JP4351936B2 - Method for producing titanium oxide photocatalyst - Google Patents
Method for producing titanium oxide photocatalyst Download PDFInfo
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- JP4351936B2 JP4351936B2 JP2004071070A JP2004071070A JP4351936B2 JP 4351936 B2 JP4351936 B2 JP 4351936B2 JP 2004071070 A JP2004071070 A JP 2004071070A JP 2004071070 A JP2004071070 A JP 2004071070A JP 4351936 B2 JP4351936 B2 JP 4351936B2
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- Prior art keywords
- titanium oxide
- titanium
- oxide photocatalyst
- sulfur
- photocatalyst
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 164
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 127
- 239000011941 photocatalyst Substances 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 39
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 33
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000010304 firing Methods 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 125000004434 sulfur atom Chemical group 0.000 claims description 12
- 238000002835 absorbance Methods 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 38
- 239000011593 sulfur Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 16
- 239000010936 titanium Substances 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 230000031700 light absorption Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- -1 titanium ions Chemical class 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- PVPBBTJXIKFICP-UHFFFAOYSA-N (7-aminophenothiazin-3-ylidene)azanium;chloride Chemical compound [Cl-].C1=CC(=[NH2+])C=C2SC3=CC(N)=CC=C3N=C21 PVPBBTJXIKFICP-UHFFFAOYSA-N 0.000 description 1
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- QIOZLISABUUKJY-UHFFFAOYSA-N Thiobenzamide Chemical compound NC(=S)C1=CC=CC=C1 QIOZLISABUUKJY-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910011210 Ti—O—N Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 1
- RLDQYSHDFVSAPL-UHFFFAOYSA-L calcium;dithiocyanate Chemical compound [Ca+2].[S-]C#N.[S-]C#N RLDQYSHDFVSAPL-UHFFFAOYSA-L 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- MWCGLTCRJJFXKR-UHFFFAOYSA-N n-phenylethanethioamide Chemical compound CC(=S)NC1=CC=CC=C1 MWCGLTCRJJFXKR-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 125000002153 sulfur containing inorganic group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- XDDVRYDDMGRFAZ-UHFFFAOYSA-N thiobenzophenone Chemical compound C=1C=CC=CC=1C(=S)C1=CC=CC=C1 XDDVRYDDMGRFAZ-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
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Description
本発明は、酸化チタン光触媒およびその製造方法に関するものであり、詳しくは、可視光応答型で光触媒活性が高く有害物分解や湿式太陽電池に有効な酸化チタン光触媒に関するものである。 The present invention relates to a titanium oxide photocatalyst and a method for producing the same, and more particularly to a titanium oxide photocatalyst that is visible light responsive and has high photocatalytic activity and is effective for harmful substance decomposition and wet solar cells.
酸化チタン粉末は、白色顔料として古くから利用されており、近年は化粧品などの紫外線遮蔽材料、光触媒、コンデンサ、サーミスタの構成材料あるいはチタン酸バリウムの原料等電子材料に用いられる焼結材料に広く利用されている。特にここ数年、光触媒としての利用が盛んに試みられており、酸化チタンにそのバンドギャップ以上のエネルギーを持つ光を照射することによって酸化チタンが励起されて、伝導帯に電子が生じ、また価電帯に正孔が生じるが、この電子による還元力または正孔による酸化力を利用した光触媒反応の用途開発が盛んに行われている。この酸化チタン光触媒の用途は非常に多岐に渡っており、水の分解による水素の発生、酸化還元反応を利用した有機化合物の合成、排ガス処理、空気清浄、防臭、殺菌、抗菌、水処理、照明機器等の汚れ防止等、数多くの用途開発が行われている。 Titanium oxide powder has long been used as a white pigment, and in recent years it has been widely used in sintered materials used in electronic materials such as UV shielding materials for cosmetics, photocatalysts, capacitors, thermistors, and barium titanate materials. Has been. In particular, there have been many attempts to use it as a photocatalyst in recent years. Titanium oxide is excited by irradiating titanium oxide with light having energy higher than its band gap, and electrons are generated in the conduction band. Holes are generated in the electric band, and development of applications for photocatalytic reactions using the reducing power of electrons or the oxidizing power of holes has been actively conducted. This titanium oxide photocatalyst has a wide variety of uses, including generation of hydrogen by water decomposition, synthesis of organic compounds using redox reactions, exhaust gas treatment, air purification, deodorization, sterilization, antibacterial, water treatment, lighting Numerous applications have been developed, such as preventing contamination of equipment.
しかしながら、酸化チタンは可視光付近の波長領域において大きな屈折率を示すため、可視光領域では殆ど光吸収は起こらない。これは、アナターゼ型二酸化チタンは３．２ｅＶ、ルチル型二酸化チタンは３．０ｅＶというバンドギャップを有することに起因しており、酸化チタンの吸収可能な光の波長は、アナターゼ型酸化チタンで３８５ｎｍ以下、ルチル型酸化チタンで４１５ｎｍ以下である。これらの波長の光は大部分が紫外線領域に該当し、地球上に無限にある太陽光にはごく一部しか含まれておらず、従来知られている酸化チタン光触媒は、紫外線照射下では光触媒特性を発現するものの、太陽光のもとでは、そのエネルギーのうちごく一部しか活用できずに、光触媒として十分な活性は期待できない。また、屋内での蛍光灯などの下での利用を考えると、蛍光灯のスペクトルは殆どが４００ｎｍ以上であるため、光触媒として十分な特性を発現することはできない。そこで可視光領域での触媒活性を発現させより利用性の高く高活性の光触媒の開発が行なわれている。 However, since titanium oxide exhibits a large refractive index in the wavelength region near visible light, light absorption hardly occurs in the visible light region. This is because anatase-type titanium dioxide has a band gap of 3.2 eV and rutile-type titanium dioxide has a band gap of 3.0 eV, and the wavelength of light that can be absorbed by titanium oxide is 385 nm or less for anatase-type titanium oxide. The rutile type titanium oxide has a thickness of 415 nm or less. Most of the light of these wavelengths falls in the ultraviolet region, and only a small portion is contained in infinite sunlight on the earth. Conventionally known titanium oxide photocatalysts are photocatalysts under ultraviolet irradiation. Although it exhibits the characteristics, only a part of its energy can be used under sunlight, and sufficient activity as a photocatalyst cannot be expected. Also, considering the use under fluorescent lamps indoors, since the spectrum of fluorescent lamps is almost 400 nm or more, sufficient characteristics as a photocatalyst cannot be expressed. In view of this, photocatalysts having higher utility and higher activity have been developed by exhibiting catalytic activity in the visible light region.
