CA2222869C - Photocatalytic body and method for making same - Google Patents
Photocatalytic body and method for making same Download PDFInfo
- Publication number
- CA2222869C CA2222869C CA002222869A CA2222869A CA2222869C CA 2222869 C CA2222869 C CA 2222869C CA 002222869 A CA002222869 A CA 002222869A CA 2222869 A CA2222869 A CA 2222869A CA 2222869 C CA2222869 C CA 2222869C
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- Prior art keywords
- sol
- titanium oxide
- amorphous
- titanium
- photocatalyst
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 126
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011941 photocatalyst Substances 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 26
- 239000011230 binding agent Substances 0.000 claims description 13
- 230000002269 spontaneous effect Effects 0.000 claims description 13
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 16
- 229920000620 organic polymer Polymers 0.000 abstract description 7
- 239000002952 polymeric resin Substances 0.000 abstract description 7
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000005329 float glass Substances 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 4
- 239000004811 fluoropolymer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229910011011 Ti(OH)4 Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 239000005084 Strontium aluminate Substances 0.000 description 2
- 229910010066 TiC14 Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910016003 MoS3 Inorganic materials 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910019899 RuO Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 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
- 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
-
- B01J35/30—
-
- B01J35/39—
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/522—Radiant or wave energy activated
Abstract
The invention relates to a photocatalytic body having a good photocatalytic function characterized by using an amorphous titanium peroxide sol, and a method for making the same. A photocatalyst such as titanium oxide in the form of powder or a sol and an amorphous titanium peroxide sol are mixed in different mixing rations depending on the purpose in use and the resultant mixture is coated onto a substrate such as an organic polymer resin, dried.cndot.solidifed and/or baked to support and fixed the photocatalyst on the substrate to make a photocatalytic body. Alternatively, a first layer consisting of an amorphous titanium peroxide sol on a substrate, and a second layer made of a photocatalyst is formed on the first layer to make a photocatalytic body.
According to the invention, the photocatalyst can be supported and fixed on the substrate without lowering the photocatalytic function of the photocatalyst to obtain a photocatalytic body which is usable over a long time.
According to the invention, the photocatalyst can be supported and fixed on the substrate without lowering the photocatalytic function of the photocatalyst to obtain a photocatalytic body which is usable over a long time.
Description
CA 02222869 1997 - 11 N28, w_to~o DESCRIPTION
PHOTOCATALYTIC BODY AND METHOD FOR MAKING SAME
TECHNICAL FIELD
This invention relates to a photocatalytic body having a good photocatalytic function, a method for making the same, and a photocatalytic composition used therefor.
BACKGROUND TECHNOLOGY
When semiconductors are irradiated with light whose wavelength has an energy greater than a band gap thereof, an oxidation-reduction reaction is brought about. Such a semiconductor is called a photocatalytic semiconductor or merely a photocatalyst.
Photocatalysts are in the form of powder and may be used as suspended in a solution, or may be used as supported on a substrate. From the standpoint of photocatalytic activity, the former is more active owing to the greater surface area. From the standpoint of practical applications, it has been frequently experienced to inevitably adopt the latter rather than the former owing to the ease in handing.
In order to support a photocatalyst on a substrate, there has been adopted a method wherein the particles of a photocatalyst are sintered at high temperatures and supported on the substrate. Another method has been proposed wherein a certain type of fluoropolymer is used as a binder, with which a photocatalyst is supported on a substrate. For instance, Japanese Laid-open Patent Application No. 4-284851 sets out a method wherein a mixture of the particles of a photocatalyst and a fluoropolymer is built up as layers and bonded under compression pressure. Japanese Laid-open Patent Application No. 4-334552 sets forth a method wherein the particles of a photocatalyst are thermally bonded to a fluoropolymer. Moreover, Japanese Laid-open Patent Application No. 7-171408 sets out a method wherein the particles of a photocatalyst is bonded on a substrate through a hard-to-decompose binder including an inorganic binder such as water glass or an organic binder such as a silicone copolymer, and also a method for manufacturing a photocatalytic body which includes, on a substrate, a first layer made of a hard-to-decompose binder, and a second layer formed on the first layer and made of a hard-to-decompose binder and the particles of a photocatalyst. In addition, Japanese Laid-open Patent Application No. 5-309267 describes a method wherein the metal oxide obtained from a metal oxide sol is used to support and fix the powder of a photocatalyst therewith. It is stated that the metal oxide sols are obtained from organometallic compounds such as alkoxides, acetylacetonate, carboxylates of metals as used in a sol-gel method, or are obtained by hydrolysis of an alcohol solution of chlorides, such as titanium tetrachloride, in the presence of an acid or alkali catalyst.
DISCLOSURE OF THE INVENTION
In recent years, attempts have been made to decompose, purify and sterilize harmful substances, offensive odor components and oily components ascribed to daily living environments by use of photocatalysts, thus leading to a quick extension of the application range of photocatalysts. This, in turn, requires a method of causing the particles of a photocatalyst to be firmly supported on all types of substrates over a long time without a sacrifice of its photocatalytic function. Especially, where a titanium oxide sol, which exhibits the good photocatalytic function but is poor in the function of bonding to a substrate, is used as a photocatalyst, it is required to improve the bonding property.
However, in these prior art methods, the bonding strength is not satisfactory, so that few methods ensures the support over a long time. If it is intended to make a photocatalytic body which has an improved bonding strength and ensures the support over a long time, there has ai-isen the problem that the photocatalytic function lowers. In case where the substrate made of an organic polymer resin is employed and rutile titanium oxide, which is weaker in photocatalytic function than anatase titanium oxide, is used, the photocatalytic reaction proceeds. Not only the organic polymer resin per se undergoes a photochemical reaction, but also the use over a long time results in degradation and decomposition.
Moreover, where organic polymer resins are used as a substrate, preliminary coating such as with a silica sol has been attempted, with the attendant problem that during the course of coagulation. drying of the silica sol, cracks or voids are formed, thus presenting a pi-oblem on their bonding performance.
In order to solve the above problems, studies have been made on how to firmly support the particles of a photocatalyst on all types of substrates over a long time without impeding its photocatalytic function. As a result, it has been unexpectedly found that when using an amorphous titanium peroxide sol as a binder, the particles of a photocatalyst can be firmly supported on all types of substrates over a long time without impeding the photocatalytic function. The invention has been accomplished based on the finding.
More particularly, the invention relates to a method for manufacturing a photocatalytic body by use of a photocatalyst such as of titanium oxide and an amorphous titanium peroxide sol so that the photocatalyst is fixedly supported on a substrate, and also to a method for manufacturing a photocatalytic body which comprises forming, on a substrate, a first layer of an amorphous titanium peroxide sol having no photocatalytic function, and further forming a second layer on the first layer wherein the second layer is made of a photocatalyst and an amorphous titanium peroxide sol. Further, the invention relates to a photocatalytic body obtained by these methods and to a photocatalyst composition used for the manufacture.
The amorphous titanium peroxide sol used in the practice of the invention may be prepared, for example, by the following manner. An alkali hydroxide such as aqueous ammonia or sodium hydroxide is added to an aqueous solution of a titanium salt such as titanium tetrachloride, TiC14. The resultant light bluish white, amorphous titanium hydroxide, Ti(OH)4, may be called ortho-titanic acid, H4TiO4. This titanium hydroxide is washed and separated, after which it is treated with an aqueous hydrogen peroxide solution to obtain an amorphous titanium peroxide solution useful in the present invention. The amorphous titanium peroxide sol has a pH of 6.0 - 7.0 and a particle size of 8- 20 nm, with its appearance being in the form of a yellow transparent liquid. The sol is stable when stored at normal temperatures over a long time. The sol concentration is usually adjusted to a level of 1.40 - 1.60%. If necessary, the concentration may be optionally controlled. If the sol is used at low concentrations, it is used by dilution such as with distilled water.
