WO2007037321A1 - 酸化チタン系光触媒とその製造方法及び用途 - Google Patents
酸化チタン系光触媒とその製造方法及び用途 Download PDFInfo
- Publication number
- WO2007037321A1 WO2007037321A1 PCT/JP2006/319286 JP2006319286W WO2007037321A1 WO 2007037321 A1 WO2007037321 A1 WO 2007037321A1 JP 2006319286 W JP2006319286 W JP 2006319286W WO 2007037321 A1 WO2007037321 A1 WO 2007037321A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photocatalyst
- titanium oxide
- titanium
- bismuth
- metal component
- Prior art date
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 195
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 177
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 107
- 239000002184 metal Substances 0.000 claims abstract description 107
- 230000001699 photocatalysis Effects 0.000 claims abstract description 76
- 239000010936 titanium Substances 0.000 claims abstract description 61
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 57
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 10
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 67
- 238000010438 heat treatment Methods 0.000 claims description 59
- 229910052719 titanium Inorganic materials 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 150000001622 bismuth compounds Chemical class 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000010586 diagram Methods 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 238000001228 spectrum Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 230000003595 spectral effect Effects 0.000 claims description 3
- 239000000383 hazardous chemical Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 43
- 230000001747 exhibiting effect Effects 0.000 abstract description 6
- IYNWNKYVHCVUCJ-UHFFFAOYSA-N bismuth Chemical compound [Bi].[Bi] IYNWNKYVHCVUCJ-UHFFFAOYSA-N 0.000 description 50
- 239000010408 film Substances 0.000 description 25
- 239000002245 particle Substances 0.000 description 21
- 239000012298 atmosphere Substances 0.000 description 19
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- -1 oxy bismuth bismuth Chemical compound 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 13
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
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- 239000010959 steel Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
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- 239000007787 solid Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 230000004298 light response Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
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- 239000005049 silicon tetrachloride Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
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- 239000011368 organic material Substances 0.000 description 3
- BAQNULZQXCKSQW-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4] BAQNULZQXCKSQW-UHFFFAOYSA-N 0.000 description 3
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- 229940036348 bismuth carbonate Drugs 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 1
- BRCWHGIUHLWZBK-UHFFFAOYSA-K bismuth;trifluoride Chemical compound F[Bi](F)F BRCWHGIUHLWZBK-UHFFFAOYSA-K 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 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 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- CFTHARXEQHJSEH-UHFFFAOYSA-N silicon tetraiodide Chemical compound I[Si](I)(I)I CFTHARXEQHJSEH-UHFFFAOYSA-N 0.000 description 1
- JXJTWJYTKGINRZ-UHFFFAOYSA-J silicon(4+);tetraacetate Chemical compound [Si+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JXJTWJYTKGINRZ-UHFFFAOYSA-J 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- MKPKCNXKRRNKMM-UHFFFAOYSA-J zirconium(4+);tetrachlorate Chemical compound [Zr+4].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O MKPKCNXKRRNKMM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
Definitions
- Titanium oxide photocatalyst its production method and use
- the present invention relates to a titanium oxide photocatalyst capable of exhibiting a photocatalytic action not only by ultraviolet rays but also by irradiation with visible light, and a production method and use thereof.
- the band gap of anatase-type titanium oxide which is generally used as a photocatalyst, is about 3.2 eV, and the reaction proceeds upon receiving ultraviolet light having a wavelength shorter than about 380 nm. Therefore, ultraviolet irradiation is required for the expression of the photocatalytic activity, and there is a problem that the installation environment and the use are limited.
- Photocatalysts having visible light activity include the following:
- Nitrogen type in which nitrogen is contained in titanium oxide for example, Chem. Phys. Lett 123 (1986) 126-128, Journal of Chemical Society of Japan, 1986 (8), ⁇ .1084, and WO 01/010552;
- Oxygen defect type in which oxygen defects are introduced into titanium oxide for example, JP 2001-205103 A
- a metal dope type in which another metal (ion) is contained in titanium oxide or a combination of metal oxides is contained in titanium oxide or a combination of metal oxides.
- JP-A-9 262482 discloses titanium oxide in which vanadium or chromium is ion-implanted.
- Chem. Commun. 2001, 2718-2719 reports titanium oxide having visible light activity containing transition metals such as V, Cr, Nb and Mo.
- Japanese Unexamined Patent Application Publication No. 2004-275999 discloses an oxide containing a metal compound selected from Si, Ti, V, Sn, Sb, W, Nb, Bi, P, Mo, Cs, Ge, As, Ce, and the like. Titanium is disclosed.
- J. Mat. Sci. Lett. 21, 2002, 1655-1656 reports on the enhancement of titanium oxide photocatalyst activity and the longer wavelength of the absorption spectrum due to the inclusion of bismuth.
- the titanium oxide photocatalyst having visible light responsiveness described above is not highly active under visible light irradiation in any of nitrogen type, oxygen defect type and metal dope type.
- there is another problem that they are not suitable for mass production because many of them require ion implantation equipment and sputtering equipment for production.
- the metal-doped type exhibits visible light activity, but the excellent UV activity inherent in titanium oxide may be lost. As a result, it was found that the photocatalytic action may be reduced.
- the present invention provides an acid-titanium-based photocatalyst capable of expressing excellent visible light photocatalytic activity while maintaining its original ultraviolet activity, and a production method suitable for mass production thereof. .
- the present invention has been completed based on the following findings (1) to (3).