例えば、特許文献１（特開平９−２６２４８２号公報）では、Ｃｒ、Ｖ、Ｃｕ、Ｆｅ、Ｍｇ、Ａｇ、Ｐｄ、Ｎｉ、ＭｎおよびＰｔからなる群から選択される１種以上の金属のイオンが１×１０15イオン／ｇ−ＴｉＯ2以上の割合で酸化チタンの表面から内部に含有させた光触媒が開示されており、これらの金属のイオンを３０ＫｅＶ以上の高エネルギーに加速して、酸化チタンに照射し、該金属イオンを酸化チタンに導入する。また、特許文献２（特開平１１−２９０６９７号公報）では、真空槽内に遷移金属を含む固体と前記遷移金属がドーピングされる酸化チタンとを保持する工程と、前記真空槽内の内部に金属プラズマを発生させ、発生した前記金属プラズマを照射することにより前記遷移金属をドーピングした光触媒酸化チタンが開示されている。しかしながら、これらの発明は、酸化チタンに金属イオンをドーピングするために金属イオンを高エネルギーに加速したり、また金属プラズマを発生させるなど非常に特別な装置を用いなければならず、工業的規模での製造には適していない。 For example, in Patent Document 1 (Japanese Patent Laid-Open No. 9-262482), one or more kinds of metal ions selected from the group consisting of Cr, V, Cu, Fe, Mg, Ag, Pd, Ni, Mn, and Pt are included. A photocatalyst containing titanium oxide from the surface at a rate of 1 × 10 15 ions / g-TiO 2 or more is disclosed, and ions of these metals are accelerated to a high energy of 30 KeV or more to form titanium oxide. Irradiation introduces the metal ions into titanium oxide. Moreover, in patent document 2 (Unexamined-Japanese-Patent No. 11-290697), the process which hold | maintains the solid containing a transition metal and the titanium oxide by which the said transition metal is doped in a vacuum chamber, and a metal inside the said vacuum chamber A photocatalytic titanium oxide doped with the transition metal by generating plasma and irradiating the generated metal plasma is disclosed. However, these inventions must use a very special apparatus such as accelerating metal ions to high energy and generating metal plasma in order to dope metal ions into titanium oxide. Not suitable for manufacturing.
このような問題を解決するために、特許文献３（特開平１２−２３７５９８号公報）には、酸化チタンなどの半導体の表面に、前記半導体の構成成分とは異なる成分であるＢ, Ｐ, Ｔｉ, Ｖ, Ｃｒ, Ｍｎ, Ｆｅ, Ｃｏ, Ｎｉ, Ｃｕ, Ｚｎ, Ｇａ, Ｚｒ, Ｎｂ, Ｍｏ, Ｐｄ, Ａｇ, Ｃｄ, Ｓｎ, Ｓｂ, Ｈｆ, Ｔａ, Ｗ, Ｐｔ, Ｈｇ, Ｐｂ, Ｂｉ, Ｐｒ, Ｎｄ, Ｐｍ, Ｓｍ, Ｅｕ, Ｇｄ,Ｔｂ, Ｄｙ, Ｈｏ, Ｅｒ, Ｔｍ, ＹｂおよびＬｕからなる群から選ばれる少なくとも１種である陽イオンを含む媒体を接触させることにより、前記半導体に前記陽イオンを含有させる第１の工程と、前記陽イオンを含有する前記半導体を還元雰囲気において加熱する第２の工程とを含むことを特徴とする可視光応答型光触媒の製造方法が開示されている。しかしながら、このような方法により金属イオンを酸化チタンにドープした光触媒は必ずしも触媒活性が十分ではなく、さらなる改良が望まれていた。 In order to solve such a problem, Patent Document 3 (Japanese Patent Laid-Open No. 12-237598) discloses that B, P, Ti, which are components different from the constituent components of the semiconductor, on the surface of the semiconductor such as titanium oxide. , V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Hf, Ta, W, Pt, Hg, Pb, Bi, Pr , Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and a medium containing at least one cation selected from the group consisting of Lu, and contacting the semiconductor A method for producing a visible light responsive photocatalyst comprising a first step of containing a cation and a second step of heating the semiconductor containing the cation in a reducing atmosphere is disclosed. . However, the photocatalyst doped with metal ions in titanium oxide by such a method does not necessarily have sufficient catalytic activity, and further improvement has been desired.
上記のように遷移金属などの金属イオンを酸化チタンにドープし可視光領域での触媒活性を発現させた光触媒の他、特許文献４（ＷＯ ０１／０１０５５２号公報）では、酸化チタン結晶の酸素サイトの一部を窒素原子で置換すること、または酸化チタン結晶の格子間に窒素原子をドーピングすること、または酸化チタンの結晶粒界に窒素原子をドーピングすることのいずれかまたはこれらの組み合わせにより酸化チタン結晶に窒素原子を含有させた光触媒物質であり、酸化チタン結晶に窒素を含有させたＴｉ−Ｏ−Ｎ構成を有した、可視光領域において光触媒作用を発現する光触媒物質が開示されている。このような光触媒物質を得る方法として、窒素ガス雰囲気中での酸化チタンのスパッタリングが挙げられているが、製造コストが高く工業的規模での製造は困難である。また、酸化チタンをアンモニア雰囲気で焼成するという簡便な方法の開示もあるが、酸化チタン中に十分に窒素原子がドーピングされず、結果として得られる光触媒は触媒活性が十分ではなかった。
従って、本発明の課題は、可視光領域で光触媒活性が発現する酸化チタン光触媒であって、高活性で、かつ低コストの酸化チタン光触媒を提供することにある。 Accordingly, an object of the present invention is to provide a titanium oxide photocatalyst exhibiting photocatalytic activity in the visible light region and having high activity and low cost.
かかる実情において、本発明者らは鋭意検討を行った結果、酸化チタンがルチル型およびアナターゼ型の混合結晶であって、かつ硫黄原子を含有する酸化チタンが、可視光領域において、高い光吸収特性を発現することを見出し、本発明を完成するに至った。 Under such circumstances, the present inventors have conducted intensive studies. As a result, titanium oxide is a mixed crystal of rutile type and anatase type, and titanium oxide containing a sulfur atom has high light absorption characteristics in the visible light region. The present invention was completed.
