KR101488598B1 - Fabrication of nanoporous TiO2-graphene composite nanofibers for dye-sensitized solar cells - Google Patents
Fabrication of nanoporous TiO2-graphene composite nanofibers for dye-sensitized solar cells Download PDFInfo
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- KR101488598B1 KR101488598B1 KR20130067066A KR20130067066A KR101488598B1 KR 101488598 B1 KR101488598 B1 KR 101488598B1 KR 20130067066 A KR20130067066 A KR 20130067066A KR 20130067066 A KR20130067066 A KR 20130067066A KR 101488598 B1 KR101488598 B1 KR 101488598B1
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 106
- 239000002121 nanofiber Substances 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002131 composite material Substances 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 69
- 239000010936 titanium Substances 0.000 claims abstract description 64
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 64
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000001965 increasing effect Effects 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 230000006911 nucleation Effects 0.000 claims abstract description 7
- 238000010899 nucleation Methods 0.000 claims abstract description 7
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 75
- 229920000642 polymer Polymers 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 30
- 239000002105 nanoparticle Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 27
- 238000001523 electrospinning Methods 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 23
- 239000004793 Polystyrene Substances 0.000 claims description 16
- 229920002223 polystyrene Polymers 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000006482 condensation reaction Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 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 description 3
- YTRBDEVYXMWAMX-UHFFFAOYSA-N oxotitanium titanium Chemical compound [Ti].[Ti]=O YTRBDEVYXMWAMX-UHFFFAOYSA-N 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 60
- 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 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000004627 transmission electron microscopy Methods 0.000 description 19
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
-
- B01J35/58—
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/10—Physical properties porous
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/16—Physical properties antistatic; conductive
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
본 발명은 전기 전도성이 높은 그래핀을 이산화티타늄 나노섬유에 도입하여 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 이는 기존의 이산화티타늄 나노섬유보다 전자 전달 속도가 더 빨라질 뿐만 아니라, 산화그래핀 내의 수산기, 카르복실기에서의 이산화티타늄의 추가적인 결정핵 생성에 의해 이산화티타늄의 낱알의 개수가 증가하고 이산화티타늄의 낱알 크기가 감소함으로써 나노섬유의 표면적이 획기적으로 향상되어 염료의 흡착량이 증가할 수 있음을 확인하였다. 이를 염료감응형 태양전지에 적용시 광전극의 태양광 이용률과 광전환 효율의 향상을 기대할 수 있게 하였다.In the present invention, titanium dioxide-graphene porous nanofiber was prepared by introducing graphene having high electrical conductivity into titanium dioxide nanofiber. Not only is the electron transfer rate faster than that of conventional titanium dioxide nanofibers, the number of titanium dioxide grains is increased by the additional crystal nucleation of titanium dioxide in the hydroxyl groups and carboxyl groups in the graphene grains, and the grain size of the titanium dioxide It was confirmed that the surface area of the nanofiber can be remarkably improved and the adsorption amount of the dye can be increased. This can be expected to improve the solar utilization and light conversion efficiency of the photoelectrode when applied to a dye-sensitized solar cell.
Description
본 발명은 다공성 구조를 가지는 이산화티타늄-그래핀 나노섬유의 제조에 관한 것으로서, 전기 방사 방법을 통해 이산화티타늄 전구체-산화그래핀-고분자 나노섬유를 제조한 후 산화그래핀의 수산기, 카르복실기를 이산화티타늄의 추가적인 결정핵 생성 위치로 적용하여 기존의 이산화티타늄 나노섬유보다 표면적을 크게 향상시키고 이후 열처리를 통해 anatase의 결정성을 가지는 이산화티타늄-그래핀 다공성 나노섬유의 제조하는 방법을 제시한다.
The present invention relates to the production of titanium dioxide-graphene nanofibers having a porous structure, which comprises preparing a titanium dioxide precursor-oxidized graphene-polymer nanofiber by an electrospinning method and then subjecting the hydroxyl group and carboxyl group of the oxidized graphene to titanium dioxide The present invention provides a method for manufacturing titanium dioxide-graphene porous nanofibers having anatase crystallinity through heat treatment by further increasing the surface area of titanium dioxide nanofibers compared to conventional titanium dioxide nanofibers.