The amorphous titanium peroxide sol remains as amorphous and is not crystallized in the form of anatase titanium oxide at normal temperatures. The sol has good adherence, a good film-forming property and is able to form a uniform flat thin film, and a dried film has such a property of being insoluble in water.
It will be noted that when the amorphous titanium peroxide sol is heated to 100 C or above, it is converted to anatase titanium oxide sol. The amorphous titanium peroxide sol, which has been dried and fixed on a substrate after coating, is converted to anatase titanium oxide when heated to 250 C or above.
The photocatalysts usable in the present invention include Ti02, ZnO, SrTi03, CdS, CdO, CaP, InP, In203, CaAs, BaTi03, K2NbO3, Fe203, Ta205, W03, Sa02, Bi203, NiO, Cu20, SiC, Si02, MoS2, MoS3, InPb, Ru02, Ce02 and the like. Of these, titanium oxide is prefei-red. Titanium oxide may be used in the form of particles or powder, or in the form of a sol.
Titanium oxide in the form of a sol, i.e. a titanium oxide sol, can be prepared by heating an amorphous titanium peroxide sol at a temperature of 100 C or above. The properties of the titanium oxide sol, more or less, change depending on the heating temperature and the heating time. For instance, an anatase titanium oxide sol which is formed by treatment at 100 C for 6 hours has a pH of 7.5 - 9.5 and a particle size of 8-- 20 nm, with its appearance being in the form of a yellow suspension.
The titanium oxide sol is stable when stored at normal temperatures over a long time and may form a precipitate on mixing with an acid or a metal aqueous solution. Moreover, the sol may be impeded in its photocatalytic activity or an acid resistance when Na ions co-exists. The sol concentration is usually adjusted to a level of 2.70 - 2.90% and may be employed after adjustment of the concentration, if necessary.
A titanium oxide sol is preferably used as a photocatalyst. Commercially available "ST-01" (ISHIHARA SANGYOU KAISHA Ltd) or "ST-31"
(ISHIHARA SANGYOU KAISHA Ltd) may also be usable.
In the practice of the invention, the substrate used may be made of inorganic materials such as ceramics, glass and the like, organic materials such as plastics, rubber, wood, paper and the like, and metals such as aluminium, steels and the like. Of these, applications to organic polymer resin materials, such as acrylonitrile resin, vinyl chloride resin, polycarbonate resins, methyl methacrylate resin (acrylic resins), polyester resins, polyurethane resins and the like, show good effects. The substrate is not ci-itical with respect to the size or shape and may be in the form of a honeycomb, fibers, a filter sheet, a bead, a foamed body or combinations thereof. If a substrate which allows transmission of W light is used, a photocatalytic body may be applied to the inner surface of the substrate. The body may also be applicable to coated articles.
In the present invention, binders which are incapable of being decomposed with a photocatalyst mean those binders incapable of being decomposed with photocatalysts and composed of inorganic binders such as water glass, colloidal silica, cement and the like, and organic binders such as fluoropolymers, silicone polymers and the like, as disclosed in the aforementioned JP-A7-171408.
The composition used to make a photocatalytic body may be prepared according to several methods.
One of such methods includes the use of a uniform suspension of titanium oxide powder in an amorphous titanium peroxide sol. For the uniform suspension, it is advantageous to employ ultrasonic wave after mechanical agitation.
Next, the titanium oxide sol and the amorphous titanium peroxide sol are mixed to obtain a mixed sol. The mixing ratio is determined depending on the portion of a product to which a photocatalytic body is applied and the use conditions of an instrument using the body. For the mixing, consideration should be taken to the adherence to a substrate, film-forming properties, corrosion resistance and decorativeness of the photocatalytic body made by use of the mixed sol. The mixing ratio can be properly determined depending on the types of articles to be applied which are broadly classified into the following three groups.
(1) Those articles which one contacts or is highly likely to contact and which need decorativeness from the visual standpoint, e.g. interior tiles, sanitary wares, various types of unit articles, tablewares, exterior materials in buildings, interior automotive trims and the like.
(2) Those articles which one does not contact but requires visual decorativeness, e.g. exterior panels for light fittings, underground passage, tunnel, materials for engineering works, and electrical equipments.
(3) Those articles which one does not usually contact or is able to see and in which the function of decomposing organic matters based on a photocatalytic function or the properties inherent to semiconductive metals are utilized, e.g. built-in members in the inside of water-purifier tanks, various types of sewage treatment equipments, water heaters, bath tubs, air conditioners, the hoods of microwave ovens, and other apparatus.
For Group (1), a photocatalytic body which is obtained, in the form of a film, from a mixed sol wherein the titanium oxide sol is mixed in an amount of wt% or below based on the total of the titanium oxide sol and an amorphous titanium peroxide sol is preferred. It has been found that articles using the body are sufficient for sterilization or decontamination in daily life and also for decomposition of residual odors. Moreover, the film surface is so hard that it is free of any wear such as by sweeping or dusting and also of any deposition of foreign matters, along with the unlikelihood of leaving fingei-pi-ints on contact.
With water-purifier tanks which belong to Group (3), for example, high photocatalytic activity is the most important property which is required for the photocatalytic body in order to lower a biological oxygen demand (BOD) in final waste water-treated water. It has been found that a photocatalytic body in the form of a film, which is formed of a mixed sol wherein the titanium oxide sol is mixed in an amount of 70 wt% or above based on the total of the titanium oxide sol and the amorphous titanium peroxide sol, is most suitable for this purpose.
This photocatalytic body is poor in decorativeness. Since the articles of this group are ones which do neither come in contact with men nor are fell on the eyes. Moreover, it has also been found that such a problem of deposition of a residue in a slight degree can be solved by periodic removal and cleaning.
For the articles of Group (2), it has been found that a photocatalytic body in the form of a film, which is formed by use of a mixed sol wherein the titanium oxide sol is mixed in an amount of 20 - 80 wt% based on the total of the titanium oxide sol and an amorphous titanium peroxide sol, is suited. This photocatalytic body exhibits properties intermediate between the former two bodies with respect to the hardness, the adherence of foreign matters, and the photocatalytic activity.
For the coating or spraying, on a substrate, of a titanium oxide sol, an amorphous titanium peroxide sol or a mixed sol, any known procedures may be utilized including, for example, dipping, spraying, coating and the like. Good results of coating are frequently obtained when repeating the coating step plural times.
After coating or spraying as mentioned above, the sol is di-ied and solidified to obtain a photocatalytic body of the invention. The sol may be baked at approximately 200 - 400 C and fixedly set on a substrate. The photocatalytic function of titanium oxide lowers by the action of sodium ions. Accordingly, if an organic polymer resin which is liable to undergo decomposition by means of a photocatalyst is used as a substrate, it is preferred to clean the resin surface with a sodium ion-containing material such as a sodium hydroxide solution to permit a sodium source to be present.
It will be noted that where an amorphous titanium peroxide sol is used as a first layer, the peroxide is converted to the crystals of anatase titanium oxide on heating to 250 C or above, thereby causing a photocatalytic function to develop. Accordingly, lower temperatures, for example, of 80 C or below are used for drying and solidification. In this case, sodiuni ions may be added to the titanium peroxide sol for the reasons set out above.
Prior to shaping, the particles made of a spontaneous UV radiating material or a light storage-type UV radiating material, or particles containing such radiating materials may be mixed with a photocatalyst.
