KR20080030823A - High photocatalytic acitivity of mesoporous tio2 and visible lingt photocatalyst with hydrotheramal treatment and methode of manufacturing thereof - Google Patents
High photocatalytic acitivity of mesoporous tio2 and visible lingt photocatalyst with hydrotheramal treatment and methode of manufacturing thereof Download PDFInfo
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- KR20080030823A KR20080030823A KR1020060097229A KR20060097229A KR20080030823A KR 20080030823 A KR20080030823 A KR 20080030823A KR 1020060097229 A KR1020060097229 A KR 1020060097229A KR 20060097229 A KR20060097229 A KR 20060097229A KR 20080030823 A KR20080030823 A KR 20080030823A
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- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000011941 photocatalyst Substances 0.000 title claims description 7
- 230000001699 photocatalysis Effects 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000004094 surface-active agent Substances 0.000 claims abstract description 42
- 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 abstract description 30
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 150000003624 transition metals Chemical class 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 229920002415 Pluronic P-123 Polymers 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 7
- 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 6
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010218 electron microscopic analysis Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- KAVBMPSEABAPIE-UHFFFAOYSA-K trichlorochromium;hydrate Chemical compound O.Cl[Cr](Cl)Cl KAVBMPSEABAPIE-UHFFFAOYSA-K 0.000 description 1
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- 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
- B01J35/30—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
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Abstract
Description
도 1a는 본 발명에 따른 실시예에서 얻어진 메조기공 이산화티타늄의 SEM 사진을 나타낸다.Figure 1a shows a SEM photograph of the mesoporous titanium dioxide obtained in the embodiment according to the present invention.
도 1b는 본 발명에 따른 실시예에서 얻어진 입자 하나의 메조기공 이산화티타늄을 확대하여 얻어진 SEM 사진을 나타낸다.1B shows an SEM image obtained by enlarging one mesoporous titanium dioxide of one particle obtained in the embodiment according to the present invention.
도 2는 본 발명에 따른 실시예에서 얻어진 메조기공 이산화티타늄의 TEM 사진을 나타낸다. Figure 2 shows a TEM photograph of mesoporous titanium dioxide obtained in the embodiment according to the present invention.
도 3은 본 발명에 따른 실시예에서 얻어진 메조기공 이산화티타늄에의 소성온도별 비표면적분석과 기공 분포 결과를 나타낸 곡선 그래프이다. 3 is a curve graph showing the specific surface area analysis and pore distribution results for different firing temperatures in mesoporous titanium dioxide obtained in the embodiment according to the present invention.
도 4는 본 발명에 따른 실시예에서 얻어진 메조기공 이산화티타늄의 메틸렌 블루 용액의 광분해에 따른 흡광도 변화를 나타낸 그래프이다. Figure 4 is a graph showing the change in absorbance according to the photolysis of the methylene blue solution of mesoporous titanium dioxide obtained in the embodiment according to the present invention.
도 5는 본 발명에 따른 실시예에서 얻어진 전이금속이 도핑된 메조기공 이산화티타늄에 대한 가시광 영역의 흡수도를 나태나는 그래프이다.FIG. 5 is a graph showing absorbance of visible light region with respect to mesoporous titanium dioxide doped transition metal obtained in the embodiment according to the present invention.
본 발명은 자외선 영역뿐만 아니라 가시광선 영역에서의 광활성을 증대시키는 가수열반응을 이용한 광활성이 높은 메조기공 이산화티타늄 및 가시광 활성광촉매 그리고 이들의 제조방법을 제공하는 것이다.The present invention provides a highly active mesoporous titanium dioxide and a visible light active photocatalyst using a hydrothermal reaction to increase the light activity in the visible region as well as the ultraviolet region and a method for producing the same.
