KR101993236B1 - Method for manufacturing visible-light active titanium dioxide photocatalyst by using chemicasurface modification - Google Patents
Method for manufacturing visible-light active titanium dioxide photocatalyst by using chemicasurface modification Download PDFInfo
- Publication number
- KR101993236B1 KR101993236B1 KR1020170082674A KR20170082674A KR101993236B1 KR 101993236 B1 KR101993236 B1 KR 101993236B1 KR 1020170082674 A KR1020170082674 A KR 1020170082674A KR 20170082674 A KR20170082674 A KR 20170082674A KR 101993236 B1 KR101993236 B1 KR 101993236B1
- Authority
- KR
- South Korea
- Prior art keywords
- titanium dioxide
- dioxide powder
- surface modification
- white
- powder
- Prior art date
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 79
- 230000004048 modification Effects 0.000 title claims abstract description 27
- 238000012986 modification Methods 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 13
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006011 modification reaction Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000003086 colorant Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 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 3
- 238000011161 development Methods 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000002155 anti-virotic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Images
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
- 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
- B01J35/002—Catalysts characterised by their physical properties
- B01J35/0046—Physical properties of the active metal ingredient
- B01J35/006—Physical properties of the active metal ingredient metal crystallite size
-
- 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
- B01J35/02—Solids
- B01J35/026—Form of the solid particles
-
- B01J35/393—
-
- B01J35/50—
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
본 발명에 따른 가시광 응답형 이산화티타늄 광촉매의 제조방법은, 백색의 이산화티타늄 분말을, 과산화수소, 수산화암모늄 및 염산을 포함하는 그룹에서 적어도 1종 이상으로 선택된 표면개질용매에 첨가하여 상온에서 교반하는 제1 단계; 상기 이산화티타늄 분말 및 상기 표면개질용매의 혼합물을 25℃ 이상 및 200℃ 이하의 온도범위에서 화학적 표면개질 반응시켜 상기 이산화티타늄 분말 표면에 비정질층을 형성하는 제2 단계; 및 상기 이산화티타늄 분말을 불활성 가스 분위기 및 200℃ 이상 및 1,000℃ 이하의 온도범위에서 열처리하는 제3 단계;를 포함하고, 여기서 상기 이산화티타늄 분말의 표면이 백색에서 유색으로 변화되는 것을 특징으로 한다.The method for producing a visible light-responsive titanium dioxide photocatalyst according to the present invention comprises the steps of adding white titanium dioxide powder to a surface modification solvent selected from the group consisting of hydrogen peroxide, ammonium hydroxide and hydrochloric acid, Stage 1; A second step of subjecting a mixture of the titanium dioxide powder and the surface modification solvent to a chemical surface modification reaction at a temperature range of 25 ° C or higher and 200 ° C or lower to form an amorphous layer on the surface of the titanium dioxide powder; And a third step of heat-treating the titanium dioxide powder in an inert gas atmosphere and a temperature range of 200 ° C or more and 1,000 ° C or less, wherein the surface of the titanium dioxide powder is changed from white to colored.
Description
본 발명은 광촉매에 관한 것으로서, 더 자세하게는 이산화티타늄 광촉매의 제조방법에 관한 것이다.The present invention relates to a photocatalyst, and more particularly, to a method for producing a titanium dioxide photocatalyst.
광촉매(Photocatalyst)는 빛(Photo) 및 촉매(Catalyst)의 합성어로서, 빛을 에너지원으로 하여 광화학반응(산화반응 또는 환원반응)을 촉진시키는 물질을 말한다. 광촉매는 각종 세균 및 오염물질을 분해시키는 효과가 있으며, 1970년대 초 후지시마(Fujishima)와 혼다(Honda)가 반도체인 TiO2(이산화티타늄) 단결정 전극에 빛을 조사하면 광산화 반응과 광환원 반응에 의하여 물이 수소와 산소로 분리됨을 발표한 이후 급속히 개발이 진행되기 시작하였으며, 일본 등 선진국에서 활발한 연구가 진행되고 있다.Photocatalyst is a compound of photo and catalyst. It refers to a substance that promotes photochemical reaction (oxidation reaction or reduction reaction) by using light as an energy source. Photocatalyst has the effect of decomposing various bacteria and pollutants. In the early 1970s Fujishima and Honda irradiated the semiconductor TiO 2 (titanium dioxide) monocrystal electrode by photo-oxidation reaction and photo-reduction reaction Since the announcement that water is separated into hydrogen and oxygen, development has begun to progress rapidly, and active research is underway in advanced countries such as Japan.
