TWI413615B - 透明穩定之二氧化鈦溶膠 - Google Patents
透明穩定之二氧化鈦溶膠 Download PDFInfo
- Publication number
- TWI413615B TWI413615B TW097132926A TW97132926A TWI413615B TW I413615 B TWI413615 B TW I413615B TW 097132926 A TW097132926 A TW 097132926A TW 97132926 A TW97132926 A TW 97132926A TW I413615 B TWI413615 B TW I413615B
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- Taiwan
- Prior art keywords
- sol
- titanium dioxide
- titanium
- transparent
- acid
- Prior art date
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 18
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- -1 titanium alkoxide Chemical class 0.000 claims description 10
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 9
- 235000014655 lactic acid Nutrition 0.000 claims description 9
- 239000011941 photocatalyst Substances 0.000 claims description 9
- 239000011975 tartaric acid Substances 0.000 claims description 9
- 235000002906 tartaric acid Nutrition 0.000 claims description 9
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 6
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 229940061720 alpha hydroxy acid Drugs 0.000 abstract description 3
- 150000001280 alpha hydroxy acids Chemical class 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract description 3
- 238000007669 thermal treatment Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 150000003609 titanium compounds Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000001935 peptisation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004627 transmission electron microscopy Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000001261 hydroxy acids Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- MJDAKKOAVKQDIR-UHFFFAOYSA-N [O-2].C(CCC)[Ti+3].[O-2].[O-2].C(CCC)[Ti+3] Chemical compound [O-2].C(CCC)[Ti+3].[O-2].[O-2].C(CCC)[Ti+3] MJDAKKOAVKQDIR-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000007689 inspection Methods 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