일반적으로 메조기공 형성은 실리카(SiO2)물질에서 가장 잘 만들어지는 것으로 알려져 있다. 1992년 Mobil사의 과학자들이 MCM-41이라고 명명한 육방형으로 배열된 메조기공 실리카를 발표한 이래로 활발한 연구가 계속되어 MCM-48, KIT-1, MSU-1, MCM-41 또는 동일한 공간군이지만 기공 크기가 더욱 큰 영역에 속하는 SBA-15 등 메조영역에서 균일한 기공 크기를 갖는 다양한 구조의 메조기공 실리카 분자체들이 합성되었다. 메조기공 실리카는 주로 계면활성제의 집합체를 구조 유도체로 이용하여 만들어지는데, 계면활성제가 이루는 마이셀 표면에 존재하는 실리카가 중합반응을 일으킴에 따라 형성되기 때문에 계면활성제를 변화시키거나 반응 온도와 조성 등 반응조건을 다르게 함으로서 다양한 기공 구조와 크기를 갖는 메조기공 실리카 제조가 가능하다. 이러한 메조기공 실리카 분자체는 흡착제와 촉매로서의 응용 가능성을 보여주었으며 나노구조의 금속, 반도체 물질의 제조 등 여러 분야에 응용될 수 있다는 예가 보고되어졌다. 그러나 광촉매로 잘 알려진 이산화티타늄의 경우에는 코팅형태를 제외하고는 구조가 정확하게 제어된 형태의 메조기공 이산화티타늄 합성이 어려운 실정이다. In general, mesoporous formation is known to be best made from silica (SiO 2) material. Since 1992, scientists at Mobil published the hexagonal array of mesoporous silica, named MCM-41, which has led to active research, leading to the use of MCM-48, KIT-1, MSU-1, MCM-41, or the same space group, but Mesoporous silica molecular sieves of various structures having uniform pore sizes were synthesized in the meso region, such as SBA-15, which belongs to a larger region. Mesoporous silica is mainly made by using aggregates of surfactants as structural derivatives.Since the silica on the surface of the micelle formed by the surfactants is formed by polymerization, the mesoporous silica is used to change the surfactants or to react the reaction temperature and composition. By varying the conditions, it is possible to produce mesoporous silica having various pore structures and sizes. These mesoporous silica molecular sieves have shown application potential as adsorbents and catalysts, and examples have been reported that they can be applied to various fields such as the production of nanostructured metals and semiconductor materials. However, in the case of titanium dioxide, which is well known as a photocatalyst, it is difficult to synthesize mesoporous titanium dioxide having a precisely controlled structure except for a coating form.
따라서 본 발명의 목적은 첫 번째, 순수한 물을 용매로 이용하여 고체 형태의 메조기공 이산화티타늄을 제조한후, 가수열반응을 통하여 결정성이 우수하여 높은 온도에서도 열적 안전성이 뛰어난 물질을 저렴한 비용으로 친환경적으로 대량생산이 가능한 방법으로 제조하는데 있다. Accordingly, an object of the present invention is to prepare a mesoporous titanium dioxide in solid form using pure water as a solvent, and then, by using a hydrothermal reaction, a material having excellent thermal stability even at high temperature at low cost. It is to manufacture in an environment-friendly mass production method.
둘째, 기공내에 크롬(Cr), 철(Fe), 바륨(V) 및 은(Ag) 등의 전이금속을 도핑시킴으로써, 자외선뿐만 아니라 가시광선 영역에서도 높은 광활성을 가지는 물질을 제조하는데 있다. Second, doping transition metals such as chromium (Cr), iron (Fe), barium (V) and silver (Ag) in the pores, to produce a material having a high photoactivity in the visible light region as well as ultraviolet light.
상기와 같은 목적을 달성하기 위한 본 발명은, 하기의 화학식 1인 중성계면활성제인 Pluronic P123과 하기의 화학식 2인 전구체 티타늄아이소프로폭사이드(Titanium isopropoxide)와 하기의 화학식 3인 2,4-펜탄이온(2, 4-pentanedione)을 이용하며, 상기의 화학식 1과 상기의 화학식 2는 1 : 40 ~ 80의 몰비로, 상기의 화학식 2와 상기의 화학식 3은 1 : 1의 몰비로 구비되는 계면활성제를 이용한 메조기공 이산화티타늄 제조방법을 제공한다.The present invention for achieving the above object, Pluronic P123 which is a neutral surfactant of Formula 1 and the precursor titanium isopropoxide of Formula 2 and 2,4-pentane of Formula 3 An interface using ions (2, 4-pentanedione), wherein Formula 1 and Formula 2 are in a molar ratio of 1:40 to 80, and Formula 2 and Formula 3 are in a molar ratio of 1: 1. It provides a method for producing mesoporous titanium dioxide using an active agent.