The spontaneous UV radiating material (i.e. a spontaneous light-emitting ceramic) is able to emit light by consumption of its internal energy, and makes use of radioactive disintegration of radiuni or promethium. The emitted light is within a UV range. In practice, a purified powder of rock containing such a component as mentioned above is set into a massive body, and the particles obtained by pulverization of the massive body into pieces are used.
The light storage-type UV radiating matei-ial (a light storage-type light emitting ceramic) is one which takes an external energy therein and emits light while releasing once taken energy. The emitted light is within a UV range.
Such a material is commercially available under the designations of "LumiNova* "
(commercial name of NEMOTO & CO., LTD) and "KEPRUS* "(commercial name of Next = I CO., LTD). These are made primarily of strontium aluminate (SrA1204) containing highly pure components sucll as alumina, strontium carbonate, europium, dysprosium and the like. The maximum point of the absorption spectra is at 360 nm, and the particle size is 20 m - 50 m.
Pulverized particles prior to powdering may be used as they are.
It will be noted that if there are some commerciallv available materials which considerably lower in their performance on absorption of moisture, they may be used after encapsulated in glass or a transparent organic polymer resin such as polycarbonate, or may be used by incorporation in a substrate or by attachment on the surface of a substrate.
When a photocatalytic body is made of a mixture of the particles of a spontaneous light-emitting ceramic or a light storage-type light-emitting ceramic or molded particles obtained by mixing the fine particles of these ceramics (hereinafter referred to as mixed particles) with a photocatalyst, the photocatalytic semiconductor of the photocatalytic body is excited by means of UV light radiated from the spontaneous light-emitting ceramic particles or generated by consumption of the energy accumulated in the particles of the light storage-type light-emitting ceramic. Thus, the photocatalytic function is continued if the UV irradiation against the photocatalytic body is interrupted.
Moreover, the particles of the spontaneous light-emitting ceramic or the light *Trade-mark storage-type light-emitting ceramic usually emanates green, blue or orange-colored visible light, which may be utilized for decoration or directional sign in the dark.
When the photocatalytic semiconductor is controlled in its composition (by addition of inorganic pigments or metals), or is controlled in thermal treatment during the course of the preparation, it can be possible to change a wavelength (absorption band) of UV light necessary for showing the catalytic function, i.e. an excitation wavelength. For instance, if Cr03 is added to Ti02 in small amounts, the absorption band is shifted toward a side of a longer wavelength. This permits the photocatalytic body to be in coincidence with the emission spectral characteristics of a spontaneous UV radiating material or a light storage-type UV radiating material. Proper choice of a photocatalytic semiconductor in coincidence with a wavelength of UV light to be applied thereto becomes possible.
In contrast, the emission spectral characteristics of a spontaneous UV
radiating material or a light storage-type UV radiating material may be brought into coincidence with the excitation wavelength of a photocatalytic semiconductor. For instance, the excitation wavelength of titanium oxide is in the range of 180 nm - 400 nm. Light storage-type UV radiating materials responsible for the wavelength have never been commercially available.
Light storage ceramics which are commercially available and permit afterglow over a long time include "Luminova" series of NEMOTO & CO., LTD, with some of the series having an afterglow time exceeding 1000 minutes. The light storage ceramics of the long-time afterglow are prepared by adding alumina to a starting main material such as strontium carbonate or calcium carbonate, further adding europium or dysprosium as an activator, and then adding an element such as of lanthanum, cerium, praseodymium, samarium, cadmium, terbium, holmium, erbium, thulium, ytterbium, ruthenium, manganese, tin and bismuth and boric acid as a flux, followed by thermal treatment at 1300 C. The product obtained by this mixing procedure is a blue light emitter having a peak of the shortest wavelength of 440 nm.
In order to shift the emission wavelength to 400 nm or below which corresponds to the excitation wavelength of titanium oxide, additive metal elements may be added for causing the absorption wavelength of the "Luminova" with a peak at 360 nm and the emission wavelength with a peak at 440 nm to come close to each other. Alternatively, if an emission wavelength of 440 nm or below does not generate on the emission of blue light at approximately 450 nm which is a phosphorescent wavelength characteristic inherent to minerals such as strontium, potassim and borax, a mineral element, which does not emanate any phosphorescent color, is shorter in wavelength than strontium, and has an emission wavelength of 400 nm or below vvithout development of any color, may be purified and formulated to develop a light storage-type UV
radiating material.
The photocatalytic semiconductor may be preliminarily supported on only the surfaces of unit particles, or may be supported on the entire surface of a molding after mixing of unit particles with the particles of a spontaneous light emitting ceramic or a light storage ceramic or the mixed particles and molding the mixture. In the former case, little photocatalytic semiconductor is deposited on the surfaces of the particles of a spontaneous light emitting ceramic or a light storage ceramic or the mixed particles, so that the quantity of UV light radiated from these particles becomes greater. With the particles of the light storage-type ceramic particles, UV light from outside can be efficiently absorbed.
The photocatalytic body may be admixed with photocatalytic function-assisting additive metals (Pt, Ag, Rh, RuO, Nb, Cu, Sn, NiO and the like) during the course of its preparation. These additives are well known as facilitating the photocatalytic reaction.
PHOTOCATALYTIC BODY AND METHOD FOR MAKING SAME
TECHNICAL FIELD
This invention relates to a photocatalytic body having a good photocatalytic function, a method for making the same, and a photocatalytic composition used therefor.
BACKGROUND TECHNOLOGY
When semiconductors are irradiated with light whose wavelength has an energy greater than a band gap thereof, an oxidation-reduction reaction is brought about. Such a semiconductor is called a photocatalytic semiconductor or merely a photocatalyst.
Photocatalysts are in the form of powder and may be used as suspended in a solution, or may be used as supported on a substrate. From the standpoint of photocatalytic activity, the former is more active owing to the greater surface area. From the standpoint of practical applications, it has been frequently experienced to inevitably adopt the latter rather than the former owing to the ease in handing.
In order to support a photocatalyst on a substrate, there has been adopted a method wherein the particles of a photocatalyst are sintered at high temperatures and supported on the substrate. Another method has been proposed wherein a certain type of fluoropolymer is used as a binder, with which a photocatalyst is supported on a substrate. For instance, Japanese Laid-open Patent Application No. 4-284851 sets out a method wherein a mixture of the particles of a photocatalyst and a fluoropolymer is built up as layers and bonded under compression pressure. Japanese Laid-open Patent Application No. 4-334552 sets forth a method wherein the particles of a photocatalyst are thermally bonded to a fluoropolymer. Moreover, Japanese Laid-open Patent Application No. 7-171408 sets out a method wherein the particles of a photocatalyst is bonded on a substrate through a hard-to-decompose binder including an inorganic binder such as water glass or an organic binder such as a silicone copolymer, and also a method for manufacturing a photocatalytic body which includes, on a substrate, a first layer made of a hard-to-decompose binder, and a second layer formed on the first layer and made of a hard-to-decompose binder and the particles of a photocatalyst. In addition, Japanese Laid-open Patent Application No. 5-309267 describes a method wherein the metal oxide obtained from a metal oxide sol is used to support and fix the powder of a photocatalyst therewith. It is stated that the metal oxide sols are obtained from organometallic compounds such as alkoxides, acetylacetonate, carboxylates of metals as used in a sol-gel method, or are obtained by hydrolysis of an alcohol solution of chlorides, such as titanium tetrachloride, in the presence of an acid or alkali catalyst.
