KR102236064B1 - Photocatalyst composite containing water-soluble conjugated polymer, manufacturing method thereof and photocatalytic reaction using the same - Google Patents
Photocatalyst composite containing water-soluble conjugated polymer, manufacturing method thereof and photocatalytic reaction using the same Download PDFInfo
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- KR102236064B1 KR102236064B1 KR1020190095272A KR20190095272A KR102236064B1 KR 102236064 B1 KR102236064 B1 KR 102236064B1 KR 1020190095272 A KR1020190095272 A KR 1020190095272A KR 20190095272 A KR20190095272 A KR 20190095272A KR 102236064 B1 KR102236064 B1 KR 102236064B1
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- Prior art keywords
- titanium dioxide
- comparative example
- formula
- dioxide nanoparticles
- conjugated polymer
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 title claims description 36
- 238000013032 photocatalytic reaction Methods 0.000 title description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 196
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 95
- 239000002105 nanoparticle Substances 0.000 claims abstract description 87
- 230000001699 photocatalysis Effects 0.000 claims abstract description 45
- 125000003277 amino group Chemical group 0.000 claims abstract description 44
- 239000000975 dye Substances 0.000 claims abstract description 36
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 23
- 125000000129 anionic group Chemical group 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 150000002894 organic compounds Chemical class 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 239000003642 reactive oxygen metabolite Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
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- 230000000052 comparative effect Effects 0.000 description 173
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- VHKQAUGSGQUCDU-UHFFFAOYSA-N (6'-methoxy-3-oxospiro[2-benzofuran-1,9'-xanthene]-3'-yl) 2-(pyridin-2-yldisulfanyl)benzoate Chemical compound C=1C(OC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=CC=3)C=1OC2=CC=3OC(=O)C1=CC=CC=C1SSC1=CC=CC=N1 VHKQAUGSGQUCDU-UHFFFAOYSA-N 0.000 description 13
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 5
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 5
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- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 4
- RQJDUEKERVZLLU-UHFFFAOYSA-N 4-Hydroxybenzylamine Chemical compound NCC1=CC=C(O)C=C1 RQJDUEKERVZLLU-UHFFFAOYSA-N 0.000 description 4
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- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 4
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- 238000010521 absorption reaction Methods 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
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- 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 description 4
- UOJCDDLTVQJPGH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(B2OC(C)(C)C(C)(C)O2)C=C1 UOJCDDLTVQJPGH-UHFFFAOYSA-N 0.000 description 3
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- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- B01J35/39—
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/002—Catalysts characterised by their physical properties
- B01J35/004—Photocatalysts
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J35/0006—Catalysts containing parts with different compositions
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/02—Solids
- B01J35/023—Catalysts characterised by dimensions, e.g. grain size
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- B01J35/19—
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- B01J35/40—
Abstract
본 발명의 광촉매 복합체는 이산화티타늄 나노입자 표면에 도입된 아민기와 정전기적 인력에 의해 음이온성 수용성 공액화 고분자가 결합됨으로써, 상기 이산화티타늄 나노입자와 수용성 공액화 고분자 사이의 전자 이동이 효율적으로 일어날 수 있다. 이에 따라 가시광 영역에서 향상된 광촉매 효율을 나타내며, 또한 그 제조 방법이 간단하며 환경친화적이다. 특히 상기 수용성 공액화 고분자가 이산화티타늄 나노입자의 표면으로부터 쉽게 탈리되지 않아 안정성과 젖음성이 향상되어 수중 분산성이 우수한 특징을 갖고, 염료의 분해반응 등 다양한 촉매반응에 적용이 가능한 특징을 갖는다. In the photocatalytic composite of the present invention, an anionic water-soluble conjugated polymer is bound by an amine group introduced on the surface of the titanium dioxide nanoparticles by electrostatic attraction, so that electron transfer between the titanium dioxide nanoparticles and the water-soluble conjugated polymer can occur efficiently. have. Accordingly, it shows improved photocatalytic efficiency in the visible light region, and the manufacturing method is simple and environmentally friendly. In particular, since the water-soluble conjugated polymer is not easily desorbed from the surface of the titanium dioxide nanoparticles, stability and wettability are improved, so that it has excellent dispersibility in water, and can be applied to various catalytic reactions such as decomposition reactions of dyes.
Description
본 발명은 가시광선 영역에서 높은 광촉매 활성을 갖는 새로운 광촉매 복합체에 관한 것으로써, 수용성 공액화 고분자가 이산화티타늄 나노입자에 도입된 광촉매 복합체와 그 제조방법 및 이를 이용한 광촉매 반응에 관한 것이다. The present invention relates to a new photocatalyst composite having high photocatalytic activity in the visible light region, and to a photocatalyst composite in which a water-soluble conjugated polymer is introduced into titanium dioxide nanoparticles, a method of manufacturing the same, and a photocatalytic reaction using the same.
최근 수질 오염과 같은 환경문제를 해결하고자 다양한 물질들이 개발되고 있다. 이러한 다양한 물질들 중 광촉매는 광을 이용하여 유기 물질과 같은 오염 물질을 분해할 수 있고, 부수적인 오염을 유발하지 않으며, 동력원인 광이 태양광으로서 그 사용이 제한되지 않는 장점이 있다. 이러한 광촉매는 이산화티타늄(TiO2), 이산화규소(SiO2), 산화아연(ZnO), 황화카드뮴(CdS)과 같은 반도체성 금속 산화물 혹은 황 화합물이 주로 이용된다. ··Recently, various materials have been developed to solve environmental problems such as water pollution. Among these various substances, the photocatalyst has the advantage that it can decompose pollutants such as organic substances by using light, does not cause incidental pollution, and the use of light as a power source as sunlight is not limited. As such a photocatalyst , semiconductor metal oxides or sulfur compounds such as titanium dioxide (TiO 2 ), silicon dioxide (SiO 2 ), zinc oxide (ZnO), and cadmium sulfide (CdS) are mainly used. ··
상기 광촉매 중 이산화티타늄(TiO2)은 반도체성 광촉매 물질이며 빛을 흡수하여 공유대(valence band: VB)로부터 전도대(Conduction band: CB)로 전자를 여기 시킨다. 이때 생성된 전하쌍이 계면으로 이동하여 전자 전이를 일으킴으로써 광촉매의 계면에서 활성산소종(Reactive Oxygen Species; ROS)을 생성하고, 이 활성산소종을 이용하여 다양한 종류의 유기물질의 분해 반응 및 산화환원 반응을 진행시킨다는 사실은 널리 알려져 있다. 또한 상기 활성산소종은 산소 원자를 포함한 화학적으로 반응성이 있는 분자로서 그 종류는 superoxide(O2 -), 과산화수소(H2O2), 하이드록시라디칼(·OH) 등이 있다. 또한 이산화티타늄은 광촉매 반응에 있어서 다른 반도체 광촉매에 비해 높은 활성을 보이는 것으로 알려져 있다. 하지만 기존의 광촉매 물질들과 유사하게 태양광의 대부분을 차지하는 가시광선 영역을 흡수하지 못해 가시광선 영역에선 광촉매 활성을 나타내지 못하는 단점이 있다. 이러한 단점을 극복하기 위해 이산화티타늄 표면에 가시광선에 감응할 수 있는 유무기 감광분자(sensitizer molecule)를 도입하여 감광분자가 가시광을 흡수하여 발생된 전자를 이산화티타늄으로 전자를 전달하게 하는 방법에 대한 연구가 활발히 이루어지고 있다. 상기 감광분자로서 수용성 공액화 고분자가 주로 이용되고 있으며, 상기 수용성 공액화 고분자는 구조적으로 p-오비탈이 중첩되며 포화결합과 불포화결합이 교대로 존재하고 있어 도핑 시 전기전도성이 발생되어 반도체적 특성을 나타내는 특징을 갖는다. 또한 유기물이 갖는 구조적 다양성과 질소, 산소, 탄소, 황 원자 등 그 원료가 풍부하고 합성하고자 하는 공액화 고분자의 구조 설계로부터 에너지 밴드갭과 전기적인 특성을 조절할 수 있는 장점이 있다. 이러한 반도체적 특성을 응용하여 유기 발광 소자, 광 기록재료, 유기 박막 트랜지스터, 유기 태양전지와 같은 전자 재료분야나, pH, 온도, 빛, 이온과 같은 외부환경의 자극에 의해 산화-환원 전위차 또는 흡수-방출 스펙트럼의 변화로 감지할 수 있는 화학-바이오 센서재료 분야 등 그 적용 분야는 매우 넓고 다양하다. 따라서, 본 발명에서는 수용성 공액화 고분자를 도입함으로써 광촉매의 성능을 향상시키고 가시광선에서 반응할 수 있는 새로운 광촉매 물질에 대한 제조 방법을 제시하고, 이를 이용한 광촉매 반응 방법을 제시하고자 한다.Among the photocatalysts, titanium dioxide (TiO 2 ) is a semiconducting photocatalyst material and absorbs light to excite electrons from a valence band (VB) to a conduction band (CB). At this time, the generated charge pair moves to the interface and causes electron transfer to generate reactive oxygen species (ROS) at the interface of the photocatalyst, and decomposition reactions and redox reactions of various types of organic substances using this reactive oxygen species. It is widely known that the reaction proceeds. In addition, the active oxygen species is chemically containing oxygen atom as with a reactive molecule that kind are superoxide (O 2 -) and the like, hydrogen peroxide (H 2 O 2), hydroxyl radicals (· OH). In addition, titanium dioxide is known to exhibit higher activity than other semiconductor photocatalysts in photocatalytic reactions. However, similar to conventional photocatalytic materials, there is a disadvantage in that it cannot absorb the visible light region, which occupies most of the sunlight, and thus does not exhibit photocatalytic activity in the visible light region. In order to overcome these shortcomings, a method of introducing an organic/inorganic sensitizer molecule capable of sensitizing visible light on the surface of titanium dioxide so that the photosensitive molecule absorbs visible light and transfers electrons to titanium dioxide. Research is being actively conducted. As the photosensitive molecule, a water-soluble conjugated polymer is mainly used, and the water-soluble conjugated polymer structurally overlaps p-orbitals and alternately contains saturated bonds and unsaturated bonds. It has the characteristic that it represents. In addition, it has the advantage of being able to control the energy band gap and electrical properties from the structural diversity of organic substances and the structural design of the conjugated polymer to be synthesized and rich in raw materials such as nitrogen, oxygen, carbon, and sulfur atoms. By applying these semiconductor properties, the oxidation-reduction potential difference or absorption by stimulation of external environments such as pH, temperature, light, and ions, or in the field of electronic materials such as organic light-emitting devices, optical recording materials, organic thin film transistors, and organic solar cells. -The field of application, such as the field of chemical-bio sensor materials that can be detected by changes in the emission spectrum, is very wide and diverse. Therefore, in the present invention, by introducing a water-soluble conjugated polymer, a method for preparing a new photocatalytic material capable of improving the performance of a photocatalyst and reacting in visible light is proposed, and a photocatalytic reaction method using the same.
본 발명은 자외선의 조사시 광촉매 역할을 하는 이산화티타늄의 특성을 개선하기 위한 것으로써, 감광물질로 수용성 공액화 고분자를 도입하여 가시광 영역에서도 광촉매 역할을 하는 광촉매 복합체를 제조하고자 한다. 따라서 이산화티타늄 나노입자에 수용성 공액화 고분자를 정전기적 인력으로 도입하여 보다 쉽고 환경친화적으로 광촉매 복합체를 제조하며, 상기 수용성 공액화 고분자가 이산화티타늄 나노입자로부터 쉽게 탈리 되지 않아 안정하게 사용할 수 있는 광촉매 복합체를 제공하기 위한 것이다. 특히, 가시광 조사 하에서 상기 수용성 공액화 고분자에 의해 생성된 전자가 이산화티타늄으로 이동함으로써 생성된 활성산소종에 의해 유기염료를 분해하거나, 유기 화합물을 산화 또는 환원시킬 수 있는 있는 광촉매 복합체를 제공하는 것을 목적으로 한다.The present invention is to improve the properties of titanium dioxide that acts as a photocatalyst when irradiated with ultraviolet rays, and an object of the present invention is to prepare a photocatalyst composite that acts as a photocatalyst even in the visible light region by introducing a water-soluble conjugated polymer as a photosensitive material. Therefore, a water-soluble conjugated polymer is introduced into the titanium dioxide nanoparticles by electrostatic attraction to make a photocatalytic complex more easily and environmentally friendly, and the water-soluble conjugated polymer is not easily desorbed from the titanium dioxide nanoparticles, so that the photocatalyst composite can be used stably. It is to provide. In particular, to provide a photocatalytic complex capable of decomposing organic dyes or oxidizing or reducing organic compounds by active oxygen species generated by moving electrons generated by the water-soluble conjugated polymer to titanium dioxide under visible light irradiation. The purpose.
상기한 목적을 달성하기 위한 본 발명의 수용성 공액화 고분자가 도입된 광촉매 복합체는, 자외선 및 가사광선 영역에서 활성을 갖는 광촉매 복합체로서, 이산화티타늄 나노입자; 상기 이산화티타늄 나노입자의 표면에 도입되는 아민기; 및 상기 아민기와 정전기적 인력에 의해 결합되는 음이온성 수용성 공액화 고분자;를 포함하는 것이 바람직하며, 상기 수용성 공액화 고분자는 하기 화학식 1 내지 화학식 3 중 어느 하나 인 것이 바람직하다. The photocatalyst composite into which the water-soluble conjugated polymer of the present invention is introduced to achieve the above object is a photocatalyst composite having activity in ultraviolet and pseudo-ray regions, including titanium dioxide nanoparticles; An amine group introduced into the surface of the titanium dioxide nanoparticles; And an anionic water-soluble conjugated polymer bonded to the amine group by electrostatic attraction, and the water-soluble conjugated polymer is preferably any one of the following Formulas 1 to 3.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
또한, 상기 아민기는 1차 아민이며, 상기 이산화티타늄 나노입자의 결정상은 아나타아제(anatase)형이며, 그 직경은 10 ~ 1,000 nm인 것이 바람직하다. In addition, the amine group is a primary amine, the crystal phase of the titanium dioxide nanoparticles is an anatase (anatase) type, the diameter is preferably 10 ~ 1,000 nm.
