salts thereof (sodium citrate, magnesium citrate, etc.), glucose (C 6 H 12 O) in the order of strong reducing power. 6 ), and also ethylene glycol.
さらに、金微粒子の担体材料としては、極性の高い官能基を表面に有さない高分子材料が用いられる。本発明で用いられる前記高分子材料としては、アニオンあるいはカチオン基などの極性の高い官能基を表面に有さない、水溶性あるいは水溶性溶剤に溶解しない通常の高分子材料が挙げられる。具体的には、ポリ塩化ビニル（ＰＶＣ）、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリビニルアルコール（ＰＶＡ）、ポリアクリロニトリル（ＰＡＮ）、ポリスチレン（ＰＳ）などのビニル系ポリマー；ポリオキシメチレン（ＰＯＭ）などのポリエーテル；ポリラクトン、ポリエチレンテレフタレート（ＰＥＴ）などのポリエステル；ポリカーボネート（ＰＣ）；ナイロン６、ナイロン６６などのポリアミド；ポリウレタン；ポリブタジエン（ＰＢｄ）、ポリイソプレン（ＰＩＰ）などのジエン系ポリマー；メラミン・ベンゾグアナミン系ポリマー；芳香族系ポリマー；ポリイミド；ポリカーボネート；ポリウレタン；ポリシラン；ポリシロキサン；ポリカプロラクトン；ポリ環状チオエーテルなどの硫黄系高分子；セルロース、蛋白質、ＤＮＡなどの天然高分子が挙げられる。これらの中では、通常、ポリ塩化ビニル、ポリメタクリル酸メチル、ポリスチレン、硫黄系高分子などが好適な材料として用いられる。一方、有機・無機ハイブリッド材料としては、前記高分子材料と無機物からなり無機物の含有量が５０重量％以下の有機・無機ハイブリッド材料、例えばシリカーアクリル複合物（日本触媒ソリオスター）などが挙げられる。
Further, as the support material of the gold particles, polymer materials having no highly polar functional groups on the surface is used. Examples of the polymer material used in the present invention include ordinary polymer materials that do not have a highly polar functional group such as an anion or a cation group on the surface and do not dissolve in a water-soluble or water-soluble solvent. Specifically, vinyl polymers such as polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polystyrene (PS); polyoxymethylene (POM), etc. Polyether; Polyester such as polylactone and polyethylene terephthalate (PET); Polycarbonate (PC); Polyamide such as nylon 6 and nylon 66; Polyurethane; Diene polymer such as polybutadiene (PBd) and polyisoprene (PIP); Melamine / benzoguanamine Polymer; Aromatic polymer; Polyimide; Polycarbonate; Polyurethane; Polysilane; Polysiloxane; Polycaprolactone; Sulfur polymer such as Polycyclic thioether; Cellulose, Protein, D And natural polymers such as A. Of these, polyvinyl chloride, polymethyl methacrylate, polystyrene, sulfur-based polymers and the like are usually used as suitable materials. On the other hand, the organic-inorganic hybrid material, wherein the polymeric material and the content of inorganic matter consists of inorganic material at most 50% by weight of an organic-inorganic hybrid materials, such as silica-acrylic composite (Nippon Shokubai SOLIO star) and like It is done.
高分子材料は、粉末（例えば、平均粒子径１０μｍ〜１０ｍｍ）、微粒子（例えば、平均粒子径１０ｎｍ〜１００μｍ）、薄膜（例えば、平均膜厚１０μｍ〜１０ｍｍ）、中空粒子（例えば、平均粒子径１０ｎｍ〜１０ｍｍ）、デンドリマー（樹枝状構造体）、多孔体などの形態を持つものなど、その形態、形状はどのようなものでもよい。触媒、着色剤などを初めとする種々の用途を考えれば、通常粒子形状が好ましく、その粒子径は目的・用途によって異なるものの、一般的には平均粒子径０．２μｍ〜１ｍｍ、より好ましくは平均粒子径０．２μｍ〜１００μｍであることが好ましい。本発明においては、平均粒子径は、球状粒子の場合は直径、楕円形粒子の場合は長径であり、例えば微細な粒径を有する場合、走査型電子顕微鏡（ＳＥＭ）観察あるいは透過型電子顕微鏡（ＴＥＭ）観察から粒子径分布を作り、平均値を求めたものである。また、ミクロンオーダーの粒子の粒径については、コールターカウンターなどにより測定することもできるし、さらに大きい場合には、篩法によることもできる。また、有機・無機ハイブリッド材料の形態も高分子材料と同様のものが挙げられ、通常粉体あるいは微粒子などの粒子形状が好ましい。
The polymer material includes powder (for example, average particle diameter of 10 μm to 10 mm), fine particles (for example, average particle diameter of 10 nm to 100 μm), thin film (for example, average film thickness of 10 μm to 10 mm), hollow particles (for example, average particle diameter of 10 nm). To 10 mm), dendrimers (dendritic structures), porous bodies, and the like. In consideration of various uses such as a catalyst and a colorant, the particle shape is usually preferable, and the particle size varies depending on the purpose and use, but generally the average particle size is 0.2 μm to 1 mm, more preferably the average particle size. The particle diameter is preferably 0.2 μm to 100 μm. In the present invention, the average particle diameter is a diameter in the case of spherical particles, and a long diameter in the case of elliptical particles. For example, when it has a fine particle diameter, it is observed with a scanning electron microscope (SEM) or a transmission electron microscope ( (TEM) A particle size distribution is created from observation, and an average value is obtained. Further, the particle size of micron order particles can be measured by a Coulter counter or the like. Further, the form of the organic-inorganic hybrid material may include the same polymer material, particle shape, such as a normal powder or fine particles are preferred.
