JP6025253B2 - Process for producing transition metal-supported alkaline rutile titanium oxide sol - Google Patents
Process for producing transition metal-supported alkaline rutile titanium oxide sol Download PDFInfo
- Publication number
- JP6025253B2 JP6025253B2 JP2012261686A JP2012261686A JP6025253B2 JP 6025253 B2 JP6025253 B2 JP 6025253B2 JP 2012261686 A JP2012261686 A JP 2012261686A JP 2012261686 A JP2012261686 A JP 2012261686A JP 6025253 B2 JP6025253 B2 JP 6025253B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- rutile
- sol
- transition metal
- alkaline
- 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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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 221
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 117
- 238000000034 method Methods 0.000 title claims description 40
- 230000007704 transition Effects 0.000 title claims description 14
- 230000008569 process Effects 0.000 title claims description 11
- 238000005406 washing Methods 0.000 claims description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229910052723 transition metal Inorganic materials 0.000 claims description 25
- 150000003624 transition metals Chemical class 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 150000003623 transition metal compounds Chemical class 0.000 claims description 19
- -1 amine compound Chemical class 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 150000003609 titanium compounds Chemical class 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 239000005749 Copper compound Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 150000001880 copper compounds Chemical class 0.000 claims description 5
- 150000002506 iron compounds Chemical class 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 150000002941 palladium compounds Chemical class 0.000 claims description 5
- 150000003058 platinum compounds Chemical class 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 229940045985 antineoplastic platinum compound Drugs 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 36
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 24
- 230000001699 photocatalysis Effects 0.000 description 24
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 24
- 239000002245 particle Substances 0.000 description 20
- 238000000108 ultra-filtration Methods 0.000 description 20
- 239000013078 crystal Substances 0.000 description 17
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000005750 Copper hydroxide Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 241000350481 Pterogyne nitens Species 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- RQDIYKFIHRHVDX-UHFFFAOYSA-K azanium;iron(3+);oxalate;trihydrate Chemical compound [NH4+].O.O.O.[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O RQDIYKFIHRHVDX-UHFFFAOYSA-K 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 2
- 229960001231 choline Drugs 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SMWOQEYXSYVTQR-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid copper Chemical compound [Cu].[Cu].OC(=O)CN(CCN(CC(O)=O)CC(O)=O)CC(O)=O SMWOQEYXSYVTQR-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- CGVPYAREDIUBOY-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;iron(2+) Chemical compound [Fe+2].[Fe+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O CGVPYAREDIUBOY-UHFFFAOYSA-K 0.000 description 1
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- BDSSZTXPZHIYHM-UHFFFAOYSA-N 2-phenoxypropanoyl chloride Chemical compound ClC(=O)C(C)OC1=CC=CC=C1 BDSSZTXPZHIYHM-UHFFFAOYSA-N 0.000 description 1
- PKQIDSVLSKFZQC-UHFFFAOYSA-N 3-oxobutanal Chemical compound CC(=O)CC=O PKQIDSVLSKFZQC-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YDGLLXOXPIAITK-UHFFFAOYSA-L Cl[Cu](Cl)[K] Chemical compound Cl[Cu](Cl)[K] YDGLLXOXPIAITK-UHFFFAOYSA-L 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- RVSAQKQAESPVRJ-UHFFFAOYSA-N [Cu].C(CN(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O.[Na].[Na] Chemical compound [Cu].C(CN(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O.[Na].[Na] RVSAQKQAESPVRJ-UHFFFAOYSA-N 0.000 description 1
- GMTXBUZKCHNBCH-UHFFFAOYSA-L [K].[Pt](Cl)Cl Chemical compound [K].[Pt](Cl)Cl GMTXBUZKCHNBCH-UHFFFAOYSA-L 0.000 description 1
- MBQYUMXAJCFWGL-UHFFFAOYSA-N [Na+].[Pt+4] Chemical compound [Na+].[Pt+4] MBQYUMXAJCFWGL-UHFFFAOYSA-N 0.000 description 1
- YFQGBVKASWRPDT-UHFFFAOYSA-N [OH-].C(C)(C)(C)[NH2+]CC Chemical compound [OH-].C(C)(C)(C)[NH2+]CC YFQGBVKASWRPDT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- VUCAVCCCXQVHAN-UHFFFAOYSA-L azane dichlorocopper Chemical compound N.Cl[Cu]Cl VUCAVCCCXQVHAN-UHFFFAOYSA-L 0.000 description 1
- KVTQOXMLIFVKOK-UHFFFAOYSA-K azanium;iron(3+);oxalate Chemical compound [NH4+].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O KVTQOXMLIFVKOK-UHFFFAOYSA-K 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- QFTWTIKOKWPUAM-UHFFFAOYSA-N dipotassium;platinum(2+);tetracyanide Chemical compound [K+].[K+].[Pt+2].N#[C-].N#[C-].N#[C-].N#[C-] QFTWTIKOKWPUAM-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011706 ferric diphosphate Substances 0.000 description 1
- 235000007144 ferric diphosphate Nutrition 0.000 description 1
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 1
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 1
- 239000004225 ferrous lactate Substances 0.000 description 1
- 235000013925 ferrous lactate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- DJXYWDRBAAVVSG-UHFFFAOYSA-J potassium;tetrachloroplatinum Chemical compound [K].Cl[Pt](Cl)(Cl)Cl DJXYWDRBAAVVSG-UHFFFAOYSA-J 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- SRFKWQSWMOPVQK-UHFFFAOYSA-K sodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(2+) Chemical compound [Na+].[Fe+2].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O SRFKWQSWMOPVQK-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- OLNCQUXQEJCISO-UHFFFAOYSA-M trimethyl(propyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](C)(C)C OLNCQUXQEJCISO-UHFFFAOYSA-M 0.000 description 1
Images
Description
本発明は、遷移金属担持アルカリ性ルチル型酸化チタンゾルの製造方法に関する。 The present invention relates to a method for producing a transition metal-supported alkaline rutile titanium oxide sol.
アナターゼ型酸化チタンからなる光触媒は、388nm以下の紫外線を吸収することにより酸化還元作用を発現し、有害物質の分解、抗菌性、超親水現象等の光触媒効果を有することが知られている。しかし、アナターゼ型酸化チタンは可視光には応答しないため、紫外線量が低い屋内照明下では光触媒効果をほとんど示さない。 It is known that a photocatalyst composed of anatase-type titanium oxide exhibits a redox action by absorbing ultraviolet rays of 388 nm or less, and has photocatalytic effects such as decomposition of harmful substances, antibacterial properties, and superhydrophilic phenomena. However, since anatase-type titanium oxide does not respond to visible light, it hardly shows a photocatalytic effect under indoor lighting with a low amount of ultraviolet rays.
一方、ルチル型酸化チタンは407nm以下の光、即ち青色の可視光を吸収することができるが、励起電子の還元力が弱いため光触媒効果をほとんど示さない。しかし、近年、ルチル型酸化チタンに遷移金属を担持させることによって可視光照射下で光触媒として機能させる技術が報告されている。 On the other hand, rutile titanium oxide can absorb light having a wavelength of 407 nm or less, that is, blue visible light, but exhibits almost no photocatalytic effect because the reducing power of excited electrons is weak. However, in recent years, a technique has been reported in which a transition metal is supported on rutile titanium oxide to function as a photocatalyst under visible light irradiation.
例えば、特許文献１には、白金等の金属を分散させた有機溶媒に二酸化チタン粉末を添加した後、これを乾燥、焼成することにより、青色可視光域であっても光触媒効果を有する金属超微粒子を担持した粉体のルチル型二酸化チタンが得られることが記載されている。 For example, in Patent Document 1, after adding titanium dioxide powder to an organic solvent in which a metal such as platinum is dispersed, the powder is dried and baked, so that a metal superb having a photocatalytic effect even in a blue visible light region. It is described that a rutile type titanium dioxide carrying fine particles can be obtained.
また、非特許文献１には、界面電荷移動による可視光吸収と多電子還元機能を有し、可視光照射下で光触媒機能を発現する銅イオンを担持した粉体のルチル型酸化チタンについて報告されている。 Non-Patent Document 1 reports on rutile-type titanium oxide in powder form supporting copper ions that have visible light absorption and multi-electron reduction functions due to interfacial charge transfer and that exhibit photocatalytic functions under visible light irradiation. ing.
一方、特許文献２の実施例には、白金を担持したルチル型二酸化チタン結晶微粒子又は鉄を担持したルチル型二酸化チタン結晶微粒子をテトラメチルアンモニウムヒドロキシド（TMAH）水溶液中に分散させた溶液をビーズミルによって粉砕することにより、pHが10.5であり平均粒子径が50nm以下である分散液を得る技術が開示されている。 On the other hand, in the example of Patent Document 2, a solution in which rutile type titanium dioxide crystal particles supporting platinum or rutile type titanium dioxide crystal particles supporting iron is dispersed in an aqueous solution of tetramethylammonium hydroxide (TMAH) is used as a bead mill. Discloses a technique for obtaining a dispersion having a pH of 10.5 and an average particle size of 50 nm or less.
ところで、ナノ粒子分散液（ゾル）の製造方法として、溶媒中で粉砕により微粒子化するブレークダウン（トップダウン）方式と、液体から化学反応等を利用して微粒子を生成させ分散液を作成するビルドアップ（ボトムアップ）方式の２つの方法が知られている。 By the way, as a manufacturing method of nanoparticle dispersion liquid (sol), a breakdown (top-down) method in which fine particles are formed by pulverization in a solvent, and a build in which fine particles are generated from a liquid using a chemical reaction or the like are created. Two methods of an up (bottom-up) method are known.
ビーズミル等の粉砕によるブレークダウン方式は、粉砕装置があれば簡便に実施できるが、粉砕時のメディアの磨耗による不純物の混入、及び均一粉砕の困難性が問題点として指摘されている。 The breakdown method by pulverization such as a bead mill can be easily carried out if there is a pulverizer. However, it is pointed out that impurities are mixed due to media wear during pulverization and difficulty in uniform pulverization.
一方、ビルドアップ方式は、製造プロセスが複雑になる傾向があるが、比較的容易に粒子径の均一性が高い微粒子を製造できる利点がある。 On the other hand, the build-up method tends to complicate the manufacturing process, but has an advantage that it is relatively easy to manufacture fine particles having a high particle size uniformity.
本発明は、ビルドアップ方式によって製造され、可視光下で光触媒活性を示し、基材の意匠性を損なうことなく塗布することが可能であり、さらにアルカリ性の水系バインダーとの混合が可能である可視光応答型光触媒ゾルの開発を課題とするものである。 The present invention is produced by a build-up method, exhibits photocatalytic activity under visible light, can be applied without impairing the design of the base material, and can be mixed with an alkaline aqueous binder. The development of a photoresponsive photocatalyst sol is an issue.