또한, 본 발명의 수용성 공액화 고분자가 도입된 광촉매 복합체의 제조방법은, 음이온성인 수용성 공액화 고분자를 제조하는 제 1 단계; 아나타아제(anatase)형의 결정상을 지닌 입자 직경 10 ~ 1,000 nm인 이산화티타늄 나노입자를 제조하는 제 2 단계; 상기 제 2 단계에서 제조된 이산화티타늄 나노입자의 표면에 아민기를 도입하는 제 3 단계; 및 상기 제 3 단계에서 아민기가 도입된 이산화티타늄 나노입자의 표면에 음이온성 수용성 공액화 고분자를 정전기적 인력으로 도입하는 제 4 단계;를 포함하는 것이 바람직하다. In addition, the method for preparing a photocatalytic composite into which the water-soluble conjugated polymer of the present invention is introduced comprises: a first step of preparing an anionic water-soluble conjugated polymer; A second step of preparing titanium dioxide nanoparticles having a particle diameter of 10 to 1,000 nm having an anatase-type crystal phase; A third step of introducing an amine group to the surface of the titanium dioxide nanoparticles prepared in the second step; And a fourth step of introducing an anionic water-soluble conjugated polymer to the surface of the titanium dioxide nanoparticles into which the amine group is introduced in the third step by electrostatic attraction.
그리고, 본 발명의 수용성 공액화 고분자가 도입된 광촉매 복합체를 이용한 광촉매 반응은, 유기 염료의 분해 반응, 유기 화합물의 산화 반응 및 유기 화합물의 환원 반응 중 어느 하나이며, 상기 유기 염료의 분해 반응은 로다민 B(Rhodamine B), 메틸렌 블루(methylene blue), 메틸 오렌지(methyl orange) 중 어느 하나를 대상으로 하며, 상기 유기 화합물의 산화 반응은 benzylamine, 4-fluorobenzylamine, 4-chlorobenzylamine, 4-bromobenzylamine, 4-hydroxybenzylamine, 4-methoxybenzylamine, 4-(Trifluoromethyl)benzylamine, benzaldehyde, 4-nitrobenzaldehyde, 4-fluorobenzaldehyde, 4-bromobenzaldehyde, 4-chlorobenzaldehyde, 4-methoxybenzaldehyde, 4-(diethylamino)benzaldehyde, 4-(dimethylamino)benzaldehyde, 2,5-bis(octyloxy)benzene-1,4-dialdehyde, 5-(hydroxymethyl)furan-2-carbaldehyde 4-triphenylaminebenzaldehyde, 2-furoic acid 중 어느 하나를 대상으로 하며, 상기 유기화합물의 환원 반응은 4-nitrophenol, 4-nitrobenzaldehyde 중 어느 하나를 대상으로 하는 것이 바람직하다. In addition, the photocatalytic reaction using the photocatalytic complex into which the water-soluble conjugated polymer of the present invention is introduced is one of a decomposition reaction of an organic dye, an oxidation reaction of an organic compound, and a reduction reaction of an organic compound, and the decomposition reaction of the organic dye is Rhoda. It targets any one of Rhodamine B, methylene blue, and methyl orange, and the oxidation reaction of the organic compound is benzylamine, 4-fluorobenzylamine, 4-chlorobenzylamine, 4-bromobenzylamine, 4 -hydroxybenzylamine, 4-methoxybenzylamine, 4-(Trifluoromethyl)benzylamine, benzaldehyde, 4-nitrobenzaldehyde, 4-fluorobenzaldehyde, 4-bromobenzaldehyde, 4-chlorobenzaldehyde, 4-methoxybenzaldehyde, 4-(diethylamino)benzaldehyde, 4-(dimethylamino)benzaldehyde, 2,5-bis(octyloxy)benzene-1,4-dialdehyde, 5-(hydroxymethyl)furan-2-carbaldehyde, 4-triphenylaminebenzaldehyde, 2-furoic acid, and the reduction reaction of the organic compound is 4 It is preferable to target any one of -nitrophenol and 4-nitrobenzaldehyde.
본 발명에 따른 이산화티타늄 나노입자 표면에 수용성 공액화 고분자가 정전기적 인력으로 도입된 광촉매 복합체는 상기 이산화티타늄 나노입자와 수용성 공액화 고분자 사이의 전자 이동이 효율적으로 일어날 수 있어, 가시광 영역에서 향상된 광촉매 효율을 나타낸다. 또한 본 발명의 광촉매 복합체는 소수성 공액화 고분자가 아닌 수용성 공액화 고분자를 도입함으로써 유기 용매가 아닌 물에서 수용성 공액화 고분자를 이산화티타늄과 같은 지지체에 도입시킬 수 있어 그 제조 방법이 간단하며 환경친화적이다. 그리고 이산화티타늄 나노입자와 수용성 공액화 고분자는 정전기적 인력으로 결합되어 사용중 쉽게 탈리 되지 않아 안정하게 유지될 수 있을 뿐 아니라, 촉매의 젖음성이 향상되어 수중 분산성이 우수하고, 물을 기반으로 하는 염료 분해 및 유기 화합물의 산화 또는 환원 반응시 유용하게 적용할 수 있는 효과를 갖는다. The photocatalytic composite in which the water-soluble conjugated polymer is introduced by electrostatic attraction on the surface of the titanium dioxide nanoparticles according to the present invention can efficiently transfer electrons between the titanium dioxide nanoparticles and the water-soluble conjugated polymer, thereby improving the photocatalyst in the visible light region. Indicates efficiency. In addition, the photocatalyst composite of the present invention can introduce a water-soluble conjugated polymer into a support such as titanium dioxide in water other than an organic solvent by introducing a water-soluble conjugated polymer rather than a hydrophobic conjugated polymer, so its manufacturing method is simple and environmentally friendly. . In addition, the titanium dioxide nanoparticles and the water-soluble conjugated polymer are combined by electrostatic attraction, so that they are not easily desorbed during use, so they can be stably maintained, and the wettability of the catalyst is improved, so that the dispersibility in water is excellent, and the water-based dye It has an effect that can be usefully applied during decomposition and oxidation or reduction reactions of organic compounds.
도 1은 본 발명에 따른 수용성 공액화 고분자가 도입된 광촉매 복합체의 제조방법에 대한 흐름도이다.1 is a flow chart of a method of manufacturing a photocatalyst composite into which a water-soluble conjugated polymer is introduced according to the present invention.
이하, 첨부된 도면들을 참조하여 본 발명의 실시예를 상세히 설명하면 다음과 같다. 그러나 본 발명은 이하에서 개시되는 실시예에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 수 있는 것으로, 이하의 실시예는 본 발명의 개시가 완전하도록 하며, 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이다. 또한 설명의 편의를 위하여 도면에서는 구성 요소들이 그 크기가 과장 또는 축소될 수 있다. 도면들에 있어서, 예를 들면, 제조 기술 및/또는 공차(tolerance)에 따라, 도시된 형상의 변형들이 예상될 수 있다. 따라서, 본 발명은 본 명세서에 도시된 영역의 특정 형상에 제한된 것으로 해석되어서는 아니 되며, 예를 들면 제조상 초래되는 형상의 변화를 포함하여야 한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and the following embodiments make the disclosure of the present invention complete, and the scope of the invention to those of ordinary skill in the art. It is provided to fully inform you. In addition, in the drawings for convenience of description, the size of the components may be exaggerated or reduced. In the drawings, for example, depending on manufacturing techniques and/or tolerances, variations of the illustrated shape can be expected. Accordingly, the present invention should not be construed as being limited to a specific shape of the region shown in the present specification, but should include, for example, a change in shape resulting from manufacturing.
이하에서 본 발명의 수용성 공액화 고분자가 도입된 광촉매 복합체와 그 제조방법 및 이를 이용한 광촉매 반응에 대하여 상세히 설명한다.Hereinafter, a photocatalyst composite into which the water-soluble conjugated polymer of the present invention is introduced, a method of manufacturing the same, and a photocatalytic reaction using the same will be described in detail.
본 발명은 하기 화학식 1 내지 3으로 표시되는 수용성 공액화 고분자가 이산화티타늄 나노입자에 정전기적 인력으로 도입된 광촉매 복합체와 그 제조방법 및 이를 이용한 광촉매 반응을 제공한다. 여기서, 상기 나노입자는 이산화티타늄 나노입자에 한정되지 않고 이산화규소(SiO2), 산화아연(ZnO), 황화카드뮴(CdS) 등이 가능하며, 상기와 같은 나노입자에 아민기를 도입한 후, 수용성 공액화 고분자를 도입함으로써 본 발명의 광촉매 복합체의 제조가 가능하다. The present invention provides a photocatalytic composite in which a water-soluble conjugated polymer represented by the following Chemical Formulas 1 to 3 is introduced into titanium dioxide nanoparticles by electrostatic attraction, a method of manufacturing the same, and a photocatalytic reaction using the same. Here, the nanoparticles are not limited to titanium dioxide nanoparticles, and may include silicon dioxide (SiO 2 ), zinc oxide (ZnO), cadmium sulfide (CdS), and the like. After introducing an amine group into the nanoparticles, water-soluble By introducing the conjugated polymer, it is possible to prepare the photocatalytic composite of the present invention.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식 1 내지 3에서 R1, R2은 서로 상이하거나 동일한 CnH2n-SO3 -M+이며, 상기 n은 1 내지 20의 정수이다. 또한, 상기 M은 양이온성 금속이며, X는 화학식 1 혹은 화학식 3의 분자량을 12,400 이상을 갖게 하는 정수인 것이 바람직하다. 그리고, Y와 Z의 값은 화학식 2의 각 반복 단위의 조성을 몰분율로 나타낸 것으로서, Y는 0 내지 0.99의 실수이고, Z는 1-Y인 것이 바람직하다. ,In the above Chemical Formulas 1 to 3 R 1, R 2 are different from each other or identical C n H 2n -SO 3 - and M +, wherein n is an integer from 1 to 20. In addition, M is a cationic metal, and X is preferably an integer having a molecular weight of 12,400 or more in Formula 1 or Formula 3. In addition, the values of Y and Z represent the composition of each repeating unit of Formula 2 by mole fraction, where Y is a real number of 0 to 0.99, and Z is preferably 1-Y. ,
또한 상기 화학식 1 내지 3에서 Ar은, 
본 발명에 따른 상기 화학식 1 내지 3의 수용성 공액화 고분자의 분자량은 원칙적으로 제한이 없으나, 정제 과정에서 molecular weight cut off 12,400 셀룰로오스 투석 튜브를 사용하여 정제함으로써, 분자량이 12,400 이상인 수용성 공액화 고분자를 사용하는 것이 특히 바람직하다.The molecular weight of the water-soluble conjugated polymers of Formulas 1 to 3 according to the present invention is not limited in principle, but in the purification process, a water-soluble conjugated polymer having a molecular weight of 12,400 or more is used by purifying using a 12,400 cellulose dialysis tube. It is particularly preferred to do.
또한, 본 발명의 수용성 공액화 고분자가 도입된 광촉매 복합체의 제조방법은 도 1에 도시된 바와 같이, 상기 화학식 1 내지 3로 표시되는 수용성 공액화 고분자를 제조하는 제 1 단계(S100); 이산화티타늄 나노입자를 제조하는 제 2 단계(S200); 이산화티타늄 나노입자 표면에 아민기를 도입하는 제 3 단계(S300); 및 상기 아민기가 도입된 이산화티타늄 나노입자 표면에 상기 수용성 공액화 고분자를 정전기적 인력으로 도입시키는 제 4 단계(S400);를 포함하는 것을 특징으로 한다.In addition, the method of manufacturing a photocatalytic composite into which the water-soluble conjugated polymer of the present invention is introduced includes a first step (S100) of preparing a water-soluble conjugated polymer represented by Chemical Formulas 1 to 3, as shown in FIG. 1; A second step of preparing titanium dioxide nanoparticles (S200); A third step (S300) of introducing an amine group to the surface of the titanium dioxide nanoparticles; And a fourth step (S400) of introducing the water-soluble conjugated polymer to the surface of the titanium dioxide nanoparticles into which the amine group is introduced by electrostatic attraction.
구체적인 상기 광촉매 복합체 제조방법은 다음과 같다.A specific method of manufacturing the photocatalyst composite is as follows.
상기 화학식 1 내지 3으로 표시되는 수용성 공액화 고분자는 본 발명의 제 1 단계(S100)에서 측쇄가 상기 CnH2n-SO3 -M+으로 이루어진 페닐렌(phenylene) 및 플루오렌(fluorine) 화합물과 페닐렌(phenylene), 벤조싸이아다이아졸(benzothiadiazole) 및 비스싸이에닐벤조싸이아다이아졸(bis-thienyl-benzothiadiazole)로 이루어진 화합물과의 스즈키 커플링 반응(Suzuki coupling reaction)에 의하여 일반적으로 제조할 수 있으나, 이에 한정되는 것은 아니다.Aqueous ball liquefied polymer represented by Formula 1 to 3, wherein the side chain is C n H 2n -SO 3 in the first step 1 (S100) of the present invention-phenylenediamine (phenylene) consisting of M + and fluorene (fluorine) compounds And phenylene, benzothiadiazole, and bis-thienyl-benzothiadiazole. It can be manufactured, but is not limited thereto.
위에서 살핀 바와 같이,. 따라서 수용성 공액화 고분자가 이산화티타늄 나노입자에 도입하는 제 4 단계(S400)는 증류수에서 진행되므로, 증류수 중에서 상기 CnH2n-SO3 -M+ 에서 -SO3 -M+ 는 해리되어 -SO3 -이 되므로 상기 수용성 공액화 고분자는 음이온성을 띄게 된다. As we saw above,. Therefore, the water-soluble polymer is a ball liquefied fourth step of introducing the titanium dioxide nanoparticles (S400) is so held in distilled water, distilled from the C n H 2n -SO 3 - M + in -SO 3 - M + is dissociated Since -SO 3 - , the water-soluble conjugated polymer has anionic properties.
또한, 본 발명의 제 2 단계(S200)에서는 에탄올과 NaCl 수용액 및 이산화티타늄 전구체인 티타늄 아이소프로폭사이드를 이용하여 이산화티타늄 나노입자를 제조한다.In addition, in the second step (S200) of the present invention, titanium dioxide nanoparticles are prepared by using ethanol and an aqueous solution of NaCl and titanium isopropoxide, which is a titanium dioxide precursor.