- Titanium oxide contains bismuth as the first additional metal component and silicon, zirconium, aluminum, and hafnium force as the second additional metal component in an appropriate range. Titanium-based complex oxides become photocatalysts with significantly improved visible light activity.
- the above-mentioned bismuth and the second additional metal both mean a metal element and exist as a compound of the metal in the photocatalyst.
- a metal compound includes an elemental metal (single metal).
- This titanium oxide-based photocatalyst becomes more prominent in visible light photocatalytic activity when exhibiting a characteristic XPS pattern
- the photocatalytic activity is further improved by controlling the content of nitrogen contained in the precursor material of the photocatalyst by a method such as washing and adjusting the firing conditions.
- the present invention provides bismuth as the first additional metal component, and the second additional metal component. It is a titanium oxide photocatalyst characterized by comprising titanium oxide containing at least one metal element with selected silicon, zirconium, aluminum and hafnium power. As described above, the bismuth and the at least one metal element may be present in the photocatalyst in the form of a compound of the metal including elemental metal.
- Preferred embodiments of the titanium oxide photocatalyst according to the present invention include the following:
- the second additional metal component is silicon.
- Oxy-titanium further contains nitrogen in a content of 0.0005 wt% or more and 1.0 wt% or less.
- the acid-titanium-based photocatalyst of the present invention can be produced by a method including the following steps (a) to (c) (however, either of step (a) and step (b) is first). Yes or even at the same time):
- step (c) A step of heat-treating the mixture containing the hydrolyzate obtained through steps (a) and (b), preferably at 400 to 700 ° C.
- the second additional metal component (silicon, zirconium, aluminum, and Z or hafnium), together with bismuth as the first additional metal component, and titanium of the main metal component It is considered that it constitutes a complex oxide and functions as one component of the catalyst for the visible light activity expression.
- a composite oxide is formed by subjecting the mixture that has undergone hydrolysis during the heat treatment in step (c) to a heat treatment.
- titanium oxide As described above, it is possible to add titanium to titanium oxide as an additional metal component. There have been reports on the development of visual light activity. However, as far as the present inventors know, two or more kinds of metals, ie, the first additional metal component (bismuth) and the second additional metal component metal are contained in the titanium oxide titanium as in the present invention. No visible light responsive photocatalyst has been reported as a specific disclosure with experimental results. As will be demonstrated in the examples below, when titanium oxide contains only the first additional metal component (bismuth) or only the second additional metal component, it is compared with titanium oxide containing no additional metal component. Thus, a sufficient increase in visible light photocatalytic activity is not observed.
- the titanium oxide photocatalyst of the present invention further contains a predetermined amount of nitrogen because the visible light response is further enhanced.
- the expression and enhancement of visible light responsiveness due to the inclusion or addition of nitrogen in titanium oxide is described in some of the above-mentioned documents. By including nitrogen in the oxygen-based photocatalyst, it is considered that nitrogen causes a new electronic interaction with the cation in the photocatalyst, leading to an enhancement of the visible light response.
- the action effect on the visible light activity by the combination of the above-described bismuth and the second additional metal component by further containing a specific amount of N.
- the visible light activity of the photocatalyst is remarkably increased.
- the titanium oxide photocatalyst according to the present invention has an X-ray diffraction pattern of a sample obtained by heat-treating the titanium oxide photocatalyst itself or its precursor substance at 600 ° C.
- substantially no peak attributed to the rutile crystal of titanium This means that the titanium oxide photocatalyst does not substantially contain rutile crystals.
- substantially no peak means that the abundance ratio of rutile crystals to anatase crystals is 1.0% or less.
- the acid-titanium is at least partially composed of an anatase crystal, and the crystallite size calculated by X-ray diffraction peak force of the anatase crystal is 20 It is preferable that it is nm or less.
- the photocatalytic function is further enhanced.
- the acid-titanium-based photocatalyst of the present invention containing silicon or the like as the second additional metal component can be analyzed by XPS (X-ray photoelectron spectroscopy).
- XPS X-ray photoelectron spectroscopy
- the fact that the XPS spectrum diagram has at least two pairs of peaks out of the three pairs of peaks located in the ranges (a) to (c) above indicates that the present invention Titanium photocatalyst
- the bismuth contained in the titanium oxide is at least partially divalent (Bi 2+ ) and Z or zero valent (Bi °), that is, It means that it exists in a reduced state, which is lower (lower valence) than trivalent. It is presumed that when the reduced bismuth content exceeds a certain level, excellent visible light photocatalytic performance is exhibited.
- titanium oxide photocatalyst of the present invention containing bismuth and a second additional metal component
- titanium oxide is maintained as anatase microcrystals, Crystal transition is unlikely to occur
- Bismuth suppresses charge recombination
- Bismuth and the second additional metal component act as additional metal components, accelerating the generation of carriers by visible light.
- the visible light activity of the base acid-titanium is considered to be significantly improved.
- the spectral diagram is more preferably one of the following:
- the total area of the pair of peaks in each of the groups (a) and (c) is a and c, respectively, and the value of the peak area ratio of cZa is 0.1 or more.
- the present invention it is possible to efficiently mass-produce a titanium oxide photocatalyst exhibiting a significantly enhanced visible light photocatalytic action while maintaining the original ultraviolet photocatalytic activity of titanium oxide. .
- This photocatalyst can be expected to have a strong environmental purification effect both outdoors and indoors and in lighting places where the photocatalytic activity is extremely strong compared to conventional visible light type titanium oxide photocatalysts.