현재까지 알려진 광촉매 물질 중 가장 유명한 것은 이산화티타늄(TiO2)이다. 이산화티타늄은 화학적으로 매우 안정하고 광활성이 우수하며 인체에 무해하다는 특성이 있다. 이산화티타늄 광촉매는 n형 반도체로서, 자외선(<400nm)을 받으면 전자(Electron) 및 전공대(Electron Hole)가 형성되어, 강한 산화력을 가진 히드록시 라디칼과 슈퍼 옥사이드를 생성하며, 이들이 유기화합물을 산화·분해시켜 물과 탄산가스로 변화시킨다.The most famous of the known photocatalytic materials to date is titanium dioxide (TiO 2 ). Titanium dioxide is chemically very stable, has excellent optical activity and is harmless to human body. Titanium dioxide photocatalysts are n-type semiconductors. When ultraviolet rays (<400 nm) are received, electrons and electron holes are formed to generate hydroxyl radicals and superoxide having strong oxidizing power. · Disintegrate into water and carbon dioxide.
하지만 이산화티타늄의 경우, 촉매 반응이 일어나기 위해서는 약 387nm [밴드갭(Band Gap) 3.2eV] 이하의 높은 에너지를 갖는 태양광이 필요하다는 단점을 가지고 있기 때문에, 현재까지 생산되고 있는 광촉매 물질은 옥외용으로 주로 이용되고 있다. 이러한 한계점을 극복하고 가시광(Visible Light) 또는 실내조명에서 사용 가능한 광촉매 물질을 개발한다면, 광촉매 산업에서의 적용 범위가 늘어나고 촉매 활성 효율이 획기적으로 증가할 것이다. 특히, 건물/차량의 실내의 유기화합물, 소독, 방오, 항균, 항바이러스 등 생활공간을 개선하기 위한 환경 친화형 나노소재인 실내조명 응답형 광촉매 개발이 필요하다.However, in the case of titanium dioxide, since a photovoltaic material having a high energy of about 387 nm (band gap 3.2 eV) or less is required for the catalytic reaction to take place, It is mainly used. If we overcome these limitations and develop photocatalytic materials that can be used in visible light or indoor lighting, the application range in the photocatalytic industry will increase and the catalytic activity efficiency will increase dramatically. Especially, it is necessary to develop indoor light response photocatalyst, which is an environmentally friendly nano material to improve living space such as organic compound, disinfection, antifouling, antibacterial and antivirus in buildings / vehicles.
현재 개발이 진행 중인 광촉매 기술동향은, 이산화티타늄이 가지는 기술적 한계인 낮은 가시광 활성도를 높이는 연구와, 이를 활용한 실용화 제품 개발이 추진 중이다.The development of photocatalytic technology, which is currently under development, is under study to increase the low visible light activity, which is the technical limit of titanium dioxide, and to develop commercialized products utilizing it.
일본에서는 질소(N) 또는 탄소(C)를 도핑(Doping)하여 가전도대(Valence Band)를 상승시킴으로써 이산화티타늄의 밴드갭을 줄이는 데 성공하였고, 이를 통해 가시광 영역에서 상대적 효율이 크게 증가된 이산화티타늄(TiO2) 광촉매가 개발되었으나, 제조가 용이하지 않으며 안정성이 떨어지는 단점 및 자외선 영역에서는 순수한 이산화티타늄 보다 광촉매 효율이 현격히 떨어지는 단점이 있다.In Japan, it has succeeded in reducing the band gap of titanium dioxide by doping nitrogen (N) or carbon (C) to increase the valence band, thereby increasing the relative efficiency in the visible region Titanium (TiO 2 ) photocatalysts have been developed. However, they are not easy to manufacture and have poor stability. In the ultraviolet region, photocatalyst efficiency is significantly lower than that of pure titanium dioxide.
또 다른 방법으로는 가시광 감응이 가능한 새로운 물질을 도입하는 방법으로 2.8 eV 이하의 밴드갭(Band Gap)을 가지고 있어서, 가시광 영역에서 전자와 정공을 생성할 수 있는 반도체를 이산화티타늄와 접합(Junction)시키면 가시광에서 활성을 보이는 광촉매를 제조하는 기술이 개발되었다. 그러나 이러한 이종 접합형 가시광 광촉매는 수소를 발생시키거나 탈수소화반응(Dehydrogenation)과 같은 환원 반응에 적합하나, 유기물을 완전히 산화시키기란 대단히 어렵기 때문에 산화반응을 통해 요염물질을 분해시키는 데는 적합하지 않다.Another method is to introduce a new material capable of visible light response and has a band gap of 2.8 eV or less so that a semiconductor capable of generating electrons and holes in a visible light region is bonded to titanium dioxide Techniques have been developed to produce photocatalysts that are active in visible light. However, such a heterogeneous visible light photocatalyst is suitable for reduction reaction such as hydrogen generation or dehydrogenation, but it is very difficult to completely oxidize the organic material, so it is not suitable for decomposing the organic material through the oxidation reaction .