이후, 제 3 단계(S300)에서 상기 제 2 단계(S200)에서 제조된 이산화티타늄 나노입자에 3-아미노프로필트리에톡시실레인을 톨루엔에서 처리함으로써 이산화티타늄 나노입자 표면에 아민기를 도입하게 된다. 이때 아민기는 1차 아민인 것이 특히 바람직하다.Thereafter, in the third step (S300), the titanium dioxide nanoparticles prepared in the second step (S200) are treated with 3-aminopropyltriethoxysilane in toluene to introduce an amine group to the surface of the titanium dioxide nanoparticles. In this case, the amine group is particularly preferably a primary amine.
상기와 같이 아민기가 도입된 이산화티타늄 나노입자를 제 4 단계(S400)에서 물에 분산하면 상기 아민기의 아민이 양성자화(protonation) 되면서 +전하를 띠게 되고, 위에서 살핀 바와 같이 투입된 수용성 공액화 고분자는 증류수 중에서 음이온성을 띄게 됨으로써, 상기 수용성 공액화 고분자는 정전기적 인력으로 아민기가 도입된 이산화티타늄 나노입자에 도입된다. When the titanium dioxide nanoparticles into which the amine group is introduced as described above are dispersed in water in the fourth step (S400), the amine of the amine group is protonated and has a positive charge, and the water-soluble conjugated polymer introduced as above By becoming anionic in distilled water, the water-soluble conjugated polymer is introduced into the titanium dioxide nanoparticles into which the amine group is introduced by electrostatic attraction.
상기와 같이 제조된 본 발명의 광촉매 복합체는 도입된 상기 화학식 1 내지 3 중 어느 하나의 수용성 공액화 고분자에 의해 가시광선 영역대에서 향상된 광촉매 활성을 갖게 된다. 구체적으로, 상기 광촉매 복합체를 물에 분산시킨 후 유기염료 분해 및 유기화합물의 산화환원 반응시 촉매로 사용할 경우 가시광역역에서 높은 촉매 효율을 나타내게 된다. The photocatalytic composite of the present invention prepared as described above has improved photocatalytic activity in the visible region by the introduced water-soluble conjugated polymer of any one of Formulas 1 to 3 above. Specifically, when the photocatalyst complex is dispersed in water and used as a catalyst for decomposition of organic dyes and redox reactions of organic compounds, high catalytic efficiency is exhibited in the visible region.
또한, 상기 광조사는 LED 램프, Xenon 램프, 솔라 시뮬레이터(solar simulator) 등 300~700nm의 파장을 갖는 광원 어느 것이면 가능하고, 특히, 복사에너지가 22 W/m2이며, 파장(λ)이 450 nm 이상인 가시광선을 조사할 수 있는 LED 램프를 사용하는 것이 바람직하나, 이에 한정되지 않는다.In addition, the light irradiation may be any light source having a wavelength of 300 to 700 nm, such as an LED lamp, a Xenon lamp, a solar simulator, etc., in particular, the radiant energy is 22 W/m 2 and the wavelength (λ) is 450 Although it is preferable to use an LED lamp capable of irradiating a visible ray of nm or more, it is not limited thereto.
이때 상기와 같이 제조된 본 발명의 광촉매 복합체는 유기 염료의 분해, 유기화합물의 산화 및 환원반응에 적용될 수 있다. 즉, 본 발명의 광촉매 복합체는 폐수 중에 포함된 염료의 분해가 가능하며, 또한 산화 또는 환원 반응을 통해 유기화합물의 합성반응 등에 적용이 가능하다.At this time, the photocatalytic composite of the present invention prepared as described above can be applied to decomposition of organic dyes and oxidation and reduction reactions of organic compounds. That is, the photocatalytic composite of the present invention can decompose dyes contained in wastewater, and can be applied to synthesis reactions of organic compounds through oxidation or reduction reactions.
본 발명의 광촉매 복합체를 이용하여 상기 분해가능한 유기 염료는 로다민 B, 메틸렌블루, 메틸오렌지이며, 상기 유기 화합물의 산화 반응은 benzylamine, 4-fluorobenzylamine, 4-chlorobenzylamine, 4-bromobenzylamine, 4-hydroxybenzylamine, 4-methoxybenzylamine, 4-(Trifluoromethyl)benzylamine, benzaldehyde, 4-nitrobenzaldehyde, 4-fluorobenzaldehyde, 4-bromobenzaldehyde, 4-chlorobenzaldehyde, 4-methoxybenzaldehyde, 4-(diethylamino)benzaldehyde, 4-(dimethylamino)benzaldehyde, 2,5-bis(octyloxy)benzene-1,4-dialdehyde, 5-(hydroxymethyl)furan-2-carbaldehyde 4-triphenylaminebenzaldehyde, 2-furoic acid 중 어느 하나를 대상으로 하며, 상기 유기화합물의 환원 반응은 4-nitrophenol, 4-nitrobenzaldehyde 중 어느 하나를 대상으로 하는 것이 바람직하다The decomposable organic dyes using the photocatalytic complex of the present invention are rhodamine B, methylene blue, and methyl orange, and the oxidation reaction of the organic compound is benzylamine, 4-fluorobenzylamine, 4-chlorobenzylamine, 4-bromobenzylamine, 4-hydroxybenzylamine, 4-methoxybenzylamine, 4-(Trifluoromethyl)benzylamine, benzaldehyde, 4-nitrobenzaldehyde, 4-fluorobenzaldehyde, 4-bromobenzaldehyde, 4-chlorobenzaldehyde, 4-methoxybenzaldehyde, 4-(diethylamino)benzaldehyde, 4-(dimethylamino)benzaldehyde, 2,5 -bis(octyloxy)benzene-1,4-dialdehyde, 5-(hydroxymethyl)furan-2-carbaldehyde 4-triphenylaminebenzaldehyde, 2-furoic acid, and the reduction reaction of the organic compound is 4-nitrophenol, It is preferable to target any one of 4-nitrobenzaldehyde
본 발명의 광촉매 복합체를 이용한 광촉매 반응 방법은 다음과 같다. 제조된 광촉매 복합체를 유기 염료 수용액 또는 산화/환원반응을 위한 반응용액이 담긴 20ml의 바이알에 분산시킨 뒤, 교반하면서 가시광선(22 W/m2, λ>450 nm)을 조사할 수 있는 LED 램프에 의해 광조사한다. 여기서, 상기 LED 램프와 바이알의 거리는 5cm~10cm의 범위에서 실시하며, 시간 별로 반응 용액을 추출해내어 UV/Vis 흡수스펙트럼 또는 핵자기공명분광(Nuclear magnetic resonance; NMR) 스펙트럼으로 염료의 분해 또는 산화/환원반응의 생성물을 확인한다. 또한 반응 중간 과정을 박막층크로마토그래피(Thin layer chromatography; TLC)를 통해서 반응의 진행을 확인하는 것도 가능하다. The photocatalytic reaction method using the photocatalytic composite of the present invention is as follows. LED lamp capable of irradiating visible light (22 W/m 2 , λ>450 nm) while stirring the prepared photocatalytic complex in a 20 ml vial containing an organic dye aqueous solution or a reaction solution for oxidation/reduction reaction Light irradiation by Here, the distance between the LED lamp and the vial is in the range of 5 cm to 10 cm, and the reaction solution is extracted over time and the dye is decomposed or oxidized in a UV/Vis absorption spectrum or a nuclear magnetic resonance (NMR) spectrum. Identify the product of the reduction reaction. In addition, it is possible to check the progress of the reaction through thin layer chromatography (TLC) in the intermediate reaction process.
본 발명의 광촉매 복합체에 도입된 수용성 공액화 고분자에 의한 광촉매 매커니즘은 다음과 같다. 300~700nm의 파장을 갖는 광원에 의해 수용성 공액화 고분자의 공유대에 존재하는 전자가 전도대로 여기(excitation)되고, 이 과정에서 발생한 정공과 전자에 의해 주변에 존재하는 삼중항 산소를 활성산소종으로 전환시킨다. 전환된 상기 활성산소종은 강력한 산화제로 작용하기 때문에 로다민 B, 메틸렌블루, 메틸오렌지와 같은 염료를 분해할 수 있을 뿐만 아니라, 벤즈알데하이드(benzaldehyde)의 산화 반응에 의한 벤조산(bezoic acid)으로의 전환, 벤질아민(benzyl amine)의 산화성 커플링반응에 의한 N-벤질-1-페닐메탄디아민(N-benzyl-1-phenyl methane) 유도체의 생성, 수소화붕소나트륨 존재 하에 4-나이트로페놀(4-nitro phenol) 유도체를 4-아미노페놀(4-amino phenol)로 전환할 수 있다.The photocatalytic mechanism by the water-soluble conjugated polymer introduced into the photocatalytic composite of the present invention is as follows. Electrons present in the shared band of the water-soluble conjugated polymer are excited by the conduction band by a light source having a wavelength of 300 to 700 nm, and the triplet oxygen present in the surroundings is converted into active oxygen species by holes and electrons generated in this process. Convert it to Since the converted reactive oxygen species act as a strong oxidizing agent, it can not only decompose dyes such as rhodamine B, methylene blue, and methyl orange, but also to benzoic acid by oxidation of benzaldehyde. Conversion, production of N-benzyl-1-phenyl methane derivatives by oxidative coupling reaction of benzyl amine, 4-nitrophenol (4) in the presence of sodium borohydride -nitro phenol) derivatives can be converted to 4-amino phenol.
이하, 본 발명을 실시예로써 상세하게 설명하기로 한다. 그러나 이들 실시예는 본 발명을 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of examples. However, these examples are intended to specifically illustrate the present invention, and the scope of the present invention is not limited to these examples.
본 발명의 음이온성 수용성 공액화 고분자가 도입된 광촉매 복합체의 제조방법은 도 1에 도시된 바와 같이, 먼저 수용성 공액화 고분자를 제조하는 제 1 단계(S100)와, 이산화티타늄 나노입자를 제조하는 제 2 단계(S200)와, 상기 제 2 단계에서 제조된 이산화티탄 나노입자에 아민기를 도입하는 제 3 단계(S300) 및 상기 제 3 단계에서 이산화티타늄 나노입자에 도입된 아민기에 수용성 공액화 고분자를 정전기적 인력에 의해 도입하는 제 4 단계(S500)를 포함하는 것이 바람직하다. As shown in FIG. 1, the method of manufacturing a photocatalyst composite into which the anionic water-soluble conjugated polymer of the present invention is introduced includes a first step (S100) of preparing a water-soluble conjugated polymer, and a first step of preparing a titanium dioxide nanoparticle. Step 2 (S200) and the third step (S300) of introducing an amine group into the titanium dioxide nanoparticles prepared in the second step, and the water-soluble conjugated polymer to the amine group introduced into the titanium dioxide nanoparticles in the third step It is preferable to include a fourth step (S500) introduced by a miracle attraction.
[제조예 1] 수용성 공액화 고분자의 제조(제 1 단계, S100)[Preparation Example 1] Preparation of water-soluble conjugated polymer (first step, S100)
[제조예 1-1] 화학식 1의 페닐렌계 수용성 공액화 고분자의 제조 [Preparation Example 1-1] Preparation of phenylene-based water-soluble conjugated polymer of Formula 1
[제조예 1-1]에서는 상기 화학식 1에서 R1과 R2는 C의 개수가 4개인 설포나토부톡시기(sulfonato butoxy)이며, Ar은 벤젠인 페닐렌계 수용성 공액화 고분자를 제조한다. 구체적으로, [제조예 1-1]에서 페닐렌계 수용성 공액화 고분자의 제조방법은 아래와 같다. In [Preparation Example 1-1], in Formula 1, R1 and R2 are sulfonato butoxy groups having 4 C, and Ar is benzene to prepare a phenylene-based water-soluble conjugated polymer. Specifically, a method of preparing a phenylene-based water-soluble conjugated polymer in [Preparation Example 1-1] is as follows.
즉, 100 mL 3 구 플라스크에 1,4-Dibromobenzene-2,5-bis(4-sulfonatobutoxy) benzene sodium salt (0.5 g, 0.825 mmol)과 1,4-benzenediboronic acid bis(pinacol) ester (272 mg, 0.825 mmol), 그리고 tetrakis(triphenylphosphine)palladium(0) (5 mol%)를 습기가 제거된 30 mL 의 THF(Tetrahydrofuran) 와 2 M Na2CO3 혼합용액에 용해시키고 85 ℃에서 48 시간 동안 환류하였다. 반응 후, 상온에서 냉각시킨 후 400 mL의 아세톤에 부어 결정을 석출 시킨 다음 석출물을 여과하였다. 여과하여 얻어진 고체는 3 차 증류수에 녹인 후 분자량 12,400 셀룰로오스 반투막으로 48 시간 동안 투석하였다. 감압 하에서 동결건조하여 [제조예 1-1]의 수용성 공액화 고분자(이하 WSP-1이라 한다)를 제조하였다. That is, 1,4-Dibromobenzene-2,5-bis(4-sulfonatobutoxy) benzene sodium salt (0.5 g, 0.825 mmol) and 1,4-benzenediboronic acid bis(pinacol) ester (272 mg, 0.825 mmol), and tetrakis(triphenylphosphine)palladium(0) (5 mol%) were dissolved in a mixed solution of 30 mL of moisture-removed THF (Tetrahydrofuran) and 2 M Na 2 CO 3 and refluxed at 85° C. for 48 hours. . After the reaction, the mixture was cooled at room temperature, poured into 400 mL of acetone to precipitate crystals, and the precipitate was filtered. The solid obtained by filtration was dissolved in tertiary distilled water and dialyzed against a 12,400 cellulose semipermeable membrane for 48 hours. Freeze-dried under reduced pressure to prepare a water-soluble conjugated polymer (hereinafter referred to as WSP-1) of [Preparation Example 1-1].
그리고 상기와 같이 제조된 WSP-1은 1H-NMR을 이용하여 아래와 같이 그 제조를 확인하였다. And WSP-1 prepared as described above was confirmed its preparation as follows using 1 H-NMR.
1H NMR (300 MHz, D2O): δ = 7.6-6.7 (m, 6H), 4.1-3.5 (m, 4H), 3.2-2.8 (t, 4H), 2.1-1.6 (d, 8H) ppm. 1 H NMR (300 MHz, D 2 O): δ = 7.6-6.7 (m, 6H), 4.1-3.5 (m, 4H), 3.2-2.8 (t, 4H), 2.1-1.6 (d, 8H) ppm .
[제조예 1-2] 화학식 1의 페닐렌계 수용성 공액화 고분자의 제조[Preparation Example 1-2] Preparation of phenylene-based water-soluble conjugated polymer of Formula 1
[제조예 1-2]에서는 상기 화학식 1에서 R1과 R2는 C의 개수가 4개인 설포나토부톡시기(sulfonato butoxy)이며, Ar은 2,1,3-벤조싸이아다이아졸(2,1,3-benzothiadiazole)인 페닐렌계 수용성 공액화 고분자를 제조한다. 구체적으로, [제조예 1-2]에서 페닐렌계 수용성 공액화 고분자의 제조방법은 아래와 같다. In [Preparation Example 1-2], in Formula 1, R1 and R2 are a sulfonato butoxy group having 4 C, and Ar is 2,1,3-benzothiadiazole (2,1, 3-benzothiadiazole), a phenylene-based water-soluble conjugated polymer is prepared. Specifically, a method of preparing a phenylene-based water-soluble conjugated polymer in [Preparation Example 1-2] is as follows.
즉, 100 mL 3 구 플라스크에 1,4-Dibromobenzene-2,5-bis(4-sulfonatobutoxy) benzene sodium salt (0.584 g, 1 mmol)과 4,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (0.388 g, 1 mmol)를 넣고 아르곤 퍼지한다. 그 후 DMF, K2CO3를 각각 16 mL 넣어 용해시킨다. 그리고 tetrakis(triphenylphosphine)palladium(0) (5 mol%)를 용해시키고 110 ℃에서 48 시간 동안 환류하였다. 반응 후, 상온에서 냉각시킨 후 500 mL의 메탄올에 부어 결정을 석출 시킨 다음 석출물을 여과하였다. 여과하여 얻어진 고체는 3 차 증류수에 녹인 후 분자량 12,400 셀룰로오스 반투막으로 48 시간 동안 투석하였다. 감압 하에서 동결건조하여 [제조예 1-2]의 수용성 공액화 고분자(이하 WSP-2라 한다)를 제조하였다. That is, 1,4-Dibromobenzene-2,5-bis(4-sulfonatobutoxy)benzene sodium salt (0.584 g, 1 mmol) and 4,7-Bis(4,4,5,5-tetramethyl) in a 100 mL 3-neck flask. Add -1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (0.388 g, 1 mmol) and purged with argon. After that, add 16 mL of DMF and K 2 CO 3 to each of them to dissolve. And tetrakis(triphenylphosphine)palladium(0) (5 mol%) was dissolved and refluxed at 110° C. for 48 hours. After the reaction, the mixture was cooled at room temperature, poured into 500 mL of methanol to precipitate crystals, and the precipitate was filtered. The solid obtained by filtration was dissolved in tertiary distilled water and dialyzed against a 12,400 cellulose semipermeable membrane for 48 hours. Freeze-dried under reduced pressure to prepare a water-soluble conjugated polymer (hereinafter referred to as WSP-2) of [Preparation Example 1-2].
그리고 상기와 같이 제조된 WSP-2는 1H-NMR을 이용하여 아래와 같이 그 제조를 확인하였다. And the WSP-2 prepared as described above was confirmed its preparation as follows using 1 H-NMR.
1H NMR (300 MHz, D2O): δ = 8.2-7.1 (br, 4H), 4.1-2.4 (br, 2H), 2.0-1.1 (br, 6H) ppm. 1 H NMR (300 MHz, D 2 O): δ = 8.2-7.1 (br, 4H), 4.1-2.4 (br, 2H), 2.0-1.1 (br, 6H) ppm.
[제조예 1-3] 화학식 2의 페닐렌계 수용성 공액화 고분자의 제조[Preparation Example 1-3] Preparation of phenylene-based water-soluble conjugated polymer of Formula 2
[제조예 1-3]에서는 상기 화학식 2에서 R1과 R2는 C의 개수가 4개인 설포나토부톡시기(sulfonato butoxy)이며, Ar은 비스싸이에닐벤조싸이아다이아졸(bis-thienyl-benzothiadiazole)인 페닐렌계 수용성 공액화 고분자를 제조한다. 구체적으로, [제조예 1-3]에서 페닐렌계 수용성 공액화 고분자의 제조방법은 아래와 같다. In [Preparation Example 1-3], in Formula 2, R1 and R2 are a sulfonato butoxy group having 4 C, and Ar is bis-thienyl-benzothiadiazole Phosphorus-phenylene-based water-soluble conjugated polymer is prepared. Specifically, a method of preparing a phenylene-based water-soluble conjugated polymer in [Preparation Example 1-3] is as follows.
즉, 100 mL 3 구 플라스크에 1,4-Dibromobenzene-2,5-bis(4-sulfonatobutoxy) benzene sodium salt (0.300 g, 0.514 mmol)과 4,7-Bis(5-bromothiophen-2-yl)benzo-2,1,3-thiadiazole (0.0216 g, 0.057 mmol)와 1,4-benzenediboronic acid bis(pinacol)ester (0.188 g, 0.571 mmol), 그리고 tetrakis(triphenylphosphine)palladium(0) (5 mol%)을 습기가 제거된 8 mL 의 DMF 와 12 mL의 2 M Na2CO3 혼합 용액에 용해시키고 100 ℃에서 48 시간 동안 환류하였다. 반응 후, 상온에서 냉각시킨 후 500 mL 의 부피 비가 10:40:50인 메탄올/아세톤/에테르 혼합 용액에 부어 결정을 석출 시킨 다음 석출물을 여과하였다. 여과하여 얻어진 고체는 3 차 증류수에 녹인 후 분자량 12,400 셀룰로오스 반투막으로 48 시간 동안 투석하였다. 감압 하에서 동결건조하여 [제조에 1-3]의 수용성 공액화 고분자(이하 WSP-3이라 한다)를 제조하였다. That is, 1,4-Dibromobenzene-2,5-bis(4-sulfonatobutoxy) benzene sodium salt (0.300 g, 0.514 mmol) and 4,7-Bis(5-bromothiophen-2-yl)benzo in a 100 mL 3-neck flask. -2,1,3-thiadiazole (0.0216 g, 0.057 mmol), 1,4-benzenediboronic acid bis(pinacol)ester (0.188 g, 0.571 mmol), and tetrakis(triphenylphosphine)palladium(0) (5 mol%) It was dissolved in a mixed solution of 8 mL of moisture-removed DMF and 12 mL of 2 M Na 2 CO 3 , and refluxed at 100° C. for 48 hours. After the reaction, the mixture was cooled at room temperature and poured into a methanol/acetone/ether mixed solution having a volume ratio of 500 mL of 10:40:50 to precipitate crystals, and then the precipitate was filtered. The solid obtained by filtration was dissolved in tertiary distilled water and dialyzed against a 12,400 cellulose semipermeable membrane for 48 hours. Freeze-dried under reduced pressure to prepare a water-soluble conjugated polymer (hereinafter referred to as WSP-3) of [Preparation 1-3].
그리고 상기와 같이 제조된 WSP-3은 1H-NMR을 이용하여 아래와 같이 그 제조를 확인하였다. And the WSP-3 prepared as described above was confirmed its preparation as follows using 1 H-NMR.
1H NMR (300 MHz, DMSO-d6): δ = 8.2-7.3 (br, 3.1H), 7.2-6.8 (br, 2H), 4.0 (br, 2.8H), 2.7 (br, 3H), 2.0-1.5 (br, 5H) ppm. 1 H NMR (300 MHz, DMSO-d6): δ = 8.2-7.3 (br, 3.1H), 7.2-6.8 (br, 2H), 4.0 (br, 2.8H), 2.7 (br, 3H), 2.0- 1.5 (br, 5H) ppm.
[제조예 1-4] 화학식 3의 플루오렌계(fluorene) 수용성 공액화 고분자의 제조[Preparation Example 1-4] Preparation of fluorene-based water-soluble conjugated polymer of Formula 3
[제조예 1-4]에서는 상기 화학식 3에서 R1과 R2는 C의 개수가 4개인 설포나토부톡시기(sulfonato butoxy)이며, Ar은 벤젠인 플루오렌계 수용성 공액화 고분자를 제조한다. 구체적으로, [제조예 1-4]에서 플루오렌계 수용성 공액화 고분자의 제조방법은 아래와 같다. In [Preparation Example 1-4], in Formula 3, R1 and R2 are sulfonato butoxy groups having 4 C, and Ar is benzene to prepare a fluorene-based water-soluble conjugated polymer. Specifically, a method of preparing a fluorene-based water-soluble conjugated polymer in [Preparation Example 1-4] is as follows.
즉, 9,9-bis-sodium butanylsulfonate-2,7-dibromo-fluorene (650mg, 1 mmol), 1,4-benzenediboronic acid bis(pinacol)ester (330 mg, 1 mmol), K2CO3 (588 mg, 4.24 mmol), tetrakis(triphenylphosphine)palladium(0) (5 mol%)을 100 mL 3구 플라스크에 넣고 습기가 제거된 DMF (20 mL), H2O (5 mL)를 플라스크에 넣어 완전히 용해시키고 90 ℃에서 24 시간 동안 환류하였다. 반응 후, 상온에서 냉각시킨 후 500 mL 의 부피 비가 10:40:50인 메탄올/아세톤/에테르 혼합 용액에 부어 결정을 석출 시킨 다음 석출물을 여과하였다. 여과하여 얻어진 고체는 3 차 증류수에 녹인 후 분자량 12,400 셀룰로오스 반투막으로 48 시간 동안 투석하였다. 감압 하에서 동결건조하여 [제조예 1-4]의 플루오렌계 수용성 공액화 고분자(이하 WSP-4라 한다)를 제조하였다. That is, 9,9-bis-sodium butanylsulfonate-2,7-dibromo-fluorene (650mg, 1 mmol), 1,4-benzenediboronic acid bis(pinacol)ester (330 mg, 1 mmol), K 2 CO 3 (588 mg, 4.24 mmol), tetrakis(triphenylphosphine)palladium(0) (5 mol%) into a 100 mL 3-neck flask, and add moisture-removed DMF (20 mL) and H 2 O (5 mL) into the flask to completely dissolve And refluxed at 90° C. for 24 hours. After the reaction, the mixture was cooled at room temperature and poured into a methanol/acetone/ether mixed solution having a volume ratio of 500 mL of 10:40:50 to precipitate crystals, and then the precipitate was filtered. The solid obtained by filtration was dissolved in tertiary distilled water and dialyzed against a 12,400 cellulose semipermeable membrane for 48 hours. Freeze-drying under reduced pressure was performed to prepare a fluorene-based water-soluble conjugated polymer (hereinafter referred to as WSP-4) of [Preparation Example 1-4].
그리고 상기와 같이 제조된 WSP-4는 1H-NMR을 이용하여 아래와 같이 그 제조를 확인하였다. And the WSP-4 prepared as described above was confirmed its preparation as follows using 1 H-NMR.
1H NMR (300 MHz, DMSO-d6): δ = 7.70 (br, 4H), 3.98-3.66 (br, 2H), 2.75-2.41 (br, 2H), 2.0-1.3 (br, 4H) ppm. 1 H NMR (300 MHz, DMSO-d6): δ = 7.70 (br, 4H), 3.98-3.66 (br, 2H), 2.75-2.41 (br, 2H), 2.0-1.3 (br, 4H) ppm.
[제조예 1-5] 화학식 3의 플루오렌계(fluorene) 수용성 공액화 고분자의 제조[Preparation Example 1-5] Preparation of fluorene-based water-soluble conjugated polymer of Formula 3
[제조예 1-5]에서는 상기 화학식 3에서 R1과 R2는 C의 개수가 4개인 설포나토부톡시기(sulfonato butoxy)이며, Ar은 벤조싸이아다이아졸(benzothiadiazole)인 플루오렌계 수용성 공액화 고분자를 제조한다. 구체적으로, [제조예 1-5]에서 플루오렌계 수용성 공액화 고분자의 제조방법은 아래와 같다. In [Preparation Example 1-5], in Formula 3, R1 and R2 are a sulfonato butoxy group having 4 C, and Ar is a fluorene-based water-soluble conjugated polymer, which is benzothiadiazole. To manufacture. Specifically, a method of preparing a fluorene-based water-soluble conjugated polymer in [Preparation Example 1-5] is as follows.
즉, 9,9-bis-sodium butanylsulfonate-2,7-dibromo-fluorene (650 mg, 1 mmol), 4,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (387 mg, 1 mmol), K2CO3 (588 mg, 4.24 mmol), tetrakis(triphenylphosphine)palladium(0) (5 mol%)을 100 mL 3구 플라스크에 넣고 습기가 제거된 DMF (20 mL), H2O (5 mL)를 플라스크에 넣어 완전히 용해시키고 90 ℃에서 24 시간 동안 환류하였다. 반응 후, 상온에서 냉각시킨 후 500 mL 의 부피 비가 10:40:50인 메탄올/아세톤/에테르 혼합 용액에 부어 결정을 석출 시킨 다음 석출물을 여과하였다. 여과하여 얻어진 고체는 3 차 증류수에 녹인 후 분자량 12,400 셀룰로오스 반투막으로 48 시간 동안 투석하였다. 감압 하에서 동결건조하여 [제조예 1-5]의 수용성 공액화 고분자(이하 WSP-5라 한다)을 얻었다. That is, 9,9-bis-sodium butanylsulfonate-2,7-dibromo-fluorene (650 mg, 1 mmol), 4,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2-yl)-2,1,3-benzothiadiazole (387 mg, 1 mmol), K 2 CO 3 (588 mg, 4.24 mmol), tetrakis(triphenylphosphine)palladium(0) (5 mol%) in 100 mL 3 DMF (20 mL) and H 2 O (5 mL) from which moisture was removed were added to the flask to completely dissolve, and refluxed at 90° C. for 24 hours. After the reaction, the mixture was cooled at room temperature and poured into a methanol/acetone/ether mixed solution having a volume ratio of 500 mL of 10:40:50 to precipitate crystals, and then the precipitate was filtered. The solid obtained by filtration was dissolved in tertiary distilled water and dialyzed against a 12,400 cellulose semipermeable membrane for 48 hours. Freeze-dried under reduced pressure to obtain a water-soluble conjugated polymer (hereinafter referred to as WSP-5) of [Preparation Example 1-5].
그리고 상기와 같이 제조된 WSP-5는 1H-NMR을 이용하여 아래와 같이 그 제조를 확인하였다. And the WSP-5 prepared as described above was confirmed its preparation as follows using 1 H-NMR.
1H NMR (300 MHz, DMSO-d6): δ = 8.31 - 7.96 (m, 8H), 2.33 (br s, 4H), 2.16 (br s, 4H), 1.48 (br s, 4H), 0.86 (br s, 4H) ppm. 1 H NMR (300 MHz, DMSO-d6): δ = 8.31-7.96 (m, 8H), 2.33 (br s, 4H), 2.16 (br s, 4H), 1.48 (br s, 4H), 0.86 (br s, 4H) ppm.
[제조예 1-6] 화학식 3의 플루오렌계(fluorene) 수용성 공액화 고분자의 제조[Preparation Example 1-6] Preparation of fluorene-based water-soluble conjugated polymer of Formula 3
[제조예 1-6]에서는 상기 화학식 3에서 R1과 R2는 C의 개수가 4개인 설포나토부톡시기(sulfonato butoxy)이며, Ar은 비스싸이에닐벤조싸이아다이아졸(bis-thienyl-benzothiadiazole)인 플루오렌계 수용성 공액화 고분자를 제조한다. 구체적으로, [제조예 1-6]에서 플루오렌계 수용성 공액화 고분자의 제조방법은 아래와 같다.In [Preparation Example 1-6], in Formula 3, R1 and R2 are a sulfonato butoxy group having 4 C, and Ar is bis-thienyl-benzothiadiazole To prepare a phosphorus fluorene-based water-soluble conjugated polymer. Specifically, a method of preparing a fluorene-based water-soluble conjugated polymer in [Preparation Example 1-6] is as follows.
즉, 9,9-bis-sodium butanylsulfonate-2,7-dibromo-fluorene (650 mg, 1 mmol), 4,7-bis-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]benzo-2,1,3-thiadiazole (552 mg, 1 mmol), K2CO3 (588 mg, 4.24 mmol), tetrakis(triphenylphosphine)palladium(0) (5 mol%)을 100 mL 3구 플라스크에 넣고 습기가 제거된 DMF (20 mL), H2O (5 mL)를 플라스크에 넣어 완전히 용해시키고 90 ℃에서 24 시간 동안 환류하였다. 반응 후, 상온에서 냉각시킨 후 500 mL 의 부피 비가 10:40:50인 메탄올/아세톤/에테르 혼합 용액에 부어 결정을 석출 시킨 다음 석출물을 여과하였다. 여과하여 얻어진 고체는 3 차 증류수에 녹인 후 분자량 12,400 셀룰로오스 반투막으로 48 시간 동안 투석하였다. 감압 하에서 동결건조하여 [제조예 1-6]의 수용성 공액화 고분자(이하 WSP-6이라 한다)를 제조하였다. That is, 9,9-bis-sodium butanylsulfonate-2,7-dibromo-fluorene (650 mg, 1 mmol), 4,7-bis-[5-(4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl)thiophen-2-yl]benzo-2,1,3-thiadiazole (552 mg, 1 mmol), K 2 CO 3 (588 mg, 4.24 mmol), tetrakis(triphenylphosphine)palladium(0 ) (5 mol%) was added to a 100 mL 3-neck flask, and DMF (20 mL) and H 2 O (5 mL) from which moisture was removed were added to the flask to completely dissolve and reflux at 90° C. for 24 hours. After the reaction, the mixture was cooled at room temperature and poured into a methanol/acetone/ether mixed solution having a volume ratio of 500 mL of 10:40:50 to precipitate crystals, and then the precipitate was filtered. The solid obtained by filtration was dissolved in tertiary distilled water and dialyzed against a 12,400 cellulose semipermeable membrane for 48 hours. Freeze-dried under reduced pressure to prepare a water-soluble conjugated polymer (hereinafter referred to as WSP-6) of [Preparation Example 1-6].
그리고 상기와 같이 제조된 WSP-6은 1H-NMR을 이용하여 아래와 같이 그 제조를 확인하였다. And the preparation of WSP-6 prepared as described above was confirmed as follows using 1 H-NMR.
1H NMR (300 MHz, DMSO-d6): δ = 8.29 - 7.43 (br, 6H), 7.32-6.9 (br, 6H), 4.0-3.8 (br, 4H), 2.5 (br, 4H), 2.1-1.6 (br, 8H) ppm. 1 H NMR (300 MHz, DMSO-d6): δ = 8.29-7.43 (br, 6H), 7.32-6.9 (br, 6H), 4.0-3.8 (br, 4H), 2.5 (br, 4H), 2.1- 1.6 (br, 8H) ppm.
[제조예 2] 이산화티타늄 나노입자의 제조(제 2 단계, S200)[Preparation Example 2] Preparation of titanium dioxide nanoparticles (second step, S200)
본 발명의 수용성 공액화 고분자가 도입된 광촉매 복합체를 제조하기 위하여 이산화티타늄 나노입자를 제조하는 제 2 단계(S200)는 아래와 같다. A second step (S200) of preparing titanium dioxide nanoparticles to prepare a photocatalytic composite into which the water-soluble conjugated polymer of the present invention is introduced is as follows.
즉, 상기 이산화티타늄 나노입자를 제조하기 위하여 500 mL 3 구 플라스크에 300 mL 에탄올과 0.1 M NaCl 1.2 mL를 넣고 교반 시킨다. 그 후 Titanium isopropoxide 5.1 mL를 넣고 뿌옇게 될 때까지 교반 시킨 후, 교반을 멈추고 12 시간 반응함으로써 이산화티타늄 나노입자의 침전물을 얻는다.That is, in order to prepare the titanium dioxide nanoparticles, 300 mL ethanol and 1.2 mL 0.1 M NaCl were added to a 500 mL three-neck flask and stirred. Thereafter, 5.1 mL of titanium isopropoxide was added and stirred until it became cloudy. The stirring was stopped and reacted for 12 hours to obtain a precipitate of titanium dioxide nanoparticles.
이때 얻어진 이산화티타늄 나노입자의 침전물은 3,300 rpm으로 원심분리하여 회수하고, 이후에 에탄올로 3번 수세하고 원심분리하여 건조하였다. 건조된 이산화티타늄 나노입자를 가열로를 이용하여 550 ℃에서 2 시간 열처리함으로써, 아나타아제(anatase)형의 결정 격자를 가진 이산화티타늄 나노입자를 제조한다. The precipitate of titanium dioxide nanoparticles obtained at this time was recovered by centrifugation at 3,300 rpm, and then washed with ethanol three times and centrifuged to dry. The dried titanium dioxide nanoparticles are heat-treated at 550° C. for 2 hours using a heating furnace to prepare titanium dioxide nanoparticles having an anatase-type crystal lattice.
[제조예 3] 이산화티타늄 나노입자에 아민기의 도입(제 3 단계, S300)[Preparation Example 3] Introduction of amine groups to titanium dioxide nanoparticles (3rd step, S300)
상기와 같이 제 2 단계에서 제조된 이산화티탄 나노입자는 이후에 제 3 단계(S300)를 통해 아민기를 도입하게 된다.The titanium dioxide nanoparticles prepared in the second step as described above are then introduced into the amine group through the third step (S300).
즉, 상기와 같이 제조된 이산화티타늄 나노입자에 아민기를 도입하기 위한 과정은 다음과 같다. Toluene 17 mL에 이산화티타늄 나노입자 600 mg과 3-aminopropyl triethoxysilane(이하 APTES 라 한다) 2.1 mL를 넣고, 110℃에서 12시간 동안 환류하였다. 이후에 상온으로 냉각하고 3,300 rpm으로 원심분리하여 회수하였다. 이때 미반응 APTES를 제거하기 위하여 에탄올로 수세한 뒤 건조하였다. That is, a process for introducing an amine group into the titanium dioxide nanoparticles prepared as described above is as follows. In 17 mL of toluene, 600 mg of titanium dioxide nanoparticles and 2.1 mL of 3-aminopropyl triethoxysilane (hereinafter referred to as APTES) were added and refluxed at 110° C. for 12 hours. After that, it was cooled to room temperature and collected by centrifugation at 3,300 rpm. At this time, to remove unreacted APTES, it was washed with ethanol and dried.
상기 이산화티타늄 나노입자를 X-선 광전자 분광법(X-ray Photoelectron. Spectroscopy, 이하 XPS)와 원소분석을 통해 이산화티타늄 나노입자에 아민기의 도입을 확인하였다. The titanium dioxide nanoparticles were subjected to X-ray photoelectron spectroscopy (XPS) and elemental analysis to confirm the introduction of an amine group into the titanium dioxide nanoparticles.
[제조예 4] 이산화티타늄 나노입자에 수용성 공액화 고분자의 도입(제 4 단계, S400)[Preparation Example 4] Introduction of a water-soluble conjugated polymer to titanium dioxide nanoparticles (4th step, S400)
상기와 같이 제 3 단계에서 아민기가 도입된 이산화티타늄 나노입자는 제 4 단계에서 이산화티타늄 나노입자에 도입된 아민기에 수용성 공액화 고분자를 정전기적 인력에 의해 도입하게 된다. 이때 상기 이산화티타늄 나노입자의 표면에 도입된 아민기와 수용성 공액화 고분자가 결합함으로써 상기 이산화티타늄 나노입자에 수용성 공액화 고분자가 도입되게 된다. As described above, in the titanium dioxide nanoparticles into which the amine group is introduced in the third step, a water-soluble conjugated polymer is introduced into the amine group introduced into the titanium dioxide nanoparticles in the fourth step by electrostatic attraction. At this time, the water-soluble conjugated polymer is introduced into the titanium dioxide nanoparticles by combining the amine group introduced on the surface of the titanium dioxide nanoparticles with the water-soluble conjugated polymer.
이때 이산화티타늄 나노입자에 수용성 공액화 고분자를 정전기적 인력에 의해 도입하기 위하여, 상기 수용성 공액화 고분자는 증류수 중에서 상기 -SO3 -M+ 가 해리되어 음이온성을 띄고, 이산화티타늄 나노입자의 표면에 도입된 아민은 양성자화(protonation) 되면서 양이온성을 띄게 된다. At this time, in order to introduce water-soluble by the ball liquefied polymer to electrostatic attraction to the titanium dioxide nano-particles, the water-soluble polymer is the ball liquefied -SO 3 in distilled water, - the M + are the anionic dissociation noticeable on the surface of the titanium dioxide nanoparticles The introduced amine becomes cationic as it becomes protonated.
상기 제 4 단계를 상세하게 살펴보면, 아민기가 도입된 이산화티타늄 나노입자 300 mg과 상기 제조예 1-1 내지 1-6에서 제조된 WSP-1 내지 WSP-6를 30 mg을 각각 증류수에 넣고 12 시간 동안 롤링시킨다. 이후에 3,300 rpm으로 원심분리하여 이산화티타늄 나노입자를 회수하였다. 이때 미반응 수용성 공액화 고분자를 제거하기 위해 증류수로 수세한 뒤 건조하여 본 발명의 수용성 공액화 고분자가 도입된 광촉매 복합체(Photocatalyst composite, 이하 PC) PC- 1 내지 PC-6를 제조하였다. Looking in detail at the fourth step, 300 mg of titanium dioxide nanoparticles into which an amine group has been introduced and 30 mg of WSP-1 to WSP-6 prepared in Preparation Examples 1-1 to 1-6 were respectively added to distilled water for 12 hours. While rolling. Thereafter, the titanium dioxide nanoparticles were recovered by centrifugation at 3,300 rpm. At this time, in order to remove the unreacted water-soluble conjugated polymer, it was washed with distilled water and then dried to prepare a photocatalyst composite (hereinafter referred to as PC) PC-1 to PC-6 into which the water-soluble conjugated polymer of the present invention was introduced.
이하에서는 상기와 같이 제조된 본 발명의 광촉매 복합체 PC-1 내지 PC-6를 이용하여 광촉매 반응을 실시하였다. 상기 본 발명의 광촉매 복합체 PC-1 내지 PC-6를 이용하여 광촉매 반응은 염료분해반응과 산화반응 및 환원반응을 대상으로 하였다. Hereinafter, a photocatalytic reaction was performed using the photocatalytic complexes PC-1 to PC-6 of the present invention prepared as described above. The photocatalytic reaction using the photocatalytic complexes PC-1 to PC-6 of the present invention was targeted for a dye decomposition reaction, an oxidation reaction, and a reduction reaction.
[실시예 1] 염료분해 반응[Example 1] Dye decomposition reaction
상업적으로 구매할 수 있는 하기 화학식 4 내지 6과 같은 염료인 로다민 B(rhodamine B), 메틸렌블루(methylene blue) 및 메틸오렌지(methyl orange)용액을 20 ppm의 농도로 각각 제조한 뒤, 20 mL의 바이알에 10 mL씩 넣고 [제조예 4]에 서 제조된 본 발명의 광촉매 복합체 PC-1 내지 PC-6 5mg을 상기 염료용액에 각각 넣고 10분 동안 분산시켜 실시예 1-1 내지 실시예 1-6의 반응용액을 제조하였다.Commercially available dyes such as the following formulas 4 to 6, rhodamine B, methylene blue, and methyl orange solutions were prepared at a concentration of 20 ppm, respectively, and then 20 mL of Add 10 mL each to a vial, and add 5 mg of the photocatalyst complexes PC-1 to PC-6 of the present invention prepared in [Preparation Example 4] to the dye solution and disperse for 10 minutes to Example 1-1 to Example 1- The reaction solution of 6 was prepared.
상기 실시예 1-1 내지 실시예 1-6의 반응용액에 4시간 동안 가시광선 (22 W/m2, λ>450 nm)을 조사하여 염료분해 반응을 실시하였으며, 이때 광원과 염료 용액의 거리는 5 cm로 하였다. 광조사 이후 셀룰로오스 아세테이트 시린지 필터(pore size: 0.85 μm)로 광촉매 복합체를 제거하고 UV-vis 흡수분광계를 이용해 염료 용액의 흡광도를 측정하였으며, 검량선을 통해 흡광도를 농도로 환산하여 아래의 [식 1]에 의거하여 염료분해율(%)을 계산하였다. 각 염료의 흡수 파장은 로다민 B의 경우 544 nm, 메틸렌블루의 경우 665 nm, 메틸오렌지의 경우 465 nm이다.The reaction solution of Examples 1-1 to 1-6 was irradiated with visible light (22 W/m 2 , λ>450 nm) for 4 hours to conduct a dye decomposition reaction, wherein the distance between the light source and the dye solution was It was set to 5 cm. After light irradiation, the photocatalyst complex was removed with a cellulose acetate syringe filter (pore size: 0.85 μm), and the absorbance of the dye solution was measured using a UV-vis absorption spectrometer, and the absorbance was converted to a concentration through a calibration curve, and the following [Equation 1] Based on the dye decomposition rate (%) was calculated. The absorption wavelength of each dye is 544 nm for rhodamine B, 665 nm for methylene blue, and 465 nm for methyl orange.
[화학식 4] [Formula 4]
Rhodamine B Rhodamine B
[화학식 5] [Formula 5]
Methylene blue Methylene blue
[화학식 6] [Formula 6]
Methyl orangeMethyl orange
[식 1] [Equation 1]
[비교예 1][Comparative Example 1]
비교예 1-1 내지 1-6는 상기 [제조예 1]에서 제조한 수용성 공액화 고분자 WSP-1 내지 WSP-6 0.21 mg을 아민기가 도입된 이산화티타늄 나노입자와 복합화시키지 않고 염료용액에 분산시켜서 염료분해율(%)을 측정하였다. In Comparative Examples 1-1 to 1-6, 0.21 mg of the water-soluble conjugated polymers WSP-1 to WSP-6 prepared in [Preparation Example 1] were dispersed in a dye solution without complexing with the titanium dioxide nanoparticles introduced with an amine group. The dye decomposition rate (%) was measured.
또한, 비교예 1-7 내지 1-12는 [제조예 2]에서 제조한 이산화티타늄 나노입자 4.5mg을 염료용액에 분산시켜서 염료분해율(%)을 측정하였다. In addition, in Comparative Examples 1-7 to 1-12, 4.5 mg of titanium dioxide nanoparticles prepared in [Preparation Example 2] were dispersed in a dye solution to measure the dye decomposition rate (%).
그리고, 비교예 1-13 내지 1-18는 [제조예 3]에서 제조한 아민기가 도입된 이산화티타늄 나노입자 4.7 mg을 염료용액에 분산시켜서 염료분해율(%)을 측정하였다. In addition, in Comparative Examples 1-13 to 1-18, 4.7 mg of titanium dioxide nanoparticles with an amine group introduced in [Preparation Example 3] were dispersed in a dye solution to measure the dye decomposition rate (%).
이때 상기 비교예 1-1 내지 비교예 1-18에서 염료분해율(%)의 측정시 기타 조건은 실시예 1과 동일하며, 상기 실시예 1과 비교예 1에서 수행한 염료분해율(%)의 결과를 표 1에 나타내었다. At this time, when measuring the dye decomposition rate (%) in Comparative Examples 1-1 to 1-18, other conditions are the same as in Example 1, and the result of the dye decomposition rate (%) performed in Example 1 and Comparative Example 1 Is shown in Table 1.
표 1에 기재된 바와 같이, 본 발명의 광촉매 복합체 PC-1 내지 PC-6를 사용하여 염료분해율(%)을 측정한 결과, 로다민 B와 메틸렌블루의 경우에는 90 % 이상이 분해되었으며, 메틸오렌지의 경우에는 70 % 이상이 분해된 것으로 측정되었다. As shown in Table 1, as a result of measuring the dye decomposition rate (%) using the photocatalytic complexes PC-1 to PC-6 of the present invention, in the case of rhodamine B and methylene blue, more than 90% were decomposed, and methyl orange In the case of, it was determined that more than 70% was decomposed.
이에 반하여, 비교예 1-1 내지 비교예 1-7의 수용성 공액화 고분자 WSP-1 내지 WSP-6를 사용한 경우와, 비교예 1-8 내지 비교예 1-12의 이산화티타늄 나노입자를 사용한 경우 및 비교예 1-13 내지 비교예 1-18의 아민기가 도입된 이산화티타늄 나노입자만을 사용하여 염료분해율(%)을 측정한 결과, 상기 염료분해율(%)이 20 % 를 넘지 않는 것을 확인할 수 있다. 즉, 본 발명의 광촉매 복합체는 염료의 분해반응에 유용하게 응용할 수 있음을 확인하였다.In contrast, when the water-soluble conjugated polymers WSP-1 to WSP-6 of Comparative Examples 1-1 to 1-7 were used, and when titanium dioxide nanoparticles of Comparative Examples 1-8 to 1-12 were used And as a result of measuring the dye decomposition rate (%) using only the titanium dioxide nanoparticles into which the amine groups of Comparative Examples 1-13 to 1-18 were introduced, it can be confirmed that the dye decomposition rate (%) does not exceed 20%. . That is, it was confirmed that the photocatalytic composite of the present invention can be usefully applied to the decomposition reaction of dyes.
[실시예 2] 벤즈알데하이드(benzaldehyde) 유도체의 산화반응 [Example 2] Oxidation reaction of benzaldehyde derivatives
상업적으로 구매할 수 있는 [식 2]의 좌측과 같은 벤즈알데하이드 유도체 1mmol을 5mL의 아세토나이트릴에 녹여 반응용액을 제조하고, 상기 [실시예 4]에서 제조된 광촉매 복합체 PC-1 내지 PC-6 5mg을 상기 반응용액에 각각 분산시켜 실시예 2-1 내지 실시예 2-6의 반응용액을 제조하였다. 상기 실시예 2-1 내지 실시예 2-6의 반응용액에 가시광선을 조사하면서 벤즈알데하이드(benzaldehyde) 유도체(반응물)에서 벤조산(benzoic acid) 유도체(생성물)로의 전환율(%)을 측정하였다.A reaction solution was prepared by dissolving 1 mmol of a commercially available benzaldehyde derivative as shown on the left of [Equation 2] in 5 mL of acetonitrile, and 5 mg of photocatalyst complexes PC-1 to PC-6 prepared in [Example 4] above. Was dispersed in each of the reaction solutions to prepare reaction solutions of Examples 2-1 to 2-6. The reaction solutions of Examples 2-1 to 2-6 were irradiated with visible light, and the conversion rate (%) from a benzaldehyde derivative (reactant) to a benzoic acid derivative (product) was measured.
이때 벤즈알데하이드 유도체의 산화반응시 화학반응식은 아래의 [식 2]로 나타낼 수 있다. 상기 벤즈알데하이드 유도체의 반응용액에 4시간 동안 가시광선(22 W/m2, λ>450 nm)을 조사하였으며, 이때 광원과 반응용액의 거리는 5 cm이다. At this time, the chemical reaction formula for the oxidation reaction of the benzaldehyde derivative can be represented by the following [Equation 2]. The reaction solution of the benzaldehyde derivative was irradiated with visible light (22 W/m 2 , λ>450 nm) for 4 hours, at which time the distance between the light source and the reaction solution was 5 cm.
광조사 이후 셀룰로오스 아세테이트 시린지필터(pore size: 0.85 μm)로 광촉매 복합체를 제거하고 반응용액의 용매를 기화하여 제거한 뒤 핵자기공명스펙트럼(1H NMR, 300 MHz, Acetone-d6)으로 분석하였다. 상기 핵자기공명스펙트럼분석에 있어서, 10 ppm에서 나타나는 벤즈알데하이드 유도체(반응물)에서 알데하이드의 수소 스펙트럼과, 12 ppm에서 나타나는 벤조산 유도체(생성물)에서 카르복실산의 수소 스펙트럼의 면적 비율로 [식 3]에 의거하여 실시예 2-1 내지 실시예 2-6의 전환율(%)을 계산하였다. After light irradiation, the photocatalyst complex was removed with a cellulose acetate syringe filter (pore size: 0.85 μm), and the solvent of the reaction solution was evaporated to remove it, and then analyzed by nuclear magnetic resonance spectrum (1 H NMR, 300 MHz, Acetone-d 6 ). In the nuclear magnetic resonance spectrum analysis, the area ratio of the hydrogen spectrum of the aldehyde in the benzaldehyde derivative (reactant) at 10 ppm and the hydrogen spectrum of the carboxylic acid in the benzoic acid derivative (product) at 12 ppm [Equation 3] Based on the conversion ratio (%) of Example 2-1 to Example 2-6 was calculated.
[식 2][Equation 2]
[식 3] [Equation 3]
상기 식 3에서 Xc는 벤조산 유도체의 카르복실산에서 수소 스펙트럼의 면적이고, Xa는 벤즈알데하이드 유도체에서 알데하이드의 수소 스펙트럼의 면적을 나타낸다.In Formula 3, Xc is the area of the hydrogen spectrum in the carboxylic acid of the benzoic acid derivative, and Xa is the area of the hydrogen spectrum of the aldehyde in the benzaldehyde derivative.
[비교예 2][Comparative Example 2]
비교예 2-1 내지 2-6는 [제조예 1]에서 제조한 수용성 공액화 고분자 WSP-1 내지 WSP-6의 0.21 mg을 아민기가 도입된 이산화티타늄 나노입자와 복합화 시키지 않고 벤즈알데하이드 반응용액에 분산시켜서 전환율(%)을 측정하였다. In Comparative Examples 2-1 to 2-6, 0.21 mg of the water-soluble conjugated polymers WSP-1 to WSP-6 prepared in [Preparation Example 1] were not mixed with the titanium dioxide nanoparticles introduced with an amine group, but in a benzaldehyde reaction solution. By dispersing, the conversion rate (%) was measured.
또한, 비교예 2-7 내지 2-12는 [제조예 2]에서 제조한 이산화티타늄 나노입자 4.5mg을 벤즈알데하이드 반응용액에 분산시켜서 전환율(%)을 측정하였다. In addition, in Comparative Examples 2-7 to 2-12, the conversion rate (%) was measured by dispersing 4.5 mg of titanium dioxide nanoparticles prepared in [Preparation Example 2] in a benzaldehyde reaction solution.
그리고, 비교예 2-13 내지 2-18는 [제조예 3]에서 제조한 아민기가 도입된 이산화티타늄 나노입자 4.7 mg을 벤즈알데하이드 반응용액에 분산시켜서 전환율(%)을 측정하였다. And, in Comparative Examples 2-13 to 2-18, the conversion rate (%) was measured by dispersing 4.7 mg of titanium dioxide nanoparticles into which an amine group prepared in [Preparation Example 3] was introduced in a benzaldehyde reaction solution.
이때 상기 비교예 2-1 내지 비교예 2-18에서 전환율(%)의 측정시 기타 조건은 실시예 2과 동일하며, 실시예 2와 비교예 2에서 수행한 전환율(%)의 결과를 표 2, 3에 나타내었다. At this time, other conditions when measuring the conversion rate (%) in Comparative Examples 2-1 to 2-18 are the same as in Example 2, and the results of the conversion rate (%) performed in Example 2 and Comparative Example 2 are shown in Table 2. , Shown in 3.
표 2, 3에 기재된 바와 같이, 본 발명의 광촉매 복합체 PC-1 내지 PC-6를 사용한 벤즈알데하이드 유도체에서 벤조산 유도체로의 전환율(%)을 측정한 결과, 실시예 2-1 내지 실시예 2-6에서 모든 벤즈알데하이드 유도체의 경우에 전환율(%)이 90 % 이상으로 나타났다. As shown in Tables 2 and 3, as a result of measuring the conversion rate (%) from the benzaldehyde derivative to the benzoic acid derivative using the photocatalytic complexes PC-1 to PC-6 of the present invention, Examples 2-1 to 2- In the case of all benzaldehyde derivatives in 6, the conversion rate (%) was 90% or more.
이에 반하여, 비교예 2-1 내지 비교예 2-7의 수용성 공액화 고분자 WSP-1 내지 WSP-6를 사용한 경우와, 비교예 2-8 내지 비교예 2-12의 이산화티타늄 나노입자를 사용한 경우 및 비교예 2-13 내지 비교예 2-18의 아민기가 도입된 이산화티타늄 나노입자만을 사용하여 전환율(%)을 측정한 결과, 20 % 이하인 것을 확인할 수 있다. 즉, 본 발명의 광촉매 복합체는 벤즈알데하이드 유도체로부터 벤조산 유도체로의 전환 반응에 유용하게 응용할 수 있음을 확인하였다.In contrast, when the water-soluble conjugated polymers WSP-1 to WSP-6 of Comparative Examples 2-1 to 2-7 were used, and when titanium dioxide nanoparticles of Comparative Examples 2-8 to 2-12 were used And as a result of measuring the conversion rate (%) using only the titanium dioxide nanoparticles introduced with the amine group of Comparative Examples 2-13 to 2-18, it can be confirmed that it is 20% or less. That is, it was confirmed that the photocatalytic complex of the present invention can be usefully applied to the conversion reaction from a benzaldehyde derivative to a benzoic acid derivative.
[실시예 3] 벤질아민(benzylamine) 유도체의 산화성 커플링 반응[Example 3] Oxidative coupling reaction of benzylamine derivatives
상업적으로 구매할 수 있는 아래의 식 4와 같은 벤질아민 유도체 1mmol을 5 mL의 아세토나이트릴(acetonitrile)에 녹여 반응용액을 제조한 후, 본 발명의 광촉매 복합체 PC-1 내지 PC-6 5 mg을 상기 반응용액에 각각 분산시켜 실시예 3-1 내지 실시예 3-6의 반응용액을 제조하였다. 상기 실시예 3-1 내지 실시예 3-6의 반응용액에 가시광선을 조사하면서 벤질아민 유도체(반응물)에서 다이벤질이민(dibenzylimine) 유도체(생성물)로의 전환율(%)을 측정하였다.After preparing a reaction solution by dissolving 1 mmol of a commercially available benzylamine derivative as shown in Equation 4 below in 5 mL of acetonitrile, 5 mg of the photocatalyst complexes PC-1 to PC-6 of the present invention were added to the above. Each of them was dispersed in the reaction solution to prepare the reaction solutions of Examples 3-1 to 3-6. The conversion ratio (%) of the benzylamine derivative (reactant) to the dibenzylimine derivative (product) was measured while irradiating the reaction solutions of Examples 3-1 to 3-6 with visible light.
이때 벤질아민 유도체의 산화성 커플링 반응시 화학반응식은 아래의 [식 4]로 나타낼 수 있다. 이후 4시간 동안 가시광선 (22 W/m2, λ>450 nm)을 조사하였으며, 이때 광원과 반응용액의 거리는 5 cm이다. At this time, the chemical reaction formula for the oxidative coupling reaction of the benzylamine derivative can be represented by the following [Equation 4]. After that, visible light (22 W/m 2 , λ>450 nm) was irradiated for 4 hours, at which time the distance between the light source and the reaction solution was 5 cm.
광조사 이후 셀룰로오스 아세테이트 시린지필터(pore size: 0.85 μm)로 광촉매 복합체를 제거하고, 반응용액의 용매를 기화하여 제거한 뒤, 핵자기공명스펙트럼(1H NMR, 300 MHz, Acetone-d6)을 이용하여 벤질아민 유도체(반응물)에서 다이벤질이민 유도체(생성물)로의 전환율(%)을 평가하였다.After light irradiation, the photocatalyst complex was removed with a cellulose acetate syringe filter (pore size: 0.85 μm), and the solvent of the reaction solution was evaporated to remove it, and then a nuclear magnetic resonance spectrum ( 1 H NMR, 300 MHz, Acetone-d 6 ) was used. Thus, the conversion rate (%) from the benzylamine derivative (reactant) to the dibenzylimine derivative (product) was evaluated.
상기 핵자기공명스펙트럼 분석에 있어서, 3.48 ppm에서 나타나는 벤질아민 유도체(반응물)의 벤질자리 탄소의 수소 스펙트럼과, 4.8 ppm에서 나타나는 다이벤질이민 유도체(생성물)의 벤질자리 탄소의 수소 스펙트럼의 면적 비율로 [식 5]에 의거하여 실시예 3-1 내지 실시예 3-6의 전환율(%)을 계산하였다.In the nuclear magnetic resonance spectrum analysis, the area ratio of the hydrogen spectrum of the benzylic carbon of the benzylamine derivative (reactant) at 3.48 ppm and the hydrogen spectrum of the benzylic carbon of the dibenzylimine derivative (product) appearing at 4.8 ppm Conversion rates (%) of Examples 3-1 to 3-6 were calculated based on [Equation 5].
[식 4][Equation 4]
[식 5][Equation 5]
상기 [식 5]에서 Xb는 생성물인 다이벤질이민 유도체의 벤질 자리 탄소의 수소 스펙트럼의 면적이고, Xd는 반응물인 벤질아민 유도체의 벤질 자리 탄소의 수소 스펙트럼의 면적을 나타낸다.In the above [Formula 5], Xb is the area of the hydrogen spectrum of the benzyl site carbon of the product dibenzylimine derivative, and Xd is the area of the hydrogen spectrum of the benzyl site carbon of the benzylamine derivative as a reactant.
[비교예 3][Comparative Example 3]
비교예 3-1 내지 3-6는 [제조예 1]에서 제조한 수용성 공액화 고분자 WSP-1 내지 WSP-6의 0.21 mg을 아민기가 도입된 이산화티타늄 나노입자와 복합화 시키지 않고 벤질아민 반응용액에 분산시켜서 전환율(%)을 측정하였다. In Comparative Examples 3-1 to 3-6, 0.21 mg of the water-soluble conjugated polymers WSP-1 to WSP-6 prepared in [Preparation Example 1] were not mixed with the titanium dioxide nanoparticles introduced with an amine group, but in a benzylamine reaction solution. By dispersing, the conversion (%) was measured.
또한, 비교예 3-7 내지 3-12는 [제조예 2]에서 제조한 이산화티타늄 나노입자 4.5mg을 벤질아민 반응용액에 분산시켜서 전환율(%)을 측정하였다. In addition, in Comparative Examples 3-7 to 3-12, the conversion rate (%) was measured by dispersing 4.5 mg of titanium dioxide nanoparticles prepared in [Preparation Example 2] in a benzylamine reaction solution.
그리고, 비교예 3-13 내지 3-18는 [제조예 3]에서 제조한 아민기가 도입된 이산화티타늄 나노입자 4.7 mg을 벤질아민 반응용액에 분산시켜서 전환율(%)을 측정하였다. And, in Comparative Examples 3-13 to 3-18, the conversion rate (%) was measured by dispersing 4.7 mg of titanium dioxide nanoparticles into which an amine group prepared in [Preparation Example 3] was introduced in a benzylamine reaction solution.
이때 상기 비교예 3-1 내지 비교예 3-18에서 전환율(%)의 측정시 기타 조건은 실시예 3과 동일하며, 실시예 3와 비교예 3에서 수행한 전환율(%)의 결과를 표 4, 5에 나타내었다. At this time, when measuring the conversion rate (%) in Comparative Example 3-1 to Comparative Example 3-18, other conditions are the same as in Example 3, and the results of the conversion rate (%) performed in Example 3 and Comparative Example 3 are shown in Table 4 , Shown in 5.
표 4, 5에 기재된 바와 같이, 본 발명의 광촉매 복합체 PC-1 내지 PC-6를 사용한 벤질아민 유도체 에서 다이벤질이민 유도체로의 전환율(%)을 측정한 결과, 실시예 3-1 내지 실시예 3-6에서 모든 벤질아민 유도체의 경우에 전환율(%)이 80 % 이상으로 나타났다. As shown in Tables 4 and 5, as a result of measuring the conversion rate (%) from the benzylamine derivative to the dibenzylimine derivative using the photocatalytic complexes PC-1 to PC-6 of the present invention, Examples 3-1 to Examples In 3-6, all of the benzylamine derivatives showed a conversion rate (%) of 80% or more.
이에 반하여, 비교예 3-1 내지 비교예 3-7의 수용성 공액화 고분자 WSP-1 내지 WSP-6를 사용한 경우와, 비교예 3-8 내지 비교예 3-12의 이산화티타늄 나노입자를 사용한 경우 및 비교예 3-13 내지 비교예 3-18의 아민기가 도입된 이산화티타늄 나노입자만을 사용하여 전환율(%)을 측정한 결과, 15 % 이하인 것을 확인할 수 있다. 즉, 본 발명의 광촉매 복합체는 벤질아민 유도체로부터 다이벤질이민 유도체로의 전환 반응에 유용하게 응용할 수 있음을 확인하였다.In contrast, when the water-soluble conjugated polymers WSP-1 to WSP-6 of Comparative Examples 3-1 to 3-7 were used, and when titanium dioxide nanoparticles of Comparative Examples 3-8 to 3-12 were used And as a result of measuring the conversion rate (%) using only the titanium dioxide nanoparticles into which the amine groups of Comparative Examples 3-13 to 3-18 were introduced, it can be confirmed that it is 15% or less. That is, it was confirmed that the photocatalytic complex of the present invention can be usefully applied to a conversion reaction from a benzylamine derivative to a dibenzylimine derivative.
[실시예 4] 퓨로산(furoic acid) 산화반응 평가[Example 4] Furoic acid oxidation reaction evaluation
상업적으로 구매할 수 있는 [식 6]의 좌측과 같은 퓨로산 1mmol을 5mL의 물에 녹여 반응용액을 제조하고, 상기 [실시예 4]에서 제조된 광촉매 복합체 PC-1 내지 PC-6의 5mg을 상기 반응용액에 각각 분산시켜 실시예 4-1 내지 실시예 4-6의 반응용액을 제조하였다. 상기 실시예 4-1 내지 실시예 4-6의 반응용액에 가시광선을 조사하면서 퓨로산(furoic acid, 반응물)에서 퓨라논(furanone, 생성물)로의 전환율(%)을 측정하였다.A reaction solution was prepared by dissolving 1 mmol of commercially available puroic acid as shown on the left of [Equation 6] in 5 mL of water, and 5 mg of the photocatalyst complexes PC-1 to PC-6 prepared in [Example 4] were added to the above. Each was dispersed in the reaction solution to prepare the reaction solutions of Examples 4-1 to 4-6. The conversion rate (%) of furoic acid (reactant) to furanone (product) was measured while irradiating visible light to the reaction solutions of Examples 4-1 to 4-6.
이때 퓨로산의 산화반응시 화학반응식은 아래의 [식 6]으로 나타낼 수 있다. 상기 퓨로산의 반응용액에 4시간 동안 가시광선(22 W/m2, λ>450 nm)을 조사하였으며, 이때 광원과 반응용액의 거리는 5 cm이다. At this time, the chemical reaction equation for the oxidation reaction of furoic acid can be represented by the following [Equation 6]. The reaction solution of furoic acid was irradiated with visible light (22 W/m 2 , λ>450 nm) for 4 hours, at which time the distance between the light source and the reaction solution was 5 cm.
광조사 이후 셀룰로오스 아세테이트 시린지필터(pore size: 0.85 μm)로 광촉매 복합체를 제거하고 상기 퓨로산 반응용액의 용매인 물을 기화하여 제거한 뒤, 핵자기공명스펙트럼(1H NMR, 300 MHz, Acetone-d6)으로 분석하였다. 상기 핵자기공명스펙트럼분석에 있어서, 7.67, 7.25, 65.7 ppm에서 나타나는 퓨로산(반응물) 수소의 스펙트럼과 7.42, 6.25 ppm에서 나타나는 퓨라논(생성물) 수소 스펙트럼의 면적 비율로 [식 7]에 의거하여 실시예 4-1 내지 실시예 4-6의 전환율(%)을 계산하였다.After light irradiation, the photocatalyst complex was removed with a cellulose acetate syringe filter (pore size: 0.85 μm), and water, which is a solvent of the furoic acid reaction solution, was removed by vaporization, and then nuclear magnetic resonance spectrum ( 1 H NMR, 300 MHz, Acetone-d 6 ) was analyzed. In the nuclear magnetic resonance spectrum analysis, based on [Equation 7] as the area ratio of the spectra of the furoic acid (reactant) hydrogen appearing at 7.67, 7.25, and 65.7 ppm and the furanone (product) hydrogen spectrum appearing at 7.42 and 6.25 ppm. Conversion rates (%) of Examples 4-1 to 4-6 were calculated.
[식 6] [Equation 6]
[식 7][Equation 7]
[비교예 4][Comparative Example 4]
비교예 4-1 내지 4-6는 [제조예 1]에서 제조한 수용성 공액화 고분자 WSP-1 내지 WSP-6의 0.21 mg을 아민기가 도입된 이산화티타늄 나노입자와 복합화 시키지 않고 퓨로산 반응용액에 분산시켜서 전환율(%)을 측정하였다. In Comparative Examples 4-1 to 4-6, 0.21 mg of the water-soluble conjugated polymers WSP-1 to WSP-6 prepared in [Preparation Example 1] were not mixed with the titanium dioxide nanoparticles introduced with an amine group, but in a furoic acid reaction solution. By dispersing, the conversion (%) was measured.
또한, 비교예 4-7 내지 4-12는 [제조예 2]에서 제조한 이산화티타늄 나노입자 4.5mg을 퓨로산 반응용액에 분산시켜서 전환율(%)을 측정하였다. In addition, in Comparative Examples 4-7 to 4-12, the conversion rate (%) was measured by dispersing 4.5 mg of titanium dioxide nanoparticles prepared in [Preparation Example 2] in a furoic acid reaction solution.
그리고, 비교예 4-13 내지 4-18는 [제조예 3]에서 제조한 아민기가 도입된 이산화티타늄 나노입자 4.7 mg을 퓨로산 반응용액에 분산시켜서 전환율(%)을 측정하였다. And, in Comparative Examples 4-13 to 4-18, the conversion rate (%) was measured by dispersing 4.7 mg of titanium dioxide nanoparticles into which the amine group prepared in [Preparation Example 3] was introduced in a furoic acid reaction solution.
이때 상기 비교예 4-1 내지 비교예 4-18에서 전환율(%)의 측정시 기타 조건은 실시예 4와 동일하며, 실시예 4와 비교예 4에서 수행한 전환율(%)의 결과를 표 6에 나타내었다. At this time, when measuring the conversion rate (%) in Comparative Examples 4-1 to 4-18, other conditions are the same as in Example 4, and the results of the conversion rate (%) performed in Examples 4 and 4 are shown in Table 6 Shown in.
표 6에 기재된 바와 같이, 본 발명의 광촉매 복합체 PC-1 내지 PC-6를 사용한 퓨로산에서 퓨라논으로의 전환율(%)을 측정한 결과, 실시예 4-1 내지 실시예 4-6에서 전환율(%)이 95 % 이상으로 나타났다. As shown in Table 6, as a result of measuring the conversion rate (%) from furoic acid to furanone using the photocatalytic complexes PC-1 to PC-6 of the present invention, the conversion rate in Examples 4-1 to 4-6 (%) was found to be 95% or more.
이에 반하여, 비교예 4-1 내지 비교예 4-7의 수용성 공액화 고분자 WSP-1 내지 WSP-6를 사용한 경우와, 비교예 4-8 내지 비교예 4-12의 이산화티타늄 나노입자를 사용한 경우 및 비교예 4-13 내지 비교예 4-18의 아민기가 도입된 이산화티타늄 나노입자만을 사용하여 전환율(%)을 측정한 결과, 15.5 % 이하인 것을 확인할 수 있다. 즉, 본 발명의 광촉매 복합체는 퓨로산으로부터 퓨라논으로의 전환 반응에 유용하게 응용할 수 있음을 확인하였다.On the other hand, when using the water-soluble conjugated polymers WSP-1 to WSP-6 of Comparative Examples 4-1 to 4-7, and when using the titanium dioxide nanoparticles of Comparative Examples 4-8 to 4-12 And as a result of measuring the conversion rate (%) using only the titanium dioxide nanoparticles introduced with the amine group of Comparative Examples 4-13 to 4-18, it can be confirmed that it is 15.5% or less. That is, it was confirmed that the photocatalytic complex of the present invention can be usefully applied to the conversion reaction from furoic acid to furanone.