本発明者らは、下記（１）〜（５）の工程を包含する製造方法により、上記課題が解決されることを見出し本発明の完成に至ったものである。 The present inventors have found that the above problems can be solved by a production method including the following steps (1) to (5), and have completed the present invention.
即ち、本発明は、下記（１）〜（５）の工程を包含することを特徴とする遷移金属担持アルカリ性ルチル型酸化チタンゾルの製造方法である。
（１）アルカリ水溶液と水溶性チタン化合物を、常にpH9以上を保ちながら中和して水和酸化チタンゲルを得た後、洗浄する第１の工程。
（２）第１の工程で得られた洗浄物を、塩酸又は硝酸でpH3以下に調整した後、加熱する第２の工程。
（３）第２の工程で得られた加熱物から無機酸根を除去する第３の工程。
（４）第３の工程で得られた無機酸根除去物を、水溶性アミン化合物の存在下で加熱することでアルカリ性ルチル型酸化チタンゾルを得る第４の工程。
（５）第４の工程で得られたアルカリ性ルチル型酸化チタンゾルと、鉄化合物、銅化合物、白金化合物及びパラジウム化合物からなる群より選ばれた１種以上の遷移金属化合物とを混合し、遷移金属を担持させる第５の工程。
That is, this invention is a manufacturing method of the transition metal carrying | support alkali rutile type titanium oxide sol characterized by including the process of following (1)-(5).
(1) The 1st process of wash | cleaning, after neutralizing alkali aqueous solution and a water-soluble titanium compound, always maintaining pH9 or more and obtaining a hydrated titanium oxide gel.
(2) A second step of heating the washed product obtained in the first step after adjusting the pH to 3 or less with hydrochloric acid or nitric acid.
(3) A third step of removing inorganic acid radicals from the heated product obtained in the second step.
(4) A fourth step of obtaining an alkaline rutile-type titanium oxide sol by heating the inorganic acid radical removed product obtained in the third step in the presence of a water-soluble amine compound.
(5) The alkaline rutile titanium oxide sol obtained in the fourth step is mixed with one or more transition metal compounds selected from the group consisting of iron compounds, copper compounds, platinum compounds and palladium compounds, and transition metals are mixed. 5th process to carry | support.
本発明の遷移金属担持アルカリ性ルチル型酸化チタンゾルは、長期安定性に優れ、薄膜としたときの透明性、平滑性に優れ、可視光照射下で光触媒活性を示すため、室内環境で使用され高度な意匠性が必要とされる光触媒薄膜用途に特に好適に用いることができる。また、アルカリ性の水系バインダーとの混合が可能であるという利点を有する。 The transition metal-supported alkaline rutile-type titanium oxide sol of the present invention has excellent long-term stability, excellent transparency and smoothness when formed into a thin film, and exhibits photocatalytic activity under visible light irradiation. It can use especially suitably for the photocatalyst thin film use for which design property is required. Moreover, it has the advantage that mixing with an alkaline aqueous binder is possible.
以下、本発明の遷移金属担持アルカリ性ルチル型酸化チタンゾルの製造方法について説明する。
本発明の遷移金属担持アルカリ性ルチル型酸化チタンゾル（以下、「本発明のゾル」とも云う）は、下記（１）〜（５）の工程を包含する製造方法によって製造されるものである。
（１）アルカリ水溶液と水溶性チタン化合物を、常にpH9以上を保ちながら中和して水和酸化チタンゲルを得た後、洗浄する第１の工程。
（２）第１の工程で得られた洗浄物を、塩酸又は硝酸でpH3以下に調整した後、加熱する第２の工程。
（３）第２の工程で得られた加熱物から無機酸根を除去する第３の工程。
（４）第３の工程で得られた無機酸根除去物を、水溶性アミン化合物の存在下で加熱することでアルカリ性ルチル型酸化チタンゾルを得る第４の工程。
（５）第４の工程で得られたアルカリ性ルチル型酸化チタンゾルと、鉄化合物、銅化合物、白金化合物及びパラジウム化合物からなる群より選ばれた１種以上の遷移金属化合物とを混合し、遷移金属を担持させる第５の工程。
Hereinafter, the manufacturing method of the transition metal carrying | support alkaline rutile type titanium oxide sol of this invention is demonstrated.
The transition metal-supported alkaline rutile titanium oxide sol of the present invention (hereinafter also referred to as “sol of the present invention”) is produced by a production method including the following steps (1) to (5).
(1) The 1st process of wash | cleaning, after neutralizing alkali aqueous solution and a water-soluble titanium compound, always maintaining pH9 or more and obtaining a hydrated titanium oxide gel.
(2) A second step of heating the washed product obtained in the first step after adjusting the pH to 3 or less with hydrochloric acid or nitric acid.
(3) A third step of removing inorganic acid radicals from the heated product obtained in the second step.
(4) A fourth step of obtaining an alkaline rutile-type titanium oxide sol by heating the inorganic acid radical removed product obtained in the third step in the presence of a water-soluble amine compound.
(5) The alkaline rutile titanium oxide sol obtained in the fourth step is mixed with one or more transition metal compounds selected from the group consisting of iron compounds, copper compounds, platinum compounds and palladium compounds, and transition metals are mixed. 5th process to carry | support.
先ず、第１の工程について説明する。
アルカリ水溶液に用いる化合物として、アルカリ金属の水酸化物、アルカリ金属の炭酸塩、アンモニア等を好例として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。アルカリ金属の水酸化物として、水酸化ナトリウム、水酸化カリウム等が例示でき、アルカリ金属の炭酸塩として、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム等が例示できる。アルカリ水溶液の濃度は、水溶性チタン化合物を添加してもpH9以上を保つことができ、水和酸化チタンゲルが生成できれば特に制限はなく、適宜設定すればよい。
First, the first step will be described.
Examples of the compound used in the alkaline aqueous solution include, but are not limited to, alkali metal hydroxides, alkali metal carbonates, and ammonia. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and examples of the alkali metal carbonate include sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate. The concentration of the alkaline aqueous solution is not particularly limited as long as it can maintain a pH of 9 or more even when a water-soluble titanium compound is added, and a hydrated titanium oxide gel can be formed, and may be set as appropriate.
水溶性チタン化合物として、塩化チタン、オキシ塩化チタン、硫酸チタン、オキシ硫酸チタン等を好例として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。これら水溶性チタン化合物は水溶液の状態で使用することが作業性の観点から好ましい。その水溶液の濃度は、特に制限されることはなく、適宜設定すればよい。 Examples of the water-soluble titanium compound include, but are not limited to, titanium chloride, titanium oxychloride, titanium sulfate, titanium oxysulfate, and the like. These water-soluble titanium compounds are preferably used in the form of an aqueous solution from the viewpoint of workability. The concentration of the aqueous solution is not particularly limited and may be set as appropriate.
アルカリ水溶液に対し水溶性チタン化合物を、常にpH9以上を保ちながら中和する方法について説明する。[1]アルカリ水溶液に対し、水溶性チタン化合物を添加し、pH9を下回らない範囲で水溶性チタン化合物の添加を終了する方法、[2]アルカリ水溶液と水溶性チタン化合物を、pH9を下回らないように同時に添加する方法、[3]設計量の内の一部のアルカリ水溶液に対し水溶性チタン化合物を添加するが、pH9を下回らないように残りのアルカリ水溶液を適宜添加する方法が挙げられる。この中でも、[1]の方法が最も容易にpH9以上を保つことができるため特に好ましい。尚、いずれの方法においても、前記pH範囲を保つように撹拌強度、添加方法等を適宜設定すればよい。前記[1]の添加方法については、水溶性チタン化合物添加による溶液pHの局所低下を避けるために、滴下が特に好ましい。水和酸化チタンゲルを得る操作における温度については特段の制限は無く、5〜100℃の範囲内であればよい。 A method for neutralizing a water-soluble titanium compound with respect to an alkaline aqueous solution while always maintaining pH 9 or higher will be described. [1] A method in which a water-soluble titanium compound is added to an alkaline aqueous solution and the addition of the water-soluble titanium compound is terminated within a range not lower than pH 9. [2] An alkaline aqueous solution and a water-soluble titanium compound should not be lower than pH 9. [3] A method in which the water-soluble titanium compound is added to a part of the alkaline aqueous solution within the designed amount, but the remaining alkaline aqueous solution is appropriately added so that the pH is not lower than 9. Among these, the method [1] is particularly preferable because it can most easily maintain pH 9 or higher. In any method, the stirring intensity, the addition method, etc. may be appropriately set so as to keep the pH range. The addition method [1] is particularly preferably dripping in order to avoid a local decrease in solution pH due to the addition of a water-soluble titanium compound. There is no special restriction | limiting about the temperature in operation which obtains a hydrated titanium oxide gel, What is necessary is just in the range of 5-100 degreeC.
水和酸化チタンゲルの濃度について云えば、酸化チタン濃度（TiO2）として、0.1〜5.0質量％の範囲を例示できる。0.1質量％を下回ると生産効率が悪くなるため、また、5.0質量％を上回ると反応時の撹拌が困難になるため好ましくない。 Regarding the concentration of the hydrated titanium oxide gel, the range of 0.1 to 5.0% by mass can be exemplified as the titanium oxide concentration (TiO 2 ). If it is less than 0.1% by mass, the production efficiency is deteriorated, and if it exceeds 5.0% by mass, stirring during the reaction becomes difficult, which is not preferable.
次に、生成した水和酸化チタンゲルを洗浄する。洗浄は、副生塩や余分なイオン性物質が除去できれば洗浄方法に特に制限はなく、水を添加しながらの限外ろ過、ヌッチェろ過、フィルタープレス等が例示でき、このうち特に限外ろ過が好ましい。洗浄終点の目安として、ろ液ECが0.3〜5mS/cmの時点を挙げることができる。
また、洗浄終了後の水和酸化チタンゲルのpHは概ね10〜12の範囲であり、ECは概ね0.4〜6mS/cmの範囲である。
Next, the produced hydrated titanium oxide gel is washed. Washing is not particularly limited as long as by-product salts and excess ionic substances can be removed, and examples include ultrafiltration while adding water, Nutsche filtration, filter press, etc. preferable. As an indication of the end point of washing, the time when the filtrate EC is 0.3 to 5 mS / cm can be mentioned.
Further, the pH of the hydrated titanium oxide gel after completion of washing is generally in the range of 10 to 12, and EC is generally in the range of 0.4 to 6 mS / cm.