(화학식 1)(Formula 1)
(PEO)20(PPO)70(PEO)20(PEO) 20 (PPO) 70 (PEO) 20
(화학식 2)(Formula 2)
Ti(OCH(CH3)CH2CH3)4 Ti (OCH (CH3) CH2CH3) 4
(화학식 3)(Formula 3)
CH3COCH2COCH3 CH3COCH2COCH3
또한 본 발명은, 물 100 중량부에 대해 3 ~ 5 중량부의 하기의 화학식 1인 중성계면활성제인 프르로닉(Pluronic) P123를 넣어 물에 용해시키는 계면활성제 용해단계와; 상기 계면활성제 용해단계에서 생성된 용액에 물 100 중량부에 대해 1 ~ 2 중량부의 황산을 첨가하는 황산 첨가단계와; 상기 계면활성제 용해단계에서 생성된 용액에 하기의 화학식 2인 전구체 티타늄아이소프로폭사이드(Titanium isopropoxide)와 하기의 화학식 3인 2,4-펜탄이온(2, 4-pentanedione)을 혼합한 티타늄전구체를 넣어 교반단계를 포함하여 제조되며, 상기 화학식 1인 중성계면활성제인 Pluronic P123과 상기 화학식 2인 전구체 티타늄아이소프로폭사이드(Titanium isopropoxide)는 1 : 40 ~ 80의 몰비로, In another aspect, the present invention, the surfactant dissolution step of dissolving 3 to 5 parts by weight of Pluronic P123, a neutral surfactant of the formula (1) to 100 parts by weight of water to dissolve in water; Sulfuric acid addition step of adding 1 to 2 parts by weight of sulfuric acid based on 100 parts by weight of water to the solution produced in the surfactant dissolving step; A titanium precursor obtained by mixing the precursor titanium isopropoxide represented by Chemical Formula 2 and 2,4-pentane ion represented by Chemical Formula 3 to the solution produced in the surfactant dissolving step It is prepared, including a stirring step, the neutral surfactant Pluronic P123 of Formula 1 and the precursor titanium isopropoxide of Formula 2 (Titanium isopropoxide) in a molar ratio of 1: 40 to 80,
상기 화학식 2인 전구체 티타늄아이소프로폭사이드(Titanium isopropoxide)와 상기 화학식 3인 2,4-펜탄이온(2, 4-pentanedione)은 1 : 1의 몰비로 구비되는 계면활성제를 이용한 메조기공 이산화티타늄 제조방법을 제공한다.The precursor titanium isopropoxide of formula (2) and 2,4-pentane ions (2,4-pentanedione) of formula (3) are prepared mesoporous titanium dioxide using a surfactant provided in a molar ratio of 1: 1. Provide a method.
(화학식 1)(Formula 1)
(PEO)20(PPO)70(PEO)20(PEO) 20 (PPO) 70 (PEO) 20
(화학식 2)(Formula 2)
Ti(OCH(CH3)CH2CH3)4 Ti (OCH (CH3) CH2CH3) 4
(화학식 3)(Formula 3)
CH3COCH2COCH3 CH3COCH2COCH3
이에 상기 계면활성제 용해단계는 반응온도 조건이 40 ~ 70 ℃로 구비되는 계면활성제를 이용한 메조기공 이산화티타늄 제조방법을 제공한다.Accordingly, the surfactant dissolving step provides a method for producing mesoporous titanium dioxide using a surfactant having a reaction temperature of 40 to 70 ° C.
상기의 제조방법에 의하여 제조되는 메조기공 이산화티타늄을 포함하며, 특히 상기 메조기공 이산화티타늄의 기공 내에 전이금속 Cr, Fe, V, 및 Ag를 포함하는 광활성광촉매를 제공한다.Provided is a photoactive photocatalyst comprising mesoporous titanium dioxide prepared by the above method, in particular the transition metals Cr, Fe, V, and Ag in the pores of the mesoporous titanium dioxide.
Cr, Fe, V, 및 Ag을 메조기공 이산화티타늄에 도핑시키기 위해서는 하기의 화학식 4, 화학식 5, 화학식 6 및 화학식 7을 이용하며, 메조기공 이산화티타늄과 하기의 화학식 4, 화학식 5, 화학식 6 및 화학식 7은 1 : 0.01 ~ 0.07의 몰비로 구비되는 가시광 활성 메조기공 이산화티타늄 제조방법을 제공한다.In order to dope Cr, Fe, V, and Ag in the mesoporous titanium dioxide, the following Chemical Formulas 4, 5, 6, and 7 are used, and the mesoporous titanium dioxide and the following Chemical Formulas 4, 5, 6, and Formula 7 provides a method for producing visible light active mesoporous titanium dioxide, which is provided at a molar ratio of 1: 0.01 to 0.07.
(화학식 4)(Formula 4)
CrCl36H2OCrCl36H2O
(화학식 5)(Formula 5)
FeCl3FeCl3
(화학식 6)(Formula 6)
VCl4VCl4
(화학식 7)(Formula 7)
AgNO3AgNO3
또한 본 발명은 에탄올 100 중량부에 10 중량부의 메조기공 이산화티타늄을 넣어 용해시키는 단계; 에탄올 100 중량부에 하기의 화학식4, 화학식5, 화학식6 및 화학식7과 메조기공 이산화티타늄의 몰비 0.01 ~ 0.07 각각 넣어 기공내에 전이금속을 함침시키는 단계; 회전진공 농축기를 이용하여 에탄올을 제거한 후 400 ℃에서 소성시키는 단계에 의해 얻어지는 전이금속 도핑 메조기공 이산화티타늄의 제조방법을 제공한다.In another aspect, the present invention comprises the steps of dissolving 10 parts by weight of mesoporous titanium dioxide in 100 parts by weight of ethanol; Impregnating transition metals into the pores by adding molar ratios of the following Formulas 4, 5, 6 and 7 to Mesoporous titanium dioxide in 100 parts by weight of ethanol, respectively; Provided is a method for preparing a transition metal-doped mesoporous titanium dioxide obtained by removing ethanol using a rotary vacuum concentrator and calcining at 400 ° C.