すなわち、本発明は、塩化チタン水溶液を加水分解またはアルカリで中和して得られた酸化チタン粉末とチオ尿素の混合物を、酸化性雰囲気下、３００〜６００℃で焼成することにより、ルチル化率が５〜９９％であるルチル型およびアナターゼ型の混合結晶であって、かつ硫黄原子を陽イオンとして含有する酸化チタン光触媒を得ることを特徴とする酸化チタン光触媒の製造方法を提供するものである。 That is, the present invention provides a rutile ratio by calcining a mixture of titanium oxide powder and thiourea obtained by hydrolysis or alkali neutralization of an aqueous titanium chloride solution at 300 to 600 ° C. in an oxidizing atmosphere. The present invention provides a method for producing a titanium oxide photocatalyst characterized by obtaining a titanium oxide photocatalyst which is a rutile-type and anatase-type mixed crystal containing 5 to 99% and containing a sulfur atom as a cation. .
本発明の酸化チタン光触媒によれば、紫外線領域だけではなく可視光領域の光触媒活性が高いことから、太陽光の当たらない蛍光灯などの室内においても十分に光触媒作用を発揮することができ、今まで紫外線領域に止まっていた光触媒の用途を拡大することが可能となる。 According to the titanium oxide photocatalyst of the present invention, the photocatalytic activity not only in the ultraviolet region but also in the visible light region is high, so that the photocatalytic action can be sufficiently exerted even in a room such as a fluorescent lamp that is not exposed to sunlight. The application of the photocatalyst that has remained in the ultraviolet region can be expanded.
本発明の酸化チタン光触媒は、酸化チタンがルチル型およびアナターゼ型の混合結晶であって、かつ硫黄原子を含有するが、酸化チタンのルチル化率は５〜９９％、好ましくは２０〜８０％、より好ましくは３０〜７０％である。本発明の酸化チタン光触媒はルチル型とアナターゼ型の混合結晶であるが、この他に非晶質の酸化チタンを含んでいてもよい。このルチル型とアナターゼ型の酸化チタン中に硫黄原子を含有するものであり、この硫黄原子は酸化チタン中のチタン原子と置換して陽イオンとして酸化チタン中にドープされたものである。具体的にはＴｉ１−ｘＳｘＯ２の化学式で表すことができ、チタン原子に対する硫黄原子の含有量であるｘは０．００１以上、好ましくは０．００２以上、より好ましくは０．００２〜０．００８である。また、平均粒径はＳＥＭ写真画像観察による１次粒子の粒径で５〜５０ｎｍ、ＢＥＴ比表面積は５０〜２５０ｍ２／ｇである。本発明の酸化チタン光触媒は、上記硫黄原子の含有量により異なるが、総じて淡黄色または黄色の粉末である。 In the titanium oxide photocatalyst of the present invention, the titanium oxide is a mixed crystal of rutile type and anatase type and contains a sulfur atom, but the rutile ratio of titanium oxide is 5 to 99%, preferably 20 to 80%, More preferably, it is 30 to 70%. The titanium oxide photocatalyst of the present invention is a mixed crystal of rutile type and anatase type, but may also contain amorphous titanium oxide. The rutile-type and anatase-type titanium oxides contain sulfur atoms, and these sulfur atoms are substituted for titanium atoms in titanium oxide and are doped into titanium oxide as cations. Specifically, it can be represented by the chemical formula Ti 1-x S x O 2 , and x, which is the content of sulfur atoms with respect to titanium atoms, is 0.001 or more, preferably 0.002 or more, more preferably 0.002. ~ 0.008. Moreover, an average particle diameter is 5-50 nm by the particle diameter of the primary particle by SEM photograph image observation, and a BET specific surface area is 50-250 m < 2 > / g. The titanium oxide photocatalyst of the present invention is generally a pale yellow or yellow powder although it varies depending on the content of the sulfur atom.
以下、本発明の酸化チタン光触媒の調製方法を述べる。 Hereafter, the preparation method of the titanium oxide photocatalyst of this invention is described.
本発明のルチル型およびアナターゼ型の混合結晶である酸化チタンは、公知の方法で得られることができ、例えばアルコキシチタンを加水分解する方法、塩化チタン水溶液の加水分解あるいは中和する方法、または硫酸チタニルを原料として用いる方法などの液相法、または四塩化チタン蒸気を加水分解あるいは酸素と反応させる気相方法が採用し得る。これらのなかでも塩化チタン水溶液を原料とした方法が本発明の酸化チタン光触媒を効率よくまた低コストで得ることができる。アルコキシチタンを原料に用いた液相法では粒径が小さく、比表面積の大きな酸化チタンを得ることができ、結果として光触媒活性の高い酸化チタン光触媒を得ることができる。しかしながら得られる酸化チタンのルチル化率の制御が難しくまたアルコキシチタンは非常に高価であり、工業的規模で生産した場合製造コストが高く光触媒を広く普及させることが難しい。一方、気相法は安価な酸化チタンを製造することができるが、得られる酸化チタンの粒径が液相法に比べて大きく、光触媒を形成した際の活性が低くなるという欠点がある。 Titanium oxide which is a mixed crystal of rutile type and anatase type of the present invention can be obtained by a known method, for example, a method of hydrolyzing alkoxy titanium, a method of hydrolyzing or neutralizing an aqueous titanium chloride solution, or sulfuric acid A liquid phase method such as a method using titanyl as a raw material, or a gas phase method in which titanium tetrachloride vapor is hydrolyzed or reacted with oxygen can be employed. Among these, the method using a titanium chloride aqueous solution as a raw material can obtain the titanium oxide photocatalyst of the present invention efficiently and at low cost. In the liquid phase method using alkoxy titanium as a raw material, titanium oxide having a small particle size and a large specific surface area can be obtained. As a result, a titanium oxide photocatalyst having high photocatalytic activity can be obtained. However, it is difficult to control the rutile ratio of the resulting titanium oxide, and alkoxy titanium is very expensive. When produced on an industrial scale, the production cost is high and it is difficult to widely disseminate the photocatalyst. On the other hand, the vapor phase method can produce inexpensive titanium oxide, but has a drawback that the particle size of the obtained titanium oxide is larger than that of the liquid phase method, and the activity when the photocatalyst is formed becomes low.