본 발명은 상술한 종래기술의 문제점을 해결하고자 한 것으로서, 보다 간단한 방법 및 저가의 제조공정으로 다양한 컬러의 가시광 응답형 이산화티타늄 광촉매를 제조하는 방법을 제공하는 것을 주된 목적으로 한다. Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above problems of the prior art, and it is a main object of the present invention to provide a method of manufacturing a visible light-responsive titanium dioxide photocatalyst of various colors by a simpler method and a low-
본 발명의 목적들은 이상에서 언급한 목적들로 제한되지 않으며, 언급되지 않은 또 다른 목적들은 아래의 기재로부터 명확하게 이해될 수 있을 것이다.The objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood from the following description.
본 발명에 따른 가시광 응답형 이산화티타늄 광촉매의 제조방법은, 백색의 이산화티타늄 분말을, 과산화수소, 수산화암모늄 및 염산을 포함하는 그룹에서 적어도 1종 이상으로 선택된 표면개질용매에 첨가하여 상온에서 교반하는 제1 단계; 상기 이산화티타늄 분말 및 상기 표면개질용매의 혼합물을 25℃ 이상 및 200℃ 이하의 온도범위에서 화학적 표면개질 반응시켜 상기 이산화티타늄 분말 표면에 비정질층을 형성하는 제2 단계; 및 상기 이산화티타늄 분말을 불활성 가스 분위기 및 200℃ 이상 및 1,000℃ 이하의 온도범위에서 열처리하는 제3 단계;를 포함하고, 여기서 상기 이산화티타늄 분말의 표면이 백색에서 유색으로 변화되는 것을 특징으로 한다.The method for producing a visible light-responsive titanium dioxide photocatalyst according to the present invention comprises the steps of adding white titanium dioxide powder to a surface modification solvent selected from the group consisting of hydrogen peroxide, ammonium hydroxide and hydrochloric acid, Stage 1; A second step of subjecting a mixture of the titanium dioxide powder and the surface modification solvent to a chemical surface modification reaction at a temperature range of 25 ° C or higher and 200 ° C or lower to form an amorphous layer on the surface of the titanium dioxide powder; And a third step of heat-treating the titanium dioxide powder in an inert gas atmosphere and a temperature range of 200 ° C or more and 1,000 ° C or less, wherein the surface of the titanium dioxide powder is changed from white to colored.
특히, 상기 제1 단계에서 상기 백색의 이산화티타늄 분말은 아나타제 결정 구조를 갖는 분말인 것이 바람직하다. 아울러, 상기 제1 단계에서 상기 이산화티타늄 분말은 10nm 이상 및 200nm 이하의 입자크기를 갖는 것이 바람직하다. 나아가, 상기 제2 단계에서 상기 화학적 표면개질 반응은 1시간 내지 20일 동안 진행되는 것이 바람직하다.Particularly, in the first step, the white titanium dioxide powder is preferably a powder having an anatase crystal structure. In addition, in the first step, the titanium dioxide powder preferably has a particle size of 10 nm or more and 200 nm or less. Further, in the second step, the chemical surface modification reaction preferably proceeds for 1 to 20 days.
다른 측면에서 본 발명은 상술한 제조방법에 따라 제조되고, 그 표면에 유색의 비정질층이 형성된 것을 특징으로 하는 가시광 응답형 이산화티타늄 광촉매를 제공한다.In another aspect, the present invention provides a visible light-responsive titanium dioxide photocatalyst, which is produced according to the above-described manufacturing method and has a colored amorphous layer formed on its surface.
본 발명에 따르면, 기존 제조 공정보다 저가인 제조공정으로서 화학적 표면 개질을 통해 비정질층(Amorphous Layer)이 형성된 이산화티타늄을 열처리함으로써, 형성된 비정질층의 두께 변화를 제어하여 이산화티타늄의 표면층의 색상을 다양하게 변화시킬 수 있다. 특히 표면층의 색상 변화에 따라 가시광 응답형 광촉매 특성이 향상되며, 건물/차량 등에서의 실내 유기화합물, 소독, 방오, 항균, 항바이러스 등 생활공간을 개선하기 위한 환경 친화형 실내조명 응답형 광촉매를 제공할 수 있다.According to the present invention, as a manufacturing process which is lower in cost than a conventional manufacturing process, the titanium dioxide having an amorphous layer formed by chemical surface modification is thermally treated to control the thickness variation of the formed amorphous layer to change the color of the surface layer of titanium dioxide . In particular, the photocatalytic properties of visible light response type are improved according to the color change of the surface layer, and the environmentally friendly indoor light responsive photocatalyst is provided to improve living space such as indoor organic compound, disinfection, antifouling, antibacterial and antivirus in buildings / vehicles can do.