次に、本発明の金微粒子を分散・固定化する方法について説明する。以下では、金微粒子担体材料が微粒子材料である場合を例に挙げて説明するが、担体材料が薄膜などである場合においては、担体材料が液中に分散されないことを除けば以下に説明する方法と同様の方法でその表面への金微粒子の分散・固定化を行うことができる。 Next, a method for dispersing and fixing the gold fine particles of the present invention will be described. Hereinafter, the case where the gold fine particle carrier material is a fine particle material will be described as an example. However, in the case where the carrier material is a thin film or the like, the following method will be described except that the carrier material is not dispersed in the liquid. The gold fine particles can be dispersed and immobilized on the surface in the same manner as described above.
以下、反応溶液を構成する溶液として水を用いる場合について説明する。
Hereinafter, it described the case of using water as a solution which constitutes the reaction solution.
先ず、水に担体材料を分散させ、この担体材料分散液に金前駆体が添加される。金化合物は直接反応溶液である水に加えられてもよいが、予め水溶液とされた後反応溶液を構成する水に加えられることが好ましい。このとき金化合物は一度に加えられてもよいし、複数回に分けて加えられてもよい。反応溶液はゆっくりと攪拌されることが好ましい。また、担体材料を分散させた後に金化合物を加えることが好ましいが、金化合物を水に溶解した後、これに担体材料を分散させてもよい。金化合物の水溶液中の濃度としては、１０ｍｏｌ／Ｌ以下であることが必要である。１０ｍｏｌ／Ｌを超えると還元剤を添加した際水中で金コロイドが形成される。通常は１ｍｍｏｌ／Ｌ以下とすることが好ましく、１０ｎｍ以下のナノ粒子を形成するためには０．１ｍｍｏｌ／Ｌ程度であることが通常好ましい。なお、あまりにも希薄すぎると金が高分子上に還元析出できなくなるという問題があり、通常は０．０１ｍｍｏｌ／Ｌ以上の濃度とされる。金化合物の水溶液中の濃度は、好ましくは０．０１ｍｍｏｌ／Ｌ〜１ｍｍｏｌ／Ｌ、より好ましくは０．０５ｍｍｏｌ／Ｌ〜０．５ｍｍｏｌ／Ｌ、更に好ましくは０．０５ｍｍｏｌ／Ｌ〜０．２ｍｍｏｌ／Ｌである。また金化合物の使用量は、一般的には、還元剤分子／Ａｕ原子＝１〜１０００、より好ましくは１〜２００、さらに好ましくは１〜１００である。更に、反応溶液中の電解質濃度は、イオン強度で１×１０-5〜０．０５であることが好ましい。 First, a carrier material is dispersed in water, and a gold precursor is added to the carrier material dispersion. The gold compound may be added directly to water which is a reaction solution, but it is preferably added to water constituting the reaction solution after being made into an aqueous solution in advance. At this time, the gold compound may be added at once, or may be added in a plurality of times. The reaction solution is preferably stirred slowly. Further, it is preferable to add the gold compound after dispersing the carrier material. However, after dissolving the gold compound in water, the carrier material may be dispersed therein. The concentration of the gold compound in the aqueous solution needs to be 10 mol / L or less. When it exceeds 10 mol / L, colloidal gold is formed in water when a reducing agent is added. Usually, it is preferably 1 mmol / L or less, and in order to form nanoparticles of 10 nm or less, it is usually preferably about 0.1 mmol / L. If it is too dilute, there is a problem that gold cannot be reduced and deposited on the polymer, and the concentration is usually 0.01 mmol / L or more. The concentration of the gold compound in the aqueous solution is preferably 0.01 mmol / L to 1 mmol / L, more preferably 0.05 mmol / L to 0.5 mmol / L, still more preferably 0.05 mmol / L to 0.2 mmol / L. It is. Moreover, generally the usage-amount of a gold compound is a reducing agent molecule | numerator / Au atom = 1-1000, More preferably, it is 1-200, More preferably, it is 1-100. Furthermore, the electrolyte concentration in the reaction solution is preferably 1 × 10 −5 to 0.05 in terms of ionic strength.