- 239000010985 leather Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/65—Coating or impregnation with inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2203/00—Production processes
- C03C2203/20—Wet processes, e.g. sol-gel process
- C03C2203/30—Additives
- C03C2203/32—Catalysts
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
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- C—CHEMISTRY; METALLURGY
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Description
本發明通常係關於用以在表面上賦予光觸媒塗層之組合物。更特定言之,本發明係關於二氧化鈦奈米微粒之溶膠,其可用於在去污及/或自動清洗的基材表面上提供透明的光觸媒塗層。
半導體材料二氧化鈦之光觸媒性質源自電子在紫外線(UV)以及近UV輻射的影響下,自價能帶激發至傳導帶。所產生的活性電子-電洞對遷移至二氧化鈦粒子表面,於該處電洞使吸附的水氧化以產生活性羥基,且電子使吸附的氧還原以產生過氧化自由基,該二者均可使空氣中的NOx
及揮發性有機化合物降解。鑒於此等性質,已在塗層等中應用光觸媒二氧化鈦以自空氣移除污染物。該塗層亦具有自動清洗的優點,因為污物(油脂、黴污、黴菌、藻類等)亦同時在該表面上被氧化。
在許多應用中,期望二氧化鈦塗層為透明以保持基材(例如瓷磚、鋪路磚、牆板等)的原有外觀或其原有透明度(例如窗玻璃、汽車擋風玻璃等),已經證明二氧化鈦膠體溶膠係用於形成該透光塗層之有用前驅物材料。
例如,Mori等人之美國專利第6,420,437號揭示一種中性二氧化鈦膠體溶膠,其在中性範圍內具有高穩定性且即使當在室溫下乾燥時亦能夠形成無色透明塗層,該專利以引用方式併入本文。藉由使包括50至100重量份之二氧化鈦膠體微粒以及5至50重量份之鈦離子之螯合劑之酸性二氧化鈦溶膠,與1至50重量份之包括至少一種鹼金屬化合物及胺化合物的鹼性物質混合,並視情況將液體混合物的pH值調整為5至10,或將液體混合物之pH值調整為6至10,以及接著將對混合物施加去離子處理從而使二氧化鈦膠體微粒帶有負電荷。
Ohmori等人之美國專利第6,627,336號(其揭示在此處以引用方式併入本文)描述二氧化鈦微粒之水性分散液,二氧化鈦顆粒之水性分散液較好主要由板鈦礦二氧化鈦微粒組成,其包括氯離子,以及氯離子以外之布忍斯特(BrΦnsted)鹼,較好為硝酸根離子及/或磷酸根粒子。水性二氧化鈦分散液係在至少一種布忍斯特酸存在下使四氯化鈦水解而製備。由水性二氧化鈦分散液形成之薄膜據稱對鹼性材料展現良好的光催化活性、透明度以及粘附性。
Amadelli等人之美國專利第6,824,826號(其揭示在此處以引用方式併入本文)係關於使用膠質二氧化鈦製備光觸媒,該膠質二氧化鈦視情況摻雜有選自週期表第I-VA族以及鑭系與錒系的金屬,用於保存原有之似水泥、石頭以及大理石製品之外觀。在該專利之實例1中提供由異丙氧化鈦藉硝酸的經控制水解製備膠質二氧化鈦。