(화학식 4)(Formula 4)
CrCl36H2OCrCl36H2O
(화학식 5)(Formula 5)
FeCl3FeCl3
(화학식 6)(Formula 6)
VCl4VCl4
(화학식 7)(Formula 7)
AgNO3AgNO3
이하 본 발명을 첨부되는 도면을 참조하여 보다 상세하게 설명하기로 한다. Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
본 발명은 화학식 1을 가지는 계면활성제를 40℃ 상태에서 물에 녹인 후 화학식 2 및 화학식 3을 가지는 물질을 1 : 1 몰비로 혼합하여 물 용매에 천천히 첨가시킴으로서 졸-겔법을 이용하여 메조기공 이산화티타늄을 제조하는 것에 주된 특징이 있다. The present invention dissolves a surfactant having Formula 1 in water at 40 ° C., and then slowly adds a substance having Formulas 2 and 3 in a 1: 1 molar ratio to a water solvent by slowly adding mesoporous titanium dioxide using a sol-gel method. There is a main feature to the preparation.
본 발명에서는 계면활성제와 티타늄 전구체의 상호작용을 원활하게 수행할 수 있도록 황산을 첨가하는데 황산으로부터의 수소이온(H+)은 티타늄 전구체의 가수분해와 축합반응에 대한 속도를 조절하는 역할을 하며 설포네이트기(SO42-)는 계면활성제와 티타늄 전구체가 상호작용으로 상호인력을 가능케 하여 메조기공 형태를 만드는데 결정적인 역할을 한다. 그 작용효과를 구체적으로 설명하면, 수소이온의 경우 티타늄 전구체가 물과 만나 가수분해 되고 중합반응이 일어나면서 6~10 nm 크기의 이산화티타늄을 형성하게 하는데 이러한 산의 농도에 따라 중합반응속도가 다르기 때문에 나노입자 이산화티타늄의 크기는 산의 농도에 따라 달라진다. In the present invention, sulfuric acid is added to facilitate the interaction between the surfactant and the titanium precursor, and hydrogen ions (H +) from the sulfuric acid serve to control the rate of hydrolysis and condensation reaction of the titanium precursor, and sulfonate. The group (SO42-) plays a decisive role in the formation of mesoporous morphologies by enabling the interaction between the surfactant and the titanium precursor. Specifically, in the case of hydrogen ions, the titanium precursor meets with water to hydrolyze and cause a polymerization reaction to form titanium dioxide having a size of 6 to 10 nm. Because of this, the size of the nanoparticle titanium dioxide depends on the concentration of the acid.
또한 이렇게 형성된 6~10 nm 크기의 이산화티타늄은 계면활성제와 상호작용을 이루어 메조기공 물질로 성장하게 되는데 이때 설포네이트기(SO42-)는 이러한 계면활성제와 나노입자 이산화티타늄과의 상호작용을 도와 나노입자가 서로 응집되는 형태로 열적으로 안정한 구형구조의 메조기공 이산화티타늄을 제조할 수 있게 한다. In addition, the formed 6-10 nm titanium dioxide interacts with the surfactant and grows into a mesoporous material. In this case, sulfonate groups (SO42-) help the interaction between the surfactant and the nanoparticle titanium dioxide. It is possible to produce thermally stable mesoporous titanium dioxide in the form of particles agglomerating with each other.
그러므로, 이러한 나노입자의 크기 조절 및 계면활성제와의 상호작용에 의한 최적화된 구형의 메조기공 이산화티타늄을 제조하기 위해서는 계면활성제의 농도조절, 계면활성제와 티타늄 전구체의 몰비 변화, 황산의 농도조절 및 계면활성제가 마이셀 구조를 이루기 위한 반응온도 조절 등 최적화된 조건을 설정하여야 한다. Therefore, in order to prepare optimized spherical mesoporous titanium dioxide by controlling the size of nanoparticles and interacting with the surfactant, the concentration of the surfactant, the change in the molar ratio of the surfactant and the titanium precursor, the concentration of sulfuric acid and the interface Optimized conditions, such as control of the reaction temperature for the activator to achieve the micelle structure, should be set.