도 1은 본 발명에 따라 화학적 표면개질된 이산화티타늄 분말의 표면에 형성된 비정질층을 열처리함에 따라 다양한 색깔로 변화되는 것을 확인한 사진이다.
도 2는 백색 이산화티타늄 및 본 발명에 따라 표면개질 후 열처리된 짙은 갈색의 이산화티타늄 각각에 대한 FE-TEM 사진이다.
도 3은 백색 이산화티타늄 및 본 발명에 따라 표면개질 후 열처리된 짙은 갈색의 이산화티타늄 각각에 대한 광분해능 평가결과를 나타낸다.FIG. 1 is a photograph showing that the amorphous layer formed on the surface of the titanium dioxide powder chemically modified according to the present invention is changed into various colors upon heat treatment.
2 is an FE-TEM photograph of each of white titanium dioxide and dark brown titanium dioxide heat treated after surface modification according to the present invention.
FIG. 3 shows the results of optical resolution evaluation for each of white titanium dioxide and dark brown titanium dioxide heat-treated after surface modification according to the present invention.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 이를 상세한 설명을 통해 상세히 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서, 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다. While the present invention has been described in connection with certain exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and similarities. It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
이하, 첨부된 도면들을 참조하여 본 발명의 실시를 위한 구체적인 내용을 설명하도록 한다.Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
본 발명은 화학적 표면 개질을 통한 다양한 컬러의 가시광 응답형 이산화티타늄(TiO2) 광촉매 제조방법에 관한 것으로서, 보다 상세하게는 백색의 이산화티타늄 분말을, 과산화수소, 수산화암모늄 및 염산을 포함하는 그룹에서 적어도 1종 이상으로 선택된 표면개질용매에 첨가하여 상온에서 교반하는 제1 단계; 상기 이산화티타늄 분말 및 상기 표면개질용매의 혼합물을 25℃ 이상 및 200℃ 이하의 온도범위에서 화학적 표면개질(Chemical Surface Modification) 반응시켜 상기 이산화티타늄 분말 표면에 비정질층(Amorphous Layer)을 형성하는 제2 단계; 및 상기 이산화티타늄 분말을 불활성 가스 분위기 및 200℃ 이상 및 1,000℃ 이하의 온도범위에서 열처리하는 제3 단계;를 포함하여 달성될 수 있다. 여기서, 화학적 표면개질반응을 통해 백색의 이산화티타늄 분말 표면에 비정질층을 형성하며, 또한 형성된 비정질층은 열처리 공정을 통해 그 두께가 제어됨으로써 다양한 컬러의 가시광 응답형 이산화티타늄 광촉매를 제조할 수 있다. 즉, 화학적 표면 개질된 이산화티타늄은 다양한 온도의 열처리 공정을 통해 표면에 형성된 비정질층의 두께 변화로 이산화티타늄의 컬러가 유색으로 다양하게 변화되며, 특히 컬러의 변화에 따라 가시광 응답형 광촉매 특성이 향상된다.The present invention relates to a method of producing visible light-responsive titanium dioxide (TiO 2 ) photocatalysts of various colors through chemical surface modification, and more particularly, to a method of preparing titanium dioxide powder of white color by reacting titanium dioxide powder in a group comprising at least hydrogen peroxide, ammonium hydroxide and hydrochloric acid Adding to a surface modification solvent selected from at least one of them and stirring at room temperature; A second surface of the titanium dioxide powder and an amorphous layer formed on the surface of the titanium dioxide powder by a chemical surface modification reaction of the mixture of the titanium dioxide powder and the surface modification solvent at a temperature range of 25 ° C or higher and 200 ° C or lower, step; And a third step of heat-treating the titanium dioxide powder in an inert gas atmosphere and a temperature range of 200 ° C or more and 1,000 ° C or less. Here, the amorphous layer is formed on the surface of the white titanium dioxide powder through the chemical surface modification reaction, and the thickness of the formed amorphous layer is controlled through the heat treatment process, so that the visible light-responsive titanium dioxide photocatalyst of various colors can be produced. In other words, titanium dioxide which is chemically modified is varied in color depending on the thickness of the amorphous layer formed on the surface through heat treatment at various temperatures, and the color of titanium dioxide is variously changed to color. Particularly, do.