また、金化合物の担体材料に対する量は、分散・固定化される金微粒子の大きさ、並びに担体材料表面にどの程度の量の金を分散・固定化するかにより異なる。金の担体材料への担持量は水溶液の濃度と量により、例えば０．０１重量％〜５０重量％までの範囲で調整することができる。したがって、金担持量に応じて、水溶液の金化合物濃度や溶液の使用量を決めればよい。触媒として用いる場合、どのような反応に関与する触媒であるかにより金担持量は異なるが、たとえば、グルコースの酸化触媒として用いられる場合、金の担持量は０．０１重量％〜５重量％程度が好ましく、より好ましくは、０．１重量％〜２．０重量％である。 The amount of the gold compound with respect to the carrier material varies depending on the size of the gold fine particles to be dispersed / immobilized and the amount of gold dispersed / immobilized on the surface of the carrier material. The amount of gold supported on the carrier material can be adjusted, for example, in the range of 0.01 wt% to 50 wt% depending on the concentration and amount of the aqueous solution. Therefore, the gold compound concentration in the aqueous solution and the amount of the solution used may be determined according to the gold loading amount. When used as a catalyst, the amount of gold supported varies depending on the type of reaction involved. For example, when used as an oxidation catalyst for glucose, the amount of supported gold is about 0.01% to 5% by weight. Is more preferable, and 0.1 to 2.0% by weight is more preferable.
高分子材料は通常疎水性であることから、水に対する濡れが悪いが、超音波をかけて分散させることにより、水への分散は可能である。このとき必要であれば、メタノールなどの水溶性有機溶媒を加えるなどの方法を採用してもよいし、溶液中にポリ（Ｎ−ビニルピロリドン）などの水溶性高分子を加えるなどしてもよい。金ナノ粒子を固定化するための反応溶液として用いられる水は、水であればどのようなものでもよく特に限定されるものではないが、形成された金微粒子への不純物の混入、付着を防ぐ意味からも、蒸留、イオン交換処理、フィルター処理、各種吸着処理等により有機不純物、金属イオンを除去したものが好ましい。また、反応液のｐＨは、通常２〜１３、好ましくは３〜９であり、使用する還元剤によって適正な範囲が決まる。温度は、担体として使用される高分子材料の軟化が起こらない範囲で、かつ溶剤の沸点以下、たとえば反応溶液として水を用いる場合、水の沸点（１００℃）以下あればよく、特に限定されないが、通常０℃から９０℃までの範囲とされ、還元剤として水素化ホウ素ナトリウムを用いる場合は特に０℃から３０℃が望ましく、クエン酸またはその塩を用いるときは３０℃から７０℃が特に望ましい。
Since the high-molecular material is typically hydrophobic, but poor wettability with respect to water, by dispersing by applying ultrasonic waves, the dispersion in water is possible. At this time, if necessary, a method such as adding a water-soluble organic solvent such as methanol may be employed, or a water-soluble polymer such as poly (N-vinylpyrrolidone) may be added to the solution. . The water used as the reaction solution for immobilizing the gold nanoparticles is not particularly limited as long as it is water, but prevents contamination and adhesion of impurities to the formed gold fine particles. In terms of meaning, those obtained by removing organic impurities and metal ions by distillation, ion exchange treatment, filter treatment, various adsorption treatments, and the like are preferable. The pH of the reaction solution is usually 2 to 13, preferably 3 to 9, and an appropriate range is determined depending on the reducing agent used. The temperature is not particularly limited as long as it does not cause softening of the polymer material used as the carrier and is not higher than the boiling point of the solvent, for example, when water is used as the reaction solution, not higher than the boiling point of water (100 ° C.). The temperature is usually in the range of 0 ° C. to 90 ° C., preferably 0 ° C. to 30 ° C. when sodium borohydride is used as the reducing agent, and particularly preferably 30 ° C. to 70 ° C. when citric acid or a salt thereof is used. .
また、反応溶液には、担体材料、金化合物のほかに、必要に応じ前記したようにポリ（Ｎ−ビニルピロリドン）やポリビニルアルコールなどの水溶性高分子などが加えられてもよい。これらは高分子微粒子の分散や金ナノ粒子の保護剤として添加されるが、その場合には、それらの濃度は金錯イオンに対して、５〜３０当量であることが好ましい。 In addition to the carrier material and the gold compound, a water-soluble polymer such as poly (N-vinylpyrrolidone) or polyvinyl alcohol may be added to the reaction solution as necessary, as described above. These are added as a dispersing agent for polymer fine particles or a gold nanoparticle protective agent. In this case, the concentration thereof is preferably 5 to 30 equivalents relative to the gold complex ion.