DISCLOSURE OF THE INVENTION
In recent years, attempts have been made to decompose, purify and sterilize harmful substances, offensive odor components and oily components ascribed to daily living environments by use of photocatalysts, thus leading to a quick extension of the application range of photocatalysts. This, in turn, requires a method of causing the particles of a photocatalyst to be firmly supported on all types of substrates over a long time without a sacrifice of its photocatalytic function. Especially, where a titanium oxide sol, which exhibits the good photocatalytic function but is poor in the function of bonding to a substrate, is used as a photocatalyst, it is required to improve the bonding property.
However, in these prior art methods, the bonding strength is not satisfactory, so that few methods ensures the support over a long time. If it is intended to make a photocatalytic body which has an improved bonding strength and ensures the support over a long time, there has ai-isen the problem that the photocatalytic function lowers. In case where the substrate made of an organic polymer resin is employed and rutile titanium oxide, which is weaker in photocatalytic function than anatase titanium oxide, is used, the photocatalytic reaction proceeds. Not only the organic polymer resin per se undergoes a photochemical reaction, but also the use over a long time results in degradation and decomposition.
Moreover, where organic polymer resins are used as a substrate, preliminary coating such as with a silica sol has been attempted, with the attendant problem that during the course of coagulation. drying of the silica sol, cracks or voids are formed, thus presenting a pi-oblem on their bonding performance.
In order to solve the above problems, studies have been made on how to firmly support the particles of a photocatalyst on all types of substrates over a long time without impeding its photocatalytic function. As a result, it has been unexpectedly found that when using an amorphous titanium peroxide sol as a binder, the particles of a photocatalyst can be firmly supported on all types of substrates over a long time without impeding the photocatalytic function. The invention has been accomplished based on the finding.
More particularly, the invention relates to a method for manufacturing a photocatalytic body by use of a photocatalyst such as of titanium oxide and an amorphous titanium peroxide sol so that the photocatalyst is fixedly supported on a substrate, and also to a method for manufacturing a photocatalytic body which comprises forming, on a substrate, a first layer of an amorphous titanium peroxide sol having no photocatalytic function, and further forming a second layer on the first layer wherein the second layer is made of a photocatalyst and an amorphous titanium peroxide sol. Further, the invention relates to a photocatalytic body obtained by these methods and to a photocatalyst composition used for the manufacture.
The amorphous titanium peroxide sol used in the practice of the invention may be prepared, for example, by the following manner. An alkali hydroxide such as aqueous ammonia or sodium hydroxide is added to an aqueous solution of a titanium salt such as titanium tetrachloride, TiC14. The resultant light bluish white, amorphous titanium hydroxide, Ti(OH)4, may be called ortho-titanic acid, H4TiO4. This titanium hydroxide is washed and separated, after which it is treated with an aqueous hydrogen peroxide solution to obtain an amorphous titanium peroxide solution useful in the present invention. The amorphous titanium peroxide sol has a pH of 6.0 - 7.0 and a particle size of 8- 20 nm, with its appearance being in the form of a yellow transparent liquid. The sol is stable when stored at normal temperatures over a long time. The sol concentration is usually adjusted to a level of 1.40 - 1.60%. If necessary, the concentration may be optionally controlled. If the sol is used at low concentrations, it is used by dilution such as with distilled water.
The amorphous titanium peroxide sol remains as amorphous and is not crystallized in the form of anatase titanium oxide at normal temperatures. The sol has good adherence, a good film-forming property and is able to form a uniform flat thin film, and a dried film has such a property of being insoluble in water.
It will be noted that when the amorphous titanium peroxide sol is heated to 100 C or above, it is converted to anatase titanium oxide sol. The amorphous titanium peroxide sol, which has been dried and fixed on a substrate after coating, is converted to anatase titanium oxide when heated to 250 C or above.
The photocatalysts usable in the present invention include Ti02, ZnO, SrTi03, CdS, CdO, CaP, InP, In203, CaAs, BaTi03, K2NbO3, Fe203, Ta205, W03, Sa02, Bi203, NiO, Cu20, SiC, Si02, MoS2, MoS3, InPb, Ru02, Ce02 and the like. Of these, titanium oxide is prefei-red. Titanium oxide may be used in the form of particles or powder, or in the form of a sol.
Titanium oxide in the form of a sol, i.e. a titanium oxide sol, can be prepared by heating an amorphous titanium peroxide sol at a temperature of 100 C or above. The properties of the titanium oxide sol, more or less, change depending on the heating temperature and the heating time. For instance, an anatase titanium oxide sol which is formed by treatment at 100 C for 6 hours has a pH of 7.5 - 9.5 and a particle size of 8-- 20 nm, with its appearance being in the form of a yellow suspension.
The titanium oxide sol is stable when stored at normal temperatures over a long time and may form a precipitate on mixing with an acid or a metal aqueous solution. Moreover, the sol may be impeded in its photocatalytic activity or an acid resistance when Na ions co-exists. The sol concentration is usually adjusted to a level of 2.70 - 2.90% and may be employed after adjustment of the concentration, if necessary.
A titanium oxide sol is preferably used as a photocatalyst. Commercially available "ST-01" (ISHIHARA SANGYOU KAISHA Ltd) or "ST-31"
(ISHIHARA SANGYOU KAISHA Ltd) may also be usable.
In the practice of the invention, the substrate used may be made of inorganic materials such as ceramics, glass and the like, organic materials such as plastics, rubber, wood, paper and the like, and metals such as aluminium, steels and the like. Of these, applications to organic polymer resin materials, such as acrylonitrile resin, vinyl chloride resin, polycarbonate resins, methyl methacrylate resin (acrylic resins), polyester resins, polyurethane resins and the like, show good effects. The substrate is not ci-itical with respect to the size or shape and may be in the form of a honeycomb, fibers, a filter sheet, a bead, a foamed body or combinations thereof. If a substrate which allows transmission of W light is used, a photocatalytic body may be applied to the inner surface of the substrate. The body may also be applicable to coated articles.
In the present invention, binders which are incapable of being decomposed with a photocatalyst mean those binders incapable of being decomposed with photocatalysts and composed of inorganic binders such as water glass, colloidal silica, cement and the like, and organic binders such as fluoropolymers, silicone polymers and the like, as disclosed in the aforementioned JP-A7-171408.
The composition used to make a photocatalytic body may be prepared according to several methods.
One of such methods includes the use of a uniform suspension of titanium oxide powder in an amorphous titanium peroxide sol. For the uniform suspension, it is advantageous to employ ultrasonic wave after mechanical agitation.
Next, the titanium oxide sol and the amorphous titanium peroxide sol are mixed to obtain a mixed sol. The mixing ratio is determined depending on the portion of a product to which a photocatalytic body is applied and the use conditions of an instrument using the body. For the mixing, consideration should be taken to the adherence to a substrate, film-forming properties, corrosion resistance and decorativeness of the photocatalytic body made by use of the mixed sol. The mixing ratio can be properly determined depending on the types of articles to be applied which are broadly classified into the following three groups.
(1) Those articles which one contacts or is highly likely to contact and which need decorativeness from the visual standpoint, e.g. interior tiles, sanitary wares, various types of unit articles, tablewares, exterior materials in buildings, interior automotive trims and the like.
(2) Those articles which one does not contact but requires visual decorativeness, e.g. exterior panels for light fittings, underground passage, tunnel, materials for engineering works, and electrical equipments.
(3) Those articles which one does not usually contact or is able to see and in which the function of decomposing organic matters based on a photocatalytic function or the properties inherent to semiconductive metals are utilized, e.g. built-in members in the inside of water-purifier tanks, various types of sewage treatment equipments, water heaters, bath tubs, air conditioners, the hoods of microwave ovens, and other apparatus.
