JP2009056348A - Photocatalyst dispersion - Google Patents
Photocatalyst dispersion Download PDFInfo
- Publication number
- JP2009056348A JP2009056348A JP2007223700A JP2007223700A JP2009056348A JP 2009056348 A JP2009056348 A JP 2009056348A JP 2007223700 A JP2007223700 A JP 2007223700A JP 2007223700 A JP2007223700 A JP 2007223700A JP 2009056348 A JP2009056348 A JP 2009056348A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- photocatalyst
- copper
- dispersion
- photocatalyst dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 95
- 239000006185 dispersion Substances 0.000 title claims abstract description 86
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 98
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000010949 copper Substances 0.000 claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 claims abstract description 44
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 3
- 230000001699 photocatalysis Effects 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 47
- 239000002612 dispersion medium Substances 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 238000000926 separation method Methods 0.000 description 23
- 239000010936 titanium Substances 0.000 description 23
- 229910052719 titanium Inorganic materials 0.000 description 21
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 20
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002609 medium Substances 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 230000001747 exhibiting effect Effects 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- -1 acyclic amine compound Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 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 6
- 150000003609 titanium compounds Chemical class 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 238000001362 electron spin resonance spectrum Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940005740 hexametaphosphate Drugs 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- PYCBFXMWPVRTCC-UHFFFAOYSA-N ammonium metaphosphate Chemical compound N.OP(=O)=O PYCBFXMWPVRTCC-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- LIZQWFITYTUEPG-UHFFFAOYSA-M bromoplatinum Chemical compound [Pt]Br LIZQWFITYTUEPG-UHFFFAOYSA-M 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- SKQUUKNCBWILCD-UHFFFAOYSA-J dicopper;chloride;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Cl-].[Cu+2].[Cu+2] SKQUUKNCBWILCD-UHFFFAOYSA-J 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- JMTCDHVHZSGGJA-UHFFFAOYSA-M potassium hydrogenoxalate Chemical compound [K+].OC(=O)C([O-])=O JMTCDHVHZSGGJA-UHFFFAOYSA-M 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- UJRAXLUXHBUNDO-UHFFFAOYSA-M sodium;hydron;oxalate Chemical compound [Na+].OC(=O)C([O-])=O UJRAXLUXHBUNDO-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
本発明は、光触媒分散液に関する。 The present invention relates to a photocatalyst dispersion.
半導体にバンドギャップ以上のエネルギーをもつ光を照射すると、価電子帯の電子が伝導帯に励起し、価電子帯に正孔、伝導帯に電子が生成する。これらはそれぞれ強い酸化力と還元力を有し、半導体に接触した分子種に酸化還元作用を及ぼす。このような作用は、光触媒作用と呼ばれており、光触媒作用を示す半導体は光触媒体と呼ばれている。光触媒体を利用することにより、その光触媒作用によって、大気中の有機物などを分解することができる。 When a semiconductor is irradiated with light having energy higher than the band gap, electrons in the valence band are excited to the conduction band, and holes are generated in the valence band and electrons are generated in the conduction band. These have strong oxidizing power and reducing power, respectively, and exert a redox action on the molecular species in contact with the semiconductor. Such an action is called a photocatalytic action, and a semiconductor exhibiting a photocatalytic action is called a photocatalyst. By utilizing the photocatalyst, organic matter in the atmosphere can be decomposed by the photocatalytic action.
このような光触媒体として酸化チタンが注目されおり、光触媒作用を示す光触媒酸化チタンを分散媒中に分散させた光触媒分散液も市販されている。かかる光触媒分散液を基材上に塗布することにより、高い光触媒活性を示す光触媒塗膜を得ることができる。 Titanium oxide attracts attention as such a photocatalyst, and a photocatalyst dispersion liquid in which photocatalytic titanium oxide exhibiting a photocatalytic action is dispersed in a dispersion medium is also commercially available. By applying such a photocatalyst dispersion on a substrate, a photocatalytic coating film exhibiting high photocatalytic activity can be obtained.
光触媒分散液としては、より高い光触媒活性を示す光触媒塗膜が得られるものが求められている。 As a photocatalyst dispersion liquid, what can obtain the photocatalyst coating film which shows higher photocatalytic activity is calculated | required.
そこで本発明者等は、より高い光触媒活性を示す光触媒塗膜を与え得る光触媒分散液について検討した結果、本発明を完成するに至った。 Therefore, the present inventors have studied a photocatalyst dispersion that can provide a photocatalyst coating film exhibiting higher photocatalytic activity, and as a result, the present invention has been completed.
すなわち本発明は、光触媒酸化チタン、銅成分、分散剤および分散媒を含み、銅換算の銅成分の含有量が光触媒酸化チタンに対して０．０１モル％〜０．６モル％であることを特徴とする光触媒分散液を提供するものである。 That is, the present invention includes a photocatalytic titanium oxide, a copper component, a dispersant, and a dispersion medium, and the content of the copper component in terms of copper is 0.01 mol% to 0.6 mol% with respect to the photocatalytic titanium oxide. The photocatalyst dispersion liquid is provided.
本発明の光触媒分散液によれば、硝子、プラスチック、金属、陶磁器、コンクリートのような基材に、高い光触媒活性を示す膜を形成することができる。 According to the photocatalyst dispersion liquid of the present invention, a film exhibiting high photocatalytic activity can be formed on a substrate such as glass, plastic, metal, ceramics, and concrete.
以下、本発明を詳細に説明する。
本発明に用いる光触媒酸化チタンとしては、光触媒活性を示す粉末状の酸化チタンが挙げられ、蛍光灯照射下で高い光触媒活性を発現する点から、可視光線の照射でも高い光触媒活性を示す酸化チタンが好ましい。
Hereinafter, the present invention will be described in detail.
Examples of the photocatalytic titanium oxide used in the present invention include powdered titanium oxide exhibiting photocatalytic activity. From the viewpoint of developing high photocatalytic activity under fluorescent lamp irradiation, titanium oxide exhibiting high photocatalytic activity even under irradiation with visible light is used. preferable.
このような光触媒酸化チタンとしては、例えばチタン化合物と塩基を反応させ、生成物にアンモニアを添加し、熟成した後、固液分離し、ついで固形分を焼成する方法により製造することができる。 Such photocatalytic titanium oxide can be produced, for example, by a method in which a titanium compound is reacted with a base, ammonia is added to the product, aging is performed, solid-liquid separation is performed, and then a solid content is baked.
この方法では、チタン化合物として、例えば三塩化チタン〔ＴｉＣｌ３〕、四塩化チタン〔ＴｉＣｌ４〕、硫酸チタン〔Ｔｉ（ＳＯ４）２・ｍＨ２Ｏ、０≦ｍ≦２０〕、オキシ硫酸チタン〔ＴｉＯＳＯ４・ｎＨ２Ｏ、０≦ｎ≦２０〕、オキシ塩化チタン〔ＴｉＯＣｌ２〕を用いることができる。 In this method, examples of titanium compounds include titanium trichloride [TiCl 3 ], titanium tetrachloride [TiCl 4 ], titanium sulfate [Ti (SO 4 ) 2 .mH 2 O, 0 ≦ m ≦ 20], titanium oxysulfate [ TiOSO 4 · nH 2 O, 0 ≦ n ≦ 20], titanium oxychloride [TiOCl 2 ] can be used.
チタン化合物と反応させる塩基としては、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、アンモニア、ヒドラジン、ヒドロキシルアミン、モノエタノールアミン、非環式アミン化合物、環式脂肪族アミン化合物を用いることができる。 As the base to be reacted with the titanium compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, hydrazine, hydroxylamine, monoethanolamine, acyclic amine compound, or cyclic aliphatic amine compound should be used. Can do.
チタン化合物と塩基の反応は、ｐＨ２以上、好ましくは３以上、また７以下、好ましくはｐＨ５以下で行われ、そのときの温度は、通常９０℃以下、好ましくは７０℃以下、さらに好ましくは５５℃以下である。製造された酸化チタンの粉砕性を向上させるために、チタン化合物と塩基の反応を過酸化水素存在下で行ってもよい。 The reaction between the titanium compound and the base is carried out at a pH of 2 or more, preferably 3 or more, and 7 or less, preferably pH 5 or less. The temperature at that time is usually 90 ° C. or less, preferably 70 ° C. or less, more preferably 55 ° C. It is as follows. In order to improve the grindability of the produced titanium oxide, the reaction between the titanium compound and the base may be performed in the presence of hydrogen peroxide.
熟成は、例えばアンモニアが添加された生成物を、攪拌しながら、０℃以上、好ましくは１０℃以上、また１１０℃以下、好ましくは８０℃以下、より好ましくは５５℃以下の温度範囲に、１分以上、好ましくは１０分以上、また１０時間以内、好ましくは２時間以内の条件で保持する方法で行うことができる。 For aging, for example, a product added with ammonia is stirred at a temperature range of 0 ° C. or higher, preferably 10 ° C. or higher, 110 ° C. or lower, preferably 80 ° C. or lower, more preferably 55 ° C. or lower. It can be carried out by a method of holding for at least 10 minutes, preferably at least 10 minutes, and within 10 hours, preferably within 2 hours.
