KR20140080204A - Method of preparing doped mesoporous Titanium dioxide microspheres - Google Patents
Method of preparing doped mesoporous Titanium dioxide microspheres Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 title description 3
- 239000002245 particle Substances 0.000 claims abstract description 85
- 239000002243 precursor Substances 0.000 claims abstract description 52
- 239000010936 titanium Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 14
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004246 zinc acetate Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- CYKMNKXPYXUVPR-UHFFFAOYSA-N [C].[Ti] Chemical compound [C].[Ti] CYKMNKXPYXUVPR-UHFFFAOYSA-N 0.000 claims description 14
- 239000011246 composite particle Substances 0.000 claims description 14
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical group CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- -1 for example Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
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- 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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- 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
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Description
본 개시는 TiO2 마이크로스피어 입자에 관한 것이며, 더욱 상세하게는, 도핑된 메조다공성 TiO2 마이크로스피어 입자에 관한 것이다. 도핑된 메조다공성 TiO2 마이크로스피어 입자는, 예를 들면, 염료감응 태양전지, 광전기화학 연료전지, 광촉매를 이용한 유기물 분해, 등의 응용분야에서 사용될 수 있다.This disclosure relates to TiO 2 microsphere particles, and more particularly, to doped mesoporous TiO 2 microsphere particles. The doped mesoporous TiO 2 microsphere particles can be used in applications such as, for example, dye-sensitized solar cells, photoelectrochemical fuel cells, and decomposition of organic materials using photocatalyst.
높은 비표면적을 유지하면서도 향상된 전기전도도, 향상된 광산란 성능, 향상된 광촉매 특성을 갖는 메조다공성 TiO2 마이크로스피어 입자가 요구되고 있다. 이러한 특성들의 향상을 위하여 메조다공성 TiO2 마이크로스피어 입자의 개질이 시도되고 있다. 메조다공성 TiO2 마이크로스피어 입자를 개질하는 대표적인 방법 중의 하나는, 상기 입자에 금속 또는 비금속 물질을 도핑하는 것이다. 예를 들어, 도핑된 이산화티타늄은 저감된 밴드갭을 가질 수 있는 것으로 알려져 있다. 저감된 밴드갭을 갖는 이산화티타늄은 가시광선에 의해서도 광촉매 반응을 일으킬 수 있다.There is a need for mesoporous TiO 2 microsphere particles having improved electrical conductivity, improved light scattering performance, and enhanced photocatalytic properties while maintaining a high specific surface area. Modification of mesoporous TiO 2 microsphere particles has been attempted to improve these properties. One of the typical methods of modifying mesoporous TiO 2 microsphere particles is to dope the particles with metal or non-metal materials. For example, doped titanium dioxide is known to have a reduced bandgap. Titanium dioxide with a reduced bandgap can cause photocatalytic reactions also by visible light.
종래에는 표면 개질을 통한 도핑법이 가장 많이 이용되고 있다. 그러나, 표면 개질을 통한 도핑법에 있어서, 일반적인 금속을 도핑하는 경우, 도핑 금속의 유해성과 높은 열적 불안정성 때문에, 도핑된 메조다공성 TiO2 마이크로스피어 입자의 광활성 효과가 저하되는 것으로 알려져 있다.In the past, the doping method through surface modification has been the most widely used. However, in the doping method through surface modification, it has been known that when doping a common metal, the photoactive effect of the doped mesoporous TiO 2 microsphere particles is degraded due to the toxicity of the doping metal and the high thermal instability.
따라서, 메조다공성 TiO2 마이크로스피어 입자를 금속 또는 비금속 물질로 효과적으로 도핑할 수 있거나, 및/또는, 도핑된 메조다공성 TiO2 마이크로스피어 입자를 대량으로 생산할 수 있는 도핑된 메조다공성 TiO2 마이크로스피어 입자 제조 방법이 요구되고 있다.Therefore, mesoporous TiO or may be effectively doped with a second microsphere particles of a metal or non-metal material, and / or, the doped mesoporous TiO 2 microsphere particles doped to produce a large amount of mesoporous TiO 2 microspheres particles prepared A method is required.
본 개시에서는, 금속 또는 비금속 물질로 효과적으로 도핑된 메조다공성 TiO2 마이크로스피어 입자를 대량으로 생산할 수 있는 "도핑된 메조다공성 TiO2 마이크로스피어 입자 제조 방법"을 제공한다.In this disclosure, there is provided a "doped mesoporous TiO 2 particles microsphere production process" of producing a meso-porous TiO 2 particles doped microspheres effectively a metallic or non-metallic materials in large quantities.
본 개시의 일구현예에 따른 "도핑된 티타늄옥사이드 메조다공성 마이크로스피어 입자 제조방법"은 다음의 단계를 포함할 수 있다:The "method for preparing doped titanium oxide mesoporous microsphere particles" according to one embodiment of the present disclosure may comprise the following steps:
(a) 제1용매 중에서 티타늄 전구체와 탄소함유 표면방향제어제를 혼합하여 티타늄-탄소 복합 입자를 형성하는 단계;(a) mixing a titanium precursor and a carbon-containing surface orientation agent in a first solvent to form a titanium-carbon composite particle;
(b) 상기 티타늄-탄소 복합 입자를 용해열(solvothermal) 처리하여, 상기 티타늄-탄소 복합 입자로부터 탄소를 제거함으로써, 티타늄 전구체 메조다공성 마이크로스피어 입자를 형성하는 단계;(b) subjecting the titanium-carbon composite particle to a solvothermal treatment to remove carbon from the titanium-carbon composite particle to form titanium precursor mesoporous microsphere particles;
(c) 상기 티타늄 전구체 메조다공성 마이크로스피어 입자에 도핑물질 전구체 함유 용액을 함침하여, 상기 티타늄 전구체 메조다공성 마이크로스피어 입자의 기공에 상기 도핑물질 전구체 함유 용액을 채움으로써, 함침된 티타늄 전구체 메조다공성 마이크로스피어 입자를 형성하는 단계; 및(c) impregnating the titanium precursor mesoporous microsphere particle with a solution containing a doping material precursor, and filling the pores of the titanium precursor mesoporous microsphere particle with the solution containing the doping material precursor, whereby the impregnated titanium precursor mesoporous microspheres Forming particles; And
(d) 상기 함침된 티타늄 전구체 메조다공성 마이크로스피어 입자를 열처리하여, 상기 티타늄 전구체 메조다공성 마이크로스피어 입자를 티타늄옥사이드 메조다공성 마이크로스피어 입자로 전환하고, 상기 티타늄 전구체 메조다공성 마이크로스피어 입자의 기공 내의 상기 도핑물질 전구체를 도핑물질로 전환시킴으로써, 도핑된 티타늄옥사이드 메조다공성 마이크로스피어 입자를 형성하는 단계.(d) heat treating the impregnated titanium precursor mesoporous microsphere particles to convert the titanium precursor mesoporous microsphere particles to titanium oxide mesoporous microsphere particles, and the doping of the titanium precursor mesoporous microsphere particles in the pores of the titanium precursor mesoporous microsphere particles, Forming a doped titanium oxide mesoporous microsphere particle by converting the material precursor into a doping material.
표면방향 제어제(suface directing agent)는 탄소함유 티타늄 전구체가 마이셀(micelle)을 형성하도록 유도한다. 또한, 표면방향제어제는 티타늄 입자가 구형으로 응결하도록 유도하는 역할을 하며, 이 응결반응을 통해 티타늄-탄소 복합 입자가 형성된다. 티타늄-탄소 복합 입자는 Ti과 탄소가 결합되어 있는 확장 구조(expanded structure)를 형성하게 된다. 입자가 확장 구조를 갖는다는 것은 입자의 기공의 크기가, 최종적으로 원하는 기공 크기보다 커진다는 것을 의미한다.The suface directing agent induces the carbon-containing titanium precursor to form a micelle. In addition, the surface orientation agent serves to induce the spherical shape of the titanium particles, and the titanium-carbon composite particles are formed through the coagulation reaction. The titanium-carbon composite particles form an expanded structure in which Ti and carbon are bonded. The fact that the particles have an extended structure means that the size of the pores of the particles ultimately becomes larger than the desired pore size.
이어서, 확장 구조를 갖는 티타늄-탄소 복합 입자를 용해열처리하여 탄소를 제거하면, 확장 구조를 갖는 티타늄 전구체 메조다공성 마이크로스피어 입자가 형성된다.Subsequently, the titanium-carbon composite particle having the expanded structure is subjected to dissolution heat treatment to remove carbon, thereby forming a titanium precursor mesoporous microsphere particle having an extended structure.
이렇게 기공 크기가 확장된 Ti 전구체 기반 메조다공성 마이크로스피어 입자에 도핑물질 전구체 함유 용액을 함침시키면, 예를 들어 아세트산 아연과 같은 도핑물질 전구체의 분자 크기가 비교적 크더라도, 도핑물질 전구체는 Ti 전구체 기반 메조다공성 마이크로스피어 입자의 확장된 기공에 용이하게 채워질 수 있다.When impregnating Ti precursor based pore size expanded mesoporous microsphere particles with a solution containing a dopant precursor in this way, even though the molecular size of the dopant precursor, such as, for example, zinc acetate, is relatively large, the dopant precursor may be a Ti precursor- The expanded pores of the porous microsphere particles can be easily filled.
이렇게 함침된 티타늄 전구체 메조다공성 마이크로스피어 입자를 열처리하는 과정에서 상기 입자의 체적 감소가 수반된다. 또한, 열처리 과정에서, Ti 전구체 기반 메조다공성 마이크로스피어 입자는 TiO2 메조다공성 마이크로스피어 입자로 전환된다. 또한, 열처리 과정에서, TiO2 메조다공성 마이크로스피어 입자의 기공 내에서, 도핑물질 전구체는 도핑물질로 전환된다. 결국, 도핑물질로 도핑된 TiO2 메조다공성 마이크로스피어 입자가 형성된다. 열처리 과정에서 수반되는 입자의 체적 감소를 통하여 입자 크기 및 기공 크기가 감소하더라도, 결국, 비교적 큰 크기의 도핑물질이 TiO2 메조다공성 마이크로스피어 입자의 작은 기공 내에 안정적으로 포획될 수 있다. In the process of heat-treating the impregnated titanium precursor mesoporous microsphere particles, the volume of the particles is reduced. Also, during the heat treatment process, Ti precursor-based mesoporous microsphere particles are converted to TiO 2 mesoporous microsphere particles. Also, in the heat treatment process, in the pores of the TiO 2 mesoporous microsphere particles, the doping material precursor is converted to a doping material. As a result, TiO 2 mesoporous microsphere particles doped with a doping material are formed. Even though the particle size and the pore size are reduced through the reduction of the volume of the particles involved in the heat treatment process, a relatively large amount of the doping material can be stably trapped in the small pores of the TiO 2 mesoporous microsphere particles.
이러한 메카니즘은, 예를 들어, 약 10 nm에 이르는 크기를 갖는 다양한 종류의 금속 및 비금속 입자 또는 양자점 등을, TiO2 메조다공성 마이크로스피어 입자의 작은 기공 내에 안정적으로 포획하는 것을 가능하게 한다. 따라서, 본 개시의 메카니즘은 TiO2 메조다공성 마이크로스피어 입자에 대한 매우 효과적이고 용이한 도핑 방법을 제공한다.This mechanism makes it possible to stably capture various kinds of metal and non-metal particles or quantum dots, for example, having a size of up to about 10 nm, in small pores of TiO 2 mesoporous microsphere particles. Thus, the mechanism of the present disclosure provides a highly effective and easy doping method for TiO 2 mesoporous microsphere particles.
도 1은 실시예 1에서 제조된 "Zn 도핑된 메조다공성 TiO2 마이크로스피어 입자" 및 비교예 1에서 제조된 "도핑되지 않은 메조다공성 TiO2 마이크로스피어 입자"에 대한 XRD 분석결과이다. 도 2는 도 1의 부분확대도이다. 도 3은 실시예 1에서 제조된 "Zn 도핑된 메조다공성 TiO2 마이크로스피어 입자" 및 비교예 1에서 제조된 "도핑되지 않은 메조다공성 TiO2 마이크로스피어 입자"에 대하여 질소 흡착 양을 비교하는 그래프이다.1 shows the XRD analysis results of "Zn-doped mesoporous TiO 2 microsphere particles" prepared in Example 1 and "undoped mesoporous TiO 2 microsphere particles" prepared in Comparative Example 1. 2 is a partially enlarged view of Fig. 3 is a graph comparing the amount of nitrogen adsorption with respect to "Zn-doped mesoporous TiO 2 microsphere particles" prepared in Example 1 and "undoped mesoporous TiO 2 microsphere particles" prepared in Comparative Example 1 .
티타늄 전구체로서는, 예를 들면, 티타늄 알콕사이드 화합물, 티타늄 할라이드 화합물, 또는 이들의 혼합물이 사용될 수 있다. 티타늄 알콕사이드 화합물은, 구체적인 예를 들면, 티타늄 이소프로폭사이드(titanium isopropoxide), 티타늄 에톡사이드(titanium ethoxide), 티타늄 부톡사이드(titanium n-butoxide), 티타늄 테트라이소프로폭사이드(titanium tetraisopropoxide), 또는 이들의 혼합물일 수 있다. 티타늄 할라이드 화합물은, 구체적인 예를 들면, 티타늄 테트라클로라이드(titanium tetrachloride)일 수 있다.
As the titanium precursor, for example, a titanium alkoxide compound, a titanium halide compound, or a mixture thereof may be used. The titanium alkoxide compound is specifically exemplified by titanium isopropoxide, titanium ethoxide, titanium n-butoxide, titanium tetraisopropoxide, or the like. Or mixtures thereof. The titanium halide compound may be a specific example, titanium tetrachloride.
표면방향 제어제로서는, 예를 들면, 헥사데실아민(hexadecylamine : HDA), 트리블록 코폴리머 P123(PEO20PPO70PEO20), 또는 이들의 혼합물이 사용될 수 있다.As the surface orientation control agent, for example, hexadecylamine (HDA), triblock copolymer P123 (PEO 20 PPO 70 PEO 20 ), or a mixture thereof may be used.
제1용매로서는, 예를 들면, 에탄올과 염화칼륨의 혼합 수용액, 1-프로판올, 또는 이들의 혼합물이 사용될 수 있다.
As the first solvent, for example, a mixed aqueous solution of ethanol and potassium chloride, 1-propanol, or a mixture thereof may be used.
티타늄-탄소 복합 입자의 용해열 처리 과정에서 사용되는 용매는, 구체적인 예를 들면, 에탄올과 수산화암모늄의 혼합 수용액이 사용될 수 있다.As the solvent used in the dissolution heat treatment process of the titanium-carbon composite particles, for example, a mixed aqueous solution of ethanol and ammonium hydroxide may be used.
티타늄-탄소 복합 입자의 용해열 처리 과정의 온도는, 예를 들면, 약 150 ℃ 내지 약 550 ℃일 수 있다. The temperature of the dissolution heat treatment process of the titanium-carbon composite particles may be, for example, from about 150 캜 to about 550 캜.
티타늄-탄소 복합 입자의 용해열 처리 과정은, 예를 들면, 오토클레이브 내에서 진행될 수 있다.
The dissolution heat treatment process of the titanium-carbon composite particles can be carried out, for example, in an autoclave.
도핑물질은, 예를 들면, 아연, 바나듐, 크롬, 니켈, 망간, 철, 또는 이들의 조합일 수 있다.The doping material may be, for example, zinc, vanadium, chromium, nickel, manganese, iron, or a combination thereof.
도핑물질이 아연인 경우, 도핑물질 전구체로서는, 예를 들면, 아세트산 아연(zinc acetate : (CH3CO2)2Zn), 염화아연(zinc chloride), 이메틸아연(di-methylzinc : Zn(CH3)2 : DMZ), 이에틸아연(diethylzinc : Zn(C2H5)2 : DEZ), 또는 이들의 혼합물이 사용될 수 있다.
When the doping material is zinc, examples of the doping material precursor include zinc acetate (CH 3 CO 2 ) 2 Zn, zinc chloride, di-methylzinc: Zn (CH 3 ) 2 : DMZ), diethylzinc: Zn (C 2 H 5 ) 2 : DEZ), or a mixture thereof.
도핑물질 전구체 함유 용액에 사용되는 용매로서는, 예를 들면, 에탄올, 디에틸렌글리콜, 또는 이들의 혼합물이 사용될 수 있다.As the solvent used in the solution containing the doping substance precursor, for example, ethanol, diethylene glycol, or a mixture thereof may be used.
티타늄 전구체 메조다공성 마이크로스피어 입자에 도핑물질 전구체 함유 용액을 함침하는 과정은, 예를 들면, 티타늄 전구체 메조다공성 마이크로스피어 입자와 도핑물질 전구체 함유 용액을 혼합한 후 교반함으로써 수행될 수 있다.
Titanium Precursor The process of impregnating the mesoporous microsphere particle with the solution containing the doping substance precursor can be performed, for example, by mixing the solution containing the titanium precursor mesoporous microsphere particle and the doping substance precursor, followed by stirring.
함침된 티타늄 전구체 메조다공성 마이크로스피어 입자를 열처리하는 과정은, 예를 들면, 티타늄 전구체 메조다공성 마이크로스피어 입자가 도핑물질 전구체 함유 용액에 분산되어 있는 상태에서 진행될 수 있다.The process of heat treating the impregnated titanium precursor mesoporous microsphere particles can proceed, for example, with the titanium precursor mesoporous microsphere particles dispersed in the solution containing the dopant precursor.
함침된 티타늄 전구체 메조다공성 마이크로스피어 입자를 열처리하는 과정의 온도는, 예를 들면, 약 150 ℃ 내지 약 550 ℃일 수 있다.
The temperature of the process of heat treating the impregnated titanium precursor mesoporous microsphere particles may be, for example, from about 150 ° C to about 550 ° C.
<실시예><Examples>
실시예Example 1 --- One --- ZnZn 도핑된Doped 메조다공성Mesoporous TiOTiO 22 마이크로스피어Microsphere 입자 제조 Particle manufacturing
먼저, 400 ml의 에탄올 (순도 99.99 wt%, Aldrich)과 1.9 ml의 0.1 M KCl 수용액 (AR(Analytical Reagent) grade, BDH Chemicals)이 혼합된 용액에, 4 g의 헥사데실아민(hexadecylamine) (순도 90 wt%, Aldrich)을 용해시켰다. 이렇게 얻은 용액에, 격렬히 교반하면서, 9 ml의 티타늄 이소프로폭사이드(titanium isopropoxide) (순도 97 wt%, Aldrich)를 첨가하여 제1 용액을 얻었다.First, 4 g of hexadecylamine (purity: 99.9 wt%, Aldrich) and 1.9 ml of 0.1 M KCl aqueous solution (Analytical Reagent grade, BDH Chemicals) were mixed with 400 ml of ethanol 90 wt%, Aldrich). To the thus obtained solution, 9 ml of titanium isopropoxide (97 wt% purity, Aldrich) was added with vigorous stirring to obtain a first solution.
그 다음, 제1 용액을 24 시간 동안 실온에서 방치하여 입자를 형성시켰다. 생성된 입자를 증류수로 3회 세척한 후 50 ℃에서 건조하였다. 4 g의 건조된 입자를 20 ml의 에탄올에 분산하였다. 이렇게 얻은 분산액에 10 ml의 증류수와 1 ml의 NH4OH 수용액 (농도 35 wt%, Aldrich)을 첨가하여 제1 분산액을 얻었다.The first solution was then left at room temperature for 24 hours to form particles. The resulting particles were washed three times with distilled water and dried at 50 ° C. 4 g of dried particles were dispersed in 20 ml of ethanol. 10 ml of distilled water and 1 ml of NH 4 OH aqueous solution (concentration of 35 wt%, Aldrich) were added to the dispersion thus obtained to obtain a first dispersion.
그 다음, 제1 분산액을 테프론으로 피복된 오토클레이브에 투입한 후, 밀폐한 상태에서, 160 ℃에서 10 시간 동안, 열처리하였다. 열처리된 입자를 여과로 회수한 다음 증류수로 3회 세척한 후 50 ℃에서 건조하였다. Then, the first dispersion liquid was put into an autoclave coated with Teflon, and then heat-treated at 160 DEG C for 10 hours in a sealed state. The heat-treated particles were collected by filtration, washed three times with distilled water, and dried at 50 ° C.
이렇게 얻은 입자를, 0.005 M 징크 아세테이트 디하이드레이트(zinc acetate dihydrate) (순도 98 wt%, Aldrich)가 용해된 에탄올 15 ml 용액에 분산한 후, 다시 24시간 동안 격렬히 교반하면서, 500 ℃에서 24 시간 동안 열처리하였다. 그에 따라, 아연이 도핑된 메조다공성 TiO2 마이크로스피어 입자를 얻었다.
The particles thus obtained were dispersed in a solution of 15 ml of ethanol dissolved with 0.005 M zinc acetate dihydrate (purity: 98 wt%, Aldrich) and then stirred vigorously for 24 hours at 500 ° C for 24 hours Heat treated. Thereby, zinc-doped mesoporous TiO 2 microsphere particles were obtained.
비교예Comparative Example 1 --- One --- ZnZn 도핑되지Not doped 않은 Not 메조다공성Mesoporous TiOTiO 22 마이크로스피어Microsphere 입자 제조 Particle manufacturing
먼저, 400 ml의 에탄올 (순도 99.99 wt%, Aldrich)과 1.9 ml의 0.1 M KCl 수용액 (AR(Analytical Reagent) grade, BDH Chemicals)이 혼합된 용액에, 4 g의 헥사데실아민(hexadecylamine) (순도 90 wt%, Aldrich)을 용해시켰다. 이렇게 얻은 용액에, 격렬히 교반하면서, 9 ml의 티타늄 이소프로폭사이드(titanium isopropoxide) (순도 97 wt%, Aldrich)를 첨가하여 제1 용액을 얻었다.First, 4 g of hexadecylamine (purity: 99.9 wt%, Aldrich) and 1.9 ml of 0.1 M KCl aqueous solution (Analytical Reagent grade, BDH Chemicals) were mixed with 400 ml of ethanol 90 wt%, Aldrich). To the thus obtained solution, 9 ml of titanium isopropoxide (97 wt% purity, Aldrich) was added with vigorous stirring to obtain a first solution.
그 다음, 제1 용액을 24 시간 동안 실온에서 방치하여 입자를 형성시켰다. 생성된 입자를 증류수로 3회 세척한 후 50 ℃에서 건조하였다. 4 g의 건조된 입자를 20 ml의 에탄올에 분산하였다. 이렇게 얻은 분산액에 10 ml의 증류수와 1 ml의 NH4OH 수용액 (농도 35 wt%, Aldrich)을 첨가하여 제1 분산액을 얻었다.The first solution was then left at room temperature for 24 hours to form particles. The resulting particles were washed three times with distilled water and dried at 50 ° C. 4 g of dried particles were dispersed in 20 ml of ethanol. 10 ml of distilled water and 1 ml of NH 4 OH aqueous solution (concentration of 35 wt%, Aldrich) were added to the dispersion thus obtained to obtain a first dispersion.
그 다음, 제1 분산액을 테프론으로 피복된 오토클레이브에 투입한 후, 밀폐한 상태에서, 160 ℃에서 10 시간 동안, 열처리하였다. 열처리된 입자를 여과로 회수한 다음 증류수로 3회 세척한 후 50 ℃에서 건조하였다. Then, the first dispersion liquid was put into an autoclave coated with Teflon, and then heat-treated at 160 DEG C for 10 hours in a sealed state. The heat-treated particles were collected by filtration, washed three times with distilled water, and dried at 50 ° C.
이렇게 얻은 입자를, 에탄올 15 ml 용액에 분산한 후, 다시 24시간 동안 격렬히 교반하면서, 500 ℃에서 24 시간 동안 열처리하였다. 그에 따라, 도핑되지 않은 메조다공성 TiO2 마이크로스피어 입자를 얻었다.
The particles thus obtained were dispersed in a solution of 15 ml of ethanol, and then heat-treated at 500 ° C for 24 hours while vigorously stirring for 24 hours. As a result, undoped mesoporous TiO 2 microsphere particles were obtained.
도 1은 실시예 1에서 제조된 "Zn 도핑된 메조다공성 TiO2 마이크로스피어 입자" 및 비교예 1에서 제조된 "도핑되지 않은 메조다공성 TiO2 마이크로스피어 입자"에 대한 XRD 분석결과이다. 도 2는 도 1의 부분확대도이다. 도 2에 결정면의 피크의 이동이 나타나 있다. 이로부터, 실시예 1에서 제조된 메조다공성 TiO2 마이크로스피어 입자에 Zn이 효과적으로 도핑되어 있음을 확인할 수 있다. 도 3은 실시예 1에서 제조된 "Zn 도핑된 메조다공성 TiO2 마이크로스피어 입자" 및 비교예 1에서 제조된 "도핑되지 않은 메조다공성 TiO2 마이크로스피어 입자"에 대하여 질소 흡착 양을 비교하는 그래프이다. 도 3으로부터 아연의 효과적인 도핑에 따라 질소 흡착 양이 증가됨을 확인할 수 있다.1 shows the XRD analysis results of "Zn-doped mesoporous TiO 2 microsphere particles" prepared in Example 1 and "undoped mesoporous TiO 2 microsphere particles" prepared in Comparative Example 1. 2 is a partially enlarged view of Fig. 2 shows the movement of the peak of the crystal plane. From this, it can be confirmed that Zn is effectively doped in the mesoporous TiO 2 microsphere particles prepared in Example 1. 3 is a graph comparing the amount of nitrogen adsorption with respect to "Zn-doped mesoporous TiO 2 microsphere particles" prepared in Example 1 and "undoped mesoporous TiO 2 microsphere particles" prepared in Comparative Example 1 . It can be seen from FIG. 3 that the amount of nitrogen adsorption increases with effective doping of zinc.
Claims (9)
(b) 상기 티타늄-탄소 복합 입자를 용해열 처리하여, 상기 티타늄-탄소 복합 입자로부터 탄소를 제거함으로써, 티타늄 전구체 메조다공성 마이크로스피어 입자를 형성하는 단계;
(c) 상기 티타늄 전구체 메조다공성 마이크로스피어 입자에 도핑물질 전구체 함유 용액을 함침하여, 상기 티타늄 전구체 메조다공성 마이크로스피어 입자의 기공에 상기 도핑물질 전구체 함유 용액을 채움으로써, 함침된 티타늄 전구체 메조다공성 마이크로스피어 입자를 형성하는 단계; 및
(d) 상기 함침된 티타늄 전구체 메조다공성 마이크로스피어 입자를 열처리하여, 상기 티타늄 전구체 메조다공성 마이크로스피어 입자를 티타늄옥사이드 메조다공성 마이크로스피어 입자로 전환하고, 상기 티타늄 전구체 메조다공성 마이크로스피어 입자의 기공 내의 상기 도핑물질 전구체를 도핑물질로 전환시킴으로써, 도핑된 티타늄옥사이드 메조다공성 마이크로스피어 입자를 형성하는 단계;를 포함하는,
도핑된 티타늄옥사이드 메조다공성 마이크로스피어 입자 제조방법.(a) mixing a titanium precursor and a carbon-containing surface orientation agent in a first solvent to form a titanium-carbon composite particle;
(b) dissolving heat of the titanium-carbon composite particles to remove carbon from the titanium-carbon composite particles to form titanium precursor mesoporous microsphere particles;
(c) impregnating the titanium precursor mesoporous microsphere particle with a solution containing a doping material precursor, and filling the pores of the titanium precursor mesoporous microsphere particle with the solution containing the doping material precursor, whereby the impregnated titanium precursor mesoporous microspheres Forming particles; And
(d) heat treating the impregnated titanium precursor mesoporous microsphere particles to convert the titanium precursor mesoporous microsphere particles to titanium oxide mesoporous microsphere particles, and the doping of the titanium precursor mesoporous microsphere particles in the pores of the titanium precursor mesoporous microsphere particles, And forming a doped titanium oxide mesoporous microsphere particle by converting the material precursor to a doping material.
Method for preparing doped titanium oxide mesoporous microsphere particles.
The method of claim 1, wherein the temperature of the impregnated titanium precursor mesoporous microsphere particles is in the range of 150 ° C to 550 ° C.
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| CN104759995A (en) * | 2015-04-08 | 2015-07-08 | 安阳工学院 | Glass polishing disk and manufacturing technique thereof |
| CN105080531A (en) * | 2015-08-13 | 2015-11-25 | 上海工程技术大学 | Method for preparing neodymium-doped mesopore titanium dioxide microballoon photocatalyst |
| CN107117650A (en) * | 2017-05-22 | 2017-09-01 | 常州大学 | A kind of monodisperse titanium dioxide microballoon and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104759995A (en) * | 2015-04-08 | 2015-07-08 | 安阳工学院 | Glass polishing disk and manufacturing technique thereof |
| CN105080531A (en) * | 2015-08-13 | 2015-11-25 | 上海工程技术大学 | Method for preparing neodymium-doped mesopore titanium dioxide microballoon photocatalyst |
| CN107117650A (en) * | 2017-05-22 | 2017-09-01 | 常州大学 | A kind of monodisperse titanium dioxide microballoon and preparation method and application |
| KR20190042478A (en) * | 2017-10-16 | 2019-04-24 | 이화여자대학교 산학협력단 | Titanium dioxide-metal composite particle, method for preparing the same, and photocatalyst including the same |
| CN110165225A (en) * | 2019-05-23 | 2019-08-23 | 中国船舶重工集团公司第七二五研究所 | A kind of modified anode nanometer composite material and preparation method of SMFC |
| CN110165225B (en) * | 2019-05-23 | 2021-11-30 | 中国船舶重工集团公司第七二五研究所 | Modified anode nanocomposite material for SMFC and preparation method thereof |
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