For Group (1), a photocatalytic body which is obtained, in the form of a film, from a mixed sol wherein the titanium oxide sol is mixed in an amount of wt% or below based on the total of the titanium oxide sol and an amorphous titanium peroxide sol is preferred. It has been found that articles using the body are sufficient for sterilization or decontamination in daily life and also for decomposition of residual odors. Moreover, the film surface is so hard that it is free of any wear such as by sweeping or dusting and also of any deposition of foreign matters, along with the unlikelihood of leaving fingei-pi-ints on contact.
With water-purifier tanks which belong to Group (3), for example, high photocatalytic activity is the most important property which is required for the photocatalytic body in order to lower a biological oxygen demand (BOD) in final waste water-treated water. It has been found that a photocatalytic body in the form of a film, which is formed of a mixed sol wherein the titanium oxide sol is mixed in an amount of 70 wt% or above based on the total of the titanium oxide sol and the amorphous titanium peroxide sol, is most suitable for this purpose.
This photocatalytic body is poor in decorativeness. Since the articles of this group are ones which do neither come in contact with men nor are fell on the eyes. Moreover, it has also been found that such a problem of deposition of a residue in a slight degree can be solved by periodic removal and cleaning.
For the articles of Group (2), it has been found that a photocatalytic body in the form of a film, which is formed by use of a mixed sol wherein the titanium oxide sol is mixed in an amount of 20 - 80 wt% based on the total of the titanium oxide sol and an amorphous titanium peroxide sol, is suited. This photocatalytic body exhibits properties intermediate between the former two bodies with respect to the hardness, the adherence of foreign matters, and the photocatalytic activity.
For the coating or spraying, on a substrate, of a titanium oxide sol, an amorphous titanium peroxide sol or a mixed sol, any known procedures may be utilized including, for example, dipping, spraying, coating and the like. Good results of coating are frequently obtained when repeating the coating step plural times.
After coating or spraying as mentioned above, the sol is di-ied and solidified to obtain a photocatalytic body of the invention. The sol may be baked at approximately 200 - 400 C and fixedly set on a substrate. The photocatalytic function of titanium oxide lowers by the action of sodium ions. Accordingly, if an organic polymer resin which is liable to undergo decomposition by means of a photocatalyst is used as a substrate, it is preferred to clean the resin surface with a sodium ion-containing material such as a sodium hydroxide solution to permit a sodium source to be present.
It will be noted that where an amorphous titanium peroxide sol is used as a first layer, the peroxide is converted to the crystals of anatase titanium oxide on heating to 250 C or above, thereby causing a photocatalytic function to develop. Accordingly, lower temperatures, for example, of 80 C or below are used for drying and solidification. In this case, sodiuni ions may be added to the titanium peroxide sol for the reasons set out above.
Prior to shaping, the particles made of a spontaneous UV radiating material or a light storage-type UV radiating material, or particles containing such radiating materials may be mixed with a photocatalyst.
The spontaneous UV radiating material (i.e. a spontaneous light-emitting ceramic) is able to emit light by consumption of its internal energy, and makes use of radioactive disintegration of radiuni or promethium. The emitted light is within a UV range. In practice, a purified powder of rock containing such a component as mentioned above is set into a massive body, and the particles obtained by pulverization of the massive body into pieces are used.
The light storage-type UV radiating matei-ial (a light storage-type light emitting ceramic) is one which takes an external energy therein and emits light while releasing once taken energy. The emitted light is within a UV range.
Such a material is commercially available under the designations of "LumiNova* "
(commercial name of NEMOTO & CO., LTD) and "KEPRUS* "(commercial name of Next = I CO., LTD). These are made primarily of strontium aluminate (SrA1204) containing highly pure components sucll as alumina, strontium carbonate, europium, dysprosium and the like. The maximum point of the absorption spectra is at 360 nm, and the particle size is 20 m - 50 m.
Pulverized particles prior to powdering may be used as they are.
It will be noted that if there are some commerciallv available materials which considerably lower in their performance on absorption of moisture, they may be used after encapsulated in glass or a transparent organic polymer resin such as polycarbonate, or may be used by incorporation in a substrate or by attachment on the surface of a substrate.
When a photocatalytic body is made of a mixture of the particles of a spontaneous light-emitting ceramic or a light storage-type light-emitting ceramic or molded particles obtained by mixing the fine particles of these ceramics (hereinafter referred to as mixed particles) with a photocatalyst, the photocatalytic semiconductor of the photocatalytic body is excited by means of UV light radiated from the spontaneous light-emitting ceramic particles or generated by consumption of the energy accumulated in the particles of the light storage-type light-emitting ceramic. Thus, the photocatalytic function is continued if the UV irradiation against the photocatalytic body is interrupted.
Moreover, the particles of the spontaneous light-emitting ceramic or the light *Trade-mark storage-type light-emitting ceramic usually emanates green, blue or orange-colored visible light, which may be utilized for decoration or directional sign in the dark.
When the photocatalytic semiconductor is controlled in its composition (by addition of inorganic pigments or metals), or is controlled in thermal treatment during the course of the preparation, it can be possible to change a wavelength (absorption band) of UV light necessary for showing the catalytic function, i.e. an excitation wavelength. For instance, if Cr03 is added to Ti02 in small amounts, the absorption band is shifted toward a side of a longer wavelength. This permits the photocatalytic body to be in coincidence with the emission spectral characteristics of a spontaneous UV radiating material or a light storage-type UV radiating material. Proper choice of a photocatalytic semiconductor in coincidence with a wavelength of UV light to be applied thereto becomes possible.
In contrast, the emission spectral characteristics of a spontaneous UV
radiating material or a light storage-type UV radiating material may be brought into coincidence with the excitation wavelength of a photocatalytic semiconductor. For instance, the excitation wavelength of titanium oxide is in the range of 180 nm - 400 nm. Light storage-type UV radiating materials responsible for the wavelength have never been commercially available.
Light storage ceramics which are commercially available and permit afterglow over a long time include "Luminova" series of NEMOTO & CO., LTD, with some of the series having an afterglow time exceeding 1000 minutes. The light storage ceramics of the long-time afterglow are prepared by adding alumina to a starting main material such as strontium carbonate or calcium carbonate, further adding europium or dysprosium as an activator, and then adding an element such as of lanthanum, cerium, praseodymium, samarium, cadmium, terbium, holmium, erbium, thulium, ytterbium, ruthenium, manganese, tin and bismuth and boric acid as a flux, followed by thermal treatment at 1300 C. The product obtained by this mixing procedure is a blue light emitter having a peak of the shortest wavelength of 440 nm.
In order to shift the emission wavelength to 400 nm or below which corresponds to the excitation wavelength of titanium oxide, additive metal elements may be added for causing the absorption wavelength of the "Luminova" with a peak at 360 nm and the emission wavelength with a peak at 440 nm to come close to each other. Alternatively, if an emission wavelength of 440 nm or below does not generate on the emission of blue light at approximately 450 nm which is a phosphorescent wavelength characteristic inherent to minerals such as strontium, potassim and borax, a mineral element, which does not emanate any phosphorescent color, is shorter in wavelength than strontium, and has an emission wavelength of 400 nm or below vvithout development of any color, may be purified and formulated to develop a light storage-type UV
radiating material.
The photocatalytic semiconductor may be preliminarily supported on only the surfaces of unit particles, or may be supported on the entire surface of a molding after mixing of unit particles with the particles of a spontaneous light emitting ceramic or a light storage ceramic or the mixed particles and molding the mixture. In the former case, little photocatalytic semiconductor is deposited on the surfaces of the particles of a spontaneous light emitting ceramic or a light storage ceramic or the mixed particles, so that the quantity of UV light radiated from these particles becomes greater. With the particles of the light storage-type ceramic particles, UV light from outside can be efficiently absorbed.