反応と熟成に用いられるアンモニアの総量は、水の存在下でチタン化合物を水酸化チタンに変えるのに必要な塩基の化学量論量を超える量であることが好ましく、例えば１．１モル倍以上であることが好ましい。塩基の量が多いほど、可視光照射によって高い光触媒活性を示す膜を形成できるコーティング液が得られやすいので好ましく、例えば１．５モル倍以上がさらに好ましい。一方、塩基の量があまり多くなっても、量に見合った効果が得られないので、２０モル倍以下、さらには１０モル倍以下が適当である。 The total amount of ammonia used for the reaction and ripening is preferably an amount exceeding the stoichiometric amount of the base required to convert the titanium compound to titanium hydroxide in the presence of water, for example, 1.1 mol times or more It is preferable that The larger the amount of the base, the easier it is to obtain a coating liquid capable of forming a film exhibiting high photocatalytic activity by irradiation with visible light. For example, 1.5 mole times or more is more preferable. On the other hand, even if the amount of the base is too large, an effect commensurate with the amount cannot be obtained, so 20 mol times or less, further 10 mol times or less is appropriate.
熟成された生成物の固液分離は、加圧濾過、減圧濾過、遠心分離、デカンテーションなどで行うことができる。また固液分離では、得られる固形分を洗浄する操作をあわせて行うことが好ましい。 Solid-liquid separation of the aged product can be performed by pressure filtration, vacuum filtration, centrifugation, decantation, or the like. In the solid-liquid separation, it is preferable to perform an operation for washing the obtained solid content.
固液分離された固形分または任意の洗浄を行った固形分の焼成は、気流焼成炉、トンネル炉、回転炉などを用いて、通常２５０℃以上、好ましくは２７０℃以上、また６００℃以下、好ましくは５００℃以下、より好ましくは４００℃以下の温度条件で行うことができる。このときの時間は、焼成温度や焼成装置の種類により異なり一義的ではないが、通常１０分以上、好ましくは３０分以上、また３０時間以内、好ましくは５時間以内である。
焼成して得られる酸化チタンには、必要に応じて、タングステン、ニオブ、鉄、ニッケルの酸化物や水酸化物などのような固体酸性を示す化合物またはランタン、セリウム、カルシウムの酸化物や水酸化物などのような固体塩基性を示す化合物、またインジウム酸化物やビスマス酸化物のような可視光線を吸収する金属化合物を担持してもよい。
The solid content separated by solid-liquid separation or the solid content subjected to arbitrary washing is usually 250 ° C or higher, preferably 270 ° C or higher, and 600 ° C or lower, using an airflow firing furnace, a tunnel furnace, a rotary furnace, or the like. Preferably it can be carried out under a temperature condition of 500 ° C. or lower, more preferably 400 ° C. or lower. The time at this time varies depending on the firing temperature and the type of firing apparatus and is not unambiguous, but is usually 10 minutes or longer, preferably 30 minutes or longer, and 30 hours or shorter, preferably 5 hours or shorter.
If necessary, the titanium oxide obtained by firing includes a compound showing solid acidity such as tungsten, niobium, iron, nickel oxide or hydroxide, or lanthanum, cerium, calcium oxide or hydroxide. You may carry | support the compound which shows solid basicity, such as a thing, and the metal compound which absorbs visible rays like an indium oxide and a bismuth oxide.
本発明で用いる光触媒体酸化チタンとしては、上記の製造方法により製造されるものの他に、以下の酸化チタンが挙げられる。
（ａ）Ｘ線光電子分光法で酸化チタンの結合エネルギー４５８ｅＶ〜４６０ｅＶの間にあるチタンのピークの半価幅を４回測定した時の１回目と２回目のチタンのピークの半価幅の平均値をＡとし、３回目と４回目のチタンのピークの半価幅の平均値をＢとし、前記半価幅ＡおよびＢから下式（Ｉ）
Ｘ＝Ｂ／Ａ （Ｉ）
で示される指数Ｘが０．９７以下であり、かつ紫外可視拡散反射スペクトルを測定したときの、波長２２０ｎｍ〜８００ｎｍでのスペクトルの吸光度の積分値をＣとし、波長４００ｎｍ〜８００ｎｍでのスペクトルの吸光度の積分値をＤとし、前記積分値ＣおよびＤから下式（II）
Ｙ＝Ｄ／Ｃ （II）
で示される指数Ｙが０．１４以上である酸化チタン（特許文献１：特開２００１−７２４１９号公報）、
The photocatalyst titanium oxide used in the present invention includes the following titanium oxides in addition to those produced by the above production method.
(A) The average half-width of the first and second titanium peaks when the half-width of the titanium peak between 458 eV and 460 eV of titanium oxide is measured four times by X-ray photoelectron spectroscopy. The value is A, the average value of the half-value widths of the third and fourth titanium peaks is B, and from the half-value widths A and B, the following formula (I)
X = B / A (I)
And the integrated value of the absorbance of the spectrum at a wavelength of 220 nm to 800 nm when the index X is 0.97 or less and the ultraviolet-visible diffuse reflection spectrum is measured, and the absorbance of the spectrum at a wavelength of 400 nm to 800 nm The integral value of D is defined as D, and from the integral values C and D, the following formula (II)
Y = D / C (II)
Titanium oxide having an index Y indicated by ≧ 0.14 (Patent Document 1: Japanese Patent Application Laid-Open No. 2001-72419),
（ｂ）電子スピン共鳴スペクトルにおいてｇ値１．９３０〜２．０３０の間に３つ以上のピークを有し、かつそれらピークの内の極大となるピークがｇ値１．９９０〜２．０２０の間に存在する酸化チタン（特許文献２：特開２００１−１９０９５３号公報）、 (B) The electron spin resonance spectrum has three or more peaks between g values of 1.930 to 2.030, and the peak among these peaks has a g value of 1.990 to 2.020. Titanium oxide (Patent Document 2: Japanese Patent Application Laid-Open No. 2001-190953) existing between
（ｃ）可視光線照射後に測定した電子スピン共鳴スペクトルから求められるスピン濃度Ｘが１．５０×１０１６ｓｐｉｎ／ｇ以上であり、可視光線照射後に測定した電子スピン共鳴スペクトルから求められるスピン濃度Ｘと、可視光線照射前に測定した電子スピン共鳴スペクトルから求められるスピン濃度Ｙとの比（Ｘ／Ｙ）が１．００を超える酸化チタン（特許文献３：特開２００１−３１６１１６号公報）、 (C) The spin concentration X determined from the electron spin resonance spectrum measured after irradiation with visible light is 1.50 × 10 16 spin / g or more, and the spin concentration X determined from the electron spin resonance spectrum measured after irradiation with visible light , Titanium oxide having a ratio (X / Y) with spin concentration Y determined from an electron spin resonance spectrum measured before irradiation with visible light exceeding 1.00 (Patent Document 3: JP 2001-316116 A)
（ｄ）Ｘ線光電子分光法により８回分析し、チタンの電子状態について、１回目と２回目の分析の積算スペクトル及び７回目と８回目の分析の積算スペクトルを求め、それぞれの積算スペクトルのうち結合エネルギー４５８ｅＶ〜４６０ｅＶにあるピークを求め、１回目と２回目の分析の積算スペクトルにあるピークの半価幅をＡ1とし、７回目と８回目の分析の積算スペクトルにあるピークの半価幅をＢ1としたとき、下式（III）
Ｘ1＝Ｂ1／Ａ1 （III）
により算出される指数Ｘ1が０．９以下であり、かつ、紫外可視拡散反射スペクトルを測
定して、波長２５０ｎｍ〜５５０ｎｍの吸光度の積分値をＣ1とし、波長４００ｎｍ〜５
５０ｎｍの吸光度の積分値をＤ1としたとき、下式（IV）
Ｙ1＝Ｄ1／Ｃ1 （IV）
により算出される指数Ｙ1が０．０７５以上である酸化チタン（特許文献４：特開２０
０１−３２２８１６号公報）、
(D) Analyzed 8 times by X-ray photoelectron spectroscopy, and for the electronic state of titanium, the integrated spectrum of the first and second analysis and the integrated spectrum of the seventh and eighth analysis were obtained, A peak at a binding energy of 458 eV to 460 eV is obtained, and the half width of the peak in the integrated spectrum of the first and second analysis is A1, and the half width of the peak in the integrated spectrum of the seventh and eighth analysis is When B1, the following formula (III)
X1 = B1 / A1 (III)
The index X1 calculated by the above equation is 0.9 or less, and the ultraviolet-visible diffuse reflection spectrum is measured. The integrated value of the absorbance at wavelengths of 250 nm to 550 nm is defined as C1, and the wavelength of 400 nm to 5