- FIGS. 1 (a) and 1 (b) show X-ray diffraction patterns of samples obtained by changing the heat treatment temperature in Example 2.
- FIG. 1 shows X-ray diffraction patterns of samples obtained by changing the heat treatment temperature in Example 2.
- the photocatalyst of the present invention having excellent visible light activity contains bismuth as the first additional metal component, and at least one metal element selected from silicon, zirconium, aluminum, and a nobium force as the second additional metal component.
- bismuth as the first additional metal component
- at least one metal element selected from silicon, zirconium, aluminum, and a nobium force as the second additional metal component.
- Made of titanium oxide Since the metal of bismuth and the second additional metal component partially forms a composite metal oxide with titanium oxide, at least a part thereof is present in the photocatalyst in the form of a metal oxide.
- the second additional metal component is silicon because of its photocatalytic activity.
- the acid oxytitanium By adding both bismuth and the second additional metal component to the acid oxytitanium to form a compound oxydide, higher visible light photocatalytic activity can be achieved compared to conventional acid-titanium-based visible light photocatalysts. It becomes the photocatalyst shown.
- the ultraviolet catalyst activity inherent to titanium oxide is maintained and enhanced.
- the contents of the first and second additional metal components in the titanium oxide titanium are preferably as follows.
- the sum of ⁇ + ⁇ is preferably 0.6 or less.
- Titanium oxide in the titanium oxide photocatalyst of the present invention may be completely crystalline or incomplete. It may contain crystalline, ie, amorphous.
- the crystal form of titanium oxide may be a single phase of either anatase, rutile, or brookite, and two or more of these may be mixed. However, in order to express high activity, it is preferable that the acid titanium is anatase single phase.
- the acid-titanium photocatalyst of the present invention As another crystallographic feature of the acid-titanium photocatalyst of the present invention, as described above, either the acid-titanium photocatalyst itself or its precursor material before heat treatment is used. X-ray diffraction pattern power of a sample obtained by heat treatment at ° C. It is preferable that the sample has substantially no peaks attributed to the rutile crystal of titanium oxide. In this case, it is assumed that the acid-titanium-based photocatalyst before the heat treatment at 600 ° C. contains rutile-type acid titanium.
- the transition to rutile does not occur, and the photocatalyst can exhibit a particularly high photocatalytic activity.
- the photocatalyst itself is! /, When its precursor substance is fixed on the surface of the substrate or the like, and even if the heat treatment temperature is higher than 600 ° C, it is affected by the substrate. Transfer to rutile may be inhibited. Therefore, when the photocatalyst or its precursor is fixed to the substrate, it is evaluated by heat-treating it at 600 ° C after separating it from the substrate.
- the heat treatment atmosphere in this heat treatment test is an oxidizing atmosphere (eg, air).
- the titanium oxide-based photocatalyst of the present invention can further contain nitrogen in order to enhance the visible light response.
- the preferable content of nitrogen in the photocatalyst is in the range of 0.0005 wt% or more and 1.0 wt% or less, more preferably 0.001 wt% or more and 0.1 wt% or less. Visible light response is not enhanced when the nitrogen content is less than 0.0005 wt%, whereas it is possible when the nitrogen content exceeds 1.0 wt%. Visible light activity decreases, and the production of the photocatalyst becomes complicated.
- a characteristic pattern of a spectrum diagram obtained by XPS analysis can be mentioned. Specifically, Bi-4f core level spectral power obtained by XPS analysis of the photocatalyst (a) 165 to 162.5 eV and 159.7 to 157.2 eV, (b) 16 3 to 161 eV and 157.7 to 155.7 eV, and (c) at least two of the three pairs of peaks located in the ranges of 162.5 to 160 eV and 157.2 to 154.7 eV.
- bismuth is contained in titanium oxide in a state where it is at least partially reduced (Bi 2+ and / or Bi Q ).
- the above XPS spectrum diagram preferably has all three pairs of peaks (a) to (c).
- bismuth is Bi 3+ , Bi 2+ , and Bi.
- Bi is Bi 3+ , Bi 2+ , and Bi.
- the total peak area of each pair of the above three pairs (a) to (c) is a, b, c respectively, and the peak area ratio value of (b + c) Za is 0.15 or more. This value is more preferably 0.2 or more. Thereby, a photocatalyst stably exhibiting excellent visible light photocatalytic activity can be obtained. b and c !, one of them may be 0! /.
- the peak area ratio value of bZa is preferably 0.05 or more, more preferably 0.1 or more.
- Such a titanium oxide photocatalyst means that at least a part of bismuth is Bi 2+ . Thereby, the visible light photocatalytic activity is enhanced.
- the value of the peak area ratio of c / a is preferably 0.1 or more, more preferably 0.2 or more.
- Such Sani ⁇ titanium-based photocatalyst means that at least a portion of bismuth is in the Bi Q. Thereby, the visible light photocatalytic activity is further enhanced.
- the peak located on the lower energy side is assigned as Bi 2+ (BiO), and it is further lower than 2 eV. If the peak located on the energy side is assigned as BiO Q (metal Bi),
- the peak intensity may be lower than the actual peak, or the peak may not be observed at all. In that case, it is preferable to perform XPS analysis after removing the surface of the sample by etching or sputtering at a depth of several nm or more with argon or the like.
- the titanium oxide photocatalyst of the present invention can be supported on a carrier having no photocatalytic action.
- the carrier include silica, alumina, zeolite and the like.
- a cocatalyst such as a noble metal such as platinum, ruthenium or palladium can be contained in the photocatalyst.