The photocatalytic body may be admixed with photocatalytic function-assisting additive metals (Pt, Ag, Rh, RuO, Nb, Cu, Sn, NiO and the like) during the course of its preparation. These additives are well known as facilitating the photocatalytic reaction.
BEST MODE FOR CARRYING OUT THE INVENTION
The invention is more particularly described by way of References and Examples, which should not be construed as limiting the scope of the invention hereto.
Reference 1 (Preparation of an amorphous titanium peroxide sol) A 1:70 dilution of a 50% solution of titanium tetrachloride, TiC14, (SUMITOMO SITX CO.) with distilled water and a 1:10 dilution of a 25% solution of ammonium hydroxide, NH40H, (TAKASUGI PURECHEMICAL INDUSTRY
Ltd) with distilled water are mixed at a ratio by volunle of 7:1 for neutralization reaction. After completion of the neutralization reaction, the pH is adjusted to 6.5 - 6.8 and the mixture was allowed to stand for a while, followed by discarding the supernatant liquid. Distilled water is added to the resultant Ti(OH)4 in an amount of about 4 times the gel, followed by sufficient agitation and allowing to stand. While checking with silver nitrate, washing is repeated until no chlorine ion was detected in the supernatant liquid. Finally, the supernatant liquid is discarded to leave a gel alone. In some case, the gel may be subjected to centrifugal dehydration. 210 ml of an aqueous 35% hydrogen peroxide solution is divided into halves and added to 3600 ml of light yellowish white Ti(OH)4 in every 30 minutes, followed by agitation at about 5 C overnight to obtain about 2500 ml of a yellow transparent amorphous titanium peroxide sol.
If the generation of heat is not suppressed in the above steps, there is the possibility that water-insoluble matters such as metatitanic acid deposits.
Thus, it is preferred to carry out all the steps while suppressing the generation of heat.
Reference 2 (Preparation of titanium oxide sol from amorphous titanium peroxide sol) When the amorphous titanium peroxide sol is heated at 100 C, it is converted to anatase titanium oxide after passage of about 3 hours and is converted to an anatase titanium oxide sol on heating for about 6 hours.
Moreover, when the sol is heated at 100 C for 8 hours, it assumes light yellow, slightly suspended fluorescence. On concentration, a yellow opaque matter is obtained. Further, when the sol is heated at 100 C for 16 hours, a very light yellow matter is obtained. These matters, more or less, lowers in dry adherence on comparison with that obtained by heating at 100 C for 6 hours.
The titanium oxide sol is lower in viscosity than amorphous titanium oxide and is employed after concentration to 2.5 wt~le because of the ease in dipping.
Exaznple.1 The decomposition test of organic substances using different mixing ratios between the amorphous titanium peroxide sol and the titanium oxide sol was conducted in the following manner. A 150 rrim long x 220 wide x 4 mm thick KERAMIT*decorative sheet (Clay Burn Ceramics CO., Ltd) was used as a substrate. Mixed sols having different mixing ratios W'ere each coated onto the substrate in a thickness of about 2 m according to spraying and dried from normal temperatures to ?0 C, followed by baking at about 400 C for 30 minutes to obtain five types of photocatalytic bodies wherein different types of photocatalysts were each supported on the substrate. These test photocatalytic bodies were each placed in a test container, into which a colored solution of an organic substance to be decomposed was charged to a depth of 1 cm. This colored solution was a 1:30 dilution of POLLUX Red OM-R (SUMIKA
COLOR CO., LTD.) which was an aqueous dispersion (red liquid) of Monoazo Red*
Next, in order to prevent the evaporation of the colored solution in the container, the container was covered with a float glass (capable of cutting a wavelength of 300 nm or below). Two UV radiators (each being a 20 W blue color fluorescent tube were set at 5 cm above the test container and at 9.5 cm from the substrate *Trade-mark while keeping apart from each other at a distance of 13 cm. The individual photocatalytic bodies were irradiated, under which at the time when the color of the colored solution was bleached, the decomposition of the organic matter was judged as completed. The results are described below.
The body wherein 100% titanium oxide sol was applied onto the substrate was able to bleach the color in 72 hours from commencement of the test. Thus, the capability of decomposing the organic substance, the photocatalytic function was good, but a residue after the decomposition was great in amount. On the other hand, with the body using 100% of the amorphous titanium peroxide sol, the color was bleached in 150 hours, so that the capability of decomposing the organic substance, i.e. the photocatalytic function, was poorer than that using 100% of the titanium oxide sol. Nevertheless, the adherence, film-forming property, corrosion resistance and decorativeness were better. The color was bleached in 78 hours for a mixing ratio between the amorphous titanium peroxide sol and the titanium oxide sol at a mixing ratio of 1:3, in 102 hours for a mixing ratio of 1:1, and in 120 hours for a mixing ratio of 3:1, respectively.
From the above text, it was confirmed that the photocatalytic function was in reverse proportion to the adherence, film-forming property, corrosion resistance and decorativeness. Thus, it was found that according to the invention, when the mixing ratio was changed, a diversity of applications (portions of articles to be applied and use conditions) were ensured Example 2 An acrylic resin plate and a methacrylic acid resin plate were each provided as a substrate. These resin plates were, respectively, immersed in a 2% sodium hydroxide solution at 80 C for 30 minutes, washed with water and dried. The titanium peroxide sol prepared in Reference 1, to which 0.5% of a surface active agent was added, was coated by repeating dipping 3-- 4 times to form a first layer. Drying was effected at 70 C for 10 minutes.
A second layer was formed by coating five mixtures of the amorphous titanium peroxide sol and the titanium oxide sol at such mixing rations as in Example 1 by repeating dipping 3 - 4 times. Drying=solidification was effected under conditions of 120 C and 3 minutes for the acrylic resin plate and was stopped for the methacrylic resin plate when the temperature of a dryer reached 119 C. The results of the photocatalytic function were similar to those of Example 1. With regard to the adhesion force on the resin plates and the unlikelihood of decomposing the resin plates with the photocatalyst, the bodies having the first layer were much more excellent.
Example 3 A highly water-absorbing commercially available tile was used as a substrate. The tile was washed with a neutral detergent, dried and applied with a surface active agent. A photocatalyst composition used was one which was obtained by adding 1 part, on the weight basis, of titanium oxide powder "ST-01"
(ISHIHARA SANGYO KAISHA Ltd) to 50 parts of the titanium peroxide sol (pH 6.4) prepared in Reference 1, mechanically agitating for about 15 minutes and further agitating by means of ultrasonic waves in order not to leave flocs.
Dipping was effected at a rate of 0.3 - 0.5 cni/second, followed by drying overnight at 30 C. This was baked at 400 C for 30 minutes to make a photocatalytic body.
The photocatalyst layer was firmly bonded to the tile surface over a long time.
On the other hand, when the tile was coated with a dispersion of the titanium oxide powder in distilled water, good bonding was not attained.
Example 4 A float glass which had been degreased and treated with a surface active agent was coated on the surface thereof with a glass beads suspension by means of a spray gun several times. After drying at 40 C, the coating was baked at 700 C for 30 minutes. The float glass on which the glass beads was fixed was further coated with a photocatalyst composition used in Example 3, dried and baked at 400 C for 30 minutes to obtain a photocatalytic body. This photocatalytic body was strongly bonded to the glass beads fixed on the float glass over a long time.