When the integrated value of absorbance at 50 nm is D1, the following formula (IV)
Y1 = D1 / C1 (IV)
Titanium oxide whose index Y1 calculated by the above is 0.075 or more (Patent Document 4: JP-A-20
01-322816)
（ｅ）Ｘ線光電子分光法により８回分析し、チタンの電子状態について、１回目と２回目の分析の積算スペクトルおよび７回目と８回目の分析の積算スペクトルを求めたときに、１回目と２回目の分析の積算スペクトルにおける少なくとも１つのピークの位置が結合エネルギー４５９〜４６０ｅＶにあり、７回目と８回目の分析の積算スペクトルにおける少なくとも１つのピークの位置が結合エネルギー４５８〜４５９ｅＶにあり、遷移金属の含有量が元素換算で酸化チタン中のチタンに対し０．００５〜３．０ｍｏｌ％である酸化チタン（特許文献５：特開２００１−２９７４９号公報）、 (E) When the X-ray photoelectron spectroscopy is used for analysis eight times, and the integrated spectrum of the first and second analyzes and the integrated spectrum of the seventh and eighth analyzes are obtained for the electronic state of titanium, The position of at least one peak in the integrated spectrum of the second analysis is in the binding energy 459 to 460 eV, and the position of at least one peak in the integrated spectrum of the seventh and eighth analysis is in the binding energy 458 to 459 eV. Titanium oxide whose metal content is 0.005 to 3.0 mol% with respect to titanium in titanium oxide in terms of element (Patent Document 5: JP 2001-29749 A),
（ｆ）熱天秤質量分析同時測定法により求められるマスクロマトグラムについて、質量数ｍとイオンの電荷数ｅの比ｍ／ｅが２８である成分の脱離ピークが６００℃以上にある酸化チタン、もしくは熱天秤質量分析同時測定法により求められるマスクロマトグラムについて、質量数ｍとイオンの電荷数ｅの比ｍ／ｅが２８である成分の脱離ピークが６００℃以上、９５０℃以下にあり、ｍ／ｅが１４である成分の脱離ピークが６００℃以上、９５０℃以下にある酸化チタン（特許文献６：特開２００２−９７０１９号公報）、 (F) For a mass chromatogram obtained by a thermobalance mass spectrometry simultaneous measurement method, titanium oxide having a desorption peak of a component having a ratio m / e of mass number m to ion charge number e of 28 at 600 ° C. or higher, Alternatively, in the mass chromatogram obtained by the thermobalance mass spectrometry simultaneous measurement method, the desorption peak of the component having a ratio m / e of the mass number m and the ion charge number e is 28 is 600 ° C. or more and 950 ° C. or less, Titanium oxide having a desorption peak of a component having an m / e of 14 at 600 ° C. or more and 950 ° C. or less (Patent Document 6: JP 2002-97019 A),
（ｇ）酸化チタン結晶の酸素サイトの一部を窒素原子で置換した酸化チタン、酸化チタン結晶の格子間に窒素を原子をドーピングした酸化チタン、酸化チタンの結晶粒界に窒素原子をドーピングしたもの（特許文献７：ＷＯ０１／１０５５２パンフレット）、 (G) Titanium oxide in which part of the oxygen sites of the titanium oxide crystal is replaced with nitrogen atoms, titanium oxide doped with nitrogen atoms between the lattices of the titanium oxide crystal, and titanium oxide crystal grain boundaries doped with nitrogen atoms (Patent Document 7: WO01 / 10552 pamphlet),
（ｈ）安定した酸素欠陥を有する酸化チタンであって、真空中、７７Ｋ、暗黒下で測定された電子スピン共鳴スペクトルにおいて、ｇ値が２．００３〜２．００４であるシグナルが観測され、かつこのｇ値が２．００３〜２．００４であるシグナルは、真空中、７７Ｋにおいて少なくとも４２０〜６００ｎｍの光を照射下で測定したとき、暗黒下で測定された場合よりシグナル強度が大きい酸化チタン（特許文献８：特開２００１−２１２４５７公報）、 (H) a titanium oxide having stable oxygen defects, a signal having a g value of 2.003 to 2.004 is observed in an electron spin resonance spectrum measured in vacuum at 77K and in the dark, and The signal having a g value of 2.003 to 2.004 is a titanium oxide having a higher signal intensity when measured under irradiation with light of at least 420 to 600 nm at 77K in vacuum than in the case of measurement under darkness. Patent Document 8: JP-A-2001-212457),
（ｉ）表面にＰｔＣｌ２、ＰｔＣｌ４、ＰｔＣｌ２・２Ｈ２Ｏ、Ｈ２[Ｐｔ(ＯＨ)２Ｃｌ４]・ｎＨ２Ｏ、ＰｔＢｒ２、ＰｔＢｒ２、ＰｔＩ２、ＰｔＩ４、ＰｔＦ４、塩化白金酸、塩化白金酸塩、ブロモ白金錯塩、ヨウ化白金酸塩などのハロゲン化白金化合物を有している紡錘形状酸化チタン（特許文献９：特開２００２−２３９３９５号公報）、 (I) PtCl 2 , PtCl 4 , PtCl 2 · 2H 2 O, H 2 [Pt (OH) 2 Cl 4 ] · nH 2 O, PtBr 2 , PtBr 2 , PtI 2 , PtI 4 , PtF 4 , chloride on the surface Spindle-shaped titanium oxide having a halogenated platinum compound such as platinic acid, chloroplatinate, bromoplatinum complex, or iodoplatinate (Patent Document 9: JP-A-2002-239395),
（ｊ）表面に金属ハロゲン化物（ＴｉＣｌ４等）、金属錯体（ヘテロポリ酸及びイソポリ酸等）、を含有している酸化チタン（特許文献１０：ＷＯ０３／０８０２４４パンフレット）、 (J) titanium oxide (Patent Document 10: WO03 / 080244 pamphlet) containing a metal halide (such as TiCl4) and a metal complex (such as a heteropolyacid and an isopolyacid) on the surface;
（ｋ）表面にアルカリ土類金属、遷移金属及びＡｌを含有している酸化チタン（特許文献１１：ＷＯ０２／０５３５０１パンフレット）、 (K) titanium oxide containing alkaline earth metal, transition metal and Al on the surface (Patent Document 11: WO02 / 053501 pamphlet),
（ｌ）Ｓｎ化合物等の粒生長抑制剤を添加して合成したルチル型酸化チタン（特許文献１２：特開２００７−６９０９３号公報）、 (L) Rutile-type titanium oxide synthesized by adding a grain growth inhibitor such as Sn compound (Patent Document 12: JP 2007-69093 A),
（ｍ）窒素とフッ素を酸素の位置に置換した酸化チタン（非特許文献１：Chemistry Letters, Vol.32, No.2, P.196-197(2003)）、 (M) Titanium oxide in which nitrogen and fluorine are substituted at the oxygen position (Non-patent Document 1: Chemistry Letters, Vol. 32, No. 2, P.196-197 (2003)),
（ｎ）硫黄をＴｉの位置に置換した酸化チタン（非特許文献２：Chemistry Letters, Vol.32, No.4, P.364-365(2003)）、 (N) Titanium oxide in which sulfur is substituted at the Ti position (Non-Patent Document 2: Chemistry Letters, Vol. 32, No. 4, P. 364-365 (2003)),
（ｏ）炭素をドープした酸化チタン（非特許文献３：Chemistry Letters, Vol.32, No.8, P.772-773(2003)、非特許文献４：Angewandte Chemie, Internationaol Edition, 42, P.4908-4911(2003)）、 (O) Titanium oxide doped with carbon (Non-patent document 3: Chemistry Letters, Vol. 32, No. 8, P. 772-773 (2003), Non-patent document 4: Angewandte Chemie, Internationaol Edition, 42, P. 4908-4911 (2003)),
（ｐ）沃素をドープした酸化チタン（非特許文献５：Chemistry of Materials, 17, P.1548-1552(2005)）。 (P) Iodine-doped titanium oxide (Non-patent Document 5: Chemistry of Materials, 17, P.1548-1552 (2005)).
（ｑ）また特許文献１３（特開２００１−２７８６２５号公報）、特許文献１４（特開２００１−２７８６２６号公報）、特許文献１５（特開２００１−２７８６２７号公報）、特許文献１６（特開２００１−３０２２４１号公報）、特許文献１７（特開２００１−３３５３２１号公報）、特許文献１８（特開２００１−３５４４２２号公報）、特許文献１９（特開２００２−２９７５０号公報）、特許文献２０（特開２００２−４７０１２号公報）、特許文献２１（特開２００２−６０２２１号公報）、特許文献２２（特開２００２−１９３６１８号公報）、特許文献２３（特開２００２−２４９３１９号公報）などに記載の方法により得られる酸化チタンなども挙げられる。 (Q) In addition, Patent Document 13 (Japanese Patent Laid-Open No. 2001-278625), Patent Document 14 (Japanese Patent Laid-Open No. 2001-278626), Patent Document 15 (Japanese Patent Laid-Open No. 2001-278627), Patent Document 16 (Japanese Patent Laid-Open No. 2001). -302241), Patent Literature 17 (Japanese Patent Laid-Open No. 2001-335321), Patent Literature 18 (Japanese Patent Laid-Open No. 2001-354422), Patent Literature 19 (Japanese Patent Laid-Open No. 2002-29750), and Patent Literature 20 (Japanese Patent Publication). No. 2002-47012), Patent Document 21 (Japanese Patent Laid-Open No. 2002-60221), Patent Document 22 (Japanese Patent Laid-Open No. 2002-193618), Patent Document 23 (Japanese Patent Laid-Open No. 2002-249319), and the like. Examples thereof include titanium oxide obtained by the method.