また、還元剤の添加（滴下）速度は、本発明の目的が達成できる範囲であればよく、特に限定されるものではないが、滴下終了までに１分以上とすることが通常好ましい。また特に上限はないがあまり時間をかけても意味がないことから、通常は２０分程度以内とされる。また、添加は連続的でなくてもよく、ある時間をおいて間歇的に添加が行われてもよいが、一度に多量の還元剤を使用することは好ましくないことから、滴下などでの連続的な投入を行い、徐々に還元剤を反応溶液中に供給してやることが好ましい。通常一度に投入する還元剤量は、例えば滴下全量の５０〜４分の１程度とすることが好ましい。 Further, the rate of addition (dropping) of the reducing agent is not particularly limited as long as the object of the present invention can be achieved, but it is usually preferably 1 minute or more by the end of dropping. Although there is no particular upper limit, there is no meaning even if it takes too much time. Further, the addition may not be continuous, and the addition may be performed intermittently after a certain time. However, since it is not preferable to use a large amount of reducing agent at a time, it is not possible to add continuously. It is preferable that the reducing agent is gradually fed into the reaction solution. Usually, it is preferable that the amount of reducing agent added at a time is, for example, about 50 to 1/4 of the total amount of dripping.
このように、金化合物の種類と濃度、溶液の種類とｐＨ、還元剤の種類と濃度、還元反応の温度、および溶液に添加する添加剤の種類と濃度を適切に選ぶことにより、好ましい結果が得られる。条件設定は、少なくとも高分子の担持体を分離した上澄み液において金コロイドの生成（赤から紫色に発色）が見られないことが必要とされる。 Thus, by properly selecting the type and concentration of the gold compound, the type and pH of the solution, the type and concentration of the reducing agent, the temperature of the reduction reaction, and the type and concentration of the additive added to the solution, a favorable result is obtained. can get. The setting of conditions requires that at least the formation of gold colloid (coloring from red to purple) is not observed in the supernatant liquid from which the polymer support is separated.
高分子材料表面に担持された金微粒子の平均粒子径は、触媒として用いる場合は２０ｎｍ以下、好ましくは５ｎｍ以下であるが、必要であればこれら以外の粒径であってもよい。
The average particle diameter of the gold fine particles supported on polymeric materials table surface, 20 nm or less is used as a catalyst, preferably although 5nm or less, may be a particle size of these non if necessary.
本発明により得られた金微粒子を担持する材料は、酸化触媒、水添触媒などの触媒として有用である他、担体材料が高分子材料の場合、金の粒子径の違い、担持量、担体となる固体高分子材料の材質の違いにより、ピンク色、赤紫ないし紫色に着色した粒子が得られる。得られた粒子は、耐久性に優れ、また化粧品、各種用途の塗料の着色剤としてすぐれた特性を有している。したがって、本発明において、前記各条件を適宜設定することにより、所望の色をした着色剤を調製することができる。さらに、本発明の金微粒子を担持する材料は、導電性材料、がん治療用マーカー、高感度ＤＮＡ検出素子、センサーなどとして優れた機能を有することが期待できる。また、還元性官能基の選択により、同一反応での触媒活性や異種反応に対する触媒活性の異なるものを得ることができる。 The material carrying the gold fine particles obtained by the present invention is useful as a catalyst such as an oxidation catalyst or a hydrogenation catalyst. In addition, when the carrier material is a polymer material, the difference in the particle size of gold, the carrying amount, Depending on the material of the solid polymer material, particles colored pink, magenta or purple can be obtained. The obtained particles are excellent in durability and have excellent characteristics as a colorant for cosmetics and paints for various uses. Therefore, in the present invention, a colorant having a desired color can be prepared by appropriately setting each of the above conditions. Furthermore, the material supporting the gold fine particles of the present invention can be expected to have excellent functions as a conductive material, a cancer treatment marker, a high-sensitivity DNA detection element, a sensor, and the like. Further, by selecting a reducing functional group, it is possible to obtain those having different catalytic activities for the same reaction and different catalytic activities for different reactions.
本発明の金微粒子が分散・固定された高分子材料は、グルコースをグルコン酸に酸化する際の酸化触媒として極めて優れた特性を有している。従来グルコースの酸化触媒としてＣｅＯ２、ＴｉＯ２、活性炭、Ｒｏｓｓｉ活性炭（Ｍ．Ｃｏｍｍｏｔｔｉ，Ｃ．Ｄ．Ｐｉｎａ，Ｒ．Ｍａｔａｒｒｅｓｅ，Ｍ．Ｒｏｓｓｉ，Ａ．Ｓｉａｎｉ，Ａｐｐｌ．Ｃａｔａｌ．Ａ：Ｇｅｎｅｒａｌ ２００５，２９１，２０４−２０９参照）などが優れたものとして知られているが、本発明の材料は、これら従来グルコースの酸化触媒として優れているとして知られたものより、更に特性の良好なものを提供することができる。また、本発明の材料は、特性が幾分落ちてくるものの繰り返し使用が可能である。
Polymeric materials which gold fine particles are dispersed and fixed in the present invention has extremely excellent characteristics as an oxidation catalyst in the oxidation of glucose to gluconic acid. Conventional oxidation catalysts for glucose include CeO 2 , TiO 2 , activated carbon, Rossi activated carbon (M. Commotti, CD Pina, R. Matarrese, M. Rossi, A. Siani, Appl. Catal. A: General 2005, 291, 204-209) is known as an excellent material, but the material of the present invention provides a material having better characteristics than those conventionally known as excellent oxidation catalysts for glucose. Can do. In addition, the material of the present invention can be used repeatedly, although the characteristics are somewhat deteriorated.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれによって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited at all by this.