계면활성제의 농도조절에서는 물 용매 100 중량부를 기준으로 3 ~ 5 중량부 영역에서만 고체상태의 물질이 얻어지며 3 중량부 이하에서는 낮은 수율의 물질이 얻어지는 반면 5 중량부 이상에서는 고체로 형성되지 않고 겔형태의 물질이 얻어지게 된다. 보다 구체적인 계면활성제의 농도는 4 중량부 이다. In the concentration control of the surfactant, a solid substance is obtained only in a region of 3 to 5 parts by weight based on 100 parts by weight of a water solvent, and a lower yield of a material is obtained at 3 parts by weight or less, whereas a gel is not formed as a solid at 5 parts by weight or more. A form of material is obtained. More specific surfactant concentration is 4 parts by weight.
계면활성제와 티타늄 전구체와의 몰 비 조절에서는 1 : 40과 1 : 80 영역에선 고체상태의 메조기공 물질을 얻을 수 있었으며 1 : 40에서는 낮은 수율의 물질을 얻을 수 있었고 제조시간도 길어지는 반면 1 : 80이상에서는 메조기공 형태의 물질이 얻어지지 않았다. 최적화된 계면활성제와 티타늄 전구체와의 몰 비는 1 : 60이다. 그리고 사용되는 티타늄 전구체는 티타늄 아이소프로폭사이드 와 2,4-펜 탄이온(2, 4-pentanedione)을 1 : 1 몰비로 혼합하였다.In the molar ratio control between the surfactant and the titanium precursor, solid mesoporous materials were obtained in the 1:40 and 1:80 regions, and low yields were obtained in the 1:40, while the production time was longer. Above 80 no mesoporous material was obtained. The molar ratio of the optimized surfactant to the titanium precursor is 1:60. The titanium precursor used was mixed with titanium isopropoxide and 2,4-pentanedione in a 1: 1 molar ratio.
황산의 농도조절에 있어서는 황산을 물 100 중량부에 대해 1 ～ 3 중량부 영역에서 수율이 높은 메조기공 이산화티타늄을 얻을 수 있었다. 1 중량부 이하에서는 메조기공 물질이 얻어지지 않았으며 3 중량부 이상에서는 고체물질이 아닌 겔 형태의 물질을 얻을 수 있었으며, 구형 모양의 메조기공 이산화티타늄을 제조하기 위한 최적조건은 1.5 중량부 이다. In the concentration control of sulfuric acid, mesoporous titanium dioxide having high yield was obtained in the range of 1-3 parts by weight based on 100 parts by weight of water. At 1 part by weight or less, no mesoporous material was obtained. At 3 parts by weight or more, a gel-like material was obtained. The optimum condition for producing spherical mesoporous titanium dioxide was 1.5 parts by weight.
또한, 본 방법에 있어서 반응온도 조절은 매우 중요한 의미를 가진다. 계면활성제로 사용된 Pluronic P123의 구조는 (PEO)20(PPO)70(PEO)20으로 이뤄져 있고 PEO의 경우 40 ℃ 이상에서 물 용매 하에서는 친수성을 가지게 되고 40 ℃이하에서는 소수성을 가지게 된다. 그러므로 40 ℃ 이상에서만 마이셀을 형성할 수 있고, 이러한 마이셀 형성 조건하에서 메조기공 이산화티타늄을 제조할 수 있다. 본 발명에서는 40℃에서 70 ℃영역의 반응온도에서 메조기공 이산화티타늄을 제조할 수 있으며, 최적화된 온도는 55 ℃이다.In addition, the reaction temperature control has a very important meaning in this method. The structure of Pluronic P123 used as a surfactant is composed of (PEO) 20 (PPO) 70 (PEO) 20, and PEO has hydrophilicity under water solvent at 40 ° C or higher and hydrophobicity at 40 ° C or lower. Therefore, micelles can be formed only at 40 ° C. or higher, and mesoporous titanium dioxide can be produced under such micelle formation conditions. In the present invention, it is possible to produce mesoporous titanium dioxide at a reaction temperature of 40 ℃ to 70 ℃ region, the optimized temperature is 55 ℃.