Chung、Hoon等人之美國專利公開案第2004/0241502號(其揭示在此處以引用方式併入本文)係關於製造中性及透明的二氧化鈦膠體溶液之方法,其中分散有二氧化鈦奈米微粒,且關於以該方法製備之二氧化鈦膠體溶液。在製備該溶膠之一方法中,將鈦化合物以及穩定劑添加至醇類中,藉添加鹼性溶液中和,並且接著在高於75℃的溫度加熱超過7小時。其中該鈦化合物可係四異丙醇鈦(異丙氧化鈦),以及在許多穩定劑中,羥基乙酸據稱係適當的。由該方法製備的中性二氧化鈦膠體溶液據稱係穩定且透明。
儘管在本技術中有此等進展,現仍存在相當的改良餘地,因為各種已知溶膠都具有缺點。因此本發明之目的係提供包括透明之光觸媒二氧化鈦的溶膠。本發明之目的亦係提供在延長時間內係穩定的透明二氧化鈦溶膠。本發明之又另一目的係提供用於製備該等穩定透明溶膠且易以工業規模執行的新穎方法。
僅提出上述討論以對本技術遭遇之問題的本質提供更佳理解,並且不應以任何方式視為對先前技術的認可,任何此處之參考的引證也不應視為認可此等參考文件構成本申請案之「先前技術」。
根據上述目的等,已意外地發現,藉由在某些α-羥基酸存在下熱處理非晶形二氧化鈦之懸浮液可形成兼具有穩定及透明的二氧化鈦溶膠。
在本發明之一態樣中,提供一種製備穩定、透明的光觸媒二氧化鈦溶膠的方法,其包括(i)提供包括含鈦化合物的溶液,該含鈦化合物例如烷氧化鈦、氯氧化鈦、硫酸氧鈦或乙醯丙酮氧鈦;(ii)自該含鈦化合物之溶液使含水二氧化鈦沉澱;(iii)形成該沉澱含水二氧化鈦之水性分散液;以及(iv)在約70℃至約150℃之間的溫度下,在一或多種α-羥基羧酸存在下混合水性分散液約3小時至約3天之時間,該α-羥基羧酸係例如乳酸、酒石酸、蘋果酸、檸檬酸及其組合。雖然在熱處理步驟中需要一或多種α-羥基羧酸,但應理解其可在任意步驟(i)-(iv)期間引入該等酸。在本發明方法之一變化中,宜進行熱處理而無事先之中和步驟。在另一變化中,該一或多種α-羥基羧酸將不包含羥基乙酸。
所得二氧化鈦溶膠意外地在寬廣pH值範圍內例如在2至12之整個pH範圍係穩定且透明。溶膠一般將包括二氧化鈦之結晶,其具有小於約10nm或在約1nm至約10nm之間的平均粒徑,大多數結晶係呈銳鈦礦形式。在一個變化中,該結晶具有在約1nm至約5nm之間的平均粒徑及/或至少90%的結晶係呈銳鈦礦形式。
參考下列詳細說明以及附圖將更易理解本發明之此等及其他態樣。
本文使用之所有術語係意指其一般使用意義,除非另外提供。術語「溶膠」係指微粒之膠態懸浮液。術語「NOx
」係指物種NO(氮氧化物)以及NO2
(二氧化氮)的總稱或個別。
當關於自空氣「移除」污染物時,將理解為包含完全或部分自空氣移除污染物。移除是否係「實質上移除」可由在實例中提供的方法決定,其中「實質上」移除係指既定污染物的定額總濃度中減少至少約5%,較佳地減少至少約10%,且更佳地減少至少約15%。
根據本發明之製備穩定、透明的膠質光觸媒二氧化鈦溶膠之方法通常包括:(1)提供含鈦化合物之溶液;(2)自溶液沉澱非晶形含水二氧化鈦;(3)在水中分散該沉澱的二氧化鈦以及在約70℃至約150℃之間的溫度將分散液與膠溶劑混合約3小時至約3天之時間;其中膠溶劑包括α-羥基羧酸;因此提供包括銳鈦礦二氧化鈦之奈米微粒的穩定透明溶膠,其具有直徑小於或等於約10奈米(nm)的粒徑,且較佳地係直徑小於或等於約5nm。
含鈦化合物可係能夠形成二氧化鈦沉澱物的任何化合物,其可包括(但不限於)烷氧化鈦、氯氧化鈦、硫酸氧鈦、乙醯丙酮氧鈦等。適當的烷氧化鈦包括(但不限於)乙氧化鈦、n-丙氧化鈦、異丙氧化鈦、第三丁氧化鈦以及n-丁氧化鈦,此處列舉數個。混合的烷氧化物亦被認為適合。異丙氧化鈦係當前根據本發明之較佳含鈦化合物,部分係由於其低成本並且相對較易水解。
含鈦化合物的溶液可係水溶液或可包含適當的有機溶劑諸如醇類,例如乙醇或異丙醇。實質上對含鈦化合物之溶液濃度沒有限制,但其較好為濃縮以使得沉澱動力學最佳化。沉澱可受任何適當方法影響,包括但不限於水解、pH調整或溶劑位移。施用的沉澱法將主要由含鈦化合物之選擇而決定。例如,水解係較佳地沉澱法,其中含鈦化合物係烷氧化鈦或乙醯丙酮酸鈦。對於可溶於水的氯氧化鈦或硫酸氧鈦,沉澱最宜由pH調整(例如,提高pH)或添加化合物實質上不溶於其中之溶劑諸如丙酮或高級醇(溶劑位移)而進行。"實質上不可溶"意指含鈦化合物在溶劑溶解度足夠低以允許當其與第二溶劑接觸時,二氧化鈦可自溶液沉澱。「高級」醇意指C5