일반적으로 염료감응형 태양전지는 이산화티타늄 나노입자의 다공성 망을 기반으로 이루어져 있다. 그리고 그 표면에 광 감응체로써 염료가 이산화티타늄 나노입자 표면에 흡착되어 있는 구조이다. 그러나 이러한 나노입자 기반 구조에서는 전자 이동이 제한된 확산에 의해 느려지게 되어 전자의 재결합이 증가하고, 또한 상대전극에서 전자가 수집되기 전에 낱알 경계에서 재결합이 되어버려 낮은 효율을 초래한다. 이러한 근본적인 염료감응형 태양전지의 문제점인 느린 전하 전달과, 낮은 수집 효율을 향상시키기 위한 우수한 광전극 소재의 제조가 강력히 요구되고 있다.In general, dye-sensitized solar cells are based on a porous network of titanium dioxide nanoparticles. And a dye is adsorbed on the surface of the titanium dioxide nanoparticle as a photosensitizer on its surface. However, in these nanoparticle-based structures, electron transport is slowed by limited diffusion, resulting in increased recombination of electrons and recombination at the grain boundaries before electrons are collected at the counter electrode, resulting in low efficiency. There is a strong demand for slow charge transfer, which is a problem of such a fundamental dye-sensitized solar cell, and production of an excellent photoelectrode material for improving the collection efficiency.
이러한 염료감응형 태양전지의 효율 감소 문제를 해결하기 위한 방법 중 하나는 나노입자 기반 구조 대신 1차원 나노구조를 구현, 즉 나노섬유를 광전극에 도입하는 것이다. 이러한 구조는 전자가 빠르게 수집되도록 직접적인 경로를 제공하고, 나노입자 기반 구조보다 낱알 경계 개수가 적어 전자가 재결합이 될 확률을 감소시켜준다. 또한 이러한 1차원 나노구조 소재는 태양광을 산란시켜 광흡수율을 향상시키는 것이 가능하다. 그러나 1차원 나노구조는 나노입자 구조보다 표면적이 상대적으로 좁아서 광전극의 염료 흡착량이 나노입자 기반의 염료감응형 태양전지에 비해 적다는 단점이 존재한다. 그리하여 이러한 1차원 나노구조 소재의 좁은 표면적 문제를 해결하기 위해 계면활성제, 실리카 나노입자, 블록 공중합체 등을 이산화티타늄 전구체 혼합 용액에 도입하여 전기 방사한 후 열처리를 하거나 에칭하는 방법 등이 제시되어 왔으나 비용이 많이 들고, 방법이 복잡하거나 환경친화적이지 않은 단점이 있었다.One of the methods for solving the problem of reduction in the efficiency of the dye-sensitized solar cell is to implement a one-dimensional nanostructure instead of a nanoparticle-based structure, that is, to introduce nanofibers into the photoelectrode. This structure provides a direct path for electrons to be collected quickly and reduces the probability that electrons will recombine because the number of grain boundaries is smaller than the nanoparticle-based structure. In addition, such a one-dimensional nanostructured material can scatter sunlight to improve the light absorption rate. However, there is a disadvantage that the one-dimensional nanostructure has a smaller surface area than the nanoparticle structure, so that the dye adsorption amount of the photoelectrode is smaller than that of the nanoparticle-based dye-sensitized solar cell. In order to solve the problem of the narrow surface area of such a one-dimensional nanostructured material, there has been suggested a method of introducing a surfactant, silica nanoparticle, block copolymer, etc. into a titanium dioxide precursor mixture solution and electrospinning the same, followed by heat treatment or etching There was a disadvantage that it was costly, the method was not complicated or environmentally friendly.
또 다른 방법으로는 높은 전기 전도도를 가진 소재, 예를 들면 탄소나노튜브, 탄소나노섬유, 흑연, 그래핀 등을 광전극에 도입하는 것이 있다. 이러한 전기 전도성 소재는 들뜬 전자의 전달 속도를 증가시켜서 전자의 수명을 늘리고 전자가 재결합이 되기 전에 상대전극에서 수집될 수 있도록 한다. 그래핀은 탄소 원자들이 벌집 모양의 육각형 그물처럼 배열되어있는 2차원 구조 물질인데, 0.2 나노미터의 얇은 두께에도 불구하고 물리적, 화학적 안정성이 매우 높을 뿐만 아니라 강도가 세고 열전도도와 전자 이동 속도도 빠른 장점을 가지고 있다. 그래핀은 구리보다 100배 이상 전기가 잘 통하고 실리콘보다 100배 이상 전자의 이동이 빠르기 때문에 이를 염료감응형 태양전지의 광전극에 도입한다면 전자의 수집 효율을 높일 수 있을 것이라 기대된다.