次に第２の工程では、第１の工程の洗浄後の水和酸化チタンゲルを含む溶液を塩酸及び/又は硝酸でpH3以下に調整した後、加熱する。塩酸及び/又は硝酸の濃度及び量は、前記pH範囲に調整できるように適宜設定すればよい。例として濃塩酸を用いた場合は、溶液中のTiO2に対して濃塩酸（HCl）をモル比で0.6〜2.0の範囲で添加することが好ましい。 Next, in the second step, the solution containing the hydrated titanium oxide gel after the washing in the first step is adjusted to pH 3 or lower with hydrochloric acid and / or nitric acid and then heated. What is necessary is just to set suitably the density | concentration and quantity of hydrochloric acid and / or nitric acid so that it can adjust to the said pH range. When concentrated hydrochloric acid is used as an example, concentrated hydrochloric acid (HCl) is preferably added in a molar ratio of 0.6 to 2.0 with respect to TiO 2 in the solution.
加熱時の酸化チタン濃度（TiO2）は1〜8質量％の範囲であることが好ましい。前記範囲で処理することで最終的に粒子径の小さいルチル型酸化チタンを効率的に得ることができる。 The titanium oxide concentration (TiO 2 ) during heating is preferably in the range of 1 to 8% by mass. By treating in the above range, rutile titanium oxide having a small particle diameter can be efficiently obtained finally.
加熱温度は、40〜90℃の範囲が好ましい。前記温度範囲において、アナターゼ型酸化チタンが生成せずに、ルチル型酸化チタンが生成し易くなる。また、加熱時間は、ルチル型酸化チタンを充分に生成させるために、10分以上であることが好ましく、特に好ましくは10分〜240分である。より好ましい加熱条件は、45〜75℃で20分〜80分である。 The heating temperature is preferably in the range of 40 to 90 ° C. In the temperature range, anatase-type titanium oxide is not generated, and rutile-type titanium oxide is easily generated. The heating time is preferably 10 minutes or more, particularly preferably 10 minutes to 240 minutes, in order to sufficiently generate rutile-type titanium oxide. More preferable heating conditions are 45 to 75 ° C. and 20 to 80 minutes.
次に第３の工程では、第２の工程で加熱された溶液中の塩素根、硝酸根等の無機酸根の除去を行う。上記無機酸根の除去は、第４の工程において分散性の良好なゾルを得るために必須であり、ルチル型酸化チタン（TiO2）に対し無機酸根をモル比で0.01以下とすることが推奨される。その方法は特に限定されないが、例えば、第２の工程の加熱物を、[1]限外ろ過洗浄する方法、[2]限外ろ過洗浄した後、アルカリ水溶液で中和し、その中和物をさらに洗浄する方法、[3]アルカリ水溶液で中和した後、洗浄する方法等が挙げられる。この中でも特に[3]の方法が最も効率的に無機酸根を除去することができるため、好適である。 Next, in a 3rd process, inorganic acid radicals, such as a chlorine radical and a nitrate radical, in the solution heated at the 2nd process are removed. The removal of the inorganic acid radical is essential for obtaining a sol with good dispersibility in the fourth step, and it is recommended that the inorganic acid radical is 0.01 or less in molar ratio with respect to rutile titanium oxide (TiO 2 ). The The method is not particularly limited. For example, the heated product in the second step is [1] an ultrafiltration washing method, [2] after ultrafiltration washing, and neutralized with an alkaline aqueous solution, and the neutralized product. And [3] a method of neutralizing with an aqueous alkali solution followed by washing. Among these, the method [3] is particularly preferable because it can remove inorganic acid radicals most efficiently.
前記[3]の方法においては、まず、第２の工程の加熱物にアルカリ水溶液を添加して中和する。アルカリ水溶液の添加時の溶液温度に関しては、特段制約はないが一般的には5〜90℃が良い。アルカリ水溶液の化合物としては、第１の工程で例示した化合物を挙げることができるが、分散剤として作用するアンモニアが特に好ましい。アルカリ水溶液の濃度と量は適宜設定すればよいが、アルカリ水溶液添加後の溶液pHが5.5以上となるように設定することが好ましい。尚、後の洗浄工程で液の粘性が高く洗浄が困難な場合は、中和した後に加熱エージングを行っても良い。加熱エージングを行う場合は50〜100℃で1〜5時間行うことが好ましい。続いて、中和した溶液を洗浄する。洗浄方法は第１の工程に記載した方法を例示することができ、このうち限外ろ過が特に好ましい。限外ろ過を例にとると、系外へ排出されるろ液のECをおよそ500μS/cm以下まで洗浄することにより、ルチル型酸化チタン（TiO2）に対し無機酸根をモル比で0.01以下にまで除去することができる。より好ましくは、ろ液ECが50μS/cm以下となるまで洗浄することにより、塩素根、硝酸根等の無機酸根だけでなくその他のイオン性物質、例えば、Na+、K+等のアルカリ金属及び遊離のアンモニア等を限外ろ過による洗浄限界まで除去することができる。 In the method [3], first, an aqueous alkali solution is added to the heated product in the second step for neutralization. The solution temperature at the time of adding the alkaline aqueous solution is not particularly limited, but generally 5 to 90 ° C. is preferable. As the compound of the alkaline aqueous solution, the compounds exemplified in the first step can be exemplified, and ammonia acting as a dispersant is particularly preferable. The concentration and amount of the aqueous alkaline solution may be set as appropriate, but it is preferably set so that the solution pH after addition of the aqueous alkaline solution is 5.5 or more. In addition, when the viscosity of the liquid is high in the subsequent washing step and washing is difficult, heat aging may be performed after neutralization. When performing heat aging, it is preferable to carry out at 50-100 degreeC for 1 to 5 hours. Subsequently, the neutralized solution is washed. As the washing method, the method described in the first step can be exemplified, and among these, ultrafiltration is particularly preferable. Taking ultrafiltration as an example, the EC of the filtrate discharged out of the system is washed to about 500 μS / cm or less, so that the inorganic acid radical is reduced to 0.01 or less in molar ratio to rutile titanium oxide (TiO 2 ). Can be removed. More preferably, by washing until the filtrate EC is 50 μS / cm or less, not only inorganic acid radicals such as chlorine radicals and nitrate radicals, but also other ionic substances such as alkali metals such as Na + and K + and Free ammonia and the like can be removed to the limit of washing by ultrafiltration.
次に第４の工程では、第３の工程の無機酸根の除去後の溶液を、水溶性アミン化合物が存在する状態で加熱を行う。一般的には、第４の工程で水溶性アミン化合物を添加する態様が長期安定化の点で好ましい。但し、第１の工程でアルカリ水溶液としてアンモニアを使用した場合、又は、第３の工程においてアンモニアで中和した後、洗浄する方法を適用した場合は、第３の工程の後の溶液中にアンモニアが残存することがある。この残存アンモニア量は製造条件により異なるが、目安としてルチル型酸化チタン（TiO2）に対してモル比で0.1以下である。この残存アンモニア量を勘案して、最終的に得られる本発明のゾル中のルチル型酸化チタン（TiO2）に対してモル比で0.005〜0.5の範囲となるように水溶性アミン化合物の添加量を調整することが好ましい。前記モル比が0.005を下回ると分散安定化効果が充分に得られなくなる。本発明に於いては粒子が小さいため、前記モル比の上限は0.5で十分である。また、0.5を上回ると薄膜生成に好影響を及ぼさない場合がある。
一方、第３の工程の後の溶液中にアンモニアがルチル型酸化チタン（TiO2）に対しモル比で0.005以上残存している場合は、第４の工程で水溶性アミン化合物を添加しないことも態様の一つである。但し、当該態様においては安定なゾルが得られ難い場合があるため、加熱前のルチル型酸化チタン（TiO2）の濃度を低く設定することが好ましい。
Next, in the fourth step, the solution after removal of the inorganic acid radical in the third step is heated in a state where a water-soluble amine compound is present. In general, an embodiment in which a water-soluble amine compound is added in the fourth step is preferable in terms of long-term stabilization. However, when ammonia is used as the alkaline aqueous solution in the first step, or when a method of washing after neutralizing with ammonia in the third step is applied, ammonia in the solution after the third step is used. May remain. The amount of residual ammonia varies depending on the production conditions, but as a guide, it is 0.1 or less in molar ratio with respect to rutile-type titanium oxide (TiO 2 ). Taking this residual ammonia amount into account, the amount of water-soluble amine compound added so that the molar ratio is in the range of 0.005 to 0.5 with respect to the rutile-type titanium oxide (TiO 2 ) in the sol of the present invention finally obtained. Is preferably adjusted. When the molar ratio is less than 0.005, a sufficient dispersion stabilizing effect cannot be obtained. In the present invention, since the particles are small, the upper limit of the molar ratio is 0.5. On the other hand, if it exceeds 0.5, the thin film formation may not be positively affected.
On the other hand, when ammonia remains in a molar ratio of 0.005 or more with respect to rutile-type titanium oxide (TiO 2 ) in the solution after the third step, the water-soluble amine compound may not be added in the fourth step. This is one of the embodiments. However, in this embodiment, it may be difficult to obtain a stable sol, so it is preferable to set the concentration of rutile titanium oxide (TiO 2 ) before heating low.
本発明に用いる水溶性アミン化合物としては、本発明のゾルのpHをアルカリ性にできれば良く、第一級アミン、第二級アミン、第三級アミン、水酸化第四級アンモニウム、アンモニア等が挙げられる。第一級アミンとしては、例えば、メチルアミン、エチルアミン、ブチルアミン、モノエタノールアミン、イソプロパノールアミン等が挙げられる。第二級アミンとしては、例えば、ジメチルアミン、ジエチルアミン、ジエタノールアミン、ジイソプロパノールアミン等が挙げられる。第三級アミンとしては、例えば、トリメチルアミン、トリエタノールアミン、トリイソプロパノールアミン等が挙げられる。水酸化第四級アンモニウムとしては、例えば、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム、水酸化トリメチルプロピルアンモニウム、水酸化ジメチルジエチルアミン、コリン等が挙げられる。この中でも水酸化第四級アンモニウムとアンモニアが分散安定性の点から好適に使用できる。上記水酸化第四級アンモニウムの中でも、特に本発明のゾルの分散安定化に効果的であることと入手の容易性の点から水酸化テトラメチルアンモニウムとコリンを推奨することができる。 The water-soluble amine compound used in the present invention is not limited as long as the pH of the sol of the present invention can be made alkaline, and examples thereof include primary amines, secondary amines, tertiary amines, quaternary ammonium hydroxides, and ammonia. . Examples of the primary amine include methylamine, ethylamine, butylamine, monoethanolamine, and isopropanolamine. Examples of the secondary amine include dimethylamine, diethylamine, diethanolamine, diisopropanolamine and the like. Examples of the tertiary amine include trimethylamine, triethanolamine, triisopropanolamine and the like. Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylpropylammonium hydroxide, dimethyldiethylamine hydroxide, and choline. . Among these, quaternary ammonium hydroxide and ammonia can be preferably used from the viewpoint of dispersion stability. Among the above quaternary ammonium hydroxides, tetramethylammonium hydroxide and choline can be recommended particularly from the viewpoint of being effective for stabilizing the dispersion of the sol of the present invention and easy availability.