醇或更高級醇,包括但不限於戊醇、己醇、庚醇、辛醇等。
非晶形含水二氧化鈦沉澱物一般由過濾收集且在再分散前以去離子水徹底洗滌。洗滌過的濕濾餅接著在大量去離子水中劇烈攪動(例如,以深層漩渦,搖動等攪拌)再分散。在形成分散液之前,去離子水通常(但不一定)於溶液中包括膠溶劑。因為膠溶劑的益處主要在隨後的熱處理步驟期間實現,所以在沉澱物再分散之前沒有嚴格要求膠溶劑存在於水溶液中。相反,亦可在形成分散液後添加膠溶劑,或可在執行沉澱前將其添加至鈦前軀物。使用之去離子水的量宜使得初始含鈦化合物(例如異丙氧化鈦)對分散液總重的重量比自約1:2至約1:10,更典型地係約1:3至約1:6,且較佳為約1:4至約1:5。
理想地膠溶劑係有機酸(例如羧酸),其較佳地係在25℃下具有第一離解常數。根據一具體實施例之較佳膠溶劑係α-羥基羧酸。適當的α-羥基羧酸一般將包括一個、兩個或三個羧酸基,並且包括(但不限於)乳酸、蘋果酸、酒石酸及檸檬酸,此處列舉一些。在一些具體實施例中,上述酸類的鹽亦認為係適合的。上述酸類的組合認為亦可用。在一具體實施例中,溶液將無羥基乙酸或實質上無羥基乙酸,因為此α-羥基酸在25℃下具有3.83之pKa1
,且因此在本發明之實施中較不佳。「實質上無」意指總共包括的羥基乙酸不超過膠溶劑之總重量的5%,較好小於約2.5重量%,且更佳係小於約1重量%。要求之膠溶劑的量一般係每莫耳TiO2
沉澱物為約0.1至約0.5莫耳範圍。不希望被任何特殊理論所束縛,相信膠溶劑可防止或抑制絮凝作用並且在熱處理期間對結晶生長發揮螯合效應,以限制結晶尺寸並且所得溶膠提供穩定性。
膠溶作用一般在自約70℃至約150℃(熱處理)的溫度下,在攪動下執行約3小時至約3天的時間。在熱處理之前未必需要中和溶液。因此,在一具體實施例中,包括膠溶劑之分散液在熱處理之前或熱處理期間未進行中和步驟,諸如添加鹼性溶液。由於伴隨著壓力的增大,在密封的熱液反應器中執行膠溶作用係有效的。已發現諸如購自Parr設備公司之氣罐式熱液反應器適合在熱液反應中使用。氣罐反應器可放置於滾筒烘箱等,以提供熱力條件並且完成攪動。
在一些具體實施例中,所得溶膠在實質上任何pH(酸性、中性或鹼性)下均係穩定並且透明,因此pH調整未必需要。然而,在本發明之範圍內若需要可視情況調整pH。酸性膠溶化溶膠之pH可藉由添加有機或無機鹼而調整,其包括(但不限於)第三丁胺、二乙胺、氫氧化四甲銨、氫氧化銨等。溶膠之透明度可由視覺觀察或由UV可見光譜學觀察。溶膠的穩定性可測量為透明度隨時間變化的函數。「穩定」溶膠係在室溫下,經過一個月、兩個月或者較佳三個月之觀察期,在透明度上無可見變化的溶膠。未必需要包含如美國公開專利第2004/0241502號(此處以引用方式併入本文)中描述之穩定劑以賦予本發明之溶膠穩定性。
粒徑與結晶度(銳鈦礦/金紅石)可由透射電子顯微鏡(TEM)或其他合適的方法決定。二氧化鈦結晶一般具有約1至約20nm之間的平均粒徑,更一般在約1nm至約10nm之間,且較佳在約1至5nm之間。在其他具體實施例中,實質上所有的二氧化鈦結晶將具有小於或等於約10nm的粒徑,且較佳係小於或等於約5nm。「實質上所有」意指以重量計,D90
值小於或等於指定的尺寸。二氧化鈦溶膠一般將包括大部分呈銳鈦礦形式的結晶(即>50%),僅小部分結晶係呈金紅石形式。在各種具體實施例中,結晶之至少60%、至少70%、至少80%或至少90%係呈銳鈦礦結晶型式。在其他具體實施例中,二氧化鈦溶膠將實質上無金紅石結晶形式,其意指小於5%、較佳小於2.5%,且更佳小於1%的二氧化鈦係具有金紅石結晶形式。在另一具體實施例中,二氧化鈦係100%呈銳鈦礦形式。