- Examples of the shape of the photocatalyst include a particulate shape, a fiber shape, and a thin film shape, and it is preferable to use them appropriately depending on the application.
- the particles extend to a granulated material having a fine powder force of about several nanometers and several tens of microns, and the size and form thereof are not limited.
- a thin film it is generally fixed on a substrate.
- the production of the titanium oxide photocatalyst may be performed by a dry synthesis method such as sputtering or CVD and a wet synthesis method such as a sol-gel method or a hydrolysis method.
- the production method includes the following steps (a) to (c):
- step (a) and step (b) may be performed first or simultaneously. Also, the step (b) and the step (c) can be performed during one heat treatment. However, from the viewpoint of the activity of the photocatalyst and the ease of production, it is preferable to perform the steps (a), (b) and (c) in this order. Note that one step is repeated twice or more, steps (a) to (c) are repeated twice or more in sequence, or steps (a) and (b) are repeated twice or more in order, and then the last step It is also possible to perform the heat treatment according to (c).
- titanium oxide which is the main component of the photocatalyst of the present invention
- any titanium oxide precursor compound that generates titanium oxide by hydrolysis and Z or heating can be used.
- examples of such compounds include inorganic titanium compounds such as titanium tetrachloride, titanium trichloride, titanium sulfate, titanium hydroxide, and titanium fluoride, and alkoxides such as titanium tetraethoxide and titanium tetraisoproxide. Examples of such organic titanium compounds are shown.
- Examples of the bismuth compound as the source of the first additional metal component include bismuth chloride, bismuth nitrate, bismuth sulfate, acid bismuth, acid bis titanium, oxy bismuth bismuth, bismuth phosphate Inorganic bismuth compounds such as bismuth fluoride and bismuth carbonate, and organic bismuth compounds such as bismuth naphthenate, bismuth acetate, and bismuth anoloxide.
- the bismuth compound is usually a trivalent bismuth compound.
- the bismuth compound may be a low-order bismuth compound in which some or all of the bismuth is divalent or less.
- any compound containing the metal element can also be used as the metal compound serving as the source of the second additional metal component (silicon, zirconium, aluminum, and Z or hafnium).
- the “compound” means a single metal itself as described above.
- Examples of the silicon compound include silica, silica colloid, silicon tetrachloride, silicon iodide, silicon nitride, silicon nitrate, silicon sulfate, and other inorganic silicon compounds, and tetraethoxysilane, methyltriethoxysilane, and the like. And alkoxide silanes, silicon acetate, silicone resins and organic silicon compounds.
- zirconium compound examples include zirconium oxide, zirconium oxide colloid, zirconium chloride, zirconium chlorate, zirconium nitrate, zirconium nitrate oxide, zirconium sulfate, and other inorganic zirconium compounds, as well as zirconium isoproxy and acetylyl Organic zirconium compounds such as cetonazirconium, zirconium butoxide, zirconium ethoxide
- aluminum compounds include inorganic aluminum compounds such as aluminum, aluminum chloride, aluminum fluoride, aluminum hydroxide, aluminum nitrate, and aluminum sulfate, and organic aluminum such as aluminum ethoxide and aluminum isopropyloxide. Compounds.
- Examples of the compound containing hafnium include hafnium ethoxide, hafnium chloride, hafnium sulfate, and the like.
- metal salts such as titanium tetrachloride, bismuth chloride, silicon tetrachloride, salt ⁇ zirconium, aluminum chloride, salt ⁇ hafnium, etc. are available at low cost and high purity. Since a titanium oxide photocatalyst having excellent photocatalytic activity can be obtained, it is a preferred metal supply source.
- the raw material compound used in the titanium oxide photocatalyst of the present invention that is, (1) a titanium oxide precursor compound, (2) a bismuth compound, and (3) a metallization serving as a supply source of the second additional metal component
- some of the compounds may be solid.
- the solid may also function as a carrier.
- a solid such as silica or silicon nitride
- these serve as a support, but the titanium oxide finally formed on the support contains silicon by contact with the solid. Become.
- the titanium oxide precursor compound is brought into contact with a metal compound serving as a supply source of the bismuth compound and the second additional metal component.
- the form of this contact is not particularly limited, but at least a part of these raw material compounds are soluble solids or volatile materials, and they are in solution or in the form of other raw material compounds. It is preferable to contact with.
- a small amount of a compound of another element may be contacted in addition to the raw material compound.
- At least one of the above raw materials is a hydrolyzable compound such as chloride or An alkoxide. Then, the hydrolyzable compound is hydrolyzed before or after the contact step or simultaneously with the contact step.
- This hydrolysis step (b) may be carried out using pure water, an acid aqueous solution, or a base aqueous solution.
- the hydrolyzable compound is a salt with an acid such as a salt compound
- it is preferably hydrolyzed while neutralizing with a base.
- the base include sodium hydroxide, sodium hydrogen carbonate, ammonia, ammine and the like.
- nitrogen-containing bases such as inorganic bases such as ammonia, ammonium salts, hydrazine, and organic amines such as triethanolamine, jetanolamine, pyridine, and pyrrolidone are at least partially hydrolyzed.
- nitrogen is added to the photocatalyst produced after heat treatment, it can also function as a reducing agent that partially reduces Bi during heat treatment, as will be described later. This is a preferred base.
- an aqueous solution of each metal salt is mixed (for example, The hydrolysis step (b) can be carried out by carrying out step (a) by neutralizing the resulting mixed salt aqueous solution with a base. As a result, a hydrolyzed precipitate of each metal, which is also hydrolytic, is produced. The precipitate is separated, washed with water or alcohol as necessary, dried, and then subjected to a heat treatment step (c ).