加熱温度は80〜150℃の範囲であることが好ましい。前記加熱温度の範囲において、平均分散粒子径15〜70nmのルチル型酸化チタンの微粒子が得られ易くなる。加熱時間は60〜600分が例示できる。 The heating temperature is preferably in the range of 80 to 150 ° C. In the range of the heating temperature, fine particles of rutile-type titanium oxide having an average dispersed particle diameter of 15 to 70 nm are easily obtained. An example of the heating time is 60 to 600 minutes.
また、必要に応じて、第４の工程の次に限外ろ過処理や加熱等により濃縮を行うことができる。限外ろ過処理する際には注水洗浄することで、残存する不純物、無機酸根、アルカリ金属をさらに除去することも可能である。この際、ルチル型酸化チタンゾルの分散に必要な分散剤も幾らか除去されるため、得られたゾルが不安定になる恐れがある。このような場合には水溶性アミン化合物を本発明の範囲内で追加添加することにより、長期に渡り安定化させることが可能である。 Further, if necessary, concentration can be performed by ultrafiltration treatment or heating after the fourth step. The remaining impurities, inorganic acid radicals and alkali metals can be further removed by washing with water when performing ultrafiltration. At this time, since the dispersant necessary for dispersing the rutile-type titanium oxide sol is also removed, the obtained sol may be unstable. In such a case, it is possible to stabilize over a long period of time by adding a water-soluble amine compound within the scope of the present invention.
次に第５の工程では、可視光照射下で光触媒性能を発現させるために、第４の工程で得られたルチル型酸化チタンゾルと、鉄化合物、銅化合物、白金化合物及びパラジウム化合物からなる群より選ばれた1種以上の遷移金属化合物（以下、「遷移金属化合物」と略す）とを混合し、遷移金属を担持させる。遷移金属化合物を混合する方法としては、第４の工程以前に遷移金属化合物を混合する方法、例えば、第３の工程の無機酸根の除去後の溶液に遷移金属化合物を混合し、水溶性アミン化合物の存在下で加熱する方法も一例として考えられる。しかしこの場合、遷移金属化合物存在下でルチル型酸化チタンが結晶成長するので、結晶格子内に遷移金属が取り込まれる傾向にあり、可視光領域の吸収は強くなるが光触媒性能は低下する傾向にある。従って、このような格子欠陥による光触媒性能の低下を引き起こすこと無く、可視光照射下で光触媒性能を発揮するためには、第４の工程までにおいてルチル型酸化チタンの結晶が充分に成長したゾルを得た後、該ゾルと遷移金属化合物とを混合し、遷移金属を担持させることが好適である。 Next, in the fifth step, from the group consisting of the rutile-type titanium oxide sol obtained in the fourth step and an iron compound, a copper compound, a platinum compound and a palladium compound in order to develop photocatalytic performance under visible light irradiation. One or more selected transition metal compounds (hereinafter abbreviated as “transition metal compounds”) are mixed to carry the transition metal. As a method for mixing the transition metal compound, a method in which the transition metal compound is mixed before the fourth step, for example, the transition metal compound is mixed in the solution after removal of the inorganic acid radical in the third step, and the water-soluble amine compound is mixed. A method of heating in the presence of is also considered as an example. However, in this case, since the rutile titanium oxide grows in the presence of the transition metal compound, the transition metal tends to be taken into the crystal lattice, and the absorption in the visible light region becomes strong, but the photocatalytic performance tends to decrease. . Therefore, in order to exhibit the photocatalytic performance under irradiation with visible light without causing the degradation of the photocatalytic performance due to such lattice defects, a sol in which crystals of rutile-type titanium oxide are sufficiently grown up to the fourth step is used. After being obtained, it is preferable to mix the sol and the transition metal compound to support the transition metal.
遷移金属化合物の種類としては、アルカリ性ルチル型酸化チタンゾルと混合した際に、粒子径の顕著な増大や沈降物の発生等の問題を起こさないものであれば特に限定されず、また2種以上の遷移金属化合物を使用してもよい。具体的な遷移金属化合物として下記のものを例示することができる（水和水の記載は省略）。 The type of transition metal compound is not particularly limited as long as it does not cause problems such as significant increase in particle size and generation of sediment when mixed with alkaline rutile titanium oxide sol. Transition metal compounds may be used. Specific examples of the transition metal compound include the following (the description of hydration water is omitted).
鉄化合物としては、塩化鉄（II）、酢酸鉄(II)、乳酸鉄(II)、シュウ酸鉄(II)、硫酸アンモニウム鉄(II)、硫酸鉄(II)、リン酸鉄(II)、鉄(II)アセチルアセトナート、塩化鉄(III)、硝酸鉄(III)、硫酸鉄(III)、リン酸鉄(III)、硫酸鉄(III)アンモニウム、ピロリン酸鉄(III)、クエン酸アンモニウム鉄（III）、シュウ酸鉄（III)アンモニウム、クエン酸鉄（III）、エチレンジアミン四酢酸鉄ナトリウム、鉄(III)アセチルアセトナート等が挙げられる。 Examples of iron compounds include iron (II) chloride, iron (II) acetate, iron (II) lactate, iron (II) oxalate, iron (II) ammonium sulfate, iron (II) sulfate, iron (II) phosphate, iron (II) Acetylacetonate, iron (III) chloride, iron (III) nitrate, iron (III) sulfate, iron (III) phosphate, iron (III) ammonium sulfate, iron (III) pyrophosphate, iron iron citrate (III), iron (III) oxalate ammonium, iron (III) citrate, sodium iron ethylenediaminetetraacetate, iron (III) acetylacetonate and the like.
銅化合物としては、塩化銅(I)、酸化銅(I)、塩化銅(II)、硝酸銅（II）、硫酸銅(II)、炭酸銅（II）、酸化銅（II）、水酸化銅（II）、塩化アンモニウム銅(II)、塩化カリウム銅（II）、ギ酸銅(II)、酢酸銅（II）、シュウ酸銅（II）、クエン酸銅(II)、エチレンジアミン四酢酸二ナトリウム銅、エチレンジアミン四酢酸二銅、銅（II）アセチルアセトナート等が挙げられる。 Copper compounds include copper chloride (I), copper oxide (I), copper chloride (II), copper nitrate (II), copper sulfate (II), copper carbonate (II), copper oxide (II), copper hydroxide (II), ammonium copper chloride (II), potassium copper chloride (II), copper formate (II), copper acetate (II), copper oxalate (II), copper citrate (II), ethylenediaminetetraacetic acid disodium copper , Ethylenediaminetetraacetic acid dicopper, copper (II) acetylacetonate, and the like.
白金化合物としては、塩化白金（II）カリウム、塩化白金酸（II）アンモニウム、塩化白金（II）ナトリウム、テトラシアノ白金（II）酸カリウム、塩化白金（IV）カリウム、塩化白金酸（IV）、塩化白金（IV）ナトリウム、塩化白金（IV）等が挙げられる。 Platinum compounds include potassium platinum (II) chloride, ammonium chloroplatinate (II), platinum (II) chloride, potassium tetracyanoplatinate (II), potassium platinum (IV) chloride, chloroplatinic acid (IV), chloride Examples include platinum (IV) sodium and platinum (IV) chloride.
パラジウム化合物としては、塩化パラジウム、塩化パラジウム(II)アンモニウム、塩化パラジウム(II)カリウム、塩化パラジウム(II)ナトリウム、酢酸パラジウム(II)、硝酸パラジウム(II)、パラジウム(II)アセチルアセトナート、ヘキサクロロパラジウム（IV）酸アンモニウム、ヘキサクロロパラジウム（IV）酸カリウム等が挙げられる。 Palladium compounds include palladium chloride, palladium (II) ammonium chloride, potassium palladium (II) chloride, sodium palladium (II) chloride, palladium (II) acetate, palladium (II) nitrate, palladium (II) acetylacetonate, hexachloro Examples include ammonium palladium (IV) and potassium hexachloropalladium (IV).
遷移金属化合物の量についていえば、可視光照射下で光触媒機能を発現する量であれば特に限定されないが、最終的に得られる本発明のゾルにおいて、遷移金属が酸化物換算で、ルチル型酸化チタン（TiO2）に対して0.01〜5質量％の範囲となるような量とすることが好ましい。上記範囲が0.01質量％未満の場合または5質量％を超える場合は、光触媒性能が低下する傾向になるので好ましくない。尚、上記酸化物換算において、各遷移金属の酸化物は、鉄がFe2O3、銅がCuO、白金がPtO2、パラジウムがPdOで表されるものである。 The amount of the transition metal compound is not particularly limited as long as it is an amount that exhibits a photocatalytic function under irradiation with visible light, but in the sol of the present invention finally obtained, the transition metal is converted into an oxide in the form of rutile oxidation. The amount is preferably in the range of 0.01 to 5% by mass with respect to titanium (TiO 2 ). If the above range is less than 0.01% by mass or more than 5% by mass, the photocatalytic performance tends to decrease, which is not preferable. In the above oxide conversion, each transition metal oxide is represented by Fe 2 O 3 for iron, CuO for copper, PtO 2 for platinum, and PdO for palladium.
遷移金属化合物の添加の形態については、遷移金属化合物が第４の工程で得られたアルカリ性ルチル型酸化チタンゾルに均一に溶解・分散すれば特に制限はなく、水溶液として添加しても固体のまま添加しても良い。 The transition metal compound is added in any form as long as the transition metal compound is uniformly dissolved and dispersed in the alkaline rutile titanium oxide sol obtained in the fourth step. You may do it.
以上の製造方法により本発明のゾルが得られる。尚、第５の工程では、遷移金属化合物を混合し、溶解・分散させるだけで、遷移金属がルチル型酸化チタンの表面に酸化物、水酸化物又は錯体の形態で担持されると推測される。この理由は、例えば、本発明のゾルを限外ろ過による洗浄を行っても、洗浄前後でゾル中の遷移金属量が蛍光X線分析ではほとんど変化しないためである。 The sol of the present invention is obtained by the above production method. In the fifth step, it is presumed that the transition metal is supported on the surface of the rutile titanium oxide in the form of an oxide, hydroxide or complex simply by mixing, dissolving and dispersing the transition metal compound. . This is because, for example, even when the sol of the present invention is washed by ultrafiltration, the amount of transition metal in the sol before and after washing hardly changes in the fluorescent X-ray analysis.