Example 5 A light storage-type UV radiating material "KEPRUS" (commercial name of Next = I CO., LTD) was mixed with an amorphous titanium peroxide sol in an amount of 25 wt% based on the titanium peroxide in the sol, agitated, sprayed over a KERAMIT decorative sheet used as a substrate, dried at normal temperature, baked at 400 C for 30 minutes, and cooled. Thereafter, a titanium oxide sol whose excitation wavelength was adjusted to an emission wavelength of the radiating material was sprayed in a thickness of 1 m, dried and baked at 40 C for 30 minutes. The resultant photocatalytic body had the photocatalytic action continued by means of the UV light emanated from the UV radiating material when irradiation of the UV light against the body was interrupted.
INDUSTRIAL APPLICABILITY
According to the invention, a photocatalyst can be supported and fixed on a substrate without lowering the photocatalytic function of the photocatalyst thereby providing a photocatalytic body which is usable over a long time. The photocatalytic body of the invention can be used as interior and exterior members for buildings such as interior and exterior tiles, sanitary wares, air conditioners, bathtubs and the like, exterior panels of vai-ious types of electric equipments such as lightning fittings, interior automotive members, inner walls of underground passage and tunnel, water-purifier tanks and the like.
The invention is more particularly described by way of References and Examples, which should not be construed as limiting the scope of the invention hereto.
Reference 1 (Preparation of an amorphous titanium peroxide sol) A 1:70 dilution of a 50% solution of titanium tetrachloride, TiC14, (SUMITOMO SITX CO.) with distilled water and a 1:10 dilution of a 25% solution of ammonium hydroxide, NH40H, (TAKASUGI PURECHEMICAL INDUSTRY
Ltd) with distilled water are mixed at a ratio by volunle of 7:1 for neutralization reaction. After completion of the neutralization reaction, the pH is adjusted to 6.5 - 6.8 and the mixture was allowed to stand for a while, followed by discarding the supernatant liquid. Distilled water is added to the resultant Ti(OH)4 in an amount of about 4 times the gel, followed by sufficient agitation and allowing to stand. While checking with silver nitrate, washing is repeated until no chlorine ion was detected in the supernatant liquid. Finally, the supernatant liquid is discarded to leave a gel alone. In some case, the gel may be subjected to centrifugal dehydration. 210 ml of an aqueous 35% hydrogen peroxide solution is divided into halves and added to 3600 ml of light yellowish white Ti(OH)4 in every 30 minutes, followed by agitation at about 5 C overnight to obtain about 2500 ml of a yellow transparent amorphous titanium peroxide sol.
If the generation of heat is not suppressed in the above steps, there is the possibility that water-insoluble matters such as metatitanic acid deposits.
Thus, it is preferred to carry out all the steps while suppressing the generation of heat.
Reference 2 (Preparation of titanium oxide sol from amorphous titanium peroxide sol) When the amorphous titanium peroxide sol is heated at 100 C, it is converted to anatase titanium oxide after passage of about 3 hours and is converted to an anatase titanium oxide sol on heating for about 6 hours.
Moreover, when the sol is heated at 100 C for 8 hours, it assumes light yellow, slightly suspended fluorescence. On concentration, a yellow opaque matter is obtained. Further, when the sol is heated at 100 C for 16 hours, a very light yellow matter is obtained. These matters, more or less, lowers in dry adherence on comparison with that obtained by heating at 100 C for 6 hours.
The titanium oxide sol is lower in viscosity than amorphous titanium oxide and is employed after concentration to 2.5 wt~le because of the ease in dipping.
Exaznple.1 The decomposition test of organic substances using different mixing ratios between the amorphous titanium peroxide sol and the titanium oxide sol was conducted in the following manner. A 150 rrim long x 220 wide x 4 mm thick KERAMIT*decorative sheet (Clay Burn Ceramics CO., Ltd) was used as a substrate. Mixed sols having different mixing ratios W'ere each coated onto the substrate in a thickness of about 2 m according to spraying and dried from normal temperatures to ?0 C, followed by baking at about 400 C for 30 minutes to obtain five types of photocatalytic bodies wherein different types of photocatalysts were each supported on the substrate. These test photocatalytic bodies were each placed in a test container, into which a colored solution of an organic substance to be decomposed was charged to a depth of 1 cm. This colored solution was a 1:30 dilution of POLLUX Red OM-R (SUMIKA
COLOR CO., LTD.) which was an aqueous dispersion (red liquid) of Monoazo Red*
Next, in order to prevent the evaporation of the colored solution in the container, the container was covered with a float glass (capable of cutting a wavelength of 300 nm or below). Two UV radiators (each being a 20 W blue color fluorescent tube were set at 5 cm above the test container and at 9.5 cm from the substrate *Trade-mark while keeping apart from each other at a distance of 13 cm. The individual photocatalytic bodies were irradiated, under which at the time when the color of the colored solution was bleached, the decomposition of the organic matter was judged as completed. The results are described below.
The body wherein 100% titanium oxide sol was applied onto the substrate was able to bleach the color in 72 hours from commencement of the test. Thus, the capability of decomposing the organic substance, the photocatalytic function was good, but a residue after the decomposition was great in amount. On the other hand, with the body using 100% of the amorphous titanium peroxide sol, the color was bleached in 150 hours, so that the capability of decomposing the organic substance, i.e. the photocatalytic function, was poorer than that using 100% of the titanium oxide sol. Nevertheless, the adherence, film-forming property, corrosion resistance and decorativeness were better. The color was bleached in 78 hours for a mixing ratio between the amorphous titanium peroxide sol and the titanium oxide sol at a mixing ratio of 1:3, in 102 hours for a mixing ratio of 1:1, and in 120 hours for a mixing ratio of 3:1, respectively.
From the above text, it was confirmed that the photocatalytic function was in reverse proportion to the adherence, film-forming property, corrosion resistance and decorativeness. Thus, it was found that according to the invention, when the mixing ratio was changed, a diversity of applications (portions of articles to be applied and use conditions) were ensured Example 2 An acrylic resin plate and a methacrylic acid resin plate were each provided as a substrate. These resin plates were, respectively, immersed in a 2% sodium hydroxide solution at 80 C for 30 minutes, washed with water and dried. The titanium peroxide sol prepared in Reference 1, to which 0.5% of a surface active agent was added, was coated by repeating dipping 3-- 4 times to form a first layer. Drying was effected at 70 C for 10 minutes.
A second layer was formed by coating five mixtures of the amorphous titanium peroxide sol and the titanium oxide sol at such mixing rations as in Example 1 by repeating dipping 3 - 4 times. Drying=solidification was effected under conditions of 120 C and 3 minutes for the acrylic resin plate and was stopped for the methacrylic resin plate when the temperature of a dryer reached 119 C. The results of the photocatalytic function were similar to those of Example 1. With regard to the adhesion force on the resin plates and the unlikelihood of decomposing the resin plates with the photocatalyst, the bodies having the first layer were much more excellent.
Example 3 A highly water-absorbing commercially available tile was used as a substrate. The tile was washed with a neutral detergent, dried and applied with a surface active agent. A photocatalyst composition used was one which was obtained by adding 1 part, on the weight basis, of titanium oxide powder "ST-01"
(ISHIHARA SANGYO KAISHA Ltd) to 50 parts of the titanium peroxide sol (pH 6.4) prepared in Reference 1, mechanically agitating for about 15 minutes and further agitating by means of ultrasonic waves in order not to leave flocs.
Dipping was effected at a rate of 0.3 - 0.5 cni/second, followed by drying overnight at 30 C. This was baked at 400 C for 30 minutes to make a photocatalytic body.
The photocatalyst layer was firmly bonded to the tile surface over a long time.
On the other hand, when the tile was coated with a dispersion of the titanium oxide powder in distilled water, good bonding was not attained.