本発明の酸化チタン光触媒を形成する好ましい方法としては、先ず、塩化チタン水溶液を加水分解またはアルカリで中和して得られる酸化チタン粉末と硫黄または含硫黄化合物との混合物を得、その後この混合物を焼成する。塩化チタン水溶液は、三塩化チタン水溶液または四塩化チタン水溶液が好ましい。三塩化チタン水溶液は、例えば塩酸に金属チタンを溶解することで得ることができる。金属チタンとしてはチタン粉末やスポンジ状チタン、または切粉などのチタンスクラップなどが用いられる。四塩化チタン水溶液は、四塩化チタンを水または塩酸に溶解させて得ることができる。塩化チタン水溶液中のチタン濃度は任意であるが、製造効率または得られる酸化チタン粉末の粒径などを考慮するとチタン含有量が１〜２０重量％、好ましくは５〜１５重量％である。また塩化チタン水溶液は不純物成分が少なく純度が高いことが望ましく、具体的にはアルミニウム、鉄、及びバナジウムがそれぞれ１ｐｐｍ以下、ケイ素及びスズがそれぞれ１０ｐｐｍ以下である。 As a preferred method for forming the titanium oxide photocatalyst of the present invention, first, a mixture of titanium oxide powder and sulfur or a sulfur-containing compound obtained by hydrolyzing or neutralizing an aqueous solution of titanium chloride with an alkali is obtained. Bake. The titanium chloride aqueous solution is preferably a titanium trichloride aqueous solution or a titanium tetrachloride aqueous solution. The aqueous titanium trichloride solution can be obtained, for example, by dissolving titanium metal in hydrochloric acid. As the metal titanium, titanium powder, sponge-like titanium, or titanium scrap such as chips are used. The titanium tetrachloride aqueous solution can be obtained by dissolving titanium tetrachloride in water or hydrochloric acid. The titanium concentration in the aqueous titanium chloride solution is arbitrary, but the titanium content is 1 to 20% by weight, preferably 5 to 15% by weight in consideration of the production efficiency or the particle size of the resulting titanium oxide powder. In addition, it is desirable that the aqueous solution of titanium chloride has few impurity components and high purity. Specifically, aluminum, iron, and vanadium are each 1 ppm or less, and silicon and tin are each 10 ppm or less.
上記塩化チタン水溶液を加水分解またはアルカリで中和して酸化チタン粉末を得るが、具体的には以下のような方法が挙げられる。
（１）塩化チタン水溶液を還流下で加熱し、加水分解して酸化チタン粉末を析出させる。このとき塩素ガスが発生するが、加圧または還流器などにより塩酸ガスの発生を抑え、低ｐＨ領域で加水分解することによって、より微粒の酸化チタン粉末を得ることができる。
（２）塩化チタン水溶液とアンモニア、アンモニア水あるいはＮａＯＨ，ＫＯＨなどのアルカリ金属の水酸化物を接触させ、酸化チタン粉末を析出させる。このときこれらのアルカリの内、金属成分を含まないアンモニアまたはアンモニア水で中和することが望ましい。
The titanium chloride aqueous solution is hydrolyzed or neutralized with an alkali to obtain a titanium oxide powder. Specific examples include the following methods.
(1) A titanium chloride aqueous solution is heated under reflux and hydrolyzed to precipitate a titanium oxide powder. Chlorine gas is generated at this time, but finer titanium oxide powder can be obtained by suppressing the generation of hydrochloric acid gas by pressurizing or refluxing and hydrolyzing in a low pH region.
(2) An aqueous titanium chloride solution is contacted with an alkali metal hydroxide such as ammonia, aqueous ammonia or NaOH, KOH to precipitate titanium oxide powder. At this time, it is desirable to neutralize with ammonia or aqueous ammonia containing no metal component among these alkalis.
上記のように塩化チタン水溶液を加水分解あるいは中和して得られた後、オルトチタン酸またはメタチタン酸が生成するが、光触媒活性を向上させるためにはメタチタン酸が生成するような条件で塩化チタン水溶液を加水分解または中和することが望ましい。その後塩酸分やアルカリ成分など不純物を除去するために洗浄を行ない、乾燥して酸化チタン粉末を得る。さらに、必要に応じて結晶水などの水分を除去するために加熱処理を行なう。 After obtaining by hydrolyzing or neutralizing the aqueous titanium chloride solution as described above, orthotitanic acid or metatitanic acid is produced, but in order to improve the photocatalytic activity, titanium chloride is produced under conditions such that metatitanic acid is produced. It is desirable to hydrolyze or neutralize the aqueous solution. Thereafter, cleaning is performed to remove impurities such as hydrochloric acid and alkali components, followed by drying to obtain titanium oxide powder. Further, heat treatment is performed as necessary to remove water such as crystal water.
上記（２）の方法において、塩化チタン水溶液をＮａＯＨ、ＫＯＨ、ＣａＯＨ（消石灰）などのアルカリ金属またはアルカリ土類金属等の金属の水酸化物で中和し、得られる酸化チタン粉末にこれらの金属成分が残留しても差し支えなく、最終的に得られる光触媒の特性にあまり影響はない。例えば、塩化チタン水溶液を消石灰溶液を添加し中和して酸化チタン水和物を析出させ、この懸濁液にポリ塩化アルミニウムのような凝集剤を添加して固形物を沈降分離させる。このような方法は、酸性水などの排水処理などに一般に用いられている工程であり、工業的規模で非常に効率よく酸化チタンン粉末を製造することが可能となる。 In the method of (2) above, the aqueous titanium chloride solution is neutralized with a hydroxide of an alkali metal such as NaOH, KOH, CaOH (slaked lime) or a metal such as an alkaline earth metal, and these metals are added to the resulting titanium oxide powder. The components may remain, and the properties of the finally obtained photocatalyst are not significantly affected. For example, an aqueous titanium chloride solution is neutralized by adding a slaked lime solution to precipitate titanium oxide hydrate, and a flocculant such as polyaluminum chloride is added to this suspension to precipitate and separate solids. Such a method is a process generally used for wastewater treatment such as acidic water, and it is possible to produce titanium oxide powder very efficiently on an industrial scale.
上記のようにして得られる酸化チタン粉末は、加水分解あるいはアルカリでの中和の条件により平均粒径、比表面積また結晶形を制御することができるが、光触媒の活性を向上させるためには、比表面積が大きいほうが好ましい。具体的にはＢＥＴ比表面積で５０ｍ２／ｇ以上、好ましくは１００ｍ２／ｇ以上、特に好ましくは１５０〜２５０ｍ２／ｇである。 The titanium oxide powder obtained as described above can control the average particle size, specific surface area, and crystal form depending on the conditions of hydrolysis or neutralization with alkali. In order to improve the activity of the photocatalyst, A larger specific surface area is preferred. Specifically 50 m 2 / g or more in BET specific surface area is preferably 100 m 2 / g or more, particularly preferably 150 to 250 2 / g.