- the titanium oxide of the present invention is usually in a powder state.
- a system photocatalyst is obtained. This photocatalyst contains a first additional metal component bismuth and a second additional metal component in the form of a composite oxide with titanium oxide.
- the heat treatment temperature in the heat treatment step (c) is preferably in the range of 300 to 800 ° C. When the heat treatment temperature is outside this range, the obtained titanium oxide composite oxide may not exhibit sufficient visible light activity.
- a more preferable range of the heat treatment temperature is 400 ° C or more and 700 ° C or less. In this temperature range, Ti, Bi, and the second additive metal component, the three types of oxides, form an orderly combination, with sufficient crystallinity and high specific surface area, and an excellent oxidation activity with visible light activity.
- a titanium-based photocatalyst is obtained.
- the temperature holding time of the heat treatment is not particularly limited, but a range of 10 component forces and 6 hours is appropriate.
- the heating rate is not particularly limited, but from the viewpoint of photocatalytic activity and productivity It is preferable to be at least 5 ° CZ.
- the atmosphere of the heat treatment may be any of an oxidative atmosphere such as air, pure air, and oxygen, an inert atmosphere such as nitrogen and argon, or a reducing atmosphere containing a reducing gas such as hydrogen and ammonia.
- an oxidative atmosphere such as air, pure air, and oxygen
- an inert atmosphere such as nitrogen and argon
- a reducing atmosphere containing a reducing gas such as hydrogen and ammonia.
- the mixture to be heat-treated contains a low-order bismuth compound or a substance capable of reducing bismuth in advance
- the mixture is heat-treated in an oxidizing atmosphere such as air.
- an oxidizing atmosphere such as air.
- the titanium oxide photocatalyst of the present invention can be obtained. Even in this case, the visible light photocatalytic activity may be further improved if the heat treatment atmosphere is a reducing atmosphere.
- Examples of compounds capable of reducing bismuth include nitrogen-containing compounds such as ammonia, ammonium ion, hydrazine, and amines, and hydrides such as NaBH. This
- the compound can be introduced at any stage into the mixture that undergoes the pre-heat treatment.
- it may be introduced by adding it to the mixture before heat treatment.
- a basic nitrogen-containing compound having a reducing action it is convenient to introduce it into the mixture by using it for neutralization in the hydrolysis step (b).
- the titanium oxide photocatalyst of the present invention obtained after the heat treatment generally contains nitrogen.
- the titanium oxide photocatalyst contains 0.0005 wt% or more and 1.0 wt% or less of nitrogen, its visible light responsiveness is enhanced.
- this nitrogen is added to the mixture subjected to heat treatment (eg, containing a nitrogen compound). The solution to be brought into contact with or absorbed nitrogen gas, ammonia gas, etc.).
- the nitrogen content in the mixture before the heat treatment is preferably 0.1 wt% or more on a dry basis. Is more preferably 1 wt% or more, still more preferably 3 wt% or more.
- the nitrogen content of the mixture can be adjusted, for example, by the degree of washing and Z or filtration of the mixture before heat treatment.
- the mixture subjected to heat treatment contains a compound capable of reducing bismuth.
- the heat treatment atmosphere is preferably a non-oxidizing atmosphere (that is, an inert atmosphere or a reducing atmosphere).
- a particularly preferable heat treatment atmosphere is a reducing atmosphere containing nitrogen compounds having a strong reducing power such as ammonia, hydrazine, and amine, and Z or hydrogen.
- titanium oxide photocatalyst obtained by heat treatment part of Bi is, Bi 3+ force ⁇ Luo lower order bismuth (Bi 2+, Bi Q) which is preferably reduced to.
- Bi 3+ force ⁇ Luo lower order bismuth Ba 2+, Bi Q
- the visible light activity of the titanium oxide photocatalyst is particularly high.
- the titanium oxide photocatalyst of the present invention produced by the above method may be used in a powder state as it is. However, from the viewpoint of handling, it is convenient to use it as a photocatalytic functional member that is fixed on the surface of the base material.
- the form of the fixing rod can be selected according to the surface shape of the base material, the use, and the like, and examples thereof include a thin film shape, a particle shape, and a fiber shape.
- the type of substrate is not limited, but carbon steel, matt steel, chromate-treated steel, metal materials such as steel, stainless steel, titanium and aluminum, inorganic materials such as ceramics, glass, ceramics and quartz, plastics and grease Organic materials such as activated charcoal are exemplified. Further, a material in which these are combined, for example, a coated steel plate may be used.
- the substrate is coated with a metal or a material whose surface is not decomposed by a photocatalyst.
- a base material whose whole or surface is an organic material may not deteriorate or decompose due to the oxidizing power of the photocatalyst.
- the base material surface is previously coated with a material that does not decompose with the photocatalyst.
- silicone resin is not easily degraded by photocatalysts, so it may not be coated depending on conditions.
- the shape of the substrate is not particularly limited, and may be any shape such as a thin plate, a thick plate, a fibrous shape (including a knitted fabric and a nonwoven fabric), a net shape, and a tubular shape. It may be an object with a complicated shape that is used as a product as it is, or an existing or in-use object.
- the surface of the substrate may be porous or dense.
- the photocatalytic functional member is obtained by dispersing particles of the titanium oxide photocatalyst of the present invention in a solvent. It can be produced by applying a dispersion or coating solution to a substrate and drying the coating film.