該溶膠一般將包含組合物總重之約0.5至大約20重量%之二氧化鈦。更典型地,該溶膠將包含基於組合物總重之約1%至大約10重量%之二氧化鈦。該溶膠在寬廣pH值範圍內顯示優異的透明度與穩定性,pH值範圍包括酸性、中性以及鹼性條件。在一具體實施例中,在分別為1至<6、6-8以及>8至13的全部pH範圍內,該溶膠係穩定並且透明。另外,溶膠之pH可自酸性調整至中性,自中性調整至鹼性,反之亦然,其對透明度或穩定性不具有可測量的影響。
根據本發明之溶膠可視情況包括額外的成分,但條件為該等成分之添加對溶膠的透明度或穩定不具有可測量的負面影響。例如,預期該溶膠可包括少量的殺菌劑、有機溶劑(例如醇)、成膜助劑、多價螯合劑、pH調節劑等。在一具體實施例中,該溶膠將不含選自週期表第I-VA族以及鑭系或錒系的金屬離子,其意指在鈦起始物或其他試劑中以雜質存在之任何微量以外,將不添加額外量之該等金屬離子至溶膠或中間物製備中。
雖然本發明之溶膠係透明的,但亦有利地發現由溶膠施加至基質時形成的薄膜亦係透明。因此本發明包括在基質上形成透明光觸媒去污、自動清洗的薄膜或塗層之方法,該方法包括將根據本發明之任何溶膠施加至基質。使薄膜乾燥成對基質具有良好黏附性的透明塗層。基質之性質實質上並無限制。水泥、金屬、玻璃、聚合物、木材、陶瓷、紙、織品以及皮革基質均被認為適宜。
穩定透明的溶膠在需要光觸媒活性之任何應用中具有特定利用性。由於溶膠之透明本質,溶膠係理想地適合於本身係透明的(例如玻璃)塗層表面,或適合於提供不改變底下基質外觀的塗層。值得注意的應用包括(但不限於),在路面、鋪路磚與瓷磚、建築外部、窗玻璃、汽車擋風玻璃等上之用於空氣去污的光觸媒塗層。該溶膠在織物、傢具、藝術品等上亦具有實用性,由於其具有自動清洗性質可提供不鏽並且污物較少產品以及UV防護。
實例1
如下,製備根據本發明之透明二氧化鈦溶膠。在強力攪動下,將由50g異丙醇稀釋的50g異丙氧化鈦(Alfa Aesar,95%)緩慢的添加至250g去離子水。在二氧化鈦沉澱後,再保持攪動10分鐘。接著過濾沉澱物並且用500g去離子水洗滌。經過洗滌的濕濾餅在去離子水中再分散成總重量250g的分散液。將6g乳酸(Alfa Aesar,85%於水中)添加至分散液中並均勻混合。將分散液裝填至氣罐式熱液反應器(125ml容量,Parr設備公司),其襯有Teflon杯與蓋。接著將氣罐置於25RPM的滾動速度以及溫度設定在80℃之滾筒烘箱。保持處理24小時。在溶膠冷卻至室溫後,其pH係2.3。將第三丁胺(Alfa Aesar,98%)添加至該溶膠中以將pH調整至7.0。最終溶膠產品係穩定並且完全透明,TEM檢視顯示其含有5nm結晶TiO2
奈米微粒。在高解析度TEM圖像上之d-空間測量顯示大部分結晶係銳鈦礦(>50%),金紅石係次要相(<50%)。
比較實例1
以與實例1相同的方法製備樣品,但使用7.6g硝酸(69wt.%溶液)作為膠溶劑代替乳酸。在膠溶作用後,溶膠呈現穩定但具有乳狀不透明外觀。
實例2
使用與實例1之相同程序製備根據本發明之透明二氧化鈦溶膠,但使用4.5g酒石酸(Alfa Aesar,99%)代替乳酸作為膠溶劑。所得溶膠係穩定並且透明。TEM檢視顯示其含有5nm Tio2
奈米微粒。高解析度TEM d-空間測量顯示大部分結晶係銳鈦礦(>50%),以及顯示約0.6nm不尋常大之d-空間之未知次要相(<50%)。
實例3
使用與實例1之相同程序製備根據本發明之透明二氧化鈦溶膠,但使用10.5g檸檬酸代替乳酸作為膠溶劑,且保持膠溶作用處理3天。所得溶膠係穩定且透明。TEM檢視顯示其含有5nm Tio2
奈米微粒。高解析度TEM d-空間測量顯示大部分微晶係銳鈦礦(>50%),以及顯示約0.6nm之不尋常大的d-空間之未知次要相(<50%)。
實例4
使用與實例1之相同程序製備根據本發明之透明二氧化鈦溶膠,但使用4.0g乳酸且在120℃下在熱液條件下執行膠溶作用2天。以第三丁胺中和酸性溶膠至pH 8.0。該溶膠產物係穩定且透明。TEM檢視圖像顯示良好結晶的5nm TiO2
奈米粒子。在高解析度TEM圖像上之d-空間測量顯示大部分結晶係銳鈦礦(>50%),以及作為次要相(<50%)的金紅石。