さらに、この時点で得られる酸化チタン粉末を所望のルチル化率に制御し、最終的にルチル型とアナターゼ型の混合結晶を含む酸化チタン光触媒を形成する。得られる酸化チタン粉末のルチル化率は、上記の塩化チタン水溶液の加水分解またはアルカリによる中和の時間または速度によって制御することができる。例えば四塩化チタン水溶液をアンモニア水などで中和する場合、短時間で中和するとアナターゼリッチのルチル化率の低い酸化チタンが得られ、また中和反応の速度を遅くするとルチル化率の高い酸化チタンを得ることができる。中和速度としてはチタン原子を重量換算で１分当たり５０〜５００ｇが好ましく、より好ましくは１００〜３００ｇである。１分当たり２００ｇのチタン原子を中和する速度より遅い場合、ルチル化率が５０％以上となる。また、塩化チタン水溶液を中和あるいは加水分解する際の反応系のｐＨによっても得られる酸化チタンのルチル化率を制御でき、例えば酸化チタン粉末が析出した後、低ｐＨ雰囲気で熟成反応するとルチル化率が向上しルチル型とアナターゼ型の混合結晶を得ることができる。 Further, the titanium oxide powder obtained at this point is controlled to a desired rutile ratio, and finally a titanium oxide photocatalyst containing mixed crystals of rutile type and anatase type is formed. The rutile ratio of the obtained titanium oxide powder can be controlled by the time or speed of hydrolysis or neutralization with the alkali of the above titanium chloride aqueous solution. For example, when neutralizing a titanium tetrachloride aqueous solution with ammonia water, etc., neutralization in a short time yields titanium oxide with a low anatase-rich rutile ratio, and slowing the neutralization reaction results in an oxidation with a high rutile ratio. Titanium can be obtained. The neutralization rate is preferably 50 to 500 g, more preferably 100 to 300 g, per minute in terms of titanium atoms. When it is slower than the rate of neutralizing 200 g of titanium atoms per minute, the rutile ratio becomes 50% or more. In addition, the rutile ratio of titanium oxide obtained can be controlled by the pH of the reaction system when neutralizing or hydrolyzing the titanium chloride aqueous solution. For example, after titanium oxide powder is precipitated, the ripening reaction is carried out in a low pH atmosphere. The rate is improved, and a rutile type and anatase type mixed crystal can be obtained.
また、上記方法で用いられる含硫黄化合物は、常温で液体あるいは固体の化合物が好ましく、含硫黄無機化合物、含硫黄有機化合物あるいは金属の硫化物などが挙げられる。具体的にはチオエーテル類、チオ尿素類、チオアミド類、チオアルコール類、チオアルデヒド類、チアジル類、メルカプタール類、チオール類、チオシアン酸塩類などであり、具体的な化合物としては、チオ尿素、スルホ酢酸、チオフェノール、チオフェン、ベンゾチオフェン、ジベンゾチオフェン、チオベンゾフェノン、ビチオフェン、フェノチアジン、スルホラン、チアジン、チアゾール、チアジアゾール、チアゾリン、チアゾリジン、チアントレン、チアン、チオアセトアニリド、チオアセトアミド、チオベンズアミド、チオアニソール、チオニン、メチルチオール、チオエーテル、チオシアン、硫酸、スルホン酸類、スルホニウム塩類、スルホンアミド類、スルフィン酸類、スルホキシド類、スルフィン類、スルファン類、などが挙げられる。なおこれらの化合物は１種または２種以上組み合わせて用いることができる。 The sulfur-containing compound used in the above method is preferably a liquid or solid compound at room temperature, and examples thereof include sulfur-containing inorganic compounds, sulfur-containing organic compounds, and metal sulfides. Specific examples include thioethers, thioureas, thioamides, thioalcohols, thioaldehydes, thiazyl, mercaptals, thiols, and thiocyanates. Specific compounds include thiourea and sulfoacetic acid. , Thiophenol, thiophene, benzothiophene, dibenzothiophene, thiobenzophenone, bithiophene, phenothiazine, sulfolane, thiazine, thiazole, thiadiazole, thiazoline, thiazolidine, thianthrene, thiane, thioacetanilide, thioacetamide, thiobenzamide, thioanisole, thionine, methyl Thiol, thioether, thiocyan, sulfuric acid, sulfonic acids, sulfonium salts, sulfonamides, sulfinic acids, sulfoxides, sulfines, sulfanes, etc. It is. These compounds can be used alone or in combination of two or more.
上記のなかでも含硫黄有機化合物が好ましく、さらには酸素原子を含まず硫黄原子と窒素原子が混在した有機化合物が特に好ましく、具体的には、チオ尿素が好ましい。 Among these, sulfur-containing organic compounds are preferable, and organic compounds containing no oxygen atom and containing sulfur and nitrogen atoms are particularly preferable, and specifically, thiourea is preferable.
本発明では上記の酸化チタン粉末と硫黄または含硫黄化合物の混合物を形成する。この混合物の形成方法は、
（１）塩化チタン水溶液に硫黄または含硫黄化合物を混合し、次いで加水分解またはアルカリで中和して酸化チタン粉末と硫黄または含硫黄化合物との混合物を得る方法、
（２）塩化チタン水溶液を加水分解またはアルカリで中和して酸化チタン粉末を得、次いで該酸化チタン粉末と硫黄または含硫黄化合物とを混合し混合物を得る方法、
（３）塩化チタン水溶液を加水分解またはアルカリで中和して酸化チタン粉末を得、得られた酸化チタン粉末を仮焼し、次いで該酸化チタン粉末と硫黄または含硫黄化合物とを混合し混合物を得る方法、
（４）塩化チタン水溶液に硫黄または含硫黄化合物を混合し、次いで加水分解またはアルカリで中和して固形物を形成した後、さらに硫黄または含硫黄化合物を混合して酸化チタン粉末と硫黄または含硫黄化合物の混合物を得る方法、
などが挙げられる。
In the present invention, a mixture of the above titanium oxide powder and sulfur or a sulfur-containing compound is formed. The method of forming this mixture is:
(1) A method of obtaining a mixture of titanium oxide powder and sulfur or a sulfur-containing compound by mixing sulfur or a sulfur-containing compound with an aqueous titanium chloride solution and then neutralizing with hydrolysis or alkali.
(2) A method in which an aqueous titanium chloride solution is hydrolyzed or neutralized with an alkali to obtain a titanium oxide powder, and then the titanium oxide powder and sulfur or a sulfur-containing compound are mixed to obtain a mixture;
(3) Titanium chloride aqueous solution is hydrolyzed or neutralized with alkali to obtain titanium oxide powder, the obtained titanium oxide powder is calcined, and then the titanium oxide powder and sulfur or a sulfur-containing compound are mixed to obtain a mixture. How to get,
(4) Sulfur or a sulfur-containing compound is mixed with an aqueous titanium chloride solution, then hydrolyzed or neutralized with alkali to form a solid, and further mixed with sulfur or a sulfur-containing compound to obtain titanium oxide powder and sulfur or a sulfur-containing compound. A method for obtaining a mixture of sulfur compounds,
Etc.