- the precursor of the titanium oxide photocatalyst of the present invention may be fixed to the substrate.
- a photocatalytic functional member can be produced by performing the steps (a) to (c) described above on the surface of the substrate.
- titanium chloride which is a precursor of titanium oxide
- the photocatalytic functional member according to the present invention can be produced by bringing the component source compounds into contact and, if necessary, hydrolyzing, followed by heat treatment.
- the coating liquid may be substantially composed of only a photocatalyst (or a precursor thereof) and a dispersion medium (liquid medium), but preferably further contains a binder.
- the titanium oxide photocatalyst produced by the above-described method generally has an average primary particle system of several to hundreds of fine particles. It becomes as large as 10 m, making it difficult to disperse uniformly in the medium.
- a dispersion of photocatalyst particles is prepared by sufficiently dispersing titanium oxide photocatalyst particles in a medium in advance. It is preferable to prepare a coating liquid by using this dispersion and incorporating a binder therein. When this coating solution is used, a thinner and more homogeneous photocatalytic film can be formed, and film characteristics and photocatalytic activity are improved.
- the average particle size of the photocatalyst in the dispersion is preferably 500 nm or less. If it is larger than this particle size, the film tends to be pulverized and storage stability is lowered.
- the average particle size of the photocatalyst is more preferably 300 nm or less, still more preferably 200.
- the liquid medium in which the photocatalyst particles are dispersed includes water such as distilled water, ion-exchanged water, and ultrapure water; alcohols such as methanol, ethanol, and 2-propanol; ketones such as methyl ethyl ketone; benzene, And aromatic hydrocarbons such as toluene and xylene. These may be arbitrarily mixed and used, but in that case, a combination of mutually compatible solvents is used.
- the dispersion treatment is preferably performed by mixing the photocatalyst with a medium so that the solid content concentration is in the range of several wt% to 50 wt%.
- the dispersibility may decrease.
- a dispersant and a peptizer may be added as necessary.
- the dispersing agent include a force group and a sulfone type, and examples of the peptizer include nitric acid, hydrochloric acid, sulfuric acid and the like. Further, a base or acid may be added for pH adjustment.
- the dispersion treatment can also be performed using a paint shaker commonly used for the preparation of a coating solution, but for example, a media mill, shearing using a rotary blade, thin film swirling, and ultrasonic waves are more powerful. It is preferable to carry out by a suitable dispersing means. Two or more types of dispersion means may be used in combination.
- the obtained dispersion contains coarse aggregated particles, it is preferable to remove them by filtration or centrifugation. This is because the coarse particles are likely to become the starting point of the powder when peeled in the film. It is possible to adjust the solid concentration by adding a solvent to the dispersion after dispersion treatment.
- This dispersion can be used as a coating liquid as it is and applied to a substrate.
- the photocatalyst becomes a fine particle having an average particle size of 500 or less
- a film can be formed without a binder, and a film that can be used only by the photocatalyst particles can be formed.
- a binder solution may be applied on the formed film, and the binder may be impregnated between the photocatalyst particles.
- a preferred coating liquid contains a binder in addition to the photocatalyst and the medium.
- the medium may be similar to that described for the above dispersion but is selected so that the binder dissolves or emulsifies it.
- the amount of the binder is adjusted so that the content of the titanium oxide-based photocatalyst in the formed film is 595 wt%. Films with a photocatalyst content of less than 5 wt% show almost no photocatalytic activity by visible light irradiation. When the content of the photocatalyst in the film exceeds 95 wt%, the binder component is too small and the film is easily peeled off.
- the photocatalyst content in the film is preferred It is preferably 30 to 90 wt%, and more preferably 50 wt% or more in order to obtain sufficient photocatalytic activity.
- binder component examples include silica, alumina, titania, magnesia, zirconia, and other metal oxide sols (gels in the film), organosilane compounds, silicone resins, fluorine Organic resins such as resin, urethane resin, and acrylic resin can be used. It is desirable to use a hard-to-decompose binder such as a metal oxide sol, a silicone resin, an acrylic silicone, or an acrylic urethane under conditions where the binder component is decomposed by the photocatalyst acid. If the photocatalytic functional member requires strong processability and high strength, an appropriate amount of organic resin such as fluorine resin, acrylic resin or urethane resin can be added to the hardly decomposable binder component. Therefore, required characteristics can be secured.
- the binder component is a key compound such as silica (eg, silica sol), a hydrolyzed Z-condensate of an organic silane compound, or a silicone resin.
- the silica may be a silica sol (colloidal silica) formed by hydrolysis and condensation of a carboxylic acid ester (eg, ethyl silicate).
- a film-forming hydrolyzable organic silane compound for example, an alkoxysilane or a silane coupling agent can be used.
- One component of the solder may be dissolved uniformly in the medium, or it may be emulsified in the medium to form an emulsion.
- the coating solution may contain other components other than those described above!
- examples of such other components include a titanium oxide photocatalyst that is not a visible light responsive type (eg, a conventional titanium oxide photocatalyst), and a carrier when the photocatalyst is a supported particle.
- Minor components such as colorants (preferably inorganic pigments) and extender pigments can also be included in the film.
- the coating liquid can be applied by selecting various known method forces in accordance with the properties of the coating liquid and the shape of the substrate. After application, the coating film is dried (further cured in some cases) while heating as necessary.
- the drying (curing) temperature may be determined according to the composition of the coating liquid (type of solvent or binder), the heat resistant temperature of the substrate, and the like.