本発明の光触媒分散液における光触媒酸化チタンの含有量は、分散液を基準として通常０．１重量％以上、好ましくは１重量％以上、通常３０重量％以下、好ましくは１５重量％以下である。 The content of the photocatalytic titanium oxide in the photocatalyst dispersion of the present invention is usually 0.1% by weight or more, preferably 1% by weight or more, usually 30% by weight or less, preferably 15% by weight or less, based on the dispersion.
本発明の光触媒分散液に使用しうる銅成分としては、例えば硝酸銅（Ｃｕ（ＮＯ３）２）、硫酸銅（Ｃｕ（ＳＯ４）２）、塩化銅（ＣｕＣｌ２，ＣｕＣｌ）、臭化銅（ＣｕＢｒ２，ＣｕＢｒ）、沃化銅（ＣｕＩ），沃素酸銅（ＣｕＩ２Ｏ６）、塩化アンモニウム銅（Ｃｕ（ＮＨ４）２Ｃｌ４）、オキシ塩化銅（Ｃｕ２Ｃｌ（ＯＨ）３）、酢酸銅（Ｃ２Ｈ３ＣｕＯ２，（ＣＨ３ＣＯＯ）２Ｃｕ）、蟻酸銅（（ＨＣＯＯ）２Ｃｕ）、炭酸銅（ＣｕＣＯ３）、金属銅、酸化銅（Ｃｕ２Ｏ，ＣｕＯ）、水酸化銅（ＣｕＯＨ，Ｃｕ（ＯＨ）２）、蓚酸銅（ＣｕＣ２Ｏ４）、クエン酸銅（Ｃｕ２Ｃ６Ｈ４Ｏ７）、リン酸銅（ＣｕＰＯ４）などが挙げられる。銅成分としては、分散媒に溶解しうるもの溶解性のものが好ましく用いられる。また、銅成分として金属銅、酸化銅などのように分散媒に溶解しない非溶解性のものを用いる場合には、コロイド粒子のような微細な粒子となっているものを用いることが、好ましい。 Examples of the copper component that can be used in the photocatalyst dispersion liquid of the present invention include copper nitrate (Cu (NO 3 ) 2 ), copper sulfate (Cu (SO 4 ) 2 ), copper chloride (CuCl 2 , CuCl), and copper bromide. (CuBr 2 , CuBr), copper iodide (CuI), copper iodate (CuI 2 O 6 ), copper ammonium chloride (Cu (NH 4 ) 2 Cl 4 ), copper oxychloride (Cu 2 Cl (OH) 3 ) , Copper acetate (C 2 H 3 CuO 2 , (CH 3 COO) 2 Cu), copper formate ((HCOO) 2 Cu), copper carbonate (CuCO 3 ), metallic copper, copper oxide (Cu 2 O, CuO), Examples thereof include copper hydroxide (CuOH, Cu (OH) 2 ), copper oxalate (CuC 2 O 4 ), copper citrate (Cu 2 C 6 H 4 O 7 ), and copper phosphate (CuPO 4 ). As the copper component, those soluble in a dispersion medium and preferably soluble are preferably used. Moreover, when using a non-soluble thing which does not melt | dissolve in a dispersion medium like metal copper, copper oxide, etc. as a copper component, it is preferable to use what is used as the fine particle like a colloid particle.
光触媒分散液における銅成分の含有量は、光触媒酸化チタンに対して０．０１モル％以上である。銅成分の含有量が多いほど、塗膜にしたときの光触媒活性は向上し、好ましくは０．１モル％以上である。一方銅成分の量があまりに多くなると、量に見合う光触媒活性の向上効果が見られない。更に光触媒分散液の安定性も損なわれ、分散液の保管中に酸化チタンが沈降し、固液分離することがある為、０．６モル％以下、好ましくは０．５モル％以下である。 Content of the copper component in a photocatalyst dispersion liquid is 0.01 mol% or more with respect to a photocatalyst titanium oxide. The greater the content of the copper component, the better the photocatalytic activity when formed into a coating film, preferably 0.1 mol% or more. On the other hand, when the amount of the copper component is too large, the effect of improving the photocatalytic activity commensurate with the amount is not observed. Furthermore, the stability of the photocatalyst dispersion liquid is also impaired, and titanium oxide may settle during storage of the dispersion liquid, resulting in solid-liquid separation. Therefore, it is 0.6 mol% or less, preferably 0.5 mol% or less.
なお、本発明の光触媒分散液を塗布して得られる塗膜において、銅成分は、光触媒酸化チタンとの相互作用によるものか、その価数が＋１価または０価となって塗膜中に存在している。＋１価または０価の銅となって存在することにより、光触媒酸化チタンの光励起によって生成する電子が、この＋１価または０価の銅を介して酸素分子を還元し、効率的に活性酸素種を生成することができ、このため高い光触媒活性を示すもの考えられる。 In the coating film obtained by applying the photocatalyst dispersion liquid of the present invention, the copper component is due to the interaction with the photocatalytic titanium oxide, or the valence is +1 or 0. is doing. By being present as +1 valence or 0 valence copper, electrons generated by photoexcitation of photocatalytic titanium oxide reduce oxygen molecules through this +1 valence or 0 valence copper, and efficiently generate active oxygen species. Therefore, it is considered that the photocatalytic activity is high.
本発明の光触媒分散液は、酸化チタンを溶媒中で安定に分散させる為に分散剤を用いる。分散剤としては、蓚酸、リン酸、縮合リン酸およびその塩が用いられる。蓚酸塩としては、例えば蓚酸アンモニウム、蓚酸水素アンモニウム、蓚酸ナトリウム、蓚酸水素ナトリウム、蓚酸カリウム、蓚酸水素カリウムなどが、リン酸塩としては、例えばリン酸アンモニウム、リン酸水素アンモニウム、リン酸二水素アンモニウム、リン酸ナトリウム、リン酸水素ナトリウム、リン酸二水素ナトリウム、リン酸カリウム、リン酸水素カリウム、リン酸二水素カリウムなどが、縮合リン酸塩としては、例えばピロリン酸、ピロリン酸アンモニウム、ピロリン酸ナトリウム、ピロリン酸カリウム、トリポリリン酸アンモニウム、トリポリリン酸ナトリウム、トリポリリン酸カリウム、テトラポリリン酸、テトラポリリン酸アンモニウム、テトラポリリン酸ナトリウム、テトラポリリン酸カリウム、ヘキサメタリン酸、ヘキサメタリン酸アンモニウム、ヘキサメタリン酸ナトリウム、ヘキサメタリン酸カリウム等がそれぞれ挙げられる。 The photocatalyst dispersion liquid of the present invention uses a dispersant in order to stably disperse titanium oxide in a solvent. As the dispersant, succinic acid, phosphoric acid, condensed phosphoric acid and salts thereof are used. Examples of oxalates include ammonium oxalate, ammonium hydrogen oxalate, sodium oxalate, sodium hydrogen oxalate, potassium oxalate, and potassium hydrogen oxalate. Examples of phosphate salts include ammonium phosphate, ammonium hydrogen phosphate, and ammonium dihydrogen phosphate. Sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, and the like. Examples of the condensed phosphate include pyrophosphate, ammonium pyrophosphate, pyrophosphate Sodium, potassium pyrophosphate, ammonium tripolyphosphate, sodium tripolyphosphate, potassium tripolyphosphate, tetrapolyphosphate, ammonium tetrapolyphosphate, sodium tetrapolyphosphate, potassium tetrapolyphosphate, hexametaphosphate, hex Ammonium metaphosphate, sodium hexametaphosphate, potassium hexametaphosphate, and the like, respectively.
光触媒分散液における分散剤の含有量は、光触媒酸化チタンに対して通常０．０５モル％以上である。分散剤の含有量が多いほど、分散液中の酸化チタンの分散安定性が向上するので好ましく、例えば０．５モル％以上、さらには１モル％以上であることが好ましい。一方、分散剤の量があまり多くなると、量に見合う酸化チタンの分散効果が得られない為、２０モル％以下、さらには１０モル％以下であることが適当である。 The content of the dispersant in the photocatalyst dispersion is usually 0.05 mol% or more with respect to the photocatalytic titanium oxide. The higher the content of the dispersant, the better the dispersion stability of titanium oxide in the dispersion, which is preferable, for example 0.5 mol% or more, and more preferably 1 mol% or more. On the other hand, if the amount of the dispersant is too large, a titanium oxide dispersing effect corresponding to the amount cannot be obtained, so that it is suitably 20 mol% or less, more preferably 10 mol% or less.