實例5使用與實例1之相同程序製備根據本發明之透明二氧化鈦溶膠,但使用6.0g酒石酸且在120℃下在熱液條件下執行膠溶作用2天。以第三丁胺中和酸性溶膠至pH 8.0。溶膠產物係穩定且透明。TEM圖像顯示良好結晶的5nm TiO2
奈米粒子。高解析度TEM d-空間測量顯示大部分結晶係銳鈦礦(>50%),以及顯示約0.6nm之不尋常大的d-空間之未知次要相(<50%)。
實例6
如下製備根據本發明之透明二氧化鈦溶膠。50g異丙氧化鈦與酒石酸的異丙醇溶液(在100g異丙醇中12.5g酒石酸)混合。在強力攪動下,將125g去離子水緩慢地添加至此混合物中。水解後,保持攪動15分鐘,隨後沉澱物由離心作用分離,並且將上部液層輕輕倒出。濕的固體層在水中再分散至250g總重量。將其裝填至氣罐反應器並且在80℃下在滾筒烘箱中處理3天。以第三丁胺將所製備的pH約為2.0之溶膠樣品調整至pH 8.0。其係穩定並且透明。
實例7
此實例提供實例5之溶膠的大規模製備。樣品與實例5中使用者相同,但使用裝備加熱器、Teflon襯裏以及磁驅動攪拌器的兩升熱液反應器代替125ml氣罐用於製備樣品。以此反應器,在每批中獲得約1.5kg的樣品。外觀、性質與光觸媒性能實質上與實例5相同。
實例8
在此實例中,使用氧硫酸鈦(TiOSO4
)作為TiO2
前軀物且藉由使用氨溶液之pH調整進行TiO2
之沉澱。將950g氧硫酸鈦水溶液(7.9%,基於TiO2
分析,Millennium無機化學製品)以25ml/min添加至含有950g去離子水的4L燒杯中。同時,將氨溶液(29%)以保持反應混合物之pH在整個沉澱處理中均處於約8.0的速率添加至燒杯中。沉澱物再攪拌30分鐘,之後過濾並以5L去離子水洗滌。接著以去離子水將經過洗滌的濕沉澱物再分散至約1,400g的分散液總重量。攪拌下將45g酒石酸添加至分散液中,以及將分散液裝填進入實例7中描述的2L熱液反應器。其在120℃下熱液處理2天。獲得外觀及性質類似於實例5中描述的樣品之透明TiO2
溶膠。
實例9
為研究自根據本發明之溶膠製備的塗層之光觸媒活性,將實例2、4、5及8的溶膠以薄層沉積在混凝土基材上(約0.3ml溶膠在18cm2
面積上)分別獲得樣品A、B、C以及D。在約4,000小時期間內,以各種時間間隔測量UV照射(2W/m2
)下對抗NOx
污染物的活性。決定NOx
還原的方法實質上如美國公開專利第2007/0167551號所述,其揭示在此處以引用方式併入本文。如圖1所示,每個樣品在整體時期內顯示相當的光觸媒活性(即大於約15%),其以NOx
移除%表示。有趣地係,以異丙氧化鈦水解製備的樣品A、B及C顯示隨時間增大的NOx
移除%,而自氧硫酸鈦(TiOSO4
)以pH誘發沉澱製備的樣品D顯示極高的(例如約50%至約75%之間)之最初NOx
移除%達約1,500小時而逐漸穩定在高於約45% NOx
移除率。
此處引用之所有包括專利申請以及出版物的參考係以引用方式將其全文併入本文,並且若個別單獨出版物或專利或專利申請係特定且單獨顯示就所有目的整體加以引用,均以相同程度全部以引用方式併入本文。本發明之許多修飾以及變化可在未脫離發明之精神與範圍內進行,其將為熟習此項技術者所熟知。此處描述之特殊具體實施例係僅以舉例方式提供,並且本發明將僅限制於附加之申請專利範圍以及與該等請求項均等之全部範圍。
圖1係比較分別由實例2、4、5及8之溶膠形成之稱為樣品A-D之四種塗層之隨時間的光觸媒活性相對於NOx
污染物之關係。
(無元件符號說明)
Claims (14)
- 一種製備穩定、透明的光觸媒二氧化鈦溶膠之方法,其包括:(i)提供一包括含鈦化合物之溶液;(ii)自該含鈦化合物的溶液使含水二氧化鈦沉澱;(iii)形成該經沉澱之含水二氧化鈦的水性分散液;及(iv)在約70℃與約150℃之間的溫度下,在一種或多種α-羥基羧酸存在下混合該水性分散液約3小時至約3天之時間;但條件為該一或多種α-羥基羧酸實質上不含羥基乙酸;藉此提供二氧化鈦之溶膠,其在2至12之整個pH範圍內之每個pH值均係穩定且透明;該溶膠包括具有小於約10 nm之平均粒徑的二氧化鈦結晶,大多數該結晶呈銳鈦礦形式。