[실시예 5] 4-나이트로페놀(4-nitrophenol)의 환원반응 [Example 5] Reduction reaction of 4-nitrophenol
상업적으로 구매할 수 있는 [식 8]의 좌측과 같은 4-나이트로페놀 1mmol을 5mL의 물에 녹여 반응용액을 제조하고, 상기 [실시예 4]에서 제조된 광촉매 복합체 PC-1 내지 PC-6의 5mg을 상기 반응용액에 각각 분산시켜 실시예 5-1 내지 실시예 5-6의 반응용액을 제조하였다. 상기 실시예 5-1 내지 실시예 5-6의 반응용액에 가시광선을 조사하면서 4-나이트로페놀(4-nitrophenol, 반응물)에서 4-아미노페놀(4-aminophenol, 생성물)로의 전환율(%)을 측정하였다.A reaction solution was prepared by dissolving 1 mmol of 4-nitrophenol as shown on the left side of [Equation 8], which can be purchased commercially, in 5 mL of water, and the photocatalytic complexes PC-1 to PC-6 prepared in [Example 4] above were Each of 5 mg was dispersed in the reaction solution to prepare the reaction solutions of Examples 5-1 to 5-6. Conversion rate (%) from 4-nitrophenol (4-nitrophenol, reactant) to 4-aminophenol (4-aminophenol, product) while irradiating the reaction solutions of Examples 5-1 to 5-6 with visible light Was measured.
이때 4-나이트로페놀의 환원반응시 화학반응식은 아래의 [식 8]로 나타낼 수 있다. 상기 4-나이트로페놀의 반응용액에 4시간 동안 가시광선(22 W/m2, λ>450 nm)을 조사하였으며, 이때 광원과 반응용액의 거리는 5 cm이다. At this time, the chemical reaction equation for the reduction reaction of 4-nitrophenol can be represented by the following [Equation 8]. The reaction solution of 4-nitrophenol was irradiated with visible light (22 W/m 2 , λ>450 nm) for 4 hours, at which time the distance between the light source and the reaction solution was 5 cm.
광조사 이후 셀룰로오스 아세테이트 시린지필터(pore size: 0.85 μm)로 광촉매 복합체를 제거하고, UV/Vis 흡수스펙트럼을 측정하였다. 4-나이트로페놀(반응물)이 4-아미노페놀(생성물)로 전환되면 4-나이트로페놀의 최대 흡수 파장인 400 nm에서 흡광도(absorbance)가 감소하게 되므로, 이를 이용하여 하기 [식 9]에 의거하여 4-나이트로페놀에서 4-아미노페놀로의 전환율(%)을 계산하였다. After light irradiation, the photocatalyst complex was removed with a cellulose acetate syringe filter (pore size: 0.85 μm), and the UV/Vis absorption spectrum was measured. When 4-nitrophenol (reactant) is converted to 4-aminophenol (product), absorbance decreases at 400 nm, which is the maximum absorption wavelength of 4-nitrophenol. Based on this, the conversion rate (%) of 4-nitrophenol to 4-aminophenol was calculated .
[식 8] [Equation 8]
[식 9][Equation 9]
[비교예 5][Comparative Example 5]
비교예 5-1 내지 5-6는 [제조예 1]에서 제조한 수용성 공액화 고분자 WSP-1 내지 WSP-6의 0.21 mg을 아민기가 도입된 이산화티타늄 나노입자와 복합화 시키지 않고 4-나이트로페놀 반응용액에 분산시켜서 전환율(%)을 측정하였다. Comparative Examples 5-1 to 5-6 are 4-nitrophenol without complexing 0.21 mg of the water-soluble conjugated polymers WSP-1 to WSP-6 prepared in [Preparation Example 1] with titanium dioxide nanoparticles introduced with amine groups. By dispersing in the reaction solution, the conversion rate (%) was measured.
또한, 비교예 5-7 내지 5-12는 [제조예 2]에서 제조한 이산화티타늄 나노입자 4.5mg을 4-나이트로페놀 반응용액에 분산시켜서 전환율(%)을 측정하였다. In addition, in Comparative Examples 5-7 to 5-12, the conversion rate (%) was measured by dispersing 4.5 mg of titanium dioxide nanoparticles prepared in [Preparation Example 2] in a 4-nitrophenol reaction solution.
그리고, 비교예 5-13 내지 5-18는 [제조예 3]에서 제조한 아민기가 도입된 이산화티타늄 나노입자 4.7 mg을 4-나이트로페놀 반응용액에 분산시켜서 전환율(%)을 측정하였다. And, in Comparative Examples 5-13 to 5-18, the conversion rate (%) was measured by dispersing 4.7 mg of titanium dioxide nanoparticles into which an amine group prepared in [Preparation Example 3] was introduced in a 4-nitrophenol reaction solution.
이때 상기 비교예 5-1 내지 비교예 5-18에서 전환율(%)의 측정시 기타 조건은 실시예 5와 동일하며, 실시예 5와 비교예 5에서 수행한 전환율(%)의 결과를 표 7에 나타내었다. At this time, when measuring the conversion rate (%) in Comparative Examples 5-1 to 5-18, other conditions are the same as in Example 5, and the results of the conversion rate (%) performed in Example 5 and Comparative Example 5 are shown in Table 7 Shown in.
표 7에 기재된 바와 같이, 본 발명의 광촉매 복합체 PC-1 내지 PC-6를 사용한 4-나이트로페놀에서 4-아미노페놀로의 전환율(%)을 측정한 결과, 실시예 5-1 내지 실시예 5-6에서 전환율(%)이 90 % 이상으로 나타났다. As shown in Table 7, as a result of measuring the conversion rate (%) from 4-nitrophenol to 4-aminophenol using the photocatalytic complexes PC-1 to PC-6 of the present invention, Examples 5-1 to Examples In 5-6, the conversion rate (%) was more than 90%.
이에 반하여, 비교예 5-1 내지 비교예 5-7의 수용성 공액화 고분자 WSP-1 내지 WSP-6를 사용한 경우와, 비교예 5-8 내지 비교예 5-12의 이산화티타늄 나노입자를 사용한 경우 및 비교예 5-13 내지 비교예 5-18의 아민기가 도입된 이산화티타늄 나노입자만을 사용하여 전환율(%)을 측정한 결과, 12.5 % 이하인 것을 확인할 수 있다. 즉, 본 발명의 광촉매 복합체는 4-나이트로페놀로부터 4-아미노페놀로의 전환 반응에 유용하게 응용할 수 있음을 확인하였다.In contrast, when the water-soluble conjugated polymers WSP-1 to WSP-6 of Comparative Examples 5-1 to 5-7 were used, and when titanium dioxide nanoparticles of Comparative Examples 5-8 to 5-12 were used And as a result of measuring the conversion rate (%) using only the titanium dioxide nanoparticles introduced with the amine group of Comparative Examples 5-13 to 5-18, it can be confirmed that it is 12.5% or less. That is, it was confirmed that the photocatalyst complex of the present invention can be usefully applied to the conversion reaction from 4-nitrophenol to 4-aminophenol.
이상에서 살펴본 바와 같이, 본 발명의 이산화티타늄 나노입자 표면에 수용성 공액화 고분자가 정전기적 인력으로 도입된 광촉매 복합체는 상기 이산화티타늄 나노입자와 수용성 공액화 고분자 사이의 전자 이동이 효율적으로 일어날 수 있어, 가시광 영역에서 향상된 광촉매 효율을 나타낸다. 또한 소수성 공액화 고분자가 아닌 수용성 공액화 고분자를 사용함으로써 유기 용매가 아닌 물에서 수용성 공액화 고분자를 이산화티타늄과 같은 지지체에 도입시킬 수 있어 제조 방법이 간단하며 환경친화적이고, 상기 수용성 공액화 고분자가 이산화티타늄의 표면으로부터 쉽게 탈리되지 않아 안정성과 젖음성이 향상되어 수중 분산성이 우수한 특징을 갖는다. As described above, the photocatalytic composite in which the water-soluble conjugated polymer is introduced by electrostatic attraction on the surface of the titanium dioxide nanoparticles of the present invention can efficiently transfer electrons between the titanium dioxide nanoparticles and the water-soluble conjugated polymer, It shows improved photocatalytic efficiency in the visible region. In addition, by using a water-soluble conjugated polymer rather than a hydrophobic conjugated polymer, a water-soluble conjugated polymer can be introduced into a support such as titanium dioxide in water other than an organic solvent, making the manufacturing method simple and environmentally friendly, and the water-soluble conjugated polymer is Since it is not easily separated from the surface of titanium dioxide, stability and wettability are improved, and thus it has excellent dispersibility in water.
본 발명은 도면에 도시된 실시예를 참고로 설명되었으나 이는 예시적인 것에 불과하며, 당해 기술분야에서 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 다른 실시예가 가능하다는 점을 이해할 것이다. 따라서 본 발명의 진정한 기술적 보호범위는 첨부된 특허청구범위의 기술적 사상에 의하여 정해져야 할 것이다.The present invention has been described with reference to the embodiments shown in the drawings, but these are merely exemplary, and those of ordinary skill in the art will appreciate that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.
Claims (8)
이산화티타늄 나노입자;
상기 이산화티타늄 나노입자의 표면에 도입되는 아민기; 및
상기 아민기와 정전기적 인력에 의해 결합되는 하기 화학식 1 내지 화학식 3 중 어느 하나의 음이온성 수용성 공액화 고분자를 포함하는 광촉매 복합체.
[화학식 1]
[화학식 2]
[화학식 3]
상기 화학식 1 내지 3에서 R1, R2은 서로 상이하거나 동일한 CnH2n-SO3 -M+이며,
상기 n은 1 내지 20의 정수이며,
상기 M은 양이온성 금속이며,
또한, X는 화학식 1 혹은 화학식 3의 분자량을 12,400 이상을 갖게 하는 정수이며,
Y와 Z의 값은 화학식 2의 각 반복 단위의 조성을 몰분율로 나타낸 것으로서, Y는 0 내지 0.99의 실수이고, Z는 1-Y이며,
또한, Ar은
As a photocatalyst complex having activity in ultraviolet and pseudo-ray regions so as to be applicable to any one of decomposition of organic dyes and oxidation and reduction reactions of organic compounds by reactive oxygen species,
Titanium dioxide nanoparticles;
An amine group introduced into the surface of the titanium dioxide nanoparticles; And
A photocatalytic composite comprising an anionic water-soluble conjugated polymer of any one of the following Formulas 1 to 3 bonded to the amine group by electrostatic attraction.
[Formula 1]
[Formula 2]
[Formula 3]
In the above Chemical Formulas 1 to 3 R 1, R 2 are different from each other or identical C n H 2n -SO 3 - and M +,
N is an integer of 1 to 20,
M is a cationic metal,
In addition, X is an integer that makes the molecular weight of Formula 1 or Formula 3 12,400 or more,
The values of Y and Z are the molar fractions of the composition of each repeating unit of Formula 2, where Y is a real number from 0 to 0.99, and Z is 1-Y,
Also, Ar is
상기 아민기는 1차 아민인 것을 특징으로 하는 광촉매 복합체.
The method according to claim 2,
The photocatalytic composite, characterized in that the amine group is a primary amine.
상기 이산화티타늄 나노입자의 결정상은 아나타아제(anatase)형인 것을 특징으로 하는 광촉매 복합체.
The method according to claim 2,
The photocatalytic complex, characterized in that the crystal phase of the titanium dioxide nanoparticles is an anatase (anatase) type.
상기 이산화티타늄 나노입자의 직경은 10 ~ 1,000 nm인 것을 특징으로 하는 광촉매 복합체.
The method according to claim 2,
The photocatalytic composite, characterized in that the diameter of the titanium dioxide nanoparticles is 10 ~ 1,000 nm.
하기 화학식 1 내지 화학식 3 중 어느 하나의 음이온성 수용성 공액화 고분자를 제조하는 제 1 단계;
아나타아제(anatase)형의 결정상을 지닌 입자 직경 100 ~ 500 nm인 이산화티타늄 나노입자를 제조하는 제 2 단계;
상기 제 2 단계에서 제조된 이산화티타늄 나노입자의 표면에 아민기를 도입하는 제 3 단계; 및
상기 제 3 단계에서 아민기가 도입된 이산화티타늄 나노입자의 표면에 음이온성 수용성 공액화 고분자를 정전기적 인력으로 도입하는 제 4 단계; 를 포함하는 광촉매 복합체의 제조방법.
[화학식 1]
[화학식 2]
[화학식 3]
상기 화학식 1 내지 3에서 R1, R2은 서로 상이하거나 동일한 CnH2n-SO3 -M+이며,
상기 n은 1 내지 20의 정수이며,
상기 M은 양이온성 금속이며,
또한, X는 화학식 1 혹은 화학식 3의 분자량을 12,400 이상을 갖게 하는 정수이며,
Y와 Z의 값은 화학식 2의 각 반복 단위의 조성을 몰분율로 나타낸 것으로서, Y는 0 내지 0.99의 실수이고, Z는 1-Y이며,
또한, Ar은
As a method for producing a photocatalyst complex having activity in ultraviolet and pseudo-light regions so as to be applicable to any one of decomposition of organic dyes and oxidation and reduction reactions of organic compounds by active oxygen species,
A first step of preparing an anionic water-soluble conjugated polymer of any one of the following Chemical Formulas 1 to 3;
A second step of preparing titanium dioxide nanoparticles having a particle diameter of 100 to 500 nm having an anatase-type crystal phase;
A third step of introducing an amine group to the surface of the titanium dioxide nanoparticles prepared in the second step; And
A fourth step of introducing an anionic water-soluble conjugated polymer to the surface of the titanium dioxide nanoparticles into which the amine group is introduced in the third step by electrostatic attraction; Method for producing a photocatalytic composite comprising a.
[Formula 1]
[Formula 2]
[Formula 3]
In the above Chemical Formulas 1 to 3 R 1, R 2 are different from each other or identical C n H 2n -SO 3 - and M +,
N is an integer of 1 to 20,
M is a cationic metal,
In addition, X is an integer that makes the molecular weight of Formula 1 or Formula 3 12,400 or more,
The values of Y and Z are the molar fractions of the composition of each repeating unit of Formula 2, where Y is a real number from 0 to 0.99, and Z is 1-Y,
Also, Ar is
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