本発明の光触媒分散液において、前記酸化チタンを分散させる分散媒には、上の分散剤を溶解するものであればよく、水、過酸化水素水のような水性媒体、エタノール、メタノール、２−プロパノール、ブタノールのようなアルコール性媒体、アセトン、２−ブタノンのようなケトン性媒体、パラフィン化合物媒体、芳香族化合物媒体などが挙げられ、これらの中でも、水性媒体、アルコール性媒体が好ましい。 In the photocatalyst dispersion of the present invention, the dispersion medium in which the titanium oxide is dispersed may be any medium that dissolves the above dispersant, such as water, an aqueous medium such as hydrogen peroxide, ethanol, methanol, 2- Examples include alcoholic media such as propanol and butanol, ketonic media such as acetone and 2-butanone, paraffin compound media, and aromatic compound media. Among these, aqueous media and alcoholic media are preferable.
本発明の光触媒分散液は、例えば光触媒酸化チタン、銅成分、分散剤および分散媒を混合することにより製造することができる。分散剤に用いる混合は、溶媒中に光触媒粉末を分散させることが可能な装置で行えばよく、例えば、媒体攪拌式分散機、転動ボールミル、振動ボールミルのような装置で行うことができ、なかでも媒体攪拌式分散機の適用が推奨される。このような装置では、媒体として、例えば、材質がジルコニア、アルミナまたはガラスであり、直径０．６５ｍｍ以下、好ましくは０．５ｍｍ以下、さらに好ましくは０．３ｍｍ以下のビーズなどが用いられる。混合は、２段階以上に分けて行ってもよく、例えば、１段目では、直径が相対的に大きい媒体を入れた装置を用い、２段目以降では、直径が順次小さいものを入れた装置を用いて行うことができる。混合を多段階で行うことにより、効率的にセラミックス粉末を溶媒中に分散させ、かつ均一に光触媒が分散した分散液組成物が得られる。混合温度は、５０℃未満、好ましくは４０℃以下、また１０℃以上、好ましくは２０℃以上である。光触媒とリン酸アンモニウム塩と溶媒の混合物には、必要に応じて、粗大粒子の除去、光触媒含有量の調整またはｐＨの調整のような操作が施される。ｐＨの調整に用いる酸としては、例えば、塩酸、硝酸、リン酸、硫酸等が挙げられ、塩基としては、例えば、アンモニア、尿素、ヒドラジン、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化セシウム、水酸化ルビジウム等が挙げられる。 The photocatalyst dispersion liquid of the present invention can be produced, for example, by mixing a photocatalytic titanium oxide, a copper component, a dispersant and a dispersion medium. The mixing used for the dispersing agent may be carried out by an apparatus capable of dispersing the photocatalyst powder in a solvent, for example, by an apparatus such as a medium stirring type dispersing machine, a rolling ball mill, or a vibrating ball mill. However, it is recommended to use a medium stirring disperser. In such an apparatus, as a medium, for example, beads made of zirconia, alumina, or glass and having a diameter of 0.65 mm or less, preferably 0.5 mm or less, more preferably 0.3 mm or less are used. Mixing may be performed in two or more stages. For example, in the first stage, a device containing a medium having a relatively large diameter is used, and in the second and subsequent stages, devices having successively smaller diameters are placed. Can be used. By performing mixing in multiple stages, a dispersion composition in which ceramic powder is efficiently dispersed in a solvent and the photocatalyst is uniformly dispersed can be obtained. The mixing temperature is less than 50 ° C, preferably 40 ° C or less, 10 ° C or more, preferably 20 ° C or more. If necessary, the mixture of the photocatalyst, ammonium phosphate salt and the solvent is subjected to operations such as removal of coarse particles, adjustment of the photocatalyst content, or adjustment of pH. Examples of the acid used for adjusting the pH include hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid. Examples of the base include ammonia, urea, hydrazine, lithium hydroxide, sodium hydroxide, potassium hydroxide, and hydroxide. Examples include cesium and rubidium hydroxide.
銅成分は、酸化チタン、分散剤、および溶媒を混合する前後に添加してもよく、分散工程中に添加してもよい。また予め酸化チタンに担持することも勿論可能である。尚、酸化チタンに対する添加量を正確に把握するという点から、酸化チタンを分散し、得られた分散液の固形分濃度を測定した後に添加するのが好ましい。 The copper component may be added before or after mixing the titanium oxide, the dispersant, and the solvent, or may be added during the dispersion step. It is of course possible to carry it on titanium oxide in advance. In addition, it is preferable to add after disperse | distributing titanium oxide and measuring the solid content concentration of the obtained dispersion liquid from the point of grasping | ascertaining the addition amount with respect to a titanium oxide correctly.
光触媒分散液中の酸化チタンの含有量は、分散液を基準に通常０．１重量％以上、好ましくは１重量％以上、また３０重量％以下である。 The content of titanium oxide in the photocatalyst dispersion is usually 0.1% by weight or more, preferably 1% by weight or more and 30% by weight or less based on the dispersion.
この光触媒分散液は、そのまま、又は塗膜としたときに塗膜の光触媒性能を向上させる添加剤と混合された後、膜形成に使用される。この添加剤としては、例えば、非晶質シリカ、シリカゾルのような珪素酸化物、非晶質アルミナ、アルミナゾルのようなアルミニウム(水)酸化物、ゼオライト、カオリナイトのようなアルミノ珪酸塩、酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウムおよび水酸化バリウムのようなアルカリ土類金属(水)酸化物、リン酸カルシウム、モレキュラーシーブまたは活性炭、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｔｃ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｚｎ、Ｇａ、Ｉｎ、Ｇｅ、Ｓｎ、Ｂｉ、ＬａまたはＣｅのような金属元素の水酸化物またはこれらの金属元素の酸化物などが挙げられる。これらは１種または２種以上組み合わせて用いることができる。 This photocatalyst dispersion liquid is used for film formation after being mixed with an additive for improving the photocatalytic performance of the coating film as it is or as a coating film. Examples of the additive include amorphous silica, silicon oxide such as silica sol, amorphous alumina, aluminum (water) oxide such as alumina sol, zeolite, aluminosilicate such as kaolinite, magnesium oxide, and the like. , Calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, alkaline earth metal (water) oxides such as strontium hydroxide and barium hydroxide, calcium phosphate, molecular sieve or activated carbon, Ti, Zr, Hf V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Zn, Ga, In, Ge, Sn, Bi, La, or Ce Or a hydroxide of a metal element such as, or an oxide of these metal elements. These can be used alone or in combination of two or more.
本発明で得られる光触媒分散液またはそれに添加剤を混合したものを用いれば、硝子、プラスチック、金属、陶磁器およびコンクリートのような基材に、光照射によって高い光触媒活性を示す膜を形成することができる。膜形成は、例えばスピンコート、ディップコート、ドクターブレード、スプレーまたはハケ塗りなどで行い、室温〜２００℃の空気中で保持して、材料表面に塗布膜を形成し、この塗布膜に光を照射するか、またはこの材料の表面に８０〜２００℃の熱風を吹き付けて、材料表面に塗布膜を形成し、この塗布膜に光を照射する。この光触媒分散液の保管は、光が当たらない条件で行うことが好ましく、例えば暗室内に置くか、または紫外線と可視光線の透過率が各々１０％以下の遮光性容器に入れることが好ましい。 By using the photocatalyst dispersion obtained in the present invention or a mixture thereof with an additive, a film showing high photocatalytic activity can be formed on a substrate such as glass, plastic, metal, ceramics and concrete by light irradiation. it can. Film formation is performed, for example, by spin coating, dip coating, doctor blade, spraying or brushing, and the coating film is formed on the surface of the material by holding in air at room temperature to 200 ° C., and this coating film is irradiated with light. Alternatively, hot air of 80 to 200 ° C. is blown onto the surface of the material to form a coating film on the surface of the material, and the coating film is irradiated with light. The photocatalyst dispersion is preferably stored under conditions where it is not exposed to light. For example, the photocatalyst dispersion is preferably placed in a dark room or placed in a light-shielding container having ultraviolet and visible light transmittances of 10% or less, respectively.
以下、本発明を実施例によって詳細に説明するが、本発明はこれらに限定されるものではない。なお、光触媒塗膜の作製、光触媒分散液の粒子径・光触媒活性の評価は以下の方法で行った。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. In addition, preparation of a photocatalyst coating film and evaluation of the particle diameter and photocatalytic activity of a photocatalyst dispersion liquid were performed by the following methods.
（１）光触媒塗布膜の作製
外径７０ｍｍ、内径６６ｍｍ、高さ１４ｍｍ、容量約４８ｍＬのガラス製シャーレ容器内に、固形分で１ｇ／ｍ２となるように光触媒分散液を滴下し、シャーレ全体に均一となるように展開した。これを１１０℃の乾燥機で１時間乾燥させ、光触媒塗布膜を作製した。その後ブラックライト（紫外線強度２ｍＷ/ｃｍ２）を１６時間照射して、光触媒塗布膜を初期化した。
(1) Preparation of photocatalyst coating film A photocatalyst dispersion liquid was dropped into a glass petri dish with an outer diameter of 70 mm, an inner diameter of 66 mm, a height of 14 mm, and a capacity of about 48 mL so that the solid content was 1 g / m 2, and the entire petri dish It was developed to be uniform. This was dried with a dryer at 110 ° C. for 1 hour to produce a photocatalyst coating film. Thereafter, black light (ultraviolet intensity 2 mW / cm 2 ) was irradiated for 16 hours to initialize the photocatalyst coating film.