本発明で用い酸化チタン粉末と混合する硫黄または含硫黄化合物の量は、硫黄原子の重量に換算すると、酸化チタンに対し、通常１重量％以上であり、好ましくは５重量％以上、より好ましくは１０〜３０重量％である。硫黄または含硫黄化合物の混合量が少ないと、最終的に光触媒酸化チタンに含まれる硫黄原子量が少なくなり、十分な可視光吸収が起こらなくなる。 The amount of sulfur or sulfur-containing compound to be mixed with the titanium oxide powder used in the present invention is usually 1% by weight or more, preferably 5% by weight or more, more preferably, based on titanium oxide when converted to the weight of sulfur atoms. 10 to 30% by weight. If the amount of sulfur or sulfur-containing compound mixed is small, the amount of sulfur atoms contained in the photocatalytic titanium oxide will eventually decrease, and sufficient visible light absorption will not occur.
次いで、上記で得られた酸化チタン粉末と硫黄または含硫黄化合物の混合物を焼成し酸化チタン光触媒を形成するが、焼成温度は２００〜８００℃、好ましくは３００〜６００℃、より好ましくは４００〜５００℃である。含硫黄有機化合物を用いた場合、その化合物が分解し硫黄原子が遊離して酸化チタン中のチタン原子と置換する温度で行なう。また焼成雰囲気は、空気、酸素などの酸化性雰囲気、水素ガスやアンモニアガスなどの還元性雰囲気、窒素ガスやアルゴンガスなどの不活性雰囲気、また真空下などで行なわれる。これらのなかでも水素ガスのような還元性雰囲気で行なうことによって、より可視光領域での光触媒活性が向上し好ましい。水素ガスのような還元性ガスのみでもよいが、水素と酸素の混合ガス、水素と酸素と不活性ガスの混合ガスの雰囲気で焼成することも有効である。さらに焼成時に硫黄が蒸発しまたは含硫黄化合物が分解して硫黄成分が焼成炉から排出しないよう、ある程度硫黄成分の分圧を保持するよう焼成雰囲気を保つことが重要である。炭素原子を有する含硫黄有機化合物など焼成時に分解して炭酸ガスなどの副生ガスを発生する場合は、ある程度焼成雰囲気から排出したほうがよい。従って、焼成する際の容器は、完全にオープンまたは密閉のものではなく、ある程度の圧力がかかりかつ副生ガスを排出し得るような、上部が開放され、この上部に非固定式の蓋体を備えた円筒形、皿状または矩形などの容器が好ましい。 Next, the titanium oxide powder obtained above and a mixture of sulfur or a sulfur-containing compound are calcined to form a titanium oxide photocatalyst. The calcining temperature is 200 to 800 ° C, preferably 300 to 600 ° C, more preferably 400 to 500. ° C. When a sulfur-containing organic compound is used, the reaction is performed at a temperature at which the compound is decomposed and sulfur atoms are liberated and replaced with titanium atoms in titanium oxide. The firing atmosphere is performed in an oxidizing atmosphere such as air or oxygen, a reducing atmosphere such as hydrogen gas or ammonia gas, an inert atmosphere such as nitrogen gas or argon gas, or under vacuum. Of these, the photocatalytic activity in the visible light region is preferably improved by carrying out in a reducing atmosphere such as hydrogen gas. Although only a reducing gas such as hydrogen gas may be used, firing in an atmosphere of a mixed gas of hydrogen and oxygen or a mixed gas of hydrogen, oxygen and inert gas is also effective. Furthermore, it is important to maintain the firing atmosphere so that the partial pressure of the sulfur component is maintained to some extent so that sulfur does not evaporate during the firing or the sulfur-containing compound decomposes and the sulfur component is not discharged from the firing furnace. When a by-product gas such as carbon dioxide gas is generated by decomposition during firing, such as a sulfur-containing organic compound having a carbon atom, it is better to exhaust from the firing atmosphere to some extent. Therefore, the container for firing is not completely open or sealed, and the upper part is opened so that a certain amount of pressure is applied and the by-product gas can be discharged, and a non-fixed lid is placed on the upper part. A cylindrical, dished or rectangular container provided is preferred.
上記のようにして得られた酸化チタン光触媒は、必要に応じて洗浄して遊離の硫黄成分やその他を除去する。また、粒子の分散性を向上させるために界面活性剤などにより表面処理することもできる。 The titanium oxide photocatalyst obtained as described above is washed as necessary to remove free sulfur components and others. Moreover, in order to improve the dispersibility of particle | grains, it can also surface-treat with surfactant etc.
また、前記酸化チタン光触媒は、可視光の光吸収特性に優れており、紫外可視拡散反射スペクトルを測定して、波長３００〜３５０ｎｍの吸光度の積分値を１として、通常、波長３５０〜４００ｎｍの吸光度の積分値が０．３〜０．９であり、且つ波長４００〜５００ｎｍの吸光度の積分値が０．３〜０．９であり、好ましくは波長３５０〜４００ｎｍの吸光度の積分値が０．４〜０．８であり、且つ波長４００〜５００ｎｍの吸光度の積分値が０．４〜０．８であり、さらに好ましくは、波長３５０〜４００ｎｍの吸光度の積分値が０．５〜０．７であり、且つ波長４００〜５００ｎｍの吸光度の積分値が０．５〜０．７５である。 Moreover, the titanium oxide photocatalyst is excellent in visible light absorption characteristics, and an ultraviolet-visible diffuse reflection spectrum is measured, and the integrated value of the absorbance at a wavelength of 300 to 350 nm is set to 1, usually, the absorbance at a wavelength of 350 to 400 nm. The integrated value of the absorbance at a wavelength of 400 to 500 nm is 0.3 to 0.9, and the integrated value of the absorbance at a wavelength of 350 to 400 nm is preferably 0.4. The integrated value of absorbance at a wavelength of 400 to 500 nm is 0.4 to 0.8, and more preferably, the integrated value of absorbance at a wavelength of 350 to 400 nm is 0.5 to 0.7. And the integrated value of the absorbance at a wavelength of 400 to 500 nm is 0.5 to 0.75.