参考例１〔カーボンナノホーン（以下ＣＮＨと略記する。）への金ナノ粒子の担持（金担持量１．０ｗｔ％）〕
ＣＮＨ（ＮＥＣエレクトロニクス研究所製）３００ｍｇをエタノール溶媒３５ｍｌ中へ分散させ、金エチレンジアミン錯体６．７ｍｇを加え５０℃で撹拌を行った。撹拌を行いながら３．２ｍＭのＮａＢＨ４水溶液をビュレットで滴下しながら５ｍｌを５分で加えた。分離、洗浄後、１００℃で一晩乾燥させた。ＴＥＭで観察したところ、金ナノ粒子が均一にＣＮＨ上に分散・固定化されており、ほとんど全ての粒子が３〜１０ｎｍの範囲で存在し、平均粒子径５．７ｎｍ、標準偏差１．０ｎｍであった（図２参照；なお、図中の線の長さは５０ｎｍである）。
Reference Example 1 [Supporting of gold nanoparticles on carbon nanohorn (hereinafter abbreviated as CNH) (gold supported amount: 1.0 wt%)]
300 mg of CNH (manufactured by NEC Electronics Research Laboratories) was dispersed in 35 ml of an ethanol solvent, 6.7 mg of a gold ethylenediamine complex was added, and the mixture was stirred at 50 ° C. While stirring, 3.2 ml of NaBH 4 aqueous solution was added dropwise with a burette, and 5 ml was added in 5 minutes. After separation and washing, it was dried at 100 ° C. overnight. When observed with TEM, the gold nanoparticles were uniformly dispersed and immobilized on CNH, almost all of the particles were present in the range of 3 to 10 nm, with an average particle diameter of 5.7 nm and a standard deviation of 1.0 nm. (See FIG. 2; the length of the line in the figure is 50 nm).
参考例２〔ナノポーラスカーボン（以下ＮＰＣと略記する。）への金ナノ粒子の担持（金担持量１．０ｗｔ％）〕
ＮＰＣ（Ｅａｓｙ Ｎａｎｏｔｅｃｈｎｏｌｏｇｙ社製）７９０ｍｇを３０％過酸化水素水中に分散させ、２４時間室温で撹拌することにより前処理を行った。これを分離、洗浄後室温で真空乾燥させた。前処理したＮＰＣを蒸留水８０ｍＬに分散させ、これに金エチレンジアミン錯体１７ｍｇを加え室温で２時間撹拌を行った。その後９０℃で撹拌しながら、蒸留水２０ｍＬに溶解させたＮａＢＨ４１５ｍｇを２０分かけてゆっくり滴下した。その後室温で３０分撹拌し、濾過、洗浄、真空乾燥させ、金ナノ粒子担持ナノポーラスカーボンを得た。ＴＥＭで観察したところ、金ナノ粒子が均一にＮＰＣ上に分散・固定化されており、ほとんど全ての金粒子が３〜１０ｎｍの範囲で存在していた。
Reference Example 2 [Supporting gold nanoparticles on nanoporous carbon (hereinafter abbreviated as NPC) (gold supporting amount 1.0 wt%)]
Pretreatment was performed by dispersing 790 mg of NPC (manufactured by Easy Nanotechnology) in 30% hydrogen peroxide water and stirring for 24 hours at room temperature. This was separated and washed, followed by vacuum drying at room temperature. Pretreated NPC was dispersed in 80 mL of distilled water, 17 mg of a gold ethylenediamine complex was added thereto, and the mixture was stirred at room temperature for 2 hours. Then, 15 mg of NaBH 4 dissolved in 20 mL of distilled water was slowly added dropwise over 20 minutes while stirring at 90 ° C. Thereafter, the mixture was stirred at room temperature for 30 minutes, filtered, washed, and vacuum dried to obtain gold nanoparticle-supported nanoporous carbon. When observed with TEM, the gold nanoparticles were uniformly dispersed and immobilized on the NPC, and almost all the gold particles were present in the range of 3 to 10 nm.