（２）平均分散粒子径（ｎｍ）：
サブミクロン粒度分布測定装置（商品名「Ｎ４Ｐｌｕｓ」、コールター製）を用いて試料の粒度分布を測定し、この装置に付属のソフトで、自動的に単分散モード解析して得られた結果を平均分散粒子径とした。
(2) Average dispersed particle size (nm):
Measure the particle size distribution of the sample using a sub-micron particle size distribution measuring device (trade name “N4Plus”, manufactured by Coulter), and average the results obtained by monodisperse mode analysis automatically with the software attached to this device. The dispersed particle size was taken.
（３）結晶構造：
Ｘ線回折装置（商品名「ＲＩＮＴ２０００／ＰＣ」、リガク製）を用いて、試料のＸ線回折スペクトルを測定し、そのスペクトルから主成分の結晶構造を求めた。
(3) Crystal structure:
The X-ray diffraction spectrum of the sample was measured using an X-ray diffractometer (trade name “RINT2000 / PC”, manufactured by Rigaku), and the crystal structure of the main component was determined from the spectrum.
（４）光触媒活性：アセトアルデヒド分解能
１Ｌガスバッグに測定サンプルを入れて密閉し、ガスバッグ内を真空にした後、酸素と窒素との体積比が１：４である混合ガスを６００ｍｌ封入した。さらに１％アセトアルデヒドを含む窒素ガス６ｍｌ封入し暗所で１時間安定化させた後、試料表面の照度が６０００ルクスになるようにシャーレを設置し、アセトアルデヒドの分解反応を行った。光源には、市販の蛍光灯を用いた。蛍光灯照射後よりガスバッグ内のガスを１．５時間毎にサンプリングして、アセトアルデヒドの残存濃度をガスクロマトグラフ（商品名「ＧＣ−１４Ａ」島津製作所製）にて測定した。
照射時間に対するアセトアルデヒドの濃度減少を対数軸にプロットし、得られた直線の傾きから一次反応速度定数を算出し、これをアセトアルデヒド分解能とした。一次反応速度定数が大きいほど、アセトアルデヒドの分解能は大きい。
(4) Photocatalytic activity: Acetaldehyde resolution 1 L measurement sample was put in a gas bag and sealed, and the gas bag was evacuated, and then 600 ml of a mixed gas having a volume ratio of oxygen and nitrogen of 1: 4 was sealed. Furthermore, after 6 ml of nitrogen gas containing 1% acetaldehyde was sealed and stabilized in the dark for 1 hour, a petri dish was placed so that the illuminance on the sample surface was 6000 lux, and acetaldehyde was decomposed. A commercially available fluorescent lamp was used as the light source. The gas in the gas bag was sampled every 1.5 hours after fluorescent lamp irradiation, and the residual concentration of acetaldehyde was measured with a gas chromatograph (trade name “GC-14A”, manufactured by Shimadzu Corporation).
The concentration reduction of acetaldehyde with respect to the irradiation time was plotted on the logarithmic axis, and the first-order rate constant was calculated from the slope of the obtained straight line, which was defined as acetaldehyde resolution. The higher the first order rate constant, the greater the resolution of acetaldehyde.
（５）Ｘ線光電子分光測定（ＸＰＳ）
光電子分光測定装置（商品名「AXIS-ULTRA」、KRATOS製）を用いて、Ｘ線源：AlKα（モノクロ）15kV 13mA、ナロースキャン、pass E=160eV、step E=0.1eV、真空度：約5×10-8torr、温度：室温、Cu2pピークの位置：C1s=284.6eVで補正、サンプルの保持：カーボンテープにワッシャーを保持し、ワッシャー内に試料を充填、の条件で行った。
(5) X-ray photoelectron spectroscopy (XPS)
Using a photoelectron spectrometer (trade name “AXIS-ULTRA”, manufactured by KRATOS), X-ray source: AlKα (monochrome) 15 kV 13 mA, narrow scan, pass E = 160 eV, step E = 0.1 eV, degree of vacuum: about 5 × 10 -8 torr, temperature: room temperature, Cu2p peak position: corrected with C1s = 284.6 eV, holding of sample: holding washer on carbon tape, filling sample in washer.
実施例１
〔酸化チタンの合成〕
オキシ硫酸チタン７５ｋｇをイオン交換水５０ｋｇに溶解させ、オキシ硫酸チタン水溶液を調製した。冷却下、このオキシ硫酸チタン水溶液に３５％過酸化水素水３０ｋｇを添加した。ｐＨ電極と、このｐＨ電極に接続され、２５重量％アンモニア水を供給してｐＨを一定に調整する機構を有するｐＨコントローラーとを備えた反応容器にイオン交換水３０ｋｇを入れた。ｐＨコントローラーのｐＨ設定を４とした。この反応容器では、容器内の液のｐＨが設定値より低くなると、アンモニア水が供給されはじめ、ｐＨが設定値になるまで前記速度にて連続供給される。この反応容器に、４２ｒｐｍで攪拌しながら、上記で得られた混合溶液を５３０ｍｌ／分で添加し、ｐＨコントローラーにより反応容器に供給されるアンモニア水と反応させて、生成物を得た。このときの反応温度は、２０℃〜３０℃の範囲であった。得られた生成物を攪拌しながら１時間保持し、ついで２５重量％アンモニア水を供給して、スラリーを得た。反応容器に供給されたアンモニア水の合計量は９０ｋｇであり、オキシ硫酸チタンを水酸化チタンに変えるために必要な量の２倍であった。上のスラリーを濾過、そのまま引き続いてリンス洗浄し、固形物（ケーキ）を得た。
上記で得られたケーキ２．３ｋｇを３０ｃｍ×４０ｃｍのステンレス製バットに入れた。このバット１２枚を箱型乾燥機（内容積；２１６リットル、商品名「スーパーテンプオーブンＨＰ−６０」、旭科学製）に入れ、４０ｍ３／ｈの乾燥空気流通下、１１５℃で５時間保持した後、続けて２５０℃で５時間乾燥を行なった。上記で得られた乾燥粉末を３５０℃の空気雰囲気下で２時間焼成を行った後、室温まで冷却して、酸化チタン粉末を得た。この酸化チタン粉末の結晶型はアナタ-ゼであった。
Example 1
[Synthesis of titanium oxide]
75 kg of titanium oxysulfate was dissolved in 50 kg of ion-exchanged water to prepare a titanium oxysulfate aqueous solution. Under cooling, 30 kg of 35% hydrogen peroxide solution was added to the aqueous titanium oxysulfate solution. 30 kg of ion-exchanged water was placed in a reaction vessel equipped with a pH electrode and a pH controller connected to the pH electrode and having a mechanism for supplying a 25 wt% aqueous ammonia to adjust the pH to a constant level. The pH setting of the pH controller was 4. In this reaction vessel, when the pH of the liquid in the vessel becomes lower than the set value, ammonia water starts to be supplied and is continuously supplied at the rate until the pH reaches the set value. While stirring at 42 rpm, the mixed solution obtained above was added to the reaction vessel at 530 ml / min and reacted with ammonia water supplied to the reaction vessel by a pH controller to obtain a product. The reaction temperature at this time was in the range of 20 ° C to 30 ° C. The resulting product was held for 1 hour with stirring, and then 25 wt% aqueous ammonia was supplied to obtain a slurry. The total amount of ammonia water supplied to the reaction vessel was 90 kg, which was twice the amount necessary to change titanium oxysulfate to titanium hydroxide. The upper slurry was filtered and rinsed as it was to obtain a solid (cake).
2.3 kg of the cake obtained above was placed in a 30 cm × 40 cm stainless steel vat. Twelve of these vats are placed in a box-type dryer (internal volume: 216 liters, trade name “Super Temp Oven HP-60”, manufactured by Asahi Kagaku) and kept at 115 ° C. for 5 hours under a flow of 40 m 3 / h of dry air. Then, drying was continued at 250 ° C. for 5 hours. The dried powder obtained above was calcined in an air atmosphere at 350 ° C. for 2 hours, and then cooled to room temperature to obtain a titanium oxide powder. The crystal form of the titanium oxide powder was anatase.