상기 제조한 메조기공 이산화티타늄을 알코올 중량부에 대해 10 중량부를 넣은 후 메조기공 이산화티타늄과 전이금속(염화크롬(Ⅲ)6수화물(CrCl36H2O), 염화철(Ⅲ) FeCl3, 사염화바나듐(VCl4), 질산은(AgNO3)) 중 어느 한가지의 몰비를 1 : 0.01 ～ 0.07로 하여 알코을 100 중량부에 첨가신 후 기공내에 전이금속을 함침시킨다. 보다 구체적인 메조기공 이산화티타늄과 전이금속의 몰비는 1 : 0.03 몰비 이다.10 parts by weight of the prepared mesoporous titanium dioxide is added to the alcohol part, and then the mesoporous titanium dioxide and the transition metal (chromium (III) chloride hydrate (CrCl36H2O), iron chloride (III) FeCl3, vanadium tetrachloride (VCl4) and silver nitrate) The molar ratio of (AgNO3)) is 1: 0.01 to 0.07, and alcohol is added to 100 parts by weight, and the transition metal is impregnated into the pores. More specific molar ratio of mesoporous titanium dioxide and transition metal is 1: 0.03 molar ratio.
상기한 바와 같이 본 발명의 특징 및 기타의 장점은 후술되는 실시예로부터 보다 명백하게 될 것이다. 단, 본 발명은 하기 실시예로 한정되는 것은 아니다. As mentioned above, features of the present invention and other advantages will become more apparent from the embodiments described below. However, the present invention is not limited to the following examples.
(( 실시예Example 1) One) 메조기공Mesoporous 이산화티타늄의 합성 Synthesis of Titanium Dioxide
뚜껑이 있는 1000 mL 플라스틱 병에, 계면활성제 4 중량부를 100 중량부의 물에 40 ℃ 조건하에서 6시간 이상 용해시킨다. 용해가 끝난 후 1.5 중량부의 황산을 첨가한다. 50 mL 비이커에 티타늄아이소프로폭사이드(Titaniumisopropoxide)와 2,4-펜탄이온(2, 4-pentanedione)을 1 : 1 몰비로 하여 혼합시킨 후, 계면활성제가 들어있는 용매에 넣고 교반기를 이용하여 천천히 교반시킨다. 이때 티타늄아이소프로폭사이드는 계면활성제에 대해 1 : 45 몰비로 하여 넣는다.In a 1000 mL plastic bottle with a lid, 4 parts by weight of the surfactant is dissolved in 100 parts by weight of water for at least 6 hours under 40 ° C. After dissolution, 1.5 parts by weight of sulfuric acid is added. Titanium isopropoxide and 2,4-pentanedione are mixed in a 50 mL beaker in a 1: 1 molar ratio, and then added to a solvent containing a surfactant and slowly stirred using a stirrer. Stir. At this time, titanium isopropoxide is added in a 1:45 molar ratio with respect to the surfactant.
첨가가 끝나면 플라스틱 병의 뚜껑을 닫고 55 ℃ 반응조건하에 교반을 하지 않은 상태에서 2시간을 놓아둔다. 고체가 형성되면 플라스틱 병을 90 ℃ 오븐에 옮긴 후 10시간 이상 방치한다. 반응이 끝난 후 실온에서 온도가 떨어질 때 까지 방치한 후 여과기를 이용하여 합성물을 거른 후 300 mL의 증류수로 충분히 세척한다. 얻어진 생성물을 80℃ 오븐에 넣고 2시간 이상 건조시킨다. 건조된 시료는 계면활성제를 제거하기 위하여 350℃ 또는 400℃에서 5시간 동안 소성 시킨다. After the addition, close the lid of the plastic bottle and leave it for 2 hours without stirring under the reaction condition of 55 ℃. Once the solid is formed, the plastic bottle is transferred to a 90 ° C. oven and left for at least 10 hours. After the reaction, the mixture was allowed to stand at room temperature until the temperature dropped, and the mixture was filtered using a filter and washed thoroughly with 300 mL of distilled water. The obtained product is put into an 80 degreeC oven and dried for 2 hours or more. The dried sample is baked at 350 ° C. or 400 ° C. for 5 hours to remove the surfactant.
(( 실시예Example 2) 전이금속이 2) transition metal 도핑된Doped 메조기공Mesoporous 이산화티타늄의 합성 Synthesis of Titanium Dioxide
상기 제조된 메조기공 이산화티타늄을 20 mL 의 에탄올 용매에 녹인 후 도핑시키고자 하는 전이금속의 양을 첨가한다. Cr의 경우 CrCl3?6H2O, Fe의 경우 FeCl3, V의 경우 VCl4, 은의 경우 AgNO3를 이용하여 메조기공 이산화티타늄과 전이금속들의 몰비를 1 : 0.03으로 하여 녹인 후, 전이금속 용액이 기공 속으로 충분히 함침시킬 수 있도록 교반한 후 회전진공 농축기를 이용하여 에탄올 용매를 완전히 제거한다. 전이금속의 결정화도를 증대시키기 위해서 400 ℃ 오분에서 5시간 동안 소성시킨다. After dissolving the prepared mesoporous titanium dioxide in 20 mL of ethanol solvent, the amount of the transition metal to be doped is added. CrCl3 ~ 6H2O for Cr, FeCl3 for V, VCl4 for V, and AgNO3 for silver to melt the molar ratio of mesoporous titanium dioxide and transition metals to 1: 0.03, and then the transition metal solution is sufficiently impregnated into the pores. After stirring, the ethanol solvent is completely removed using a rotary vacuum concentrator. In order to increase the crystallinity of the transition metal, it is calcined at 400 ° C. for 5 minutes for 5 hours.