本発明のゾルは可視光照射下においても光触媒機能を発現するが、第５の工程の後にさらに加熱を行うことにより、担持状態がさらに最適化され、光触媒性能が高まる傾向にある。加熱の条件は、遷移金属がルチル型酸化チタンの結晶格子に取り込まれず、且つ、ルチル型酸化チタン表面に強固に担持される温度で行われるのが好ましく、例えば40〜100℃の範囲が挙げられる。100℃を超えて加熱すると、ルチル型酸化チタンの結晶格子中に遷移金属が取り込まれることがあり、光触媒性能が低下する恐れがあるので好ましくない。 The sol of the present invention exhibits a photocatalytic function even under irradiation with visible light, but further heating after the fifth step tends to further optimize the supported state and increase the photocatalytic performance. The heating is preferably performed at a temperature at which the transition metal is not taken into the crystal lattice of the rutile type titanium oxide and is firmly supported on the surface of the rutile type titanium oxide, for example, in the range of 40 to 100 ° C. . Heating above 100 ° C. is not preferable because a transition metal may be taken into the crystal lattice of rutile-type titanium oxide and the photocatalytic performance may be lowered.
以上の工程で得られた遷移金属担持アルカリ性ルチル型酸化チタンゾルは、遷移金属化合物の添加に伴う副生塩やルチル型酸化チタン表面に担持されなかった遷移金属を除去するために洗浄を行っても良い。洗浄方法は上記第１の工程に記載した方法を例示することができ、このうち限外ろ過が特に好ましい。洗浄程度は適宜設定すれば良いが、概ね洗浄ろ液のECが500μS/cm〜30μS/cmとなるまで洗浄することが好ましい。 The transition metal-supported alkaline rutile titanium oxide sol obtained in the above steps can be washed to remove by-product salts accompanying the addition of transition metal compounds and transition metals not supported on the rutile titanium oxide surface. good. As the washing method, the method described in the first step can be exemplified, and among these, ultrafiltration is particularly preferable. The degree of washing may be set as appropriate, but washing is preferably performed until the EC of the washing filtrate is approximately 500 μS / cm to 30 μS / cm.
以下、本発明の遷移金属担持アルカリ性ルチル型酸化チタンゾルについて詳細に説明する。
本発明のゾルは、上記のように遷移金属がルチル型酸化チタンに担持されていると考えられるが、一部に担持されていない遷移金属を含有したものであっても構わない。しかし、担持されていない遷移金属は光触媒機能の向上に対する寄与度が低いため、遷移金属のほぼ全量が担持されていることが好ましく、例えば、遷移金属の含有量が、酸化物換算で、ルチル型酸化チタン（TiO2）に対し、0.01〜5質量％の範囲である。また、上記のように、水溶性アミン化合物の含有量がルチル型酸化チタン（TiO2）に対し、モル比で0.005〜0.5の範囲であることが好ましい。
Hereinafter, the transition metal-supported alkaline rutile titanium oxide sol of the present invention will be described in detail.
The sol of the present invention is considered that the transition metal is supported on the rutile type titanium oxide as described above, but may contain a transition metal not supported on a part thereof. However, since the unsupported transition metal has a low contribution to the improvement of the photocatalytic function, it is preferable that almost all of the transition metal is supported. For example, the content of the transition metal is a rutile type in terms of oxide. to titanium oxide (TiO 2), it is in the range of 0.01 to 5 mass%. Further, as described above, with respect to content rutile type titanium oxide water-soluble amine compound (TiO 2), it is preferably in the range of 0.005 to 0.5 molar ratio.
本発明のゾルはアルカリ性であるが、pHで示すと概ね8以上であることが好ましく、さらに好ましくはpH9.5〜13.0の範囲である。 Although the sol of the present invention is alkaline, it is preferably about 8 or more in terms of pH, and more preferably in the range of pH 9.5 to 13.0.
本発明のゾルの酸化チタンの結晶構造は、ゾルを100℃で乾燥させた後、粉末Ｘ線回折によって分析すると、チタンの結晶構造に関してはルチル型構造に由来するピークのみが検出されるので、実質的にルチル型のみがゾル中に含まれる。 Since the crystal structure of titanium oxide in the sol of the present invention is analyzed by powder X-ray diffraction after the sol is dried at 100 ° C., only the peak derived from the rutile structure is detected with respect to the crystal structure of titanium. Substantially only the rutile form is included in the sol.
本発明のゾルにおけるルチル型酸化チタンの比表面積について云えば、40〜250m2/gであることが好ましい。前記比表面積が40m2/gを下回ると、分散剤の吸着点が減少することでやや分散性が低下し、保存中に沈殿が生じやすくなる。一方、前記比表面積が250m2/gを上回ると、ルチル型酸化チタンの結晶化が不十分なために凝集し易くなり、また、光触媒活性を低下させる傾向がある。前記比表面積のより好ましい範囲は、60〜230m2/gである。 The specific surface area of the rutile titanium oxide in the sol of the present invention is preferably 40 to 250 m 2 / g. When the specific surface area is less than 40 m 2 / g, the adsorption point of the dispersant is decreased, so that the dispersibility is slightly lowered and precipitation is likely to occur during storage. On the other hand, when the specific surface area exceeds 250 m 2 / g, the rutile titanium oxide is not sufficiently crystallized, so that it tends to aggregate and the photocatalytic activity tends to decrease. A more preferable range of the specific surface area is 60 to 230 m 2 / g.
また、本発明のゾルにおけるルチル型酸化チタンの平均分散粒子径は、15〜70nmの範囲であることが好ましい。前記平均分散粒子径は、（株）堀場製作所製「動的光散乱式粒径分布測定装置 LB-500」で測定した際のメジアン径である。本発明のゾルの平均分散粒子径が前記範囲にあれば、とりわけゾルとして安定に分散し、また塗布した場合には平滑で透明な薄膜を得ることができる。前記平均分散粒子径の範囲は、15〜60nmの範囲であることがより好ましい。 Further, the average dispersed particle diameter of the rutile type titanium oxide in the sol of the present invention is preferably in the range of 15 to 70 nm. The average dispersed particle diameter is a median diameter as measured by “Dynamic Light Scattering Particle Size Distribution Measuring Device LB-500” manufactured by Horiba, Ltd. When the average dispersed particle size of the sol of the present invention is in the above range, a smooth and transparent thin film can be obtained particularly when the sol is stably dispersed as a sol. The range of the average dispersed particle size is more preferably in the range of 15 to 60 nm.
本発明のゾルを塗布した場合、平滑で透明な薄膜が得られ易い。例えば、TiO2濃度が3質量％である本発明のゾルをガラス板にスピンコートし（1000rpm、10秒）、105℃で5分乾燥させた薄膜のHazeを日本電色工業（株）製 ヘーズメーター COH400で測定した場合に、Hazeは大略5％以下となる。Hazeは塗膜の濁りを示すものであり、その値が小さいほど透明、平滑な薄膜であるといえる。 When the sol of the present invention is applied, a smooth and transparent thin film is easily obtained. For example, a sol of the present invention having a TiO 2 concentration of 3% by mass is spin-coated on a glass plate (1000 rpm, 10 seconds), and dried at 105 ° C. for 5 minutes. A thin film Haze is produced by Nippon Denshoku Industries Co., Ltd. When measured with the meter COH400, Haze is approximately 5% or less. Haze indicates the turbidity of the coating film. The smaller the value, the clearer and smoother the film is.
本発明のゾルを乾燥させて得られる粉末及び薄膜は、可視光照射下で光触媒機能を発揮する。乾燥条件については、担持した遷移金属が酸化チタンの結晶格子内にドーピングされない温度であれば良く、目安として室温から400℃を例示できる。 The powder and thin film obtained by drying the sol of the present invention exhibit a photocatalytic function under visible light irradiation. The drying condition may be any temperature at which the supported transition metal is not doped in the crystal lattice of titanium oxide, and examples include room temperature to 400 ° C.
また、本発明のゾルは、通常TiO2として2〜20質量％で製造されることが望ましい。2質量％未満は塗布液として利用するのに十分な濃度とはいい難く、製造上、輸送上も経済的でない。一方、20質量％を超えると粘度が高くなり、ハンドリング性が損なわれるため好ましくない。通常は5〜15質量％程度で製造、利用することが好ましい。 Moreover, it is desirable that the sol of the present invention is usually produced at 2 to 20% by mass as TiO 2 . If it is less than 2% by mass, it is difficult to say that the concentration is sufficient for use as a coating solution, and it is not economical in terms of production and transportation. On the other hand, if it exceeds 20% by mass, the viscosity becomes high and handling properties are impaired, which is not preferable. Usually, it is preferable to manufacture and use at about 5 to 15% by mass.
本発明のゾルは、水を分散媒としたものであるが、水溶媒を有機溶媒で置換することにより、有機溶媒分散型ゾルとすることもできる。有機溶媒としては、メタノール、エタノール、イソプロパノール等のアルコール類、テトラヒドロフラン、ジエチルエーテル等のエーテル類、2-メトキシプロパノール、2-n-ブトキシエタノール等のセロソルブ類、メチルエチルケトン、メチルイソブチルケトン等のケトン類やホルムアミド、ジメチルスルホキシド等が例示できる。 The sol of the present invention uses water as a dispersion medium, but an organic solvent-dispersed sol can also be obtained by replacing the aqueous solvent with an organic solvent. Examples of the organic solvent include alcohols such as methanol, ethanol and isopropanol; ethers such as tetrahydrofuran and diethyl ether; cellosolves such as 2-methoxypropanol and 2-n-butoxyethanol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; Examples include formamide and dimethyl sulfoxide.
また、本発明のゾルは、アルカリ性の水系バインダーと混合して均一分散させることが可能であり、珪酸ナトリウム、珪酸リチウム、珪酸カリウム、炭酸ジルコニルアンモニウム、アルカリ性のシリカゾル、シリコンアルコキシド、シランカップリング剤等がその好例として挙げられる。しかし、その他の中性、酸性バインダーであってもゾル状態を維持することができる範囲内でこれを使用することができる。 Further, the sol of the present invention can be mixed and dispersed uniformly with an alkaline aqueous binder, such as sodium silicate, lithium silicate, potassium silicate, zirconyl ammonium carbonate, alkaline silica sol, silicon alkoxide, silane coupling agent, etc. Is a good example. However, other neutral and acidic binders can be used as long as the sol state can be maintained.
本発明のゾルを基材表面に被覆することにより可視光応答型光触媒部材とすることができる。基材は特に制限されるものではなく、例えば、金属、セラミックス、タイル、プラスチック等が挙げられる。被覆方法は、公知の方法を用いればよく、例えば、塗布による被覆後に乾燥させることが一例として挙げられる。 By coating the surface of the substrate with the sol of the present invention, a visible light responsive photocatalytic member can be obtained. The substrate is not particularly limited, and examples thereof include metals, ceramics, tiles, and plastics. As the coating method, a known method may be used. For example, drying after coating by coating is an example.