実施例１〔ＰＭＭＡ（ポリメチルメタクリレート）微粒子への金ナノ粒子の担持（金担持量０．５ｗｔ％）〕
ＰＭＭＡ微粒子（（株）日本触媒製 エポスターＭＡ−１００２（粒子径２．６μｍ））１ｇを２００ｍＬのイオン交換水に加え、よく分散させた。これに金エチレンジアミン錯体１０．７ｍｇをイオン交換水５４ｍＬと共に加え、０℃で３０分間撹拌した。その後、予め０℃に冷却しておいた０．０１Ｍ ＮａＢＨ４ ３．８１ｍＬを４分間かけて滴下した。滴下後、濾過、イオン交換水で洗浄、乾燥させ、金ナノ粒子担持高分子微粒子を得た。ＴＥＭで観察したところ、金ナノ粒子が高分子微粒子表面にほぼ均一に分散・固定化されており、粒子径３〜１０ｎｍの金ナノ粒子が多数見られた。平均粒子径は６．９ｎｍ、標準偏差は５．５ｎｍであった（図３参照；なお、図中の線の長さは１００ｎｍである）。
Example 1 [Support of gold nanoparticles on PMMA (polymethyl methacrylate) fine particles (gold support amount 0.5 wt%)]
1 g of PMMA fine particles (Epaster MA-1002 (particle diameter 2.6 μm) manufactured by Nippon Shokubai Co., Ltd.) was added to 200 mL of ion-exchanged water and well dispersed. To this was added 10.7 mg of a gold ethylenediamine complex together with 54 mL of ion-exchanged water, and the mixture was stirred at 0 ° C. for 30 minutes. Thereafter, 3.81 mL of 0.01M NaBH 4 that had been cooled to 0 ° C. in advance was added dropwise over 4 minutes. After dropping, filtration, washing with ion exchange water and drying were performed to obtain gold nanoparticle-supported polymer fine particles. When observed by TEM, the gold nanoparticles were dispersed and fixed almost uniformly on the surface of the polymer fine particles, and many gold nanoparticles having a particle diameter of 3 to 10 nm were observed. The average particle diameter was 6.9 nm, and the standard deviation was 5.5 nm (see FIG. 3; the length of the line in the figure is 100 nm).
実施例２〔メラミン−ホルムアルデヒド縮合樹脂微粒子への金ナノ粒子担持（金担持量０．５ｗｔ％）〕
メラミン−ホルムアルデヒド縮合樹脂微粒子（（株）日本触媒製 エポスターＳ（粒子径０．２２μｍ））１ｇを２５２ｍＬのイオン交換水に加え、よく分散させた。これに０．０１Ｍ ＨＡｕＣｌ４ ２．５４ｍＬを加え、０℃で３０分間撹拌した。その後、予め０℃に冷却しておいた０．０１Ｍ ＮａＢＨ４ ３．８１ｍＬを４分間かけて滴下した。滴下後、濾過、イオン交換水で洗浄、乾燥させ、金ナノ粒子担持高分子微粒子を得た。ＴＥＭで観察したところ、金ナノ粒子が高分子微粒子表面にほぼ均一に分散・固定化されており、粒子径２〜１０ｎｍの金ナノ粒子が多数見られた。平均粒子径は４．７ｎｍ、標準偏差は４．１ｎｍであった。
Example 2 [Gold nanoparticle support on melamine-formaldehyde condensation resin fine particles (gold support amount 0.5 wt%)]
1 g of melamine-formaldehyde condensed resin fine particles (Epester S (particle diameter 0.22 μm) manufactured by Nippon Shokubai Co., Ltd.) was added to 252 mL of ion-exchanged water and well dispersed. To this, 2.54 mL of 0.01M HAuCl 4 was added and stirred at 0 ° C. for 30 minutes. Thereafter, 3.81 mL of 0.01M NaBH 4 that had been cooled to 0 ° C. in advance was added dropwise over 4 minutes. After dropping, filtration, washing with ion exchange water and drying were performed to obtain gold nanoparticle-supported polymer fine particles. When observed by TEM, the gold nanoparticles were dispersed and fixed almost uniformly on the surface of the polymer fine particles, and many gold nanoparticles having a particle diameter of 2 to 10 nm were observed. The average particle size was 4.7 nm and the standard deviation was 4.1 nm.
実施例３〔ポリスチレン微粒子への金ナノ粒子担持（金担持量０．５ｗｔ％）〕
ＰＭＭＡ微粒子に代えてポリスチレン微粒子（積水化成工業（株）製 テクポリマーＳＢＸ−６（粒子径６μｍ））を用いることを除き実施例１と同様にして、金ナノ粒子担持ポリスチレン微粒子を得た。ＴＥＭで観察したところ、金ナノ粒子がポリスチレン微粒子表面にほぼ均一に分散・固定化されており、粒子径３〜１０ｎｍの金ナノ粒子が多数見られた。平均粒子径は１３ｎｍであった（図４参照；なお、図中の線の長さは２００ｎｍである）。
Example 3 [Gold nanoparticle support on polystyrene fine particles (gold support amount 0.5 wt%)]
Gold nanoparticle-carrying polystyrene fine particles were obtained in the same manner as in Example 1 except that polystyrene fine particles (Techpolymer SBX-6 (particle diameter 6 μm) manufactured by Sekisui Chemical Co., Ltd.) were used instead of PMMA fine particles. When observed by TEM, the gold nanoparticles were dispersed and fixed almost uniformly on the surface of the polystyrene fine particles, and many gold nanoparticles having a particle diameter of 3 to 10 nm were observed. The average particle size was 13 nm (see FIG. 4; the line length in the figure is 200 nm).