- 如請求項1之方法,其中步驟(iv)係在密封的熱液反應器(sealed hydrothermal reactor)中進行。
- 如請求項1之方法,其中該含鈦化合物係選自由烷氧化鈦、氯氧化鈦、硫酸氧鈦以及乙醯丙酮氧鈦組成的群組。
- 如請求項3之方法,其中該含鈦化合物係異丙氧化鈦。
- 如請求項1之方法,其中該一或多種α-羥基羧酸包括選自由乳酸、酒石酸、蘋果酸、檸檬酸及其組合組成的群組之α-羥基羧酸。
- 如請求項5之方法,其中該一或多種α-羥基羧酸包括乳 酸。
- 如請求項5之方法,其中該一或多種α-羥基羧酸包括酒石酸。
- 如請求項5之方法,其中該一或多種α-羥基羧酸包括檸檬酸。
- 如請求項1之方法,其進而包括以鹼中和所得溶膠之步驟。
- 如請求項1之方法,其中該溶膠包括具有小於約5 nm之平均粒徑之二氧化鈦微晶。
- 如請求項1之方法,其中該溶膠包括二氧化鈦結晶,至少90%之該二氧化鈦結晶係呈銳鈦礦形式。
- 透明溶膠,包括約1至約10重量%之具有平均結晶尺寸在約1 nm至約10 nm之間的光觸媒二氧化鈦微粒,大多數該結晶係呈銳鈦礦形式,其中該溶膠於酸性、中性以及鹼性pH時均係穩定並透明。
- 如請求項12之穩定、透明溶膠,其中該二氧化鈦結晶具有在約1 nm至約5 nm之間的平均粒徑。
- 如請求項12之穩定、透明溶膠,其中至少90%之該結晶係呈銳鈦礦形式。
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CN101827650B (zh) | 2013-03-20 |
JP5231553B2 (ja) | 2013-07-10 |
AU2008292827B2 (en) | 2012-04-19 |
KR20100080509A (ko) | 2010-07-08 |
CA2697542C (en) | 2012-10-23 |
UA100530C2 (ru) | 2013-01-10 |
BRPI0815786A2 (pt) | 2015-02-24 |
EP2200742B1 (en) | 2018-07-11 |
EP2200742A1 (en) | 2010-06-30 |
AR101012A2 (es) | 2016-11-16 |
NZ583550A (en) | 2011-02-25 |
US20110183838A1 (en) | 2011-07-28 |
SA08290536B1 (ar) | 2011-09-04 |
AU2008292827A1 (en) | 2009-03-05 |
TW200927662A (en) | 2009-07-01 |
WO2009029856A1 (en) | 2009-03-05 |
BRPI0815786B1 (pt) | 2018-02-06 |
CA2697542A1 (en) | 2009-03-05 |
US20100267550A1 (en) | 2010-10-21 |
ES2679126T3 (es) | 2018-08-22 |
KR101265660B1 (ko) | 2013-05-22 |
EP2200742A4 (en) | 2016-02-24 |
AR069730A1 (es) | 2010-02-17 |
US20090062111A1 (en) | 2009-03-05 |
US7932208B2 (en) | 2011-04-26 |
RU2010107391A (ru) | 2011-10-10 |
MX2010002241A (es) | 2010-03-25 |
CN101827650A (zh) | 2010-09-08 |
US7763565B2 (en) | 2010-07-27 |
JP2010537809A (ja) | 2010-12-09 |
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