본 발명에서 사용되는 백색의 이산화티타늄은, 저가의 상용화된 루타일(Rutile), 아나타제(Anatase), 부루카이트(Brookite)의 결정구조를 갖는 입자일 수 있으며, 특히 아나타제 결정 구조를 갖는 이산화티타늄 분말을 사용하는 것이 바람직하다. 아울러, 제1 단계에서 사용되는 이산화티타늄 분말의 입자크기는 10nm 이상 및 200nm 이하인 것이 바람직한데, 입자 크기가 작을수록 비표면적(Specific Surface Area)이 높아서 광촉매 특성 향상에 유리하다.The white titanium dioxide used in the present invention may be low-cost commercialized particles having a crystal structure of rutile, anatase and brookite, and titanium dioxide powder having an anatase crystal structure Is preferably used. The particle size of the titanium dioxide powder used in the first step is preferably 10 nm or more and 200 nm or less. The smaller the particle size, the higher the specific surface area, which is advantageous for improving the photocatalytic property.
아울러, 제2 단계의 화학적 표면개질 공정의 반응시간은 1시간에서 20일까지 및 반응온도는 25℃ 이상 및 200℃ 이하의 온도범위에서 이루어지는 것이 바람직하다. In addition, the reaction time of the chemical surface modification step of the second step is preferably 1 hour to 20 days, and the reaction temperature is preferably 25 ° C. or more and 200 ° C. or less.
또한, 제3 단계에서, 표면개질된 이산화티타늄 분말의 열처리 온도는 5 ~ 20 ℃/min의 승온 속도로 200℃ 이상 및 1,000℃ 이하의 온도범위에서 열처리하며, 특히 불활성 분위기에서 이루어지는 것이 바람직하다. 여기서, 열처리 온도가 200℃ 미만이면 표면개질에 의해 형성된 비정질층의 결정화가 이루어지지 않으며, 반대로 1,000℃ 초과이면 표면개질된 비정질층이 다시 백색의 이산화티타늄으로 변화되어 광촉매 특성이 감소된다. In the third step, the heat-treated temperature of the surface-modified titanium dioxide powder is preferably heat-treated at a temperature raising rate of 5 to 20 占 폚 / min in a temperature range of 200 占 폚 to 1,000 占 폚, particularly in an inert atmosphere. If the annealing temperature is less than 200 ° C, the amorphous layer formed by the surface modification is not crystallized. If the annealing temperature is more than 1,000 ° C, the amorphous layer is changed to white titanium dioxide again to decrease the photocatalytic property.
본 발명에 따라 제조된 다양한 컬러의 이산화티타늄은 기존 백색 이산화티타늄 대비 가시광 영역에서 광촉매 효율이 향상됨을 확인할 수 있으며, 이하에서는 실시예들을 통해 본 발명에 따른 제조방법 및 그에 따라 제조된 이산화티타늄 분말의 광촉매 특성에 대해 설명한다.The titanium dioxide prepared in various colors according to the present invention has improved photocatalytic efficiency in the visible light region compared to the conventional white titanium dioxide. In the following, the production method according to the present invention and the titanium dioxide powder The characteristics of the photocatalyst will be described.
[제조예 1][Production Example 1]
상용 백색 이산화티타늄(20nm)을, 과산화수소 및 수산화암모늄이 혼합된 표면개질용매에 첨가한 후, 상온에서 24시간 동안 교반하였다. 이후, 건조오븐(Dry oven)을 이용하여 100℃에서 12시간 동안 유지함으로써 이산화티타늄 분말에 화학적 표면개질반응을 유도하였다. 이렇게 화학적 표면개질된 이산화티타늄은 백색에서 노란색으로 변하였다. 화학적 표면개질된 노란색 이산화티타늄을 불활성 가스 분위기 하에서 5℃/min 승온 속도로 200 ~ 1,000℃까지 열처리하여 다양한 컬러의 이산화티타늄 광촉매를 제조하였다.Commercial white titanium dioxide (20 nm) was added to the surface modification solvent mixed with hydrogen peroxide and ammonium hydroxide, followed by stirring at room temperature for 24 hours. Thereafter, a chemical surface modification reaction was induced in the titanium dioxide powder by keeping it at 100 ° C for 12 hours using a dry oven. These chemically surface modified titanium dioxide changed from white to yellow. Titanium dioxide photocatalysts of various colors were prepared by heat treating the yellow titanium dioxide modified at 200 ° C to 1,000 ° C at an elevated rate of 5 ° C / min in an inert gas atmosphere.