- the coating solution contains a precursor of a titanium oxide photocatalyst
- heating is performed so that the precursor is changed to titanium oxide.
- the thickness of the film containing the photocatalyst formed on the substrate is preferably 0.1 ⁇ m or more.
- the thickness of the film can be appropriately selected depending on the required catalyst performance and cost, but is more preferably 1 ⁇ m or more and 5 ⁇ m or more from the viewpoint of stability of catalyst performance and catalyst activity. Even more preferred.
- the upper limit of the thickness is not particularly specified, but it is 50 m or less, preferably 20 m or less in consideration of cost and effect saturation.
- the titanium oxide photocatalyst of the present invention and the photocatalytic functional member provided on the surface of the titanium oxide photocatalyst are not only irradiated with ultraviolet rays, but are brought into contact with a substance to be treated under irradiation with visible light having a wavelength of 400 ° It can exhibit photocatalytic action to decompose, remove, or detoxify various harmful substances and adhered substances.
- the photocatalyst may be used in an environment in which a substance to be decomposed can be brought into contact with it and can be irradiated with visible light.
- the light source includes at least a part of the wavelength range of visible light
- visible light for example, sunlight, fluorescent lamp, halogen lamp, black light, xenon lamp, mercury lamp, or the like
- the photocatalyst of the present invention exhibits activity even with ultraviolet rays
- the light source may contain visible light and ultraviolet light, and the photocatalytic activity is higher in that case.
- Hazardous substances or deposits that can be processed by the acid-titanium-based photocatalyst of the present invention include VOC gases such as formaldehyde, acetoaldehyde, and toluene; air pollution gases such as NO, SO, and Freon; ammonia, Odor gases such as hydrogen sulfide and mercaptans; Organic compounds such as alcohols, BTX and phenols; Organic halogens such as trihalomethanes, trichloroethylene and chlorofluorocarbons; Various biological oxygen demand substances such as amino acids; surfactants; inorganic compounds such as cyanide and sulfur compounds; various heavy metal ions; fungi such as Escherichia coli, staphylococci, and green bacteria, molds, and algae Examples include microorganisms; oil, tobacco crabs, fingerprints, rain stripes, mud, and the like.
- VOC gases such as formaldehyde, acetoaldehyde, and toluene
- Ti content 9.3 wt%)
- the crystal form of titanium oxide in the obtained photocatalyst was substantially 100% anatase.
- the nitrogen content in the photocatalyst was 0.004 wt%.
- Aqueous ammonia (7 wt%) was added dropwise to an acidic aqueous solution containing bismuth chloride to hydrolyze bismuth chloride.
- the precipitate was filtered, washed with distilled water, and vacuum-dried at 80 ° C. for 6 hours to obtain a hydrolyzate of salt and bismuth.
- Sample No. 1 is an example of the present invention
- Samples ⁇ . 2 to 6 are ratios
- the No. 1 titanium oxide photocatalyst according to the invention is No. 6 or No. 2 titanium oxide photocatalyst containing only one of bismuth and silicon, and No. 3 containing neither of them. It can be seen that the decomposition activity of acetoaldehyde is significantly higher than that of acid-titanium-based photocatalysts (ie, titanium oxide).
- Sample Nos. 7 to 14 are examples of the present invention, and Sample Nos. 15 to 17 are comparative examples.
- the titanium-based oxide photocatalyst of the present invention already showed high photocatalytic activity even when the heat treatment temperature was 350 ° C, and even higher when the heat treatment temperature was 500 ° C to 650 ° C. It was. In particular, the photocatalytic activity increased in the heat treatment temperature range of 500 to 600 ° C. On the other hand, with the titanium oxide of the comparative example, the photocatalytic activity decreased dramatically as the heat treatment temperature increased from 600 ° C to 700 ° C.
- the titanium oxide photocatalysts of Nos. 8, 10, 12 and 14 of the present invention shown in Table 2 were subjected to titanium oxide under any heat treatment conditions.
- a diffraction peak around 20: 25 ° attributed to anatase crystals was observed.
- the crystallite size of anatase determined by the Scherrer equation was 10 nm or less when the heat treatment temperature was at least 700 ° C.
- the acid-titanium photocatalyst according to the present invention was subjected to XPS analysis under the following conditions: Apparatus used: Scanning X-ray photoelectron spectrometer (PHI Quantum 20 00 manufactured by ULVAC, Huai)
- X-ray source used mono- A1 ⁇ ⁇ -ray 44.8 W, 17 kV
- X-ray beam diameter approx. 200 / ⁇ ⁇ ⁇
- Neutralizing gun 1.0 V, 20 mA (combined with Ar + low-speed ion gun)
- Vacuum about 2.0 X 10- 8 torr.
- Table 4 shows (a) 165 to 162.5 eV and 159.7 to 157.2 eV, (b) 163 to 161 eV and 157.7 to 155.7 eV, and (c) 162.5 to 160 eV and 157.2 to C / a, bZa, and (b where the position and area of each peak of the three pairs of peaks located in each range of 154.7 eV and the total area of each pair of peaks are a, b, and c. + Summarize peak area ratio values for c) / a.
- the titanium oxide photocatalyst according to the present invention prepared in Sample No. 1 of Example 1 was pulverized, dispersed in water, and the dispersion was applied to a glass plate (16 cm 2 ) and dried.
- a photocatalytic functional member having a photocatalyst layer on the surface of the base material was prepared (Sample No. 21).