Example 4 A float glass which had been degreased and treated with a surface active agent was coated on the surface thereof with a glass beads suspension by means of a spray gun several times. After drying at 40 C, the coating was baked at 700 C for 30 minutes. The float glass on which the glass beads was fixed was further coated with a photocatalyst composition used in Example 3, dried and baked at 400 C for 30 minutes to obtain a photocatalytic body. This photocatalytic body was strongly bonded to the glass beads fixed on the float glass over a long time.
Example 5 A light storage-type UV radiating material "KEPRUS" (commercial name of Next = I CO., LTD) was mixed with an amorphous titanium peroxide sol in an amount of 25 wt% based on the titanium peroxide in the sol, agitated, sprayed over a KERAMIT decorative sheet used as a substrate, dried at normal temperature, baked at 400 C for 30 minutes, and cooled. Thereafter, a titanium oxide sol whose excitation wavelength was adjusted to an emission wavelength of the radiating material was sprayed in a thickness of 1 m, dried and baked at 40 C for 30 minutes. The resultant photocatalytic body had the photocatalytic action continued by means of the UV light emanated from the UV radiating material when irradiation of the UV light against the body was interrupted.
INDUSTRIAL APPLICABILITY
According to the invention, a photocatalyst can be supported and fixed on a substrate without lowering the photocatalytic function of the photocatalyst thereby providing a photocatalytic body which is usable over a long time. The photocatalytic body of the invention can be used as interior and exterior members for buildings such as interior and exterior tiles, sanitary wares, air conditioners, bathtubs and the like, exterior panels of vai-ious types of electric equipments such as lightning fittings, interior automotive members, inner walls of underground passage and tunnel, water-purifier tanks and the like.
Claims (17)
1. A method for making a photocatalytic body wherein titanium oxide as a photocatalyst is supported and fixed on a substrate, which comprises:
uniformly suspending particles of titanium oxide or powder of titanium oxide in an amorphous titanium peroxide sol to form a uniform suspension or admixing a titanium oxide sol and an amorphous titanium peroxide sol to form a mixed sol; and fixing the uniform suspension or the mixed sol to the substrate by using the amorphous titanium peroxide sol as a binder.
uniformly suspending particles of titanium oxide or powder of titanium oxide in an amorphous titanium peroxide sol to form a uniform suspension or admixing a titanium oxide sol and an amorphous titanium peroxide sol to form a mixed sol; and fixing the uniform suspension or the mixed sol to the substrate by using the amorphous titanium peroxide sol as a binder.
2. The method as claimed in claim 1, wherein the uniform suspension of the particles of titanium oxide or the powder of titanium oxide in the amorphous titanium peroxide sol is fixed to the substrate.
3. The method as claimed in claim 1, wherein the mixed sol of the titanium oxide sol and the amorphous titanium peroxide sol is fixed to the substrate.
4. The method as claimed in claim 3, wherein the titanium oxide sol is mixed, in an amount of 30 wt% or less based on the total weight of the titanium oxide sol and the amorphous titanium peroxide sol, with the amorphous titanium peroxide sol to form the mixed sol.
5. The method as claimed in claim 3, wherein the titanium oxide sol is mixed, in an amount of 20 to 80 wt%
based on the total weight of the titanium oxide sol and the amorphous titanium peroxide sol, with the amorphous titanium peroxide sol to form the mixed sol.
based on the total weight of the titanium oxide sol and the amorphous titanium peroxide sol, with the amorphous titanium peroxide sol to form the mixed sol.
6. The method as claimed in claim 3, wherein the titanium oxide sol is mixed, in an amount of 70 wt% or more based on the total weight of the titanium oxide sol and the amorphous titanium peroxide sol, with the amorphous titanium peroxide sol to form the mixed sol.
7. A method for making a photocatalytic body, which comprises:
forming on a substrate a first layer comprising a binder incapable of decomposition by action of a photocatalyst, and forming a second layer on the first layer, which second layer comprises titanium oxide as a photocatalyst and an amorphous titanium peroxide sol.
forming on a substrate a first layer comprising a binder incapable of decomposition by action of a photocatalyst, and forming a second layer on the first layer, which second layer comprises titanium oxide as a photocatalyst and an amorphous titanium peroxide sol.
8. A method for making a photocatalytic body, which comprises:
forming on a substrate a first layer comprising an amorphous titanium peroxide sol and having no photocatalytic function, and forming a second layer on the first layer, which second layer comprises titanium oxide as a photocatalyst and an amorphous titanium peroxide sol.
forming on a substrate a first layer comprising an amorphous titanium peroxide sol and having no photocatalytic function, and forming a second layer on the first layer, which second layer comprises titanium oxide as a photocatalyst and an amorphous titanium peroxide sol.
9. The method as claimed in claim 7 or 8, wherein the photocatalyst comprises particles of titanium oxide or powder of titanium oxide.
10. The method as claimed in claim 8, wherein the titanium oxide is in the form of a titanium oxide sol.
11. The method as claimed in claim 1, 3, 4, 5, 6 or 10, wherein the titanium oxide sol is obtained by thermal treatment of an amorphous titanium peroxide sol at 100°C or above.
12. The method as claimed in any one of claims 1 to 11, wherein sodium ions are present in a surface of the substrate.
13. The method as claimed in any one of claims 7 to 10, wherein sodium ions are present in the first layer.
14. The method as claimed in any one of claims 1 to 13, wherein particles of a spontaneous UV radiating material or a light storage-type UV radiating material, or particles containing a spontaneous UV radiating material or a light storage-type UV radiating material, are used along with the titanium oxide.
15. The method as claimed in claim 14, wherein the spontaneous UV radiating material has an emission wavelength, and the light storage-type UV radiating material has a stored light wavelength, corresponding to an excitation wavelength of the photocatalyst.
16. The method as claimed in any one of claims 1 to 15, wherein the amorphous titanium peroxide sol has a pH
of 6.0-7.0, a particle size of 8-20 nm and a yellow transparent appearance.
of 6.0-7.0, a particle size of 8-20 nm and a yellow transparent appearance.
17. The method as claimed in claim 16, wherein the amorphous titanium peroxide sol is obtained by adding an alkali hydroxide to an aqueous titanium salt solution to form an amorphous titanium hydroxide, and reacting an aqueous hydrogen peroxide solution with the amorphous titanium hydroxide to form the amorphous titanium peroxide sol.
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JP07554396A JP3690864B2 (en) | 1996-03-29 | 1996-03-29 | Production method of photocatalyst |
PCT/JP1997/000767 WO1997036677A1 (en) | 1996-03-29 | 1997-03-12 | Photocatalyst body and method of production thereof |
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- 1996-03-29 JP JP07554396A patent/JP3690864B2/en not_active Expired - Lifetime
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- 1997-03-12 WO PCT/JP1997/000767 patent/WO1997036677A1/en active IP Right Grant
- 1997-03-12 US US08/952,983 patent/US6107241A/en not_active Expired - Lifetime
- 1997-03-12 CA CA002222869A patent/CA2222869C/en not_active Expired - Fee Related
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- 1997-03-12 EP EP97907275A patent/EP0846494B1/en not_active Expired - Lifetime
- 1997-03-26 TW TW086103817A patent/TW460321B/en not_active IP Right Cessation
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US6429169B1 (en) | 2002-08-06 |
CA2222869A1 (en) | 1997-10-09 |
EP0846494B1 (en) | 2006-08-30 |
WO1997036677A1 (en) | 1997-10-09 |
TW460321B (en) | 2001-10-21 |
US6107241A (en) | 2000-08-22 |
KR19990022108A (en) | 1999-03-25 |
EP0846494A1 (en) | 1998-06-10 |
JPH09262481A (en) | 1997-10-07 |
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