以下、本発明の詳細を実施例を挙げて説明するが、本発明はそれらの実施例によって限定されるものではない。尚、特に断らない限り％は全て質量％を示す。また、各実施例及び比較例におけるゾルの作製では、超音波処理、限外ろ過洗浄処理を除いて、基本的には撹拌下において操作を行うものとする。 EXAMPLES Hereinafter, although an Example is given and the detail of this invention is demonstrated, this invention is not limited by those Examples. In addition, unless otherwise indicated, all% shows the mass%. Moreover, in preparation of sol in each Example and a comparative example, fundamentally, operation is performed under stirring except for ultrasonic treatment and ultrafiltration washing treatment.
［実施例1］
3.2％水酸化ナトリウム水溶液20722gにオキシ塩化チタン水溶液（TiO2=27.4％、Cl=32.7％）1200gをローラーポンプを用いて30分かけて添加した。得られた水和酸化チタンゲルのpHは13.1であった。これを限外ろ過洗浄し、ろ液ECが1.0mS/cmになるまで洗浄を行い、洗浄水和酸化チタンゲルを得た（TiO2=4.5％、pH11.1、EC 1.2mS/cm）。この洗浄水和酸化チタンゲル4000gに純水220gと35％塩酸を282g添加した（pH0.4）。この溶液を60℃に加温し30分経過した時点で18％アンモニア水溶液をpH8.0になるまで添加した後、これを95℃に加温し2時間加熱した。これを限外ろ過洗浄し、ろ液ECが35μS/cmになるまで洗浄を行い、ルチル型結晶構造を持つ酸化チタンゲルを得た（TiO2=10.5％、pH8.1、EC 0.56mS/cm、比表面積275m2/g）。この酸化チタンゲル1600gに25％水酸化テトラメチルアンモニウム（以下、「TMAH」という）23.0gを添加し、120℃で5時間加熱することでアルカリ性ルチル型酸化チタンゾルを得た（TiO2=10.4％、TMAH/TiO2(モル比)=0.03、NH3/TiO2（モル比）=0.04、Cl/TiO2(モル比)=0.0004、Na/TiO2(モル比)=0.02、pH12.2、平均分散粒子径36nm、比表面積80m2/g）。このアルカリ性ルチル型酸化チタンゾル100gに水酸化銅(II)を0.013g添加し溶解・分散させることで銅担持アルカリ性ルチル型酸化チタンゾルを得た。
上記で得られたゾルにおける銅の担持状態を調べるために、該ゾルを限外ろ過による洗浄を行い、洗浄前後の銅含量を蛍光X線分析により調査した。その結果、洗浄前後で銅含量に変化が無いことを確認した。
[Example 1]
1200 g of titanium oxychloride aqueous solution (TiO 2 = 27.4%, Cl = 32.7%) was added to 20722 g of 3.2% sodium hydroxide aqueous solution over 30 minutes using a roller pump. The pH of the obtained hydrated titanium oxide gel was 13.1. This was subjected to ultrafiltration washing, and washing was performed until the filtrate EC reached 1.0 mS / cm, to obtain a washed hydrated titanium oxide gel (TiO 2 = 4.5%, pH 11.1, EC 1.2 mS / cm). To 4000 g of this washed hydrated titanium oxide gel, 220 g of pure water and 282 g of 35% hydrochloric acid were added (pH 0.4). When this solution was heated to 60 ° C. and 30 minutes passed, an 18% aqueous ammonia solution was added until pH 8.0, and then this was heated to 95 ° C. and heated for 2 hours. This was subjected to ultrafiltration washing, and washing was performed until the filtrate EC became 35 μS / cm to obtain a titanium oxide gel having a rutile crystal structure (TiO 2 = 10.5%, pH 8.1, EC 0.56 mS / cm, Specific surface area 275 m 2 / g). To 1600 g of this titanium oxide gel, 23.0 g of 25% tetramethylammonium hydroxide (hereinafter referred to as “TMAH”) was added and heated at 120 ° C. for 5 hours to obtain an alkaline rutile type titanium oxide sol (TiO 2 = 10.4%, TMAH / TiO 2 (molar ratio) = 0.03, NH 3 / TiO 2 (molar ratio) = 0.04, Cl / TiO 2 (molar ratio) = 0.0004, Na / TiO 2 (molar ratio) = 0.02, pH 12.2, average (Dispersed particle size 36 nm, specific surface area 80 m 2 / g). To 100 g of this alkaline rutile type titanium oxide sol, 0.013 g of copper hydroxide (II) was added and dissolved and dispersed to obtain a copper supported alkaline rutile type titanium oxide sol.
In order to investigate the copper loading state in the sol obtained above, the sol was washed by ultrafiltration, and the copper content before and after washing was examined by fluorescent X-ray analysis. As a result, it was confirmed that there was no change in the copper content before and after washing.
［実施例2］
実施例1のアルカリ性ルチル型酸化チタンゾル100gに酸化銅(I)を0.009g添加し溶解・分散させることで銅担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 2]
To 100 g of the alkaline rutile type titanium oxide sol of Example 1, 0.009 g of copper oxide (I) was added and dissolved and dispersed to obtain a copper-supporting alkaline rutile type titanium oxide sol.
［実施例3］
実施例1のアルカリ性ルチル型酸化チタンゾル100gに塩化鉄(III)水溶液（Fe2O3濃度=5%）を0.21g添加し、超音波処理により鉄担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 3]
0.21 g of an iron (III) chloride aqueous solution (Fe 2 O 3 concentration = 5%) was added to 100 g of the alkaline rutile titanium oxide sol of Example 1, and an iron-supported alkaline rutile titanium oxide sol was obtained by ultrasonic treatment.
［実施例4］
実施例1のアルカリ性ルチル型酸化チタンゾル100gにシュウ酸鉄(III)アンモニウム・3水和物を0.056g添加し溶解・分散させることで鉄担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 4]
0.056 g of iron (III) ammonium oxalate trihydrate was added to 100 g of the alkaline rutile type titanium oxide sol of Example 1 and dissolved and dispersed to obtain an iron-supported alkaline rutile type titanium oxide sol.
［実施例5］
実施例1のアルカリ性ルチル型酸化チタンゾル100gに塩化パラジウム(II)を0.015g添加し、超音波処理によりパラジウム担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 5]
0.015 g of palladium (II) chloride was added to 100 g of the alkaline rutile type titanium oxide sol of Example 1, and a palladium-supported alkaline rutile type titanium oxide sol was obtained by ultrasonic treatment.
［実施例6］
実施例1のアルカリ性ルチル型酸化チタンゾル100gに塩化白金(IV)酸・6水和物を0.024g添加し、超音波処理により白金担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 6]
0.024 g of chloroplatinic acid (IV) hexahydrate was added to 100 g of the alkaline rutile-type titanium oxide sol of Example 1, and platinum-supported alkaline rutile-type titanium oxide sol was obtained by ultrasonic treatment.
［実施例7］
実施例1のアルカリ性ルチル型酸化チタンゾル100gに水酸化銅(II)を0.064g添加し溶解・分散させることで銅担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 7]
By adding 0.064 g of copper (II) hydroxide to 100 g of the alkaline rutile type titanium oxide sol of Example 1, and dissolving and dispersing it, a copper-supporting alkaline rutile type titanium oxide sol was obtained.
［実施例8］
実施例1のアルカリ性ルチル型酸化チタンゾル100gに水酸化銅(II)を0.128g添加し溶解・分散させることで銅担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 8]
To 100 g of the alkaline rutile type titanium oxide sol of Example 1, 0.128 g of copper hydroxide (II) was added and dissolved and dispersed to obtain a copper-supporting alkaline rutile type titanium oxide sol.
［実施例9］
実施例1のアルカリ性ルチル型酸化チタンゾル100gに水酸化銅(II)を0.013g添加した後、90℃で1時間加熱することで銅担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 9]
After adding 0.013 g of copper (II) hydroxide to 100 g of the alkaline rutile type titanium oxide sol of Example 1, copper-supported alkaline rutile type titanium oxide sol was obtained by heating at 90 ° C. for 1 hour.
［実施例10］
実施例1のアルカリ性ルチル型酸化チタンゾル100gに水酸化銅(II)を0.013g添加した後、90℃で1時間加熱した。これをろ液ECが0.1mS/cmになるまで限外ろ過洗浄することで銅担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 10]
After adding 0.013 g of copper hydroxide (II) to 100 g of the alkaline rutile type titanium oxide sol of Example 1, it was heated at 90 ° C. for 1 hour. This was subjected to ultrafiltration washing until the filtrate EC became 0.1 mS / cm to obtain a copper-supporting alkaline rutile titanium oxide sol.
［実施例11］
実施例1のアルカリ性ルチル型酸化チタンゾル100gにシュウ酸鉄(III)アンモニウム・3水和物を0.056g添加した後、90℃で1時間加熱した。これをろ液ECが0.1mS/cmになるまで限外ろ過洗浄することで鉄担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 11]
After adding 0.056 g of iron (III) ammonium oxalate trihydrate to 100 g of the alkaline rutile type titanium oxide sol of Example 1, the mixture was heated at 90 ° C. for 1 hour. This was subjected to ultrafiltration washing until the filtrate EC became 0.1 mS / cm to obtain an iron-supported alkaline rutile titanium oxide sol.
［実施例12］
実施例1の洗浄水和酸化チタンゲル800gに純水1756gと35％塩酸を56.3g添加した（pH0.8）。この溶液を60℃に加温し30分経過した時点で18％アンモニア水溶液をpH8.0になるまで添加し、室温まで放冷した。これを限外ろ過洗浄し、ろ液ECが35μS/cmになるまで洗浄を行い、ルチル型結晶構造を持つ酸化チタンゲルを得た（TiO2=6.5％、pH7.5、EC 0.49mS/cm、比表面積305m2/g）。この酸化チタンゲル300gを120℃で5時間加熱することでアルカリ性ルチル型酸化チタンゾルを得た（TiO2=6.5％、NH3/TiO2(モル比)=0.04、Cl/TiO2(モル比)=0.0004、Na/TiO2(モル比)=0.02、pH10.7、平均分散粒子径32nm、比表面積120m2/g）。このアルカリ性ルチル型酸化チタンゾル200gに水酸化銅(II)を0.016g添加し溶解・分散させることで銅担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 12]
1756 g of pure water and 56.3 g of 35% hydrochloric acid were added to 800 g of the washed and hydrated titanium oxide gel of Example 1 (pH 0.8). When this solution was heated to 60 ° C. and 30 minutes passed, an 18% aqueous ammonia solution was added until the pH reached 8.0, and the mixture was allowed to cool to room temperature. This was subjected to ultrafiltration washing, and washing was performed until the filtrate EC became 35 μS / cm to obtain a titanium oxide gel having a rutile crystal structure (TiO 2 = 6.5%, pH 7.5, EC 0.49 mS / cm, Specific surface area of 305 m 2 / g). An alkaline rutile type titanium oxide sol was obtained by heating 300 g of this titanium oxide gel at 120 ° C. for 5 hours (TiO 2 = 6.5%, NH 3 / TiO 2 (molar ratio) = 0.04, Cl / TiO 2 (molar ratio)) = 0.0004, Na / TiO 2 (molar ratio) = 0.02, pH 10.7, average dispersed particle size 32 nm, specific surface area 120 m 2 / g). To 200 g of this alkaline rutile type titanium oxide sol, 0.016 g of copper (II) hydroxide was added and dissolved and dispersed to obtain a copper-supported alkaline rutile type titanium oxide sol.