実施例４〔ポリビニルクロライド微粒子への金ナノ粒子担持（金担持量０．５ｗｔ％）〕
ＰＭＭＡ微粒子に代えてポリビニルクロライド微粒子（ヴイテック（株）製（粒子径０．２５μｍ））を用いることを除き実施例１と同様にして、金ナノ粒子担持ポリビニルクロライド微粒子を得た。ＴＥＭで観察したところ、金ナノ粒子がポリビニルクロライド微粒子表面にほぼ均一に分散・固定化されており、粒子径３〜１０ｎｍの金ナノ粒子が多数見られた。平均粒子径は８．４ｎｍであった。
Example 4 [Supporting gold nanoparticles on polyvinyl chloride fine particles (gold supported amount 0.5 wt%)]
Gold nanoparticle-supporting polyvinyl chloride fine particles were obtained in the same manner as in Example 1 except that polyvinyl chloride fine particles (manufactured by Vitec Co., Ltd. (particle size: 0.25 μm)) were used instead of PMMA fine particles. When observed by TEM, the gold nanoparticles were dispersed and fixed almost uniformly on the surface of the polyvinyl chloride fine particles, and many gold nanoparticles having a particle diameter of 3 to 10 nm were observed. The average particle size was 8.4 nm.
比較例１〔ＰＭＭＡ微粒子への金ナノ粒子担持（金担持量０．５ｗｔ％）〕
高分子微粒子（粒子径２．６μｍ）１ｇを２００ｍＬのイオン交換水に加え、よく分散させた。これに金エチレンジアミン錯体１０．７ｍｇをイオン交換水５４ｍＬと共に加え、０℃で３０分間撹拌した。その後、予め０℃に冷却しておいた０．０１Ｍ ＮａＢＨ4３．８１ｍＬをすばやく加えた。添加後、濾過、イオン交換水で洗浄、乾燥させ、金ナノ粒子担持高分子微粒子を得た。ＴＥＭで観察したところ、金ナノ粒子が高分子微粒子表面に固定化されており、一部は分散していたが、凝集も多く見られ１００ｎｍ以上の大きな凝集体もあった。平均粒子径は１２．６ｎｍ、標準偏差は１６．２ｎｍであった（凝集体はカウントせず）（図５参照；なお、図中の線の長さは５０ｎｍである）。
Comparative Example 1 [Gold nanoparticle support on PMMA fine particles (gold support amount 0.5 wt%)]
1 g of polymer fine particles (particle diameter 2.6 μm) was added to 200 mL of ion exchange water and well dispersed. To this was added 10.7 mg of a gold ethylenediamine complex together with 54 mL of ion-exchanged water, and the mixture was stirred at 0 ° C. for 30 minutes. Thereafter, 3.81 mL of 0.01 M NaBH 4 that had been cooled to 0 ° C. in advance was quickly added. After the addition, filtration, washing with ion-exchanged water, and drying were performed to obtain gold nanoparticle-supported polymer fine particles. When observed with TEM, the gold nanoparticles were immobilized on the surface of the polymer fine particles, and some of them were dispersed, but a large amount of aggregation was observed, and there was a large aggregate of 100 nm or more. The average particle diameter was 12.6 nm, and the standard deviation was 16.2 nm (aggregates were not counted) (see FIG. 5; the line length in the figure was 50 nm).
比較例２〔ＰＭＭＡ微粒子への金ナノ粒子担持（金担持量０．５ｗｔ％）〕
高分子微粒子（粒子径２．６μｍ）１ｇを０．０１Ｍ ＮａＣｌ水溶液（２００ｍＬ）に分散させた他は実施例３と同様に行った。ＴＥＭで観察したところ、金ナノ粒子がＰＭＭＡ微粒子表面に固定化されていた。比較例１に比べて金ナノ粒子は分散された状態で固定化されていたが、実施例３と比較するとより大きな金ナノ粒子（２０〜３０ｎｍ）や凝集体も存在した。平均粒子径は９．５ｎｍ標準偏差は７．６ｎｍであった（凝集体はカウントせず）（図６参照；なお、図中の線の長さは５０ｎｍである）。
Comparative Example 2 [Gold nanoparticle support on PMMA fine particles (gold support amount 0.5 wt%)]
The same procedure as in Example 3 was performed except that 1 g of polymer fine particles (particle diameter 2.6 μm) was dispersed in 0.01 M NaCl aqueous solution (200 mL). When observed with TEM, the gold nanoparticles were immobilized on the surface of the PMMA fine particles. Compared to Comparative Example 1, the gold nanoparticles were immobilized in a dispersed state, but larger gold nanoparticles (20 to 30 nm) and aggregates were also present than Example 3. The average particle size was 9.5 nm and the standard deviation was 7.6 nm (aggregates were not counted) (see FIG. 6; the line length in the figure was 50 nm).