〔光触媒分散液の調製〕
イオン交換水７３.０６ｋｇにシュウ酸二水和物（試薬特級、和光純薬製）９４６ｇに添加し、更に上の粉末状酸化チタン２０．０ｋｇを混合し、これを媒体攪拌式分散機（商品名「ダイノーミル ＫＤＬ‐ＰＩＬＯＴ Ａ型」、シンマルエンタープライゼス製）に入れ、媒体：直径０．３ｍｍのジルコニア製ビーズ４．２ｋｇ、攪拌速度：周速８ｍ／秒、流速：１Ｌ／ｍｉｎ、処理時間合計：４１０分の条件で分散処理した。このスラリーを媒体攪拌式分散機（商品名「ウルトラアペックスミル ＵＡＭ−５ １００１」、コトブキ技研製）に入れ、媒体：直径０．０５ｍｍのジルコニア製ビーズ１３ｋｇ、攪拌速度：周速１２．６ｍ／秒、流速：１Ｌ／ｍｉｎ、処理時間：合計３５６分の条件で分散処理した。平均分散粒子径は６２ｎｍであった。また、この酸化チタンスラリー中の蓚酸の量は、酸化チタンに対して３モル％であり、ｐＨは２．４であった。得られた分散液を１Ｌ用遠沈管に各１Ｌ採取し、１５００ｒｐｍで３０分間遠心分離を行い、粗粒分を除去したところ、平均分散粒径が５３ｎｍであった。またこの光触媒分散液をエバポレーターにて４０℃で乾燥し、結晶型を測定したところ、アナタ―ゼであった。
(Preparation of photocatalyst dispersion)
Add 946 g of oxalic acid dihydrate (reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.) to ion exchange water 73.06 kg, and further mix 20.0 kg of powdered titanium oxide above. Name: “Dynomill KDL-PILOT Type A”, manufactured by Shinmaru Enterprises), medium: 4.2 kg of zirconia beads having a diameter of 0.3 mm, stirring speed: peripheral speed 8 m / sec, flow speed: 1 L / min, processing time Total: Dispersion treatment was performed under conditions of 410 minutes. This slurry is put into a medium stirring type disperser (trade name “Ultra Apex Mill UAM-5 1001”, manufactured by Kotobuki Giken Co., Ltd.), medium: 13 kg of zirconia beads having a diameter of 0.05 mm, stirring speed: peripheral speed 12.6 m / sec. , Flow rate: 1 L / min, treatment time: dispersion treatment under the conditions of a total of 356 minutes. The average dispersed particle size was 62 nm. The amount of succinic acid in the titanium oxide slurry was 3 mol% with respect to titanium oxide, and the pH was 2.4. 1 L each of the obtained dispersion was collected in a 1 L centrifuge tube, centrifuged at 1500 rpm for 30 minutes to remove coarse particles, and the average dispersed particle size was 53 nm. The photocatalyst dispersion was dried at 40 ° C. with an evaporator and the crystal form was measured. As a result, it was an anatase.
上記で得られた光触媒分散液に濃度１８８ｍＭの硝酸銅三水和物（特級、和光純薬製）を溶解した水溶液を加え、酸化チタン濃度を５重量％、チタンに対する銅の添加量を０．０３モル％とした。この硝酸銅を添加した光触媒分散液を用い、〔光触媒塗布膜の形成〕と同じ操作を行ってシャーレ上に光触媒塗布膜を形成した。この塗布膜の光触媒活性を測定し、結果を第１表に記載した。硝酸銅を添加した後も、光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。 An aqueous solution obtained by dissolving copper nitrate trihydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) having a concentration of 188 mM was added to the photocatalyst dispersion obtained above, the titanium oxide concentration was 5 wt%, and the amount of copper added to titanium was 0.00. It was set to 03 mol%. Using the photocatalyst dispersion liquid to which copper nitrate was added, the same operation as [Formation of photocatalyst coating film] was performed to form a photocatalyst coating film on the petri dish. The photocatalytic activity of this coating film was measured, and the results are shown in Table 1. Even after adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed.
実施例２
チタンに対する銅の添加量を０．０７５モル％とした以外は実施例１と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第１表に記載した。硝酸銅を添加した後も、光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。
Example 2
A photocatalyst dispersion was prepared in the same manner as in Example 1 except that the amount of copper added to titanium was 0.075 mol%, and the photocatalytic activity was measured. The results are shown in Table 1. Even after adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed.
実施例３
チタンに対する銅の添加量を０．１５モル％とした以外は実施例１と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第１表に記載した。硝酸銅を添加した後も、光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。
Example 3
A photocatalyst dispersion was prepared in the same manner as in Example 1 except that the amount of copper added to titanium was 0.15 mol%, and the photocatalytic activity was measured. The results are shown in Table 1. Even after adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed.
実施例４
チタンに対する銅の添加量を０．３モル％とした以外は実施例１と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第１表に記載した。硝酸銅を添加した後も、光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。
Example 4
A photocatalyst dispersion was prepared in the same manner as in Example 1 except that the amount of copper added to titanium was 0.3 mol%, and the photocatalytic activity was measured. The results are shown in Table 1. Even after adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed.
実施例５
チタンに対する銅の添加量を０．４５モル％とした以外は実施例１と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第１表に記載した。硝酸銅を添加した後も、光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。また十分に脱脂したスライドガラスに、この光触媒分散液を酸化チタン換算で１ｇ／ｃｍ２となるように塗布し、空気中で１１０℃で１時間乾燥してＸＰＳにて測定したところ、９３２ｅＶにＣｕ２ｐの起因するピークを観測した。ここから銅の価数は＋１価若しくは０価であることがわかった。
Example 5
A photocatalyst dispersion was prepared in the same manner as in Example 1 except that the amount of copper added to titanium was 0.45 mol%, the photocatalytic activity was measured, and the results are shown in Table 1. Even after adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed. Further, this photocatalyst dispersion was applied to a sufficiently degreased slide glass so as to be 1 g / cm 2 in terms of titanium oxide, dried in air at 110 ° C. for 1 hour, and measured by XPS. The peak attributed to was observed. From this, it was found that the valence of copper was +1 or 0.
比較例１
硝酸銅を添加しない以外は実施例１と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第１表に記載した。光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。
Comparative Example 1
A photocatalyst dispersion was prepared in the same manner as in Example 1 except that copper nitrate was not added, and the photocatalytic activity was measured. The results are shown in Table 1. Dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed.
比較例２
チタンに対する銅の添加量を０．７５モル％とした以外は実施例１と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第１表に記載した。硝酸銅を添加した後、光触媒分散液中の酸化チタンの分散性は低下し、固液分離が見られた。
Comparative Example 2
A photocatalyst dispersion was prepared in the same manner as in Example 1 except that the amount of copper added to titanium was changed to 0.75 mol%. Further, the photocatalytic activity was measured, and the results are shown in Table 1. After adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion decreased, and solid-liquid separation was observed.
比較例３
チタンに対する銅の添加量を１．５モル％とした以外は実施例１と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第１表に記載した。硝酸銅を添加した後、光触媒分散液中の酸化チタンの分散性は低下し、固液分離が見られた。
Comparative Example 3
A photocatalyst dispersion was prepared in the same manner as in Example 1 except that the amount of copper added to titanium was 1.5 mol%, and the photocatalytic activity was measured. The results are shown in Table 1. After adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion decreased, and solid-liquid separation was observed.
実施例６
イオン交換水１０．７４ｋｇにリン酸二水素アンモニウム１７２．８ｇ（和光特級試薬）を溶解して分散液を調製した。得られた水溶液と実施例１で得られた酸化チタン粉末４．０ｋｇを媒体攪拌式分散機（商品名「ダイノーミルＫＤＬ−ＰＩＬＯＴ Ａ型」、シンマルエンタープライゼス製）に入れ、媒体：直径０．３ｍｍのジルコニア製ビーズ ４．２ｋｇ、攪拌速度：周速８ｍ／秒、処理液循環：あり、循環液量：３Ｌ、合計処理時間：６０分間の条件で混合した。得られた混合物中の酸化チタンは、平均分散散子径が４２０ｎｍであった。さらにこの混合物を、媒体攪拌式分散機（商品名「ウルトラアペックスミル」、コトブキ技研製）で、媒体：直径０．０５ｍｍのジルコニア製ビーズ １３ｋｇ、攪拌速度：周速１２．６ｍ／秒（２０００ｒｐｍ）の条件で３７分間混合した。得られた分散液中の酸化チタンは、平均粒子径が１９３ｎｍであった。また、この酸化チタンスラリー中のリン酸アンモニウム塩の量は、酸化チタンに対して３モル％であり、ｐＨは６．９であった。得られた分散液を１Ｌ用遠沈管に各１Ｌ採取し、１５００ｒｐｍで３０分間遠心分離を行い、粗粒分を除去したところ、平均分散粒径が１５５ｎｍであった。またこの光触媒分散液をエバポレーターにて４０℃で乾燥し、結晶型を測定したところ、アナタ―ゼであった。
Example 6
A dispersion was prepared by dissolving 172.8 g of ammonium dihydrogen phosphate (Wako Special Grade Reagent) in 10.74 kg of ion-exchanged water. The obtained aqueous solution and 4.0 kg of the titanium oxide powder obtained in Example 1 were placed in a medium agitating disperser (trade name “Dynomill KDL-PILOT A type”, manufactured by Shinmaru Enterprises). Mixing was performed under the conditions of 4.2 kg of 3 mm zirconia beads, stirring speed: peripheral speed 8 m / sec, treatment liquid circulation: yes, circulation liquid volume: 3 L, total treatment time: 60 minutes. The titanium oxide in the obtained mixture had an average dispersed powder size of 420 nm. Further, this mixture was mixed with a medium stirring type disperser (trade name “Ultra Apex Mill”, manufactured by Kotobuki Giken), medium: 13 kg of zirconia beads having a diameter of 0.05 mm, stirring speed: peripheral speed 12.6 m / second (2000 rpm) For 37 minutes. The titanium oxide in the obtained dispersion had an average particle size of 193 nm. The amount of ammonium phosphate in the titanium oxide slurry was 3 mol% with respect to titanium oxide, and the pH was 6.9. 1 L each of the obtained dispersion was collected in a 1 L centrifuge tube, centrifuged at 1500 rpm for 30 minutes to remove coarse particles, and the average dispersed particle size was 155 nm. The photocatalyst dispersion was dried at 40 ° C. with an evaporator and the crystal form was measured. As a result, it was an anatase.