［実施例13］
実施例1の洗浄水和酸化チタンゲル1000gに純水430gと35％塩酸を70.4g添加した（pH0.6）。この溶液を60℃に加温し100分経過した時点で18％アンモニア水溶液をpH5.5になるまで添加し、室温まで放冷した。これをろ液ECが35μS/cmになるまで限外ろ過洗浄し、ルチル型結晶構造を持つ酸化チタンゲルを得た（TiO2=6.5％、pH7.5、EC 0.33mS/cm、比表面積305m2/g）。この酸化チタンゲル300gに25％TMAH 2.7gを添加し、90℃で5時間加熱することでアルカリ性ルチル型酸化チタンゾルを得た（TiO2=6.4％、TMAH/TiO2(モル比）=0.03、NH3/TiO2（モル比）=0.001、Cl/TiO2(モル比)=0.0011、Na/TiO2(モル比)=0.002、pH10.8、平均分散粒子径24nm、比表面積198m2/g）。このアルカリ性ルチル型酸化チタンゾル200gに水酸化銅(II)を0.015g添加し溶解・分散させることで銅担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 13]
To 1000 g of the washed and hydrated titanium oxide gel of Example 1, 430 g of pure water and 70.4 g of 35% hydrochloric acid were added (pH 0.6). When this solution was heated to 60 ° C. and 100 minutes had passed, an 18% aqueous ammonia solution was added until pH 5.5, and the mixture was allowed to cool to room temperature. This was subjected to ultrafiltration washing until the filtrate EC became 35 μS / cm to obtain a titanium oxide gel having a rutile crystal structure (TiO 2 = 6.5%, pH 7.5, EC 0.33 mS / cm, specific surface area 305 m 2). / g). 2.7 g of 25% TMAH was added to 300 g of this titanium oxide gel, and an alkaline rutile type titanium oxide sol was obtained by heating at 90 ° C. for 5 hours (TiO 2 = 6.4%, TMAH / TiO 2 (molar ratio) = 0.03, NH) 3 / TiO 2 (molar ratio) = 0.001, Cl / TiO 2 (molar ratio) = 0.0011, Na / TiO 2 (molar ratio) = 0.002, pH 10.8, average dispersed particle size 24 nm, specific surface area 198 m 2 / g) . To 200 g of this alkaline rutile titanium oxide sol, 0.015 g of copper hydroxide (II) was added and dissolved and dispersed to obtain a copper-supporting alkaline rutile titanium oxide sol.
[実施例14]
実施例13のルチル型結晶構造を持つ酸化チタンゲル300gに50%トリイソプロパノールアミン（以下、「TIPA」という）を3.4g添加した後、120℃で3時間加熱することでアルカリ性ルチル型酸化チタンゾルを得た（TiO2=6.4％、TIPA/TiO2(モル比)=0.03、NH3/TiO2（モル比）=0.001、Cl/TiO2(モル比)=0.0011、Na/TiO2(モル比)=0.002、pH10.0、平均分散粒子径40nm、比表面積80m2/g）。このアルカリ性ルチル型酸化チタンゾル200gに水酸化銅(II)を0.015g添加し、撹拌下で90℃1時間加熱した。これをろ液ECが0.1mS/cmになるまで限外ろ過洗浄することで銅担持アルカリ性ルチル型酸化チタンゾルを得た。
[Example 14]
After adding 3.4 g of 50% triisopropanolamine (hereinafter referred to as “TIPA”) to 300 g of the titanium oxide gel having the rutile crystal structure of Example 13, an alkaline rutile titanium oxide sol was obtained by heating at 120 ° C. for 3 hours. (TiO 2 = 6.4%, TIPA / TiO 2 (molar ratio) = 0.03, NH 3 / TiO 2 (molar ratio) = 0.001, Cl / TiO 2 (molar ratio) = 0.0011, Na / TiO 2 (molar ratio)) = 0.002, pH 10.0, average dispersed particle size 40 nm, specific surface area 80 m 2 / g). To 200 g of this alkaline rutile type titanium oxide sol, 0.015 g of copper (II) hydroxide was added and heated at 90 ° C. for 1 hour with stirring. This was subjected to ultrafiltration washing until the filtrate EC became 0.1 mS / cm to obtain a copper-supporting alkaline rutile titanium oxide sol.
［比較例1］
実施例1のアルカリ性ルチル型酸化チタンゾル100gに塩化コバルト(II)水溶液（CoO濃度=5%）0.21g添加した後、撹拌、超音波処理しゾルを得た。
[Comparative Example 1]
After adding 0.21 g of cobalt (II) chloride aqueous solution (CoO concentration = 5%) to 100 g of the alkaline rutile type titanium oxide sol of Example 1, stirring and ultrasonic treatment were performed to obtain a sol.
［比較例2］
実施例1のアルカリ性ルチル型酸化チタンゾル100gに塩化マンガン(II)水溶液（MnO濃度=5%）0.21g添加した後、撹拌、超音波処理しゾルを得た。
[Comparative Example 2]
After adding 0.21 g of an aqueous manganese (II) chloride solution (MnO concentration = 5%) to 100 g of the alkaline rutile type titanium oxide sol of Example 1, stirring and ultrasonic treatment were performed to obtain a sol.
［比較例3］
実施例1の洗浄水和酸化チタンゲル800gに純水44gと35％塩酸を56.3g添加した（pH0.5）。この溶液を60℃に加温し30分経過した時点で10％水酸化ナトリウム水溶液をpH5.5になるまで添加した。これを限外ろ過洗浄し、ろ液ECが35μS/cmになるまで洗浄を行い、ルチル型結晶構造を持つ酸化チタンゲルを得た（TiO2=6.5％、pH7.2、EC 0.35mS/cm、比表面積310m2/g）。この酸化チタンゲル300gを120℃で5時間水熱処理したが、得られた溶液は粘度が高くスラリー状の外観であり、ゾルは得られなかった。
[Comparative Example 3]
44 g of pure water and 56.3 g of 35% hydrochloric acid were added to 800 g of the washed and hydrated titanium oxide gel of Example 1 (pH 0.5). When this solution was heated to 60 ° C. and 30 minutes passed, a 10% aqueous sodium hydroxide solution was added until the pH reached 5.5. This was subjected to ultrafiltration washing and washing until the filtrate EC became 35 μS / cm to obtain a titanium oxide gel having a rutile crystal structure (TiO 2 = 6.5%, pH 7.2, EC 0.35 mS / cm, Specific surface area 310 m 2 / g). Although 300 g of this titanium oxide gel was hydrothermally treated at 120 ° C. for 5 hours, the resulting solution had a high viscosity and a slurry-like appearance, and no sol was obtained.
［比較例4］
実施例1のアルカリ性ルチル型酸化チタンゾルを用いた。即ち、このゾルは遷移金属化合物を添加していないものである。
[Comparative Example 4]
The alkaline rutile type titanium oxide sol of Example 1 was used. That is, this sol does not contain a transition metal compound.
［比較例5］
純水95gとルチル型酸化チタン粉末（(株)高純度化学製）5gと25%TMAH 0.68gを混合し、120℃で5時間水熱処理を行ったが、ゾルは得られなかった。
[Comparative Example 5]
Although 95 g of pure water, 5 g of rutile type titanium oxide powder (manufactured by Kojun Chemical Co., Ltd.) and 0.68 g of 25% TMAH were mixed and hydrothermally treated at 120 ° C. for 5 hours, no sol was obtained.
[比較例6]
純水95gとルチル型酸化チタン粉末（(株)高純度化学製）5gに塩化鉄(III)水溶液（Fe2O3濃度=5%）0.1gと25%TMAH 0.68gを混合し、120℃で5時間水熱処理したが、ゾルは得られなかった。
[Comparative Example 6]
Mixing 95 g of pure water and 5 g of rutile titanium oxide powder (manufactured by Kojun Chemical Co., Ltd.) with 0.1 g of iron (III) chloride aqueous solution (Fe 2 O 3 concentration = 5%) and 0.68 g of 25% TMAH, 120 ° C However, no sol was obtained.
[参考例]
多木化学(株)製アナターゼ型酸化チタンゾル「タイノック A-6」を用いた。
[Reference example]
Anatase-type titanium oxide sol “Tynoch A-6” manufactured by Taki Chemical Co., Ltd. was used.
〈分析〉
以下、「ゾル」とは上記各実施例、比較例で最終的に得られたゾル、及び参考例のゾルのことをいう。
<analysis>
Hereinafter, “sol” refers to the sol finally obtained in each of the above Examples and Comparative Examples, and the sol of Reference Example.
[結晶構造]
結晶構造は、ゾルを100℃で乾燥させたものを(株)島津製作所製 Ｘ線回折装置 XRD-7000で測定して解析した。
その結果、実施例1〜14及び比較例1〜6のいずれにおいてもルチル型酸化チタンの結晶構造が認められた。
代表例として、実施例１の銅担持アルカリ性ルチル型酸化チタンゾルのXRDパターンを図１に示した。
[Crystal structure]
The crystal structure was analyzed by measuring a sol dried at 100 ° C. with an X-ray diffractometer XRD-7000 manufactured by Shimadzu Corporation.
As a result, in any of Examples 1 to 14 and Comparative Examples 1 to 6, a crystal structure of rutile-type titanium oxide was observed.
As a representative example, an XRD pattern of the copper-supported alkaline rutile titanium oxide sol of Example 1 is shown in FIG.
[アンモニア量]
ゾルのアンモニア量をTecator社製 ケルダール自動蒸留滴定装置 ケルテック 2300により測定した。
[Ammonia amount]
The amount of ammonia in the sol was measured with a Kjeldahl automatic distillation titrator, Keltec 2300, manufactured by Tecator.