[제조예 2][Production Example 2]
상용 백색 이산화티타늄(20nm)을, 과산화수소 및 염산이 혼합된 표면개질용매에 첨가한 후, 상온에서 24시간 동안 교반하였다. 이후, 건조오븐(Dry oven)을 이용하여 100℃에서 12시간 동안 건조시켰다. 이렇게 화학적 표면개질된 이산화티타늄은 백색에서 엷은 회색으로 변하였다. 화학적 표면개질된 엷은 회색 이산화티타늄을 불활성 가스 분위기 하에서 5℃/min 승온 속도로 200 ~ 1,000℃ 까지 열처리하여 다양한 컬러의 이산화티타늄 광촉매를 제조하였다.Commercial white titanium dioxide (20 nm) was added to a surface modification solvent mixed with hydrogen peroxide and hydrochloric acid, and then stirred at room temperature for 24 hours. Thereafter, it was dried at 100 DEG C for 12 hours using a dry oven. This chemically surface modified titanium dioxide changed from white to light gray. Titanium dioxide photocatalysts of various colors were prepared by heat treating the chemically modified light gray titanium dioxide at 200 ° C to 1,000 ° C at a heating rate of 5 ° C / min in an inert gas atmosphere.
[실시예 3 내지 5][Examples 3 to 5]
제조예 1과 동일하게 진행하되, 다만 화학적 표면개질 공정에서 반응 시간을 3시간 기준으로 반응 온도를 40℃(실시예 3), 60℃(실시예 4), 80℃(실시예 5)로 다양하게 변화시켜 제조하였다.The procedure of Preparation Example 1 was repeated except that the reaction time varied from 3 ° C (Example 3) to 60 ° C (Example 4) and 80 ° C (Example 5) .
도 1은 화학적 표면개질 공정 후 다양한 온도에서 열처리된 이산화티타늄 분말의 사진이다. 상온에서 화학적 표면 개질된 이산화티타늄의 컬러는 노란색으로 변화된 것을 확인할 수 있으며, 열처리 온도가 증가될수록 연주황색에서 짙은 갈색 및 회색으로 컬러가 변화되는 것을 확인할 수 있다. 여기서, 좌측에서 첫번째 사진은 백색 이산화티타늄 분말을 나타내고, 좌측에서 두번째 사진은 표면개질반응에 의해 비정질층이 형성된 상태를 나타내며, 좌측에서 세번째 내지 다섯번째 사진은 각기 다른 온도에서 열처리된 상태를 나타낸다.Figure 1 is a photograph of a titanium dioxide powder heat treated at various temperatures after a chemical surface modification process. It can be seen that the color of the titanium dioxide modified at the room temperature is changed to yellow. As the heat treatment temperature is increased, the color changes from playing yellow to dark brown and gray. Here, the first photo on the left side shows a white titanium dioxide powder, the second photo on the left side shows a state in which an amorphous layer is formed by the surface modification reaction, and the third to fifth photos on the left side show heat-treated state at different temperatures.
도 2는 백색 이산화티타늄(White TiO2)과 화학적 표면개질 후 500℃에서 열처리된 짙은 갈색의 이산화티타늄(Dark Brown TiO2)의 FE-TEM 사진이다. 백색 이산화티타늄은 입자 표면에 결정격자가 형성되어 있으나, 화학적 표면개질 후 500℃에서 열처리된 짙은 갈색의 이산화티타늄은 약 1.5nm 정도의 비정질층이 형성되어 있는 것을 확인할 수 있다. 따라서 이산화티타늄 입자가 화학적 표면개질공정을 통해 약 1.5 nm의 비정질층이 형성되어 컬러가 백색에서 짙은 갈색으로 변화된 것을 확인할 수 있다.FIG. 2 is an FE-TEM image of dark brown TiO 2 heat-treated at 500 ° C after white titanium dioxide (White TiO 2 ) and chemical surface modification. The white titanium dioxide has a crystal lattice on the surface of the particles, but it can be confirmed that the dark brown titanium dioxide heat-treated at 500 ° C. after the chemical surface modification has an amorphous layer of about 1.5 nm. Thus, it can be seen that the titanium dioxide particles are changed from a white color to a dark brown color by forming an amorphous layer of about 1.5 nm through a chemical surface modification process.