- a photocatalyst functional member was prepared by attaching a glass plate to a commercially available photocatalyst powder for ultraviolet rays (ST-01, manufactured by Ishihara Sangyo Co., Ltd.) (Sample No. 22).
- Test No. 21 is an example of the present invention
- Test No. 22 is a comparative example
- the titanium oxide-based photocatalyst of the present invention maintains the same ultraviolet activity as that of the conventional product even under ultraviolet irradiation.
- the conventional product did not substantially exhibit a photocatalytic function under irradiation with visible light, whereas the photocatalyst of the present invention showed excellent visible light activity.
- Example 6
- the present invention uses zirconium tetrachloride or aluminum trichloride in place of silicon tetrachloride, and contains bismuth and zirconium or aluminum as the second additional metal component. Titanium-based photocatalysts (Test Nos. 23 and 24) were prepared. Using this photocatalyst, the ability to decompose acetaldehyde with visible light was evaluated in the same manner as in Example 1. Table 6 summarizes the photocatalyst composition and photocatalytic activity.
- Sample Nos. 23 and 24 are examples of the present invention, and sample No. 3 is a comparative example.
- a photocatalyst dispersion was prepared in the same manner as in Example 7, except that the dispersant was changed to nitric acid.
- a photocatalytic functional steel plate was produced by applying this coating solution to a coated steel plate as follows. First, a primer layer having a thickness of 1.0 m was formed on a coated steel plate (thickness: 0.3 mm, polyester-based coating) using a primer coating mainly composed of a silicone resin. On the silicone primer layer, the above coating solution is applied using a bar coater (20 #), dried at 150 ° C for 2 minutes, and a photocatalytic function having a film containing the titanium oxide photocatalyst of the present invention. A steel plate was obtained. The film thickness was about 2.0 m. Using this photocatalytic functional steel plate, a decomposition test of acetoaldehyde was conducted in the same manner as in Example 1. The CO production rate was 0.8 molZ.
- Visible light irradiation was performed using a white fluorescent lamp as a light source, and a commercially available talil plate (Sumitomo Chemical-LF39) as a UV cut filter.
- the illuminance was 15,000 lux.
- the degree of hydrophilization was evaluated by measuring the contact angle of the steel sheet surface with water. As a result, the contact angle with water decreased to about 10 ° after 24 hours of visible light irradiation, which was about 50 ° before visible light irradiation.
- the photocatalytic functional member of the present invention has a superhydrophilic function as well as exhibiting photocatalytic degradation activity when irradiated with visible light.
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EP06810734A EP1930077A4 (en) | 2005-09-29 | 2006-09-28 | TITANIUM OXIDE PHOTOCATALYZER, METHOD OF MANUFACTURING THEREOF AND USE THEREOF |
CA2624092A CA2624092C (en) | 2005-09-29 | 2006-09-28 | Titanium oxide photocatalyst, method for producing same and use thereof |
CN2006800445615A CN101316654B (zh) | 2005-09-29 | 2006-09-28 | 氧化钛类光催化剂及其制造方法和用途 |
KR1020087010265A KR100935065B1 (ko) | 2005-09-29 | 2006-09-28 | 산화티탄계 광촉매와 그 제조 방법 및 용도 |
JP2007537672A JP4803180B2 (ja) | 2005-09-29 | 2006-09-28 | 酸化チタン系光触媒とその製造方法及び用途 |
US12/057,983 US7858201B2 (en) | 2005-09-29 | 2008-03-28 | Titanium oxide photocatalyst, method for producing same and use thereof |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007117999A (ja) * | 2005-09-29 | 2007-05-17 | Sumitomo Metal Ind Ltd | 酸化チタン系光触媒とその用途 |
WO2009052510A2 (en) * | 2007-10-19 | 2009-04-23 | Worthington Technologies, Llc | Method of surface modifying titania using metal and compositions therefrom |
WO2009052510A3 (en) * | 2007-10-19 | 2009-08-27 | Worthington Technologies, Llc | Method of surface modifying titania using metal and compositions therefrom |
JP2014054600A (ja) * | 2012-09-12 | 2014-03-27 | Dainippon Printing Co Ltd | 光触媒機能材料の製造方法 |
CN104492465A (zh) * | 2014-11-27 | 2015-04-08 | 青岛科技大学 | 一种具有棉花状结构的BiOCl光催化剂及其制备方法 |
CN104492465B (zh) * | 2014-11-27 | 2017-01-04 | 青岛科技大学 | 一种具有棉花状结构的BiOCl光催化剂及其制备方法 |
JP2017007897A (ja) * | 2015-06-23 | 2017-01-12 | 国立大学法人東京工業大学 | 二酸化炭素発生システムおよびそれに搭載する液体カートリッジ |
Also Published As
Publication number | Publication date |
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US20080268268A1 (en) | 2008-10-30 |
EP1930077A4 (en) | 2012-06-20 |
EP1930077A1 (en) | 2008-06-11 |
KR20080050631A (ko) | 2008-06-09 |
CN101316654A (zh) | 2008-12-03 |
TW200734047A (en) | 2007-09-16 |
CA2624092A1 (en) | 2007-04-05 |
JPWO2007037321A1 (ja) | 2009-04-09 |
KR100935065B1 (ko) | 2009-12-31 |
US7858201B2 (en) | 2010-12-28 |
CA2624092C (en) | 2011-04-26 |
JP4803180B2 (ja) | 2011-10-26 |
TWI317650B (ja) | 2009-12-01 |
CN101316654B (zh) | 2010-10-13 |
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