메조기공Mesoporous 이산화티타늄의 구조분석 Structural Analysis of Titanium Dioxide
본 발명의 메조기공 이산화티타늄의 SEM을 이용하여 형성된 구조 형태를 분석하였고, TEM 사진을 통하여 메조기공을 확인하였으며, 비표면적과 기공분포를 측정하였고, 메조기공 이산화티타늄의 광분해 효율 및 전이금속 도핑 메조기공 이산화티타늄의 가시광 영역 흡수도를 확인하였다.The structure of the mesoporous titanium dioxide of the present invention was analyzed by SEM, the mesopores were identified through TEM photographs, the specific surface area and pore distribution were measured, the photolysis efficiency of the mesoporous titanium dioxide, and the transition metal doping mesos. The absorbance of visible light region of pore titanium dioxide was confirmed.
(시험예 1) 메조기공 이산화티타늄 의 SEM 측정Test Example 1 SEM Measurement of Mesoporous Titanium Dioxide
실시예 1을 대상으로 합성된 메조기공 이산화티타늄은 주사 전자 현미경(Scanning Electron Microscopy, SEM)으로 구조를 분석하였다. 주사 전자 현미경 분석을 위해서 0.03 g의 메조기공 이산화티타늄을 아세톤 20 g에 분산시키고 30분간 초음파 처리하여 분산용액을 제조하였다. 도 1a에서는 구형의 메조기공 이산화티타늄이 합성된 것을 보여주고 있으며, 도 1b는 구형의 메조기공 이산화티타늄 한개를 확대하여 얻어진 사진을 보여주고 있으며, 메조기공이 형성되어 있다는 것을 알 수 있다. Mesoporous titanium dioxide synthesized in Example 1 was analyzed by Scanning Electron Microscopy (SEM). For scanning electron microscopic analysis, 0.03 g of mesoporous titanium dioxide was dispersed in 20 g of acetone and sonicated for 30 minutes to prepare a dispersion solution. FIG. 1A shows that spherical mesoporous titanium dioxide is synthesized. FIG. 1B shows a photograph obtained by enlarging one spherical mesoporous titanium dioxide, and it can be seen that mesopores are formed.
(시험예 2) 메조기공 이산화티타늄 의 TEM 측정Test Example 2 TEM Measurement of Mesoporous Titanium Dioxide
실시예 1을 대상으로 합성된 메조기공 이산화티타늄의 기공크기 및 배열 구 조를 조사하기 위하여 전자 현미경으로 특성 분석하였다. 투과 전자 현미경 상은 Phillips CM20 apparatus (100 kV)를 이용하여 얻었다. 투과 전자 현미경 분석을 위해서 0.03 g의 메조기공 이산화티타늄을 아세톤 20 g에 분산시키고 30분간 초음파 처리하여 분산용액을 제조하였다. 탄소막 처리된 구리 그리드를 분석용액과 수초간 접촉시킨 후 실온에서 건조시켜 TEM(Transmission Electron Microcope, 투과전자현미경) 시편을 준비하였다. 도 2에서는 불규칙한 배열 구조의 메조기공이 형성되어 있다는 것을 보여주고 있다. In order to investigate the pore size and arrangement of the mesoporous titanium dioxide synthesized in Example 1, it was characterized by an electron microscope. Transmission electron microscopy images were obtained using a Phillips CM20 apparatus (100 kV). For transmission electron microscopic analysis, 0.03 g of mesoporous titanium dioxide was dispersed in 20 g of acetone and sonicated for 30 minutes to prepare a dispersion solution. The carbon film-treated copper grid was contacted with the analytical solution for several seconds and dried at room temperature to prepare a TEM (Transmission Electron Microcope) specimen. Figure 2 shows that the mesopores of irregular arrangement structure is formed.