本発明の酸化チタン光触媒は、上記のように粉末でも用いることができるが、一般的な光触媒の用途として、排ガス処理、防臭、防汚などの基材に酸化チタン光触媒を塗布し酸化チタン光触媒層を形成して用いられることが多いため、水または有機溶媒の分散液、コーティング液または塗料にすることが望ましい。近年ではアセトアルデヒドなどシックハウスの問題から光触媒材料も水系の環境型のコーティング剤または塗料が要求されており、本発明の酸化チタン光触媒も水系の分散液または塗料として用いることが望ましい。 The titanium oxide photocatalyst of the present invention can be used as a powder as described above, but as a general photocatalyst application, a titanium oxide photocatalyst layer is applied by applying a titanium oxide photocatalyst to a substrate for exhaust gas treatment, deodorization, antifouling, etc. Therefore, it is desirable to use water or an organic solvent dispersion, coating liquid or paint. In recent years, water-based environmental coating agents or paints are also required for photocatalyst materials due to the problem of sick house such as acetaldehyde, and the titanium oxide photocatalyst of the present invention is desirably used as an aqueous dispersion or paint.
上記のようにして得られる本発明の酸化チタン光触媒は、可視光領域での吸収特性に優れており、ブラックライトなど特に紫外光の光源がなくとも、太陽光や室内における蛍光灯による光源で十分に光触媒活性が発現する。また、酸化チタンに窒素原子をドープしたものなど従来の可視光応答型光触媒に比べて、効率的にかつ低コストで製造できるため工業的に非常に有利であり、排ガス処理、空気清浄、防臭、殺菌、抗菌、水処理、照明機器等の汚れ防止、酸化作用による有害物の分解作用を利用した光触媒装置などを目的とした光触媒塗料や光触媒コーティング材などに広く適用できる。 The titanium oxide photocatalyst of the present invention obtained as described above has excellent absorption characteristics in the visible light region, and even if there is no ultraviolet light source such as black light, a light source using sunlight or a fluorescent lamp in a room is sufficient. Photocatalytic activity is exhibited. In addition, compared to conventional visible light responsive photocatalysts such as titanium oxide doped with nitrogen atoms, it is industrially very advantageous because it can be produced efficiently and at low cost, exhaust gas treatment, air purification, deodorization, It can be widely applied to photocatalyst paints and photocatalyst coating materials for the purpose of sterilization, antibacterial, water treatment, prevention of soiling of lighting equipment, etc., and photocatalytic devices utilizing the action of decomposing harmful substances due to oxidation.
次に、実施例を挙げて本発明を更に具体的に説明するが、これは単に例示であって、本発明を制限するものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.
実施例および比較例において酸化チタン光触媒の評価は以下のように実施した。
（１）酸化チタン光触媒中の硫黄含有量の測定
エネルギー分散型蛍光Ｘ線分析装置（ＥＤＸ）を付帯した電界放出型走査型電子顕微鏡（Field Emission-SEM:FE-SEM）（日立電子走査顕微鏡Ｓ−４７００）にて酸化チタン中の硫黄原子の定量分析を行なった。
（２）可視光吸収特性の測定
積分球付き紫外可視分光光度計（日本分光株式会社製Ｖ−５５０−ＤＳ）により酸化チタン光触媒の拡散反射吸収スペクトルを測定した。
（３）ルチル化率の測定
ＡＳＴＭ Ｄ 3720-84に従いＸ線回折パターンにおける、ルチル型結晶酸化チタンの最強干渉線（面指数１１０）のピーク面積（Ｉｒ）と、酸化チタン粉末の最強干渉線（面指数１０１）のピーク面積（Ｉａ）を求め前述の算出式より求めた。なお、Ｘ線回折測定条件は下記の通りである。
In the examples and comparative examples, the titanium oxide photocatalyst was evaluated as follows.
(1) Measurement of sulfur content in titanium oxide photocatalyst Field Emission-SEM (FE-SEM) with an energy dispersive X-ray fluorescence spectrometer (EDX) (Hitachi Electron Scanning Microscope S) -4700), a quantitative analysis of sulfur atoms in titanium oxide was performed.
(2) Measurement of visible light absorption characteristics The diffuse reflection absorption spectrum of the titanium oxide photocatalyst was measured with an ultraviolet-visible spectrophotometer with an integrating sphere (V-550-DS manufactured by JASCO Corporation).
(3) Measurement of the rutile ratio The peak area (Ir) of the strongest interference line (surface index 110) of rutile crystalline titanium oxide in the X-ray diffraction pattern according to ASTM D 3720-84, and the strongest interference line of titanium oxide powder ( The peak area (Ia) of the plane index 101) was obtained and obtained from the above formula. The X-ray diffraction measurement conditions are as follows.
（Ｘ線回折測定条件）
回折装置 ＲＡＤ−１Ｃ（株式会社リガク製）
Ｘ線管球 Ｃｕ
管電圧・管電流４０ｋＶ、３０ｍＡ
スリット ＤＳ−ＳＳ：１度、ＲＳ：０．１５ｍｍ
モノクロメータグラファイト
測定間隔 ０．００２度
計数方法 定時計数法 (X-ray diffraction measurement conditions)
Diffraction device RAD-1C (manufactured by Rigaku Corporation)
X-ray tube Cu
Tube voltage / tube current 40kV, 30mA
Slit DS-SS: 1 degree, RS: 0.15mm
Monochromator graphite measurement interval 0.002 degrees
Counting method Constant clock method
攪拌器を具備した容量１０００ミリリッターの丸底フラスコにチタン濃度４重量％の四塩化チタン水溶液２９７ｇ挿入し、次いで６０℃に加熱した。次いで反応系のｐＨが７．４に維持させるようにアンモニア水を添加して、６０℃で１時間中和処理を行なった。得られた固形物を濾過し純水で洗浄し、これに１００ｍｌの純水に溶解させたチオ尿素９．７ｇを添加し３０分攪拌した。その後、固形物を６０℃で乾燥して、ボールミルにて粉砕して酸化チタン粉末とチオ尿素の混合物を得た。この混合物を焼成炉に装入し４００℃で３時間焼成した。その後ボールミルにて粉砕して、純水で洗浄した後、６０℃で乾燥して淡黄色の酸化チタン光触媒を得た。得られた酸化チタン光触媒中の硫黄含有量を測定したところ０．１３重量％、比表面積は１０９ｍ２／ｇ、ルチル化率は１０％であった。また可視光吸収特性を図１に示した。 297 g of a titanium tetrachloride aqueous solution having a titanium concentration of 4% by weight was inserted into a 1000-milliliter round bottom flask equipped with a stirrer, and then heated to 60 ° C. Next, ammonia water was added so that the pH of the reaction system was maintained at 7.4, and neutralization was performed at 60 ° C. for 1 hour. The obtained solid was filtered and washed with pure water, and 9.7 g of thiourea dissolved in 100 ml of pure water was added thereto and stirred for 30 minutes. Thereafter, the solid was dried at 60 ° C. and pulverized with a ball mill to obtain a mixture of titanium oxide powder and thiourea. This mixture was placed in a firing furnace and fired at 400 ° C. for 3 hours. Thereafter, it was pulverized by a ball mill, washed with pure water, and then dried at 60 ° C. to obtain a pale yellow titanium oxide photocatalyst. When the sulfur content in the obtained titanium oxide photocatalyst was measured, it was 0.13% by weight, the specific surface area was 109 m 2 / g, and the rutile ratio was 10%. The visible light absorption characteristics are shown in FIG.
攪拌器を具備した容量１０００ミリリッターの丸底フラスコにチタン濃度４重量％の四塩化チタン水溶液２９７ｍｌ挿入し、次いで１００ｍｌの純水に溶解させたチオ尿素９．７ｇを添加して６０℃に加熱した。次いで反応系のｐＨが７．４に維持させるようにアンモニア水を添加して、６０℃で１時間中和処理を行なった。得られた固形物を濾過し純水で洗浄し３０分攪拌した。その後、固形物を６０℃で乾燥して、ボールミルにて粉砕して酸化チタン粉末とチオ尿素の混合物を得た。この混合物を焼成炉に装入し４００℃で３時間焼成した。その後ボールミルにて粉砕して、純水で洗浄した後、６０℃で乾燥して淡黄色の酸化チタン光触媒を得た。得られた酸化チタン光触媒中の硫黄含有量を測定したところ０．０５重量％、比表面積は１２０ｍ２／ｇ、ルチル化率は６０％であった。また可視光吸収特性を図１に示した。 297 ml of titanium tetrachloride aqueous solution having a titanium concentration of 4% by weight was inserted into a 1000 ml round bottom flask equipped with a stirrer, and then 9.7 g of thiourea dissolved in 100 ml of pure water was added and heated to 60 ° C. did. Next, ammonia water was added so that the pH of the reaction system was maintained at 7.4, and neutralization was performed at 60 ° C. for 1 hour. The obtained solid was filtered, washed with pure water, and stirred for 30 minutes. Thereafter, the solid was dried at 60 ° C. and pulverized with a ball mill to obtain a mixture of titanium oxide powder and thiourea. This mixture was placed in a firing furnace and fired at 400 ° C. for 3 hours. Thereafter, it was pulverized by a ball mill, washed with pure water, and then dried at 60 ° C. to obtain a pale yellow titanium oxide photocatalyst. When the sulfur content in the obtained titanium oxide photocatalyst was measured, it was 0.05% by weight, the specific surface area was 120 m 2 / g, and the rutile ratio was 60%. The visible light absorption characteristics are shown in FIG.
比較例１
攪拌器を具備した容量１０００ミリリッターの丸底フラスコにチタン濃度４重量％の四塩化チタン水溶液２９７ｍｌ挿入し６０℃に加熱した。次いで反応系のｐＨが７．４に維持させるようにアンモニア水を添加して、６０℃で１時間中和処理を行なった。得られた固形物を濾過し純水で洗浄し３０分攪拌した。その後、固形物を６０℃で乾燥して、ボールミルにて粉砕して酸化チタン粉末を得た。この酸化チタン粉末を焼成炉に装入し、アンモニアガスを焼成炉に導入してアンモニア雰囲気で４００℃で３時間焼成した。その後ボールミルにて粉砕して、純水で洗浄した後、６０℃で乾燥して淡黄色の酸化チタン光触媒を得た。得られた酸化チタンの比表面積は５７９ｍ２／ｇルチル化率は１５％であった。また可視光吸収特性を図１に示した。
Comparative Example 1
297 ml of a titanium tetrachloride aqueous solution having a titanium concentration of 4% by weight was inserted into a 1000-ml round bottom flask equipped with a stirrer and heated to 60 ° C. Next, ammonia water was added so that the pH of the reaction system was maintained at 7.4, and neutralization was performed at 60 ° C. for 1 hour. The obtained solid was filtered, washed with pure water, and stirred for 30 minutes. Thereafter, the solid was dried at 60 ° C. and pulverized with a ball mill to obtain a titanium oxide powder. This titanium oxide powder was charged into a firing furnace, ammonia gas was introduced into the firing furnace, and firing was performed at 400 ° C. for 3 hours in an ammonia atmosphere. Thereafter, it was pulverized by a ball mill, washed with pure water, and then dried at 60 ° C. to obtain a pale yellow titanium oxide photocatalyst. The specific surface area of the obtained titanium oxide was 579 m 2 / g rutile, and the rate was 15%. The visible light absorption characteristics are shown in FIG.
比較例２
攪拌器を具備した容量１０００ミリリッターの丸底フラスコにエタノール５００ｍｌを装入し、４０℃に加熱し、ここにチオ尿素２４．２ｇを添加して溶解させた。次いで、テトライソプロポキシチタン２６．２ｍｌを添加して攪拌しながら８０℃に加熱してテトライソプロポキシチタンを加水分解して固形物を析出させた。得られた固形物を６０℃で乾燥して、ボールミルにて粉砕して酸化チタン粉末とチオ尿素の混合物を得た。この混合物を焼成炉に装入し、４００℃で３時間焼成した。その後ボールミルにて粉砕して、純水で洗浄した後、６０℃で乾燥して淡黄色の酸化チタン光触媒を得た。得られた酸化チタンの比表面積は１９０ｍ２／ｇ、ルチル化率は０％であった。また可視光吸収特性を図１に示した。
Comparative Example 2
Was charged ethanol 500ml round bottom flask equipped with a stirrer capacity 1000 milliliters, it was heated to 40 ° C., and here was added and dissolved thiourea 24.2 g. Next, 26.2 ml of tetraisopropoxytitanium was added and heated to 80 ° C. with stirring to hydrolyze tetraisopropoxytitanium and precipitate a solid. The obtained solid was dried at 60 ° C. and pulverized with a ball mill to obtain a mixture of titanium oxide powder and thiourea. This mixture was placed in a firing furnace and fired at 400 ° C. for 3 hours. Thereafter, it was pulverized by a ball mill, washed with pure water, and then dried at 60 ° C. to obtain a pale yellow titanium oxide photocatalyst. The obtained titanium oxide had a specific surface area of 190 m 2 / g and a rutile ratio of 0%. The visible light absorption characteristics are shown in FIG.
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