実施例５〔金ナノ粒子担持高分子微粒子の触媒特性（過酸化水素分解）〕
実施例１で調製した試料を用いて、過酸化水素分解反応を行った。５ｗｔ％過酸化水素水１００ｍＬに試料０．１ｇを入れ、室温で撹拌した。一定時間毎に反応液５ｍＬを採取し、これに水を加えて２００ｍＬとした。撹拌しながらこれに濃硫酸５ｍＬを加え、フェロイン試薬３滴を落とした。この溶液を０．１ｍｏｌ／Ｌ硫酸セリウム（IV）水溶液で残存する過酸化水素量を求めることにより、過酸化水素分解率を算出した。実施例１の試料を用いた場合においては、６０分後に分解率８３％であった。なお、比較例１の試料を用いた場合においては、６０分後に分解率６５％であった。
Example 5 [Catalytic properties of gold nanoparticle-supported polymer fine particles (hydrogen peroxide decomposition)]
Using the sample prepared in Example 1 , a hydrogen peroxide decomposition reaction was performed. 0.1 g of a sample was placed in 100 mL of 5 wt% hydrogen peroxide water and stirred at room temperature. 5 mL of the reaction solution was collected at regular intervals, and water was added to make 200 mL. While stirring, 5 mL of concentrated sulfuric acid was added thereto, and 3 drops of ferroin reagent were dropped. The hydrogen peroxide decomposition rate was calculated by determining the amount of hydrogen peroxide remaining in this solution with a 0.1 mol / L cerium (IV) sulfate aqueous solution. In the case of using the sample of Example 1 , the decomposition rate was 83% after 60 minutes. When the sample of Comparative Example 1 was used, the decomposition rate was 65% after 60 minutes.
参考例３〔金ナノ粒子担持カーボンナノホーンの触媒特性（グルコース酸化）〕
参考例１で調製した試料を用いて、水溶液中でのグルコースの酸素酸化を行った。金／グルコースのモル比を１：１６０００として、グルコース濃度５重量％の水溶液に攪拌下、６０℃で、酸素を６０ｍＬ／ｍｉｎでバブリングした。水溶液のｐＨを９．５に保つよう、０．１Ｍ水酸化ナトリウム水溶液を随時滴下し、水酸化ナトリウムの滴下量からグルコン酸の生成量を反応時間の関数として測定した。その結果、１００分後に転化率９７％となり、上記の金ナノ粒子担持活性炭は比較的低温でグルコースの酸素酸化に高い触媒活性を有することが判明した。
Reference Example 3 [Catalytic properties of carbon nanohorn supported on gold nanoparticles (glucose oxidation)]
Using the sample prepared in Reference Example 1, oxygen oxidation of glucose in an aqueous solution was performed. With a gold / glucose molar ratio of 1: 16000, oxygen was bubbled into an aqueous solution having a glucose concentration of 5% by weight at 60 ° C. with stirring at 60 mL / min. To maintain the pH of the aqueous solution at 9.5, a 0.1 M aqueous sodium hydroxide solution was dropped as needed, and the amount of gluconic acid produced was measured as a function of reaction time from the amount of sodium hydroxide added. As a result, the conversion was 97% after 100 minutes, and it was found that the gold nanoparticle-supported activated carbon had high catalytic activity for oxygen oxidation of glucose at a relatively low temperature.
本発明の方法により製造された表面に貴金属微粒子が分散・固定された固体高分子材料は、酸化触媒、水添触媒、顔料、着色剤、導電剤、その他各種検出素子材料として有用に利用することができる。 The solid polymer material in which noble metal fine particles are dispersed and fixed on the surface produced by the method of the present invention is useful as an oxidation catalyst, a hydrogenation catalyst, a pigment, a colorant, a conductive agent, and other various sensing element materials. Can do.
Claims (7)
前記高分子材料が、粉末、微粒子、薄膜、中空粒子、多孔体またはデンドリマー形態であるとともに、ビニル系ポリマー、ポリエーテル、ポリエステル、ポリカーボネート、ポリアミド、ポリウレタン、ジエン系ポリマー、メラミン・ベンゾグアナミン系ポリマー、芳香族系ポリマー、ポリイミド、ポリシラン、ポリシロキサン、ポリカプロラクトン、硫黄系ポリマーおよび天然高分子から選択される少なくとも１種の高分子材料であることを特徴とする、高分子材料上に金微粒子を分散・固定化する方法。 Reducing agent is gradually added to an aqueous solution of a gold compound in contact with a polymer material that does not have a highly polar functional group on the surface, or an organic / inorganic hybrid material composed of the polymer material and an inorganic material and containing 50% by weight or less of the inorganic material. A method of dispersing and immobilizing gold fine particles on a polymer material characterized by:
The polymer material is in the form of powder, fine particles, thin film, hollow particle, porous body or dendrimer, and is also a vinyl polymer, polyether, polyester, polycarbonate, polyamide, polyurethane, diene polymer, melamine / benzoguanamine polymer, aromatic family-based polymer, polyimide, positive Rishiran, polysiloxanes, polycaprolactone, and wherein the at least one polymeric material selected from sulfur-based polymers and natural polymers, dispersed gold particles on a polymer material・ Method of immobilization.
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