(시험예 3) 메조기공 이산화티타늄의 비표면적 및 기공분포 측정(Test Example 3) Measurement of specific surface area and pore distribution of mesoporous titanium dioxide
실시예1을 대상으로 합성된 메조기공 이산화티타늄의 비표면적과 기공크기를 조사하기 위해서 표면적 및 기공분포를 측정하였다. 표면적 및 기공분포는 ASAP 2000 분석장비를 이용하여 분석하였으며, 0.05 g의 시료를 10-6 토르에서 10시간 동안 진공으로 한 후 분석하였다. 도 3a 는 온도별로 소성하였을 때의 메조기공 이산화티타늄의 비표면적과 도 3b는 이에 따른 기공크기의 변화를 보여주고 있다. In order to investigate the specific surface area and pore size of mesoporous titanium dioxide synthesized in Example 1, the surface area and pore distribution were measured. Surface area and pore distribution were analyzed using an ASAP 2000 analyzer, and 0.05 g of the sample was analyzed after 10 hours of vacuum at 10-6 Torr. Figure 3a shows the specific surface area of mesoporous titanium dioxide when firing by temperature and Figure 3b shows the change in pore size accordingly.
(시험예 4) 메조기공 이산화티타늄의 광분해 분석Test Example 4 Photolysis Analysis of Mesoporous Titanium Dioxide
실시예 1을 대상으로 합성된 메조기공 이산화티타늄의 광분해 효과를 분석하기 위하여 메틸렌블루 용액을 이용하여 측정하였다. 25 mL의 물에 25 mg의 메틸렌블루를 용해시킨 용액에 25 mg의 메조기공 이산화티타늄을 넣은 후 자외선 영역에서 메틸렌블루의 광분해 효율을 측정하였다. 일정기간에 일정량의 메틸렌블루용액 을 취하여 자외선-가시광선 분광광도계를 이용하여 흡광도를 측정하였다. 도 4는 자외선 노출시간에 따른 메틸렌블루용액의 흡광도 변화이다.In order to analyze the photodegradation effect of the mesoporous titanium dioxide synthesized in Example 1 was measured using a methylene blue solution. 25 mg of mesoporous titanium dioxide was added to a solution of 25 mg of methylene blue dissolved in 25 mL of water, and then the photolysis efficiency of methylene blue was measured in the ultraviolet region. A certain amount of methylene blue solution was taken over a period of time and absorbance was measured using an ultraviolet-visible spectrophotometer. 4 is a change in absorbance of the methylene blue solution according to the ultraviolet exposure time.
(시험예 5) 전이금속 도핑 메조기공 이산화티타늄의 가시광 광흡수 분석Test Example 5 Analysis of Visible Light Absorption of Transition Metal Doped Mesopores Titanium Dioxide
실시예 2을 대상으로 합성된 전이금속 도핑 메조기공 이산화티타늄의 가시광선 영역의 흡수도 실험을 측정하였다. 전이금속별로 도핑된 메조기공 이산화티타늄을 얇은 판에 밀착시킨 후 자외선-가시광선 분광광도계의 반사각을 이용하여 자외선 영역에서의 빛 흡수도를 측정하였다. 도 5는 자외선 영역에서의 메조기공 이산화티타늄과 전이금속별 몰비 1 : 0.03에서의 자외선 영역 흡수도이다.The absorbance experiment of visible light region of the transition metal-doped mesoporous titanium dioxide synthesized in Example 2 was measured. The mesoporous titanium dioxide doped with each transition metal was brought into close contact with a thin plate, and the light absorption in the ultraviolet region was measured using the reflection angle of the ultraviolet-visible spectrophotometer. FIG. 5 is an ultraviolet region absorption diagram at a molar ratio 1: 0.03 of mesoporous titanium dioxide and transition metal in the ultraviolet region.
상기한 바와 같이 본 발명은 높은 온도에서도 기공이 무너지지 않도록 메조기공 이산화티타늄을 제조하며. 이러한 메조기공 이산화티타늄은 비표면적이 매우 높아서 광촉매로서의 활용가치가 매우 높을 뿐만 아니라 기공 내에 전이금속을 도핑 시킨 후 고온으로 소성시킬 수 있어, 전이금속의 결정성을 높여주고 결과적으로 자외선 영역뿐만 아니라 가시광선 영역에서도 광활성을 가지는 물질을 제조하였으며, 이를 이용하여 악취물질 및 VOC(휘발성유기화합물) 등을 효과적으로 제거할 수 있는 촉매로 활용될 수 있는 효과가 있다. As described above, the present invention produces mesoporous titanium dioxide so that the pores do not collapse even at high temperatures. The mesoporous titanium dioxide has a very high specific surface area, which is very useful as a photocatalyst and can be sintered at high temperature after doping the transition metal in the pores, thereby increasing the crystallinity of the transition metal and consequently not only the visible region but also the visible region. A material having photoactivity was also prepared in the light ray region, and it can be used as a catalyst that can effectively remove odorous substances and VOCs (volatile organic compounds).
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