KR100442919B1 - Preparation method for photocatalyst sol having high transparency photoactivity - Google Patents
Preparation method for photocatalyst sol having high transparency photoactivity Download PDFInfo
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- KR100442919B1 KR100442919B1 KR10-2001-0056564A KR20010056564A KR100442919B1 KR 100442919 B1 KR100442919 B1 KR 100442919B1 KR 20010056564 A KR20010056564 A KR 20010056564A KR 100442919 B1 KR100442919 B1 KR 100442919B1
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- photocatalyst sol
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 49
- 239000011230 binding agent Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002834 transmittance Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000003609 titanium compounds Chemical class 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 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 4
- 239000013504 Triton X-100 Substances 0.000 claims description 3
- 229920004890 Triton X-100 Polymers 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 241001296405 Tiso Species 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical class C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 239000000843 powder Substances 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- TUGGFUSCPLPUFY-UHFFFAOYSA-N 3-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCN.CCO[Si](OCC)(OCC)CCCN TUGGFUSCPLPUFY-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 titanium alkoxide Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/08—Heat treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
본 발명은 광촉매 졸의 제조방법에 관한 것으로, 상세하게는 코팅된 표면이 투명하게 유지되면서도 광활성이 높은 광촉매 졸의 제조 방법에 관한 것이다.The present invention relates to a method for preparing a photocatalyst sol, and more particularly, to a method for preparing a photocatalyst sol having high photoactivity while maintaining a transparent surface.
Description
본 발명은 광촉매 졸 및 그 제조 방법에 관한 것으로, 상세하게는 코팅된 표면이 투명하게 유지되면서도 광활성이 높은 광촉매 졸의 제조 방법에 관한 것이다.The present invention relates to a photocatalyst sol and a method for manufacturing the same, and more particularly, to a method for preparing a photocatalyst sol having high photoactivity while maintaining a transparent surface.
광촉매는 빛에너지를 받으면 활성이 높은 물질을 생성하여 화학반응을 촉진시키는 물질로서, 광촉매를 이용한 오염 물질 처리에 대한 연구가 진행되고 있다. 광촉매에는 이산화티탄(TiO2), 산화아연(ZnO), 황화아연(ZnS), 및 황화카드뮴(CdS) 등이 있으며, 광안정성 및 광활성이 우수한 이산화티탄이 대표적인 광촉매로 사용되고 있다. 이산화티탄은 아나타제(anatase), 루타일(rutile), 및 브루카이트(brookite) 형을 지니며, 이 중에서 아나타제 형이 대부분의 광촉매 반응에서 광활성이 우수하다.Photocatalyst is a substance that promotes chemical reaction by generating a highly active substance upon receiving light energy, and research on the treatment of pollutants using the photocatalyst is being conducted. Photocatalysts include titanium dioxide (TiO2), zinc oxide (ZnO), zinc sulfide (ZnS), and cadmium sulfide (CdS), and titanium dioxide having excellent photostability and photoactivity is used as a representative photocatalyst. Titanium dioxide has the anatase, rutile, and brookite types, of which the anatase type has excellent photoactivity in most photocatalytic reactions.
광촉매로서 이산화티탄을 사용하는 방법으로는 아나타제형의 이산화티탄을분말 형태로 사용하는 것과 특정 지지체에 졸-겔 법(sol-gel methogd)에 의해 아나타제형 이산화티탄 박막을 형성하여 사용하는 것이 많이 사용되고 있다. 이 중, 분말 형태의 광촉매는 지지체에 고정할 수 없으므로, 사용 후 회수하여 재사용하기 어렵다는 단점이 있다. 이 때문에, 분말 형태의 광촉매는 다시 용해하여 코팅에 사용하거나, 비교 실험을 위한 재료에 국한하여 사용해 왔다.As a method of using titanium dioxide as a photocatalyst, anatase type titanium dioxide in powder form and anatase type titanium dioxide thin film formed by a sol-gel method on a specific support are widely used. have. Among these, since the photocatalyst in powder form cannot be fixed to the support, it is difficult to recover and reuse after use. For this reason, the photocatalyst in powder form has been melt | dissolved again and used for coating, or it was limited to the material for comparative experiments.
종래의 졸-겔 법에 의한 티타늄 광촉매 코팅은 티타늄 알콕사이드를 용매와 혼합하여 광촉매 졸을 제조하고, 제조된 광촉매 졸을 지지체에 코팅하고 소성하여 산화티탄 광촉매 박막을 형성하는 방법으로 이루어진다. 이 때, 졸의 투명도를 증가시키기 위해서는 졸용액의 분산질인 광촉매 분말의 양이 적으면서도 고르게 분산되어 있어야 하므로, 광촉매 분말의 함량을 적게 하면, 광촉매 분말의 함량이 적으므로 광활성도는 떨어진다는 문제점이 있다. 반대로, 광활성도를 높이기 위하여 광촉매 분말의 함량을 늘이면 코팅이 불투명해지거나 촉매 표면에 얼룩이 남는다는 문제점이 있다.Titanium photocatalyst coating by a conventional sol-gel method comprises a method of preparing a photocatalyst sol by mixing titanium alkoxide with a solvent, coating the prepared photocatalyst sol on a support and firing to form a titanium oxide photocatalyst thin film. In this case, in order to increase the transparency of the sol, the amount of the photocatalyst powder, which is a dispersant of the sol solution, should be small and evenly dispersed. Therefore, if the content of the photocatalyst powder is small, the photocatalyst powder content is small, and thus the photoactivity decreases. There is this. On the contrary, when the content of the photocatalyst powder is increased to increase the photoactivity, the coating becomes opaque or stains remain on the surface of the catalyst.
대한민국 특허 공개번호 제 2001-0028286 호에는 광활성이 높은 아나타제형 졸을 제조하는 방법이 개시되어 있으나, 분말을 졸로 제조할 수 있는 특성에 국한되어 있으며, 형성된 코팅면의 투명성 및 균일성에 대한 내용은 기재되어 있지 않다. 그 외에도 대한민국 특허 공개번호 제 2000-063580 호, 제 1998-035033 호, 제 1999-026277 호, 미국 특허 제 5403513 호, 일본 특허 평2001-48679 호 등에는 나노 크기의 광촉매 입자 제조방법에 관한 것을 개시하고 있으나, 실제 형성된 코팅면의 투명성 및 균일성에 대해서는 보장하지 못하고 있다. 이 중 대한민국 특허공개번호 제 2000-063580 호에는 광촉매 졸 용액을 형성하는 방법이 기재되어 있으나, 휘발성 유기 용매를 휘발시켜 코팅면의 투명성 및 균일성을 확보하는 것에 대해서는 언급된 바가 없다.Korean Patent Publication No. 2001-0028286 discloses a method for preparing anatase-type sol having high photoactivity, but it is limited to the property of preparing a powder into a sol, and the transparency and uniformity of the formed coating surface are described. It is not. In addition, Korean Patent Publication Nos. 2000-063580, 1998-035033, 1999-026277, US Pat. No. 5,403,513, Japanese Patent No. 2001-48679, etc. discloses a method for preparing nano-sized photocatalyst particles. However, the transparency and uniformity of the coating surface actually formed is not guaranteed. Among these, Korean Patent Publication No. 2000-063580 describes a method for forming a photocatalyst sol solution, but it is not mentioned to volatilize the volatile organic solvent to secure the transparency and uniformity of the coating surface.
본 발명은 상기한 종래 기술의 문제점을 고려하여, 본 발명자들은 용매휘발정도에 따라 투명도가 달라진다는 사실을 발견하고 이에 기초하여 높은 투명도와 광활성도를 갖는 티타늄 화합물을 포함하는 광촉매 졸을 제공한다.In view of the above problems of the prior art, the present inventors have found that transparency varies according to the degree of solvent volatilization, and based on this, the present invention provides a photocatalyst sol comprising a titanium compound having high transparency and photoactivity.
본 발명의 또다른 목적은 티타늄 화합물, 유기 용매, 물, 촉매를 혼합하여 열처리하고, 바인더용액을 첨가하고, 휘발성 유기 용매를 휘발시켜 코팅된 표면이 투명하게 유지되면서도 광활성이 높은 광촉매 졸의 제조 방법을 제공하는 것을 목적으로 한다.Still another object of the present invention is a method for preparing a photocatalyst sol having high photoactivity while maintaining a transparent surface by adding a titanium compound, an organic solvent, water, and a catalyst to heat treatment, adding a binder solution, and evaporating a volatile organic solvent. The purpose is to provide.
도 1은 본 발명의 실시예 6에 따른 광활성도 비교 그래프.1 is a graph comparing the photoactivity according to Example 6 of the present invention.
상기 목적을 달성하기 위하여, 본 발명은 또한 다음 단계로 이루어지는 높은 투명도와 광활성도를 갖는 광촉매용 졸의 제조방법에 관한 것이다.In order to achieve the above object, the present invention also relates to a method for producing a photocatalyst sol having a high transparency and photoactivity consisting of the following steps.
(a) 티타늄 화합물, 물, 유기용매, 촉매 및 계면활성제를 혼합하여 70 내지 100 ℃에서 열처리하는 단계;(a) mixing the titanium compound, water, an organic solvent, a catalyst, and a surfactant to heat treatment at 70 to 100 ° C .;
(b) 상온에서 바인더, 물, 유기용매, 촉매를 포함하는 바인더 용액을 상기 열처리된 혼합액에 첨가하는 단계; 및(b) adding a binder solution containing a binder, water, an organic solvent, and a catalyst to the heat-treated mixture at room temperature; And
(c) 상기 혼합액을 상온에서 2 내지 24 시간 동안 교반하여 용매를 휘발시키는 단계를 포함하는 높은 투명도를 갖는 광촉매의 졸 제조방법을 제공한다.(c) a method of preparing a sol for a photocatalyst having a high transparency comprising the step of volatilizing the solvent by stirring the mixture at room temperature for 2 to 24 hours.
본 발명은 또한 티타늄 화합물을 주성분으로 하며, 슬라이드 글라스에 1회 침적 코팅시 600 nm에서 투과도가 90% 이상이고, 메틸렌블루 용액에 대해 광활성도가 500%/hr/% 이상인 광촉매 졸에 관한 것이다. 본 발명의 광촉매 졸은 본 발명에 기재된 모든 광촉매 졸의 제조방법에 따라 제조될 수 있는 광촉매 졸을 포함한다.The present invention also relates to a photocatalyst sol having a titanium compound as a main component, having a transmittance of at least 90% at 600 nm and a photoactivity of at least 500% / hr /% for a methylene blue solution upon coating the slide glass once. The photocatalyst sol of the present invention includes a photocatalyst sol that can be prepared according to the method for producing all the photocatalyst sol described in the present invention.
단계 (a)에서, 상기 티타늄 화합물을 물 및 유기용매에 첨가하고, 촉매 및 계면활성제를 첨가하여 혼합하고 이 혼합용액을 70 내지 100 ℃에서 열처리하여, 아나타제형 광촉매 졸용액을 얻는다. 상기 열처리 온도는 70 내지 80 ℃가 더욱 바람직하다. 상기 열처리 온도 범위를 벗어날 경우, 목적하고자 하는 물과 유기용매의 구성비가 달라져 부분적으로 축합반응이 일어나게 되어 구형의 콜로이드 상 입자를 얻기가 어렵다. 또한, 졸을 건조시켜 박막을 얻을 때, 물과 유기용매가 휘발하면서 발생하는 모세관 압력 및 수축 현상으로 인해 박막층에 균열이 생기기 쉬우며, 투명도가 나빠질 수 있다.In step (a), the titanium compound is added to water and an organic solvent, mixed by addition of a catalyst and a surfactant, and the mixed solution is heat-treated at 70 to 100 ° C. to obtain an anatase photocatalyst sol solution. The heat treatment temperature is more preferably 70 to 80 ℃. When the temperature is out of the heat treatment range, a condensation reaction occurs due to a change in the composition ratio of the desired water and the organic solvent, making it difficult to obtain spherical colloidal particles. In addition, when the sol is dried to obtain a thin film, it is easy to cause cracks in the thin film layer due to capillary pressure and shrinkage caused by volatilization of water and an organic solvent, and the transparency may be deteriorated.
열처리 시간은 용액의 양에 따라 달라질 수 있으며, 상기 혼합용액이 반투명해질 때까지, 바람직하게는 2 내지 4 시간 동안 열처리한다.The heat treatment time may vary depending on the amount of the solution, and the heat treatment is preferably performed for 2 to 4 hours until the mixed solution becomes translucent.
상기 티타늄 화합물은 TiCl4, TiSO4, 티타늄 이소프로폭사이드(titanium isopropoxide), 또는 티타늄 에톡사이드(titanium ethoxide)일 수 있다.The titanium compound may be TiCl 4 , TiSO 4 , titanium isopropoxide, or titanium ethoxide.
상기 유기용매는 에탄올, 2-부탄올, 이소프로판올, 또는 에틸렌글리콜일 수 있으며, 이에 한정되는 것은 아니다.The organic solvent may be ethanol, 2-butanol, isopropanol, or ethylene glycol, but is not limited thereto.
상기 촉매는 산촉매 또는 염기성 촉매일 수 있으며, 질산, 및 황산과 같이통상적인 산촉매를 사용할 수 있다. 산촉매를 사용할 경우에는 졸의 pH가 1.5 내지 2.5의 범위를 유지하도록 하는 것이 바람직하고, 염기성 촉매의 경우에는 졸의 pH가 7.5 내지 8.5 범위를 얻도록 첨가하는 것이 바람직하다.The catalyst may be an acid catalyst or a basic catalyst, and conventional acid catalysts such as nitric acid and sulfuric acid may be used. In the case of using an acid catalyst, it is preferable to maintain the pH of the sol in the range of 1.5 to 2.5, and in the case of the basic catalyst, it is preferable to add so that the pH of the sol is obtained in the range of 7.5 to 8.5.
계면활성제는 코팅표면을 균일하게 하기 위해 첨가되며, 트리톤 X-100(triton X-100), 또는 트윈 20 및 트윈 80과 같은 트윈(tween) 계열의 상용화된 계면활성제를 사용할 수 있다.Surfactants are added to make the coating surface uniform, and may use a triton-based commercialized surfactant such as Triton X-100, or Tween 20 and Tween 80.
상기 (b)단계에서, 열처리로 얻어진 반투명한 광촉매원료 졸용액의 물성을 향상시키기 위하여, 바인더, 물, 유기 용매, 촉매 용액을 포함하는 바인더 용액을 첨가하여 상온에서 혼합한다. 상기 바인더 용액은 광촉매원료 졸용액과 동일한 조성으로 물, 유기용매 및 촉매를 포함하나 계면활성제를 포함하지 않으며, 광촉매원료 졸용액의 티타늄 화합물 대신 바인더 물질을 첨가하여 제조한다. 상기 바인더 용액의 용매 및 촉매는 (a) 단계에서 사용한 용매 및 산촉매와 동일한 것을 사용할 수 있다. 상기 바인더 물질은 테트라에틸오르쏘실리케이트(tetraethylorthosilacate), 디할로실란(dihalosilane), 트리할로실란(trihalosilane), 테트라할로실란(tetrahalosilane), 알킬트리할로실란(alkyltrihalosilane), 디알킬디할로실란(dialkyldihalosilane), 아릴트리할로실란(aryltrihalosilane), 디아릴디할로실란(diaryldihalosilane), 디알콕시실란(dialkoxysilane), 트리알콕시실란(trialkoxysilane), 메틸트리클로로실란(methyltrichlorosilane), 메틸트리메톡시실란(methyltrimethoxysilane),메틸트리에톡시실란(methyltriethoxysilane), 또는 3-아미노프로필트리에톡시실란(3-aminopropyltriethoxysilane) 등이 있으나 이에 한정되지 않는다.In the step (b), in order to improve the physical properties of the semi-transparent photocatalyst sol solution obtained by heat treatment, a binder solution including a binder, water, an organic solvent, and a catalyst solution is added and mixed at room temperature. The binder solution includes water, an organic solvent and a catalyst in the same composition as the photocatalyst raw sol solution but does not include a surfactant, and is prepared by adding a binder material instead of the titanium compound of the photocatalyst raw sol solution. The solvent and the catalyst of the binder solution may be the same as the solvent and acid catalyst used in step (a). The binder material is tetraethylorthosilacate, dihalosilane, trihalosilane, tetrahalosilane, alkyltrihalosilane, dialkyldihalo Silane (dialkyldihalosilane), aryltrihalosilane, diaryldihalosilane, diaryldihalosilane, dialkoxysilane, trialkoxysilane, methyltrichlorosilane, methyltrimethoxysilane (methyltrimethoxysilane), methyltriethoxysilane (methyltriethoxysilane), or 3-aminopropyltriethoxysilane (3-aminopropyltriethoxysilane) and the like, but are not limited thereto.
본 발명의 일례에서, 티타늄 화합물과 바인더의 혼합 중량비가 0.5:1 내지 1:1로 하는 것이 바람직하고, 바인더 용액중 사용된 바인더 물질과 물의 중량비는 1 : 5 내지 1 : 9가 바람직하다. 이러한 원료비로 반응시켜 3차원으로 성장한 구형의 콜로이드상 입자를 생성하게 함으로써 분산도가 높은 안정적인 졸을 확보하여 불투명도와 크랙의 발생을 제어하여 높은 투명도와 광활성도를 갖는 광촉매 졸을 제조할 수 있다.In one example of the present invention, the weight ratio of the titanium compound and the binder is preferably 0.5: 1 to 1: 1, and the weight ratio of the binder material and water used in the binder solution is preferably 1: 5 to 1: 9. By reacting with such a raw material ratio to produce spherical colloidal particles grown in three dimensions, a stable sol having a high dispersion degree can be secured to control the occurrence of opacity and cracks, thereby preparing a photocatalyst sol having high transparency and photoactivity.
본 발명에 따라 제조된 광촉매용 졸 용액의 투명도는 용매 및 바인더 물질의 종류나 함량 및 지지체의 종류에 따라 다르게 나타난다. 예를 들어, 지지체가 도전성 물질인 경우에는 이소프로판올 용매와 아미노실란 바인더를 사용하는 것이 바람직하고, 지지체가 유리와 같은 비도전성 물질인 경우에는 에탄올 용매와 테트라오르쏘실리케이트 바인더를 사용하는 것이 바람직하다. 또한, 지지체가 금속인 경우에는 광촉매 졸이 산성이면 금속에 부식을 초래할 수 있기 때문에, 염기성 바인더인 3-아미노프로필트리에톡시실란을 사용하여 염기성 촉매를 사용하는 것이 바람직하다.The transparency of the photocatalyst sol solution prepared according to the present invention is different depending on the kind or content of the solvent and binder material and the kind of the support. For example, when the support is a conductive material, it is preferable to use an isopropanol solvent and an aminosilane binder, and when the support is a non-conductive material such as glass, it is preferable to use an ethanol solvent and a tetraorthosilicate binder. In the case where the support is a metal, if the photocatalyst sol is acidic, it may cause corrosion to the metal. Therefore, it is preferable to use a basic catalyst using 3-aminopropyltriethoxysilane as the basic binder.
상기 (c)단계에서, 반투명한 광촉매원료 졸용액과 바인더 용액의 혼합용액을 상온에서 2 내지 24 시간 동안 교반하여 혼합용액 중의 유기 용매를 휘발시키고, 광촉매원료 졸용액을 제조한다. 용매를 휘발시키는 시간은 용액의 양과 용매의 종류에 따라 차이가 있을 수 있으며, 용매가 휘발됨에 따라 재질에 코팅된 면이 균일하고 투명하게 되는데, 지나치게 휘발시킬 경우 졸(sol)이 다시 겔(gel)화 되므로 휘발시킨 지 2 시간 이후부터는 현미경 슬라이드 글라스 등에 침적 코팅을 수행하여 투과도를 점검하면서 휘발시킨다. 즉, 슬라이드 글라스에 1회 침적 코팅을 실시하고 가시광선 600 nm를 투과하여 투과도를 조사하였을 때, 투과도가 90 % 이상에서 겔화되기 전에 휘발을 종료시킨다. 이 때, 상기 투과도는 1-흡광도로 측정된다.In the step (c), the mixed solution of the semitransparent photocatalyst sol solution and the binder solution is stirred at room temperature for 2 to 24 hours to volatilize the organic solvent in the mixed solution, thereby preparing a photocatalyst raw sol solution. The time to volatilize the solvent may vary depending on the amount of the solution and the type of the solvent. As the solvent is volatilized, the surface coated on the material becomes uniform and transparent. If the volatilization is excessive, the sol becomes a gel again. 2 hours after the volatilization is performed, the coating is deposited on a microscope slide glass, and volatilized while checking the transmittance. That is, when the coating of the slide glass was applied once and irradiated with 600 nm of visible light, the volatilization was terminated before the transmittance was gelated at 90% or more. At this time, the transmittance is measured as 1-absorbance.
본 발명의 광촉매 졸용액을 지지체에 코팅하여 광촉매를 제조한다. 지지체로는 유리 또는 타일과 같은 비금속 지지체나 스테인리스 스틸 또는 아연도금강판과 같은 금속 지지체를 사용할 수 있다.The photocatalyst sol solution of the present invention is coated on a support to prepare a photocatalyst. As the support, a non-metal support such as glass or tile or a metal support such as stainless steel or galvanized steel sheet may be used.
이하 바람직한 실시예를 들어 본 발명을 더욱 자세히 설명할 것이나, 하기 실시예는 본 발명의 바람직한 일 실시예일 뿐 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to preferred examples, but the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.
실시예 1: 에탄올 용매를 이용한 졸 제조Example 1 Preparation of Sol Using Ethanol Solvent
증류수 70 ㎖를 교반하면서 99 % 에탄올 수용액 15 ㎖(Junsei 사 제조)을 첨가하고, 티타늄 화합물로 티타늄(Ⅳ) 이소프로폭사이드 (Aldrich 사 제조)용액 10 ㎖를 상기 혼합용매에 천천히 첨가하였다. 상기 혼합용액에 계면활성제로 트리톤 X-100 1%를 1 ㎖ 첨가하여 교반한 다음, 산촉매로 질산 2 ㎖를 상기 혼합액에 첨가하였다. 상기 혼합용액을 85 ℃에서 4 시간 가열하여, 반투명의 아나타제형 광촉매원료 졸 용액을 얻었다. (상기 아나타제형 광촉매원료 졸용액을 이하 A 용액이라하기로 한다.)15 ml of 99% aqueous ethanol solution (manufactured by Junsei) was added while stirring 70 ml of distilled water, and 10 ml of a titanium (IV) isopropoxide (manufactured by Aldrich) solution was slowly added to the mixed solvent as a titanium compound. 1 ml of Triton X-100 1% was added to the mixed solution as a surfactant, followed by stirring. Then, 2 ml of nitric acid was added to the mixed solution using an acid catalyst. The mixed solution was heated at 85 ° C. for 4 hours to obtain a translucent anatase photocatalyst raw material sol solution. (The anatase type photocatalyst raw sol solution will be referred to as A solution hereinafter.)
바인더 용액을 제조하기 위하여, 에탄올 15 ㎖, 증류수 10 ㎖, 질산 1 ㎖ 및 바인더로 테트라에틸오르쏘실리케이트 10 ㎖를 첨가하여 혼합용액을 제조하였다. (상기 바인더 용액을 이하 B 용액이라 하기로 한다.)To prepare a binder solution, 15 ml of ethanol, 10 ml of distilled water, 1 ml of nitric acid, and 10 ml of tetraethylorthosilicate were added as a binder to prepare a mixed solution. (The binder solution is hereinafter referred to as B solution.)
제조된 B 용액을 상기 A 용액에 교반하면서 서서히 주입하고, 상온에서 용매를 서서히 휘발시켰다. 이 때, 용매가 휘발됨에 따라 재질에 코팅된 면이 균일하고 투명하게 되는데, 지나치게 휘발시킬 경우 졸(sol)이 다시 겔(gel)화 되므로 휘발시킨지 2 시간 이후부터는 현미경 슬라이드 글라스에 침적코팅을 실시하여 투과도를 점검하며 휘발시켰다. 투과도는 코팅면에 가시광선 600 nm를 조사하였을 때 나타나는 1-흡광도로 측정하였다. 상기 A용액에 B용액을 주입한 뒤, 상온에서 6 시간 동안 용매를 서서히 휘발시켜 광촉매원료 졸용액을 제조하였다.The prepared solution B was slowly injected into the solution A while stirring, and the solvent was slowly volatilized at room temperature. At this time, as the solvent is volatilized, the surface coated on the material becomes uniform and transparent. If the volatilization is excessive, the sol becomes a gel again, and after 2 hours, the immersion coating is applied to the microscope slide glass. Volatilization was carried out to check the permeability. The transmittance was measured by 1-absorbance when the coating surface was irradiated with visible light 600 nm. After injecting the B solution to the A solution, the solvent was gradually volatilized for 6 hours at room temperature to prepare a photocatalyst raw sol solution.
실시예 2: 2-부탄올 용매를 이용한 졸 제조Example 2: Sol Preparation with 2-Butanol Solvent
반투명의 아나타제형 광촉매 졸 용액을 제조하는데 있어서, 용매를 에탄올 대신 99 % 2-부탄올 수용액 15 ㎖를 첨가한 것을 제외하고는 상기 실시예 1과 동일한 공정을 수행하여 광촉매 졸을 제조하였다.In preparing a translucent anatase photocatalyst sol solution, a photocatalyst sol was prepared in the same manner as in Example 1 except that 15 ml of an aqueous 99% 2-butanol solution was added instead of ethanol.
실시예 3: 이소프로판올 용매를 이용한 졸 제조Example 3: Sol Preparation Using Isopropanol Solvent
반투명의 아나타제형 광촉매 졸 용액을 제조하는데 있어서, 용매를 에탄올 대신 99% 이소프로판올 수용액 15 ㎖를 첨가한 것을 제외하고는 상기 실시예 1과 동일한 공정을 수행하여 광촉매 졸을 제조하였다.In preparing a translucent anatase photocatalyst sol solution, a photocatalyst sol was prepared in the same manner as in Example 1, except that 15 ml of an aqueous 99% isopropanol solution was added instead of ethanol.
실시예 4: 에틸렌글리콜 용매를 이용한 졸 제조Example 4 Preparation of Sol Using Ethylene Glycol Solvent
반투명의 아나타제형 광촉매 졸 용액을 제조하는데 있어서, 용매를 에탄올 대신 99 % 에틸렌글리콜 수용액 15 ㎖를 첨가한 것을 제외하고는 상기 실시예 1과 동일한 공정을 수행하여 광촉매 졸을 제조하였다.In preparing a translucent anatase photocatalyst sol solution, a photocatalyst sol was prepared in the same manner as in Example 1 except that 15 ml of an aqueous 99% ethylene glycol aqueous solution was added instead of ethanol.
실시예 5: 가시광선 투과도 비교Example 5 Comparison of Visible Light Transmittance
실시예 1 내지 4의 광촉매 졸 및 기존의 상용화졸들을 코팅하고, 코팅면에 가시광선 600 nm을 투과하여 투과도를 조사하였다. 투과도는 1-흡광도로 계산되었다. 상용화졸로는 데구사(Degusa)사 제품 P-25, 이시하라 사 제품 ST-K03(Ishihara ST-K03), 및 국내 N사 제품 Ra를 사용하였다.The photocatalyst sol of Examples 1 to 4 and existing commercial sols were coated, and the transmittance was examined by transmitting 600 nm of visible light on the coated surface. Permeability was calculated as 1-absorbance. P-25 from Degusa, Ishihara ST-K03 from Ishihara, and Ra from N from Korea were used as commercialization sols.
상기 표 1에서와 같이, 상용화된 광촉매 졸의 경우 동일 조건에서 가시광선 투과도가 90 %를 넘지 못하였으나, 실시예 1 내지 4의 광촉매 졸은 약 90 %의 높은 투과도를 나타내었다. 특히, 에탄올을 용매로 사용한 실시예 1의 광촉매 졸 코팅은 약 98 % 의 높은 투과도를 나타내었다.As shown in Table 1, in the case of a commercially available photocatalyst sol, visible light transmittance did not exceed 90% under the same conditions, but the photocatalyst sol of Examples 1 to 4 exhibited a high transmittance of about 90%. In particular, the photocatalyst sol coating of Example 1 using ethanol as a solvent showed a high transmittance of about 98%.
실시예 6: 광활성 비교Example 6: Photoactivity Comparison
실시예 1의 광촉매 졸과 실시예 5의 ST-K03, 및 Ra의 광촉매 졸 동일 함량을 코팅하여 메틸렌블루 염색액의 색도 변화를 측정하여 광활성을 비교하였다. 메틸렌블루는 분해됨에 따라 청색에서 무색으로 변화하므로, 청색을 나타내는 파장인 450 nm에서 분광기를 통해 흡광도를 측정하면 메틸렌블루의 분해정도를 알 수 있다.The photocatalyst sol of Example 1 and the photocatalyst sol contents of ST-K03 and Ra of Example 5 were coated, and color change of the methylene blue dye solution was measured to compare photoactivity. Since methylene blue changes from blue to colorless as it is decomposed, the degree of decomposition of methylene blue can be determined by measuring absorbance at a spectrometer at 450 nm, the wavelength of blue.
세 개의 비이커에 약 2 ppm 농도로 증류수에 녹인 메틸렌블루 용액 250 ㎖를 각각 넣고, 실시예 1, ST-K03, 및 Ra의 졸들을 1 ㎖씩 각각의 메틸렌블루 용액에 넣었다. 상기 용액들에 365 nm의 자외선 램프를 조사하고, 시간에 따라 흡광도를 조사하였다. 졸이 투입되지 않은 메틸렌블루 용액을 대조군으로 삼아, 도 1에 대조군 및 각 졸을 첨가한 메틸렌블루의 용액의 흡광도 변화를 나타내었다.250 ml of methylene blue solution dissolved in distilled water at a concentration of about 2 ppm were added to three beakers, respectively, and 1 ml of sol of Example 1, ST-K03, and Ra were added to each methylene blue solution. The solutions were irradiated with an ultraviolet lamp of 365 nm and absorbance was examined over time. The methylene blue solution to which no sol was added was used as a control, and FIG. 1 shows the change in absorbance of the solution of methylene blue to which the control and each sol were added.
표 2는 시판되는 광촉매졸인 ST-K03, 및 Ra와 비교하여 상기 실시예 1의 광촉매졸의 광활성 및 고형물의 함량을 비교한 표이다. 광활성도(%/hr/%)는 메틸렌블루 용액 중의 광촉매 고형물 함량(%)에 대한 시간(hr)에 따른 흡광도의 감소율(%)로 나타내었다.Table 2 is a table comparing the photoactivity and solids content of the photocatalyst sol of Example 1 compared with commercially available photocatalyst sol ST-K03, and Ra. The photoactivity (% / hr /%) is expressed as percent reduction in absorbance with time (hr) relative to the photocatalytic solids content (%) in methylene blue solution.
도 1에서와 같이, Ra의 광촉매 졸은 비교적 높은 가시광선 투과도를 보이는데 반해 광활성도는 저조하였다. 반면, 실시예 1의 광촉매 졸은 높은 광활성도를 나타내었다. 상기 실시예에서와 같이, 본 발명의 광촉매 졸은 가시광선 투과도도 우수할 뿐만 아니라, 광활성도 높다는 것을 알 수 있다.As shown in FIG. 1, the photocatalyst sol of Ra exhibited relatively high visible light transmittance, while the photoactivity was low. On the other hand, the photocatalyst sol of Example 1 showed high photoactivity. As in the above embodiment, it can be seen that the photocatalyst sol of the present invention not only has excellent visible light transmittance but also has high photoactivity.
표 2에서, 실시예 1의 광촉매 졸은 시간이 지나도 우수한 광활성도를 나타냄을 알 수 있다.In Table 2, it can be seen that the photocatalyst sol of Example 1 shows excellent photoactivity over time.
본 발명은 원재료의 외관을 보호하면서 투명하고 균일한 광촉매 코팅층을 얻을 수 있는 광촉매 졸 제조기술을 제공할 수 있다. 또한, 건축내외장용 타일, 유리, 알루미늄 샤시, 조명기구, 및 주방기구 등에 쉽게 광촉매의 특성을 부여할 수 있게 한다.The present invention can provide a photocatalyst sol manufacturing technology capable of obtaining a transparent and uniform photocatalyst coating layer while protecting the appearance of raw materials. In addition, the interior and exterior tiles, glass, aluminum chassis, lighting fixtures, and kitchen utensils can be easily given the characteristics of the photocatalyst.
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| KR20010028286A (en) * | 1999-09-20 | 2001-04-06 | 구자홍 | Method for Preparing an Anatase Typed-Titanium Dioxide Photocatalyst and Photocatalyst Produced by the same |
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