[炭素を含有した水溶性アミン量]
炭素を含有した水溶性アミン、即ちTMAH及びTIPAを用いて作製したゾルについては、島津製作所製 全有機体炭素計 TOC-Vを用いて全有機炭素量 TOC（％）を測定し、下式からルチル型酸化チタン(TiO2)に対する水溶性アミンのモル比を計算した。
（式） 水溶性アミン/TiO2（モル比）＝｛TOC÷(水溶性アミンの炭素数×12)｝÷(TiO2濃度÷80）
[Amount of water-soluble amine containing carbon]
For sols made using carbon-containing water-soluble amines, ie TMAH and TIPA, the total organic carbon content TOC (%) was measured using the TOC-V total organic carbon meter manufactured by Shimadzu Corporation. The molar ratio of water-soluble amine to rutile titanium oxide (TiO 2 ) was calculated.
(Formula) Water-soluble amine / TiO 2 (Molar ratio) = {TOC ÷ (Carbon number of water-soluble amine × 12)} ÷ (TiO 2 concentration ÷ 80)
[遷移金属の含有量]
ゾルを300℃で乾燥させた後、フィリップス製 蛍光Ｘ線分析装置 PW-2400により測定した。
[Transition metal content]
The sol was dried at 300 ° C. and then measured with a fluorescent X-ray analyzer PW-2400 manufactured by Philips.
[平均分散粒子径]
ゾルをTiO2濃度1％に希釈した後、(株)堀場製作所製 動的光散乱色粒度分布測定装置 LB-500により測定した。
[Average dispersion particle size]
The sol was diluted to a TiO 2 concentration of 1%, and then measured with a dynamic light scattering color particle size distribution analyzer LB-500 manufactured by Horiba, Ltd.
[比表面積]
ゾル中の粒子の比表面積は、日本ベル(株)製 高精度比表面積・細孔分布測定装置 BELSORP-miniにより測定し、ＢＥＴ法で解析することで求めた。
[Specific surface area]
The specific surface area of the particles in the sol was determined by measuring with a high precision specific surface area / pore distribution measuring device BELSORP-mini manufactured by Nippon Bell Co., Ltd. and analyzing by the BET method.
[塗膜Haze]
ゾルを純水でTiO2濃度3％に希釈した後、それをガラス基板上に1000rpmで10秒間スピンコートした。これを105℃で5分乾燥させた後、その薄膜のHazeを日本電色工業（株）製 ヘーズメーター COH400で測定した。
[Coating Haze]
After the sol was diluted with pure water to a TiO 2 concentration of 3%, it was spin-coated on a glass substrate at 1000 rpm for 10 seconds. After drying this at 105 ° C. for 5 minutes, Haze of the thin film was measured with a haze meter COH400 manufactured by Nippon Denshoku Industries Co., Ltd.
[光触媒性能(可視光)]
アセトアルデヒドの分解試験にて評価を行った。
先ず、ゾルを100℃で乾燥して得られた乾燥粉0.5gを直径2.5cmの円盤容器に平らに載せた。この円盤容器をセパラブルフラスコ(容量1900ml)の所定の位置にセットし、蓋を閉じた。そこにアセトアルデヒドガス（465ppm）を25秒間流し込み（初期値約80ppmとなるように設定）、容器内の撹拌羽根を回転させた状態で20分間放置した。その後、初期の容器内アセトアルデヒド濃度を検知管（ガステック 92M）で測定した。
次に、紫外線カットフィルターを通した蛍光灯光を照射し（サンプル位置で約1mW/cm2(405nm)）、上記検知管で1時間ごとに3時間後までのアセトアルデヒド濃度測定を行った。
検知管による測定では、密閉容器1900mlから検知管を装着した検知器で100mlのガスを引き抜くことで測定が行われ、その後大気開放することで減圧を解除する。この際、ガス濃度が低下するので、式1で補正した。
（式1） アセトアルデヒド濃度（ppm）＝アセトアルデヒド測定値（ppm）×0.95n (nは測定回数)
また、分解性能を示す指標として式2からアセトアルデヒド減少率を計算した。
（式2）アセトアルデヒド減少率（ppm/h）＝−{（照射3時間後のアセトアルデヒド濃度−初期のアセトアルデヒド濃度）/3}
サンプルを入れない状態で上記と同条件でブランク測定をしたところ、アセトアルデヒド減少率は0.8ppm/hであったので、各サンプルのアセトアセトアルデヒド減少率から0.8ppm/hを引いた値を光触媒活性値とした。
[Photocatalytic performance (visible light)]
Evaluation was performed by a decomposition test of acetaldehyde.
First, 0.5 g of dried powder obtained by drying the sol at 100 ° C. was placed flat on a disk container having a diameter of 2.5 cm. This disk container was set at a predetermined position of a separable flask (capacity 1900 ml), and the lid was closed. Acetaldehyde gas (465 ppm) was allowed to flow there for 25 seconds (set to an initial value of about 80 ppm) and left for 20 minutes with the stirring blade in the container rotated. Thereafter, the initial acetaldehyde concentration in the container was measured with a detector tube (Gastech 92M).
Next, fluorescent light passing through an ultraviolet cut filter was irradiated (about 1 mW / cm 2 (405 nm) at the sample position), and the concentration of acetaldehyde was measured every 3 hours with the above detection tube until 3 hours later.
In the measurement using the detection tube, the measurement is performed by extracting 100 ml of gas from a closed container 1900 ml with a detector equipped with the detection tube, and then releasing the atmosphere to release the decompression. At this time, the gas concentration was reduced, so correction was made using Equation 1.
(Formula 1) Acetaldehyde concentration (ppm) = Acetaldehyde measured value (ppm) x 0.95n (n is the number of measurements)
In addition, the acetaldehyde reduction rate was calculated from Equation 2 as an index indicating the degradation performance.
(Formula 2) Acetaldehyde reduction rate (ppm / h) = − {(Acetaldehyde concentration after 3 hours irradiation−Initial acetaldehyde concentration) / 3}
When a blank measurement was performed under the same conditions as above with no sample, the acetaldehyde reduction rate was 0.8 ppm / h. It was.
[光触媒性能(紫外光)]
蛍光灯をブラックライトに変更し、紫外線カットフィルターをはずした以外は可視光での試験と同様に行った。測定位置に置ける紫外線強度（365nm）は約0.35mW/cm2である。ブランク測定時のアセトアルデヒド減少率は1.2ppm/hであったので、各サンプルのアセトアセトアルデヒド減少率から1.2ppm/hを引いた値を光触媒活性値とした。
[Photocatalytic performance (ultraviolet light)]
The test was performed in the same manner as in the visible light test except that the fluorescent lamp was changed to black light and the ultraviolet cut filter was removed. The UV intensity (365 nm) that can be placed at the measurement position is about 0.35 mW / cm 2 . Since the acetaldehyde reduction rate at the time of blank measurement was 1.2 ppm / h, the value obtained by subtracting 1.2 ppm / h from the acetoacetaldehyde reduction rate of each sample was taken as the photocatalytic activity value.
ゾルの分析値を表１に示し、ゾルの評価を表２に示した。
また、50℃で30日間静置保存したときの安定性について調べたところ、実施例1〜14及び比較例1、2、4ではいずれも性状の変化は認められなかったが、比較例5、6では沈殿の発生が認められた。
The analytical values of the sol are shown in Table 1, and the evaluation of the sol is shown in Table 2.
Further, when examined for stability when stored at 50 ° C. for 30 days, in Examples 1 to 14 and Comparative Examples 1, 2, and 4, no change in properties was observed, Comparative Example 5, In 6, the occurrence of precipitation was observed.
表２の結果より、実施例1〜14のゾルは、塗膜にしたときの透明性が高く、且つ、可視光照射下においても高い光触媒活性を有することが示された。
From the results in Table 2, it was shown that the sols of Examples 1 to 14 had high transparency when formed into a coating film and high photocatalytic activity even under visible light irradiation.
Claims (7)
（１）アルカリ水溶液と水溶性チタン化合物を、常にpH9以上を保ちながら中和して水和酸化チタンゲルを得た後、洗浄する第１の工程。
（２）第１の工程で得られた洗浄物を、塩酸又は硝酸でpH3以下に調整した後、加熱する第２の工程。
（３）第２の工程で得られた加熱物から無機酸根を除去する第３の工程。
（４）第３の工程で得られた無機酸根除去物を、水溶性アミン化合物の存在下で加熱することでアルカリ性ルチル型酸化チタンゾルを得る第４の工程。
（５）第４の工程で得られたアルカリ性ルチル型酸化チタンゾルと、鉄化合物、銅化合物、白金化合物及びパラジウム化合物からなる群より選ばれた１種以上の遷移金属化合物とを混合し、遷移金属を担持させる第５の工程。 The manufacturing method of the transition metal carrying | support alkaline rutile type titanium oxide sol characterized by including the process of following (1)-(5).
(1) The 1st process of wash | cleaning, after neutralizing alkali aqueous solution and a water-soluble titanium compound, always maintaining pH9 or more and obtaining a hydrated titanium oxide gel.
(2) A second step of heating the washed product obtained in the first step after adjusting the pH to 3 or less with hydrochloric acid or nitric acid.
(3) A third step of removing inorganic acid radicals from the heated product obtained in the second step.
(4) A fourth step of obtaining an alkaline rutile-type titanium oxide sol by heating the inorganic acid radical removed product obtained in the third step in the presence of a water-soluble amine compound.
(5) The alkaline rutile titanium oxide sol obtained in the fourth step is mixed with one or more transition metal compounds selected from the group consisting of iron compounds, copper compounds, platinum compounds and palladium compounds, and transition metals are mixed. 5th process to carry | support.
水溶性アミン化合物の含有量が、ルチル型酸化チタン（TiO2）に対し、モル比で0.005〜0.5の範囲である
請求項１記載の遷移金属担持アルカリ性ルチル型酸化チタンゾルの製造方法。 The transition metal-supported alkaline rutile according to claim 1, wherein the content of the water-soluble amine compound in the transition metal-supported alkaline rutile titanium oxide sol is in the range of 0.005 to 0.5 in terms of a molar ratio with respect to the rutile-type titanium oxide (TiO 2 ). Of manufacturing type titanium oxide sol.
遷移金属の含有量が、酸化物換算で、ルチル型酸化チタン（TiO2）に対し、0.01〜5質量％の範囲である
請求項１又は２記載の遷移金属担持アルカリ性ルチル型酸化チタンゾルの製造方法。 Transition content of the transition metal of the transition metal supported alkaline rutile in sol is in terms of oxide, relative to rutile titanium oxide (TiO 2), according to claim 1 or 2 wherein in the range of 0.01 to 5 mass% A method for producing a metal-supported alkaline rutile-type titanium oxide sol.
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