도 3은 백색 이산화티타늄(White TiO2)과 화학적 표면 개질 후 500℃에서 열처리된 짙은 갈색 이산화티타늄(Dark Brown TiO2)의 광분해능을 평가한 결과를 나타낸다. 일정량의 백색 이산화티타늄 및 짙은 갈색 이산화티타늄을 메틸렌블루(Methylene Blue) 용액에 첨가한 후 형광등(가시광) 하에서 시간에 따른 메틸렌블루의 감소량을 UV-vis 분석법을 이용하여 평가하였다. 도 3에서 볼 수 있듯이, 짙은 갈색 이산화티타늄의 경우, 120분 조사 후 메틸렌블루(Methylene Blue)가 약 99% 감소된 반면에, 백색 이산화티타늄은 약 10% 감소되었다. 이러한 결과는, 이산화티타늄의 컬러가 백색에서 화학적 표면 개질 반응 후 짙은 갈색으로 변화되면 가시광 영역에서 광촉매 효율이 향상됨을 보여준다.FIG. 3 shows the results of evaluating the optical resolution of white titanium dioxide (White TiO 2 ) and dark brown TiO 2 heat-treated at 500 ° C. after chemical surface modification. A certain amount of white titanium dioxide and dark brown titanium dioxide were added to a solution of methylene blue and the amount of decrease in methylene blue over time under a fluorescent lamp (visible light) was evaluated by UV-vis analysis. As can be seen from FIG. 3, in the case of the dark brown titanium dioxide, the amount of white titanium dioxide was reduced by about 10% while the amount of methylene blue was reduced by about 99% after 120 minutes of irradiation. These results show that the photocatalytic efficiency is improved in the visible light region when the color of titanium dioxide changes from white to dark brown after the chemical surface modification reaction.
지금까지 본 발명의 바람직한 실시예에 대해 설명하였으나, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 본질적인 특성을 벗어나지 않는 범위 내에서 변형된 형태로 구현할 수 있을 것이다. 그러므로 여기서 설명한 본 발명의 실시예는 한정적인 관점이 아니라 설명적인 관점에서 고려되어야 하고, 본 발명의 범위는 상술한 설명이 아니라 특허청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함되는 것으로 해석되어야 한다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. It is therefore to be understood that the embodiments of the invention described herein are to be considered in all respects as illustrative and not restrictive, and the scope of the invention is indicated by the appended claims rather than by the foregoing description, Should be interpreted as being included in.
Claims (5)
상기 이산화티타늄 분말 및 상기 표면개질용매의 혼합물을 25℃ 이상 및 200℃ 이하의 온도범위에서 화학적 표면개질 반응시켜 상기 이산화티타늄 분말 표면에 비정질층을 형성하는 제2 단계; 및
상기 이산화티타늄 분말을 불활성 가스 분위기 및 200℃ 이상 및 1,000℃ 이하의 온도범위에서 열처리하는 제3 단계;를 포함하고,
상기 제3 단계에서 열처리된 이산화티타늄 분말 표면에 유색의 비정질층이 형성된 것을 특징으로 하는, 가시광 응답형 이산화티타늄 광촉매의 제조방법.
Adding a white titanium dioxide powder to a surface modification solvent of a surface modification solvent mixed with hydrogen peroxide and ammonium hydroxide or a surface modification solvent mixed with hydrogen peroxide and hydrochloric acid and stirring at room temperature;
A second step of subjecting a mixture of the titanium dioxide powder and the surface modification solvent to a chemical surface modification reaction at a temperature range of 25 ° C or higher and 200 ° C or lower to form an amorphous layer on the surface of the titanium dioxide powder; And
And a third step of subjecting the titanium dioxide powder to an inert gas atmosphere and a heat treatment in a temperature range of 200 ° C or more and 1,000 ° C or less,
A method of manufacturing a visible light-responsive titanium dioxide photocatalyst, comprising: forming a colored amorphous layer on the surface of a titanium dioxide powder heat-treated in the third step.
상기 제1 단계에서 상기 백색의 이산화티타늄 분말은 아나타제 결정 구조를 갖는 분말인 것을 특징으로 하는, 가시광 응답형 이산화티타늄 광촉매의 제조방법.
The method according to claim 1,
Wherein the white titanium dioxide powder in the first step is a powder having an anatase crystal structure.
상기 제1 단계에서 상기 이산화티타늄 분말은 10nm 이상 및 200nm 이하의 입자크기를 갖는 것을 특징으로 하는, 가시광 응답형 이산화티타늄 광촉매의 제조방법.
The method according to claim 1,
Wherein the titanium dioxide powder has a particle size of 10 nm or more and 200 nm or less in the first step.
상기 제2 단계에서 상기 화학적 표면개질 반응은 1시간 내지 20일 동안 진행되는 것을 특징으로 하는, 가시광 응답형 이산화티타늄 광촉매의 제조방법.