上記で得られた光触媒分散液に濃度１８８ｍＭの硝酸銅三水和物（特級、和光純薬製）を溶解した水溶液を加え、酸化チタン濃度を５重量％、チタンに対する銅の添加量を０．０３モル％とした。この硝酸銅を添加した光触媒分散液を用いた以外は実施例１と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第２表に記載した。硝酸銅を添加した後も、光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。 An aqueous solution obtained by dissolving copper nitrate trihydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) having a concentration of 188 mM was added to the photocatalyst dispersion obtained above, the titanium oxide concentration was 5 wt%, and the amount of copper added to titanium was 0.00. It was set to 03 mol%. A photocatalyst dispersion was prepared in the same manner as in Example 1 except that this photocatalyst dispersion added with copper nitrate was used. Photocatalytic activity was further measured, and the results are shown in Table 2. Even after adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed.
実施例７
チタンに対する銅の添加量を０．０７５モル％とした以外は実施例６と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第２表に記載した。硝酸銅を添加した後も、光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。
Example 7
A photocatalyst dispersion was prepared in the same manner as in Example 6 except that the amount of copper added to titanium was 0.075 mol%, and the photocatalytic activity was measured. The results are shown in Table 2. Even after adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed.
実施例８
チタンに対する銅の添加量を０．１５モル％とした以外は実施例６と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第２表に記載した。硝酸銅を添加した後も、光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。
Example 8
A photocatalyst dispersion was prepared in the same manner as in Example 6 except that the amount of copper added to titanium was 0.15 mol%, and the photocatalytic activity was measured. The results are shown in Table 2. Even after adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed.
実施例９
チタンに対する銅の添加量を０．３モル％とした以外は実施例６と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第２表に記載した。硝酸銅を添加した後も、光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。
Example 9
A photocatalyst dispersion was prepared in the same manner as in Example 6 except that the amount of copper added to titanium was 0.3 mol%, and the photocatalytic activity was measured. The results are shown in Table 2. Even after adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed.
実施例１０
チタンに対する銅の添加量を０．４５モル％とした以外は実施例６と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第１表に記載した。硝酸銅を添加した後も、光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。また十分に脱脂したスライドガラスに、この光触媒分散液を酸化チタン換算で１ｇ／ｃｍ２となるように塗布し、空気中で１１０℃で１時間乾燥してＸＰＳにて測定したところ、９３２ｅＶにＣｕ２ｐの起因するピークを観測した。ここから銅の価数は＋１価若しくは０価であることがわかった。
Example 10
A photocatalyst dispersion was prepared in the same manner as in Example 6 except that the amount of copper added to titanium was 0.45 mol%, and the photocatalytic activity was measured. The results are shown in Table 1. Even after adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed. Further, this photocatalyst dispersion was applied to a sufficiently degreased slide glass so as to be 1 g / cm 2 in terms of titanium oxide, dried in air at 110 ° C. for 1 hour, and measured by XPS. The peak attributed to was observed. From this, it was found that the valence of copper was +1 or 0.
比較例４
硝酸銅を添加しない以外は実施例６と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第２表に記載した。光触媒分散液中の酸化チタンの分散性は良好で、固液分離は見られなかった。
Comparative Example 4
A photocatalyst dispersion was prepared in the same manner as in Example 6 except that copper nitrate was not added, and the photocatalytic activity was measured. The results are shown in Table 2. Dispersibility of titanium oxide in the photocatalyst dispersion was good, and solid-liquid separation was not observed.
比較例５
チタンに対する銅の添加量を０．７５モル％とした以外は実施例６と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を表６に記載した。硝酸銅を添加した後、光触媒分散液中の酸化チタンの分散性は低下し、固液分離が見られた。
Comparative Example 5
A photocatalyst dispersion was prepared in the same manner as in Example 6 except that the amount of copper added to titanium was changed to 0.75 mol%, and the photocatalytic activity was measured. The results are shown in Table 6. After adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion decreased, and solid-liquid separation was observed.
比較例６
チタンに対する銅の添加量を１．５モル％とした以外は実施例６と同じ操作で光触媒分散液を調製し、更に光触媒活性を測定し、結果を第２表に記載した。硝酸銅を添加した後、光触媒分散液中の酸化チタンの分散性は低下し、固液分離が見られた。
Comparative Example 6
A photocatalyst dispersion was prepared in the same manner as in Example 6 except that the amount of copper added to titanium was 1.5 mol%, and the photocatalytic activity was measured. The results are shown in Table 2. After adding copper nitrate, the dispersibility of titanium oxide in the photocatalyst dispersion decreased, and solid-liquid separation was observed.
第 １ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
銅成分の添加量 反応速度定数 銅成分添加後の固液分離
（モル％） （１／ｈ）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１ ０．０３ ０．３８ 無し
実施例２ ０．０７５ ０．３７ 無し
実施例３ ０．１５ ０．５０ 無し
実施例４ ０．３ ０．４３ 無し
実施例５ ０．４５ ０．５３ 無し
比較例１ ０ ０．２２ 無し
比較例２ ０．７５ ０．４８ 有り
比較例３ １．５ ０．１８ 有り
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Table 1
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Addition amount of copper component Reaction rate constant Solid-liquid separation after addition of copper component
(Mol%) (1 / h)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 0.03 0.38 None
Example 2 0.075 0.37 None
Example 3 0.15 0.50 None
Example 4 0.3 0.43 None
Example 5 0.45 0.53 None
Comparative Example 1 0 0.22 None
Comparative Example 2 0.75 0.48 Yes
Comparative Example 3 1.5 0.18 Yes
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
第 ２ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
銅成分の添加量 反応速度定数 銅成分添加後の固液分離
（モル％） （１／ｈ）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例６ ０．０３ ０．５４ 無し
実施例７ ０．０７５ ０．５８ 無し
実施例８ ０．１５ ０．６８ 無し
実施例９ ０．３ ０．６９ 無し
実施例10 ０．４５ ０．６２ 無し
比較例４ ０ ０．３３ 無し
比較例５ ０．７５ ０．５３ 有り
比較例６ １．５ ０．４６ 有り
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Table 2
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Addition amount of copper component Reaction rate constant Solid-liquid separation after addition of copper component
(Mol%) (1 / h)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 6 0.03 0.54 None
Example 7 0.075 0.58 None
Example 8 0.15 0.68 None
Example 9 0.3 0.69 None
Example 10 0.45 0.62 None
Comparative Example 4 0 0.33 None
Comparative Example 5 0.75 0.53 Yes
Comparative Example 6 1.5 0.46 Yes
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
得られた光触媒塗布膜について、アセトアルデヒド分解能を測定した。表１に示す通り、分散剤として蓚酸を用いた実施例１〜５と比較例１〜３の光触媒塗布膜のアセトアルデヒド分解能を比較すると、最適量の銅成分を添加することにより、酸化チタンの分散性を損なうことなく光触媒塗布膜の光触媒活性が高くなることを確認した。また、分散剤にリン酸二水素アンモニウムを用いた実施例６〜１０と比較例４〜６のアセトアルデヒド分解能を比較すると、表２の通り、最適量の銅成分を添加することにより、酸化チタンの分散性を損なうことなく光触媒塗布膜の光触媒活性が高くなることを確認できた。 About the obtained photocatalyst coating film, the acetaldehyde resolution was measured. As shown in Table 1, when comparing the acetaldehyde resolution of the photocatalyst coating films of Examples 1 to 5 and Comparative Examples 1 to 3 using oxalic acid as a dispersant, the dispersion of titanium oxide can be achieved by adding an optimal amount of copper component. It was confirmed that the photocatalytic activity of the photocatalyst coating film was increased without impairing the properties. Moreover, when comparing the acetaldehyde resolution of Examples 6 to 10 and Comparative Examples 4 to 6 using ammonium dihydrogen phosphate as a dispersant, as shown in Table 2, by adding an optimal amount of copper component, It was confirmed that the photocatalytic activity of the photocatalyst coating film was increased without impairing the dispersibility.
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