Another method is to introduce materials having high electrical conductivity, such as carbon nanotubes, carbon nanofibers, graphite, and graphene, into the photoelectrode. Such an electrically conductive material increases the transfer rate of excited electrons, thereby increasing the lifetime of the electrons and allowing electrons to be collected at the counter electrode before recombination. Graphene is a two-dimensional structural material in which carbon atoms are arranged like a honeycomb hexagonal net. Not only is the physical and chemical stability very high despite its thinness of 0.2 nm, it also has a high strength and a high thermal conductivity and electron migration rate Lt; / RTI > Graphene is 100 times more electricity than copper and 100 times more electrons than silicon. Therefore, it is expected that the efficiency of collecting electrons can be improved by introducing it into the photoelectrode of the dye - sensitized solar cell.
본 발명의 목적은 이러한 종래기술의 문제점을 일거에 해결하고자 이산화티타늄 나노섬유에 그래핀을 도입하여 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 이를 염료감응형 태양전지의 광전극에 도입하게 되면 1차원 나노구조와 전기 전도성 물질의 장점, 즉 전자의 직접적인 경로 제공, 향상된 광산란, 그리고 전자의 전달 속도 증가를 동시에 이용하여 염료감응형 태양전지 광전극의 태양광 이용률과 광전환 효율의 향상을 기대할 수 있다.It is an object of the present invention to provide titanium dioxide-graphene porous nanofiber by introducing graphene into titanium dioxide nanofibers in order to resolve the problems of the prior art. When the dye-sensitized solar cell is introduced into the photoelectrode of the dye-sensitized solar cell, the advantage of the one-dimensional nanostructure and the electroconductive material, that is, the direct path of electrons, the improved light scattering, It is expected that the use efficiency of the electrode and the light conversion efficiency of the electrode can be improved.
본 발명가들은 수많은 실험과 심도있는 연구를 거듭한 끝에, 이제껏 알려진 방법과는 전혀 다른 방법, 즉 이산화티타늄 전구체 용액에 산화그래핀을 분산시킨 후 이를 전기 방사하여 산화그래핀의 수산기, 카르복실기를 이산화티타늄의 추가적인 결정핵 생성 위치로 적용하였다. 이후 열처리를 통해 anatase의 결정성을 가지는 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 그 결과, 이산화티타늄-그래핀 다공성 나노섬유는 기존의 이산화티타늄 나노섬유보다 전자의 전달 속도 증가 효과 뿐만 아니라 표면적이 확연하게 증가하는 것을 확인하였다. 이는 본 발명에서 도입한 산화그래핀에서 이산화티타늄의 추가적인 결정핵이 생성되어 나노섬유에서 이산화티타늄의 낱알개수가 증가하고 낱알 크기는 감소하기 때문이다. 이는 1차원 나노구조의 단점인 좁은 표면적 문제를 해결할 수 있도록 한다. 이를 염료감응형 태양전지에 광전극에 도입함으로써 기존 이산화티타늄 나노섬유에 비해 향상된 전자 전달 속도와 향상된 표면적을 동시에 이용하여 염료감응형 태양전지 광전극의 태양광 이용률과 광전환 효율이 향상을 기대할 수 있음을 확인하고 본 발명에 이르게 되었다.
The inventors of the present invention have conducted numerous experiments and in-depth studies, and have found that the method of dissolving the graphene oxide in a titanium dioxide precursor solution and electrospinning it to prepare a titanium dioxide precursor solution by dispersing the hydroxyl group and the carboxyl group of the oxidized graphene into titanium dioxide Lt; RTI ID = 0.0 > nucleation site. ≪ / RTI > Through the heat treatment, titanium dioxide - graphene porous nanofiber having crystallinity of anatase was prepared. As a result, it was confirmed that the titanium dioxide - graphene porous nanofiber significantly increased the surface area as well as the electron transfer rate increase effect than the conventional titanium dioxide nanofiber. This is because the additional crystal nuclei of titanium dioxide are generated in the oxidized graphene introduced in the present invention, whereby the number of grains of titanium dioxide in the nanofiber increases and the grain size decreases. This makes it possible to solve the problem of narrow surface area which is a drawback of one-dimensional nanostructures. By introducing this into the dye-sensitized solar cell, it can