The method according to claim 1,
Wherein the chemical surface modification reaction is performed for 1 to 20 days in the second step. ≪ RTI ID = 0.0 > 11. < / RTI >
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020170082674A KR101993236B1 (en) | 2017-06-29 | 2017-06-29 | Method for manufacturing visible-light active titanium dioxide photocatalyst by using chemicasurface modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020170082674A KR101993236B1 (en) | 2017-06-29 | 2017-06-29 | Method for manufacturing visible-light active titanium dioxide photocatalyst by using chemicasurface modification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20190002159A KR20190002159A (en) | 2019-01-08 |
| KR101993236B1 true KR101993236B1 (en) | 2019-06-26 |
Family
ID=65021137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020170082674A KR101993236B1 (en) | 2017-06-29 | 2017-06-29 | Method for manufacturing visible-light active titanium dioxide photocatalyst by using chemicasurface modification |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101993236B1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115676879A (en) * | 2021-07-30 | 2023-02-03 | 北京化工大学常州先进材料研究院 | Preparation method of titanium dioxide for efficiently degrading liquid-phase pollutants |
| KR102558794B1 (en) * | 2022-11-18 | 2023-07-24 | 주식회사 대수하이테크 | Hydrophilic hard coating composition containing titanium dioxide nanoparticles |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003230834A (en) | 2002-02-07 | 2003-08-19 | Tama Kagaku Kogyo Kk | Surface-modified titanium oxide having selective photolysis reactivity and selective photolysis catalyst |
| JP2005298295A (en) | 2004-04-14 | 2005-10-27 | Daicel Chem Ind Ltd | Method for refining titanium oxide |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08252461A (en) * | 1995-03-17 | 1996-10-01 | Ebara Corp | Preparation of photocatalyst |
| JP3374305B2 (en) * | 1996-07-08 | 2003-02-04 | 中部電力株式会社 | Method for producing titania-based catalyst |
-
2017
- 2017-06-29 KR KR1020170082674A patent/KR101993236B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003230834A (en) | 2002-02-07 | 2003-08-19 | Tama Kagaku Kogyo Kk | Surface-modified titanium oxide having selective photolysis reactivity and selective photolysis catalyst |
| JP2005298295A (en) | 2004-04-14 | 2005-10-27 | Daicel Chem Ind Ltd | Method for refining titanium oxide |
Non-Patent Citations (1)
| Title |
|---|
| CHEM COMMUN ( 2016)* |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190002159A (en) | 2019-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zaleska | Doped-TiO2: a review | |
| KR100945035B1 (en) | Tungstates based visible-light induced oxides photocatalysts and synthesis methods thereof | |
| Rahbar et al. | S, N co-doped carbon quantum dots/TiO2 nanocomposite as highly efficient visible light photocatalyst | |
| KR101954792B1 (en) | Method of manufacturing metal-loaded TiO2/graphene composites through one-pot hydrothermal synthesis and the TiO2/graphene composites manufactured by the same | |
| JPWO2006064799A1 (en) | Composite metal oxide photocatalyst with visible light response | |
| KR101725059B1 (en) | System for photocatalytic activation | |
| JP2006021112A (en) | Ultraviolet and visible ray responsive titania based photocatalyst | |
| EP2205684A1 (en) | Particle comprising core and shell and applications thereof | |
| KR20130113770A (en) | Hydrid photocatalyst nanoparticle with improved photoactivity and method for preparing the same | |
| JP4135921B2 (en) | Titanium dioxide fine particles and method for producing the same | |
| US8940183B2 (en) | Method of making a nano-particle photocatalyst | |
| KR101993236B1 (en) | Method for manufacturing visible-light active titanium dioxide photocatalyst by using chemicasurface modification | |
| KR101065804B1 (en) | Method for preparation of monodispersed anatase titanium dioxide nanoparticle | |
| JP4140770B2 (en) | Titanium dioxide fine particles, method for producing the same, and method for producing visible light active photocatalyst | |
| KR20160011725A (en) | THE MANUFACTURING METHOD OF TiO2/GRAPHENE COMPOSITE FOR PHOTOCATALYST | |
| JP4639355B2 (en) | Method for producing visible light responsive photocatalyst | |
| KR101548296B1 (en) | Manufacturing method of bimetallic transition metal doped titanium dioxide | |
| KR101706846B1 (en) | A manufacturing method of nanocomposite photocatalyst | |
| KR102562529B1 (en) | Transition Metal Doped Complex Photocatalyst and Manufacturing Method thereof | |
| JP4883913B2 (en) | Photocatalyst and method for producing the same | |
| Zhang et al. | Carbon-dot-modified TiO 2− x mesoporous single crystals with enhanced photocatalytic activity for degradation of phenol | |
| KR101943921B1 (en) | Manufacturing method of nitrogen doped-TiO2/graphene composite | |
| KR101400633B1 (en) | Visible ray reaction type Zirconium TiO2/SiO2 photocatalyst and preparation method thereof | |
| KR102308030B1 (en) | Titania core/shell structure and manufacturing method for the same | |
| CN105498822A (en) | Preparation method for nitrogen-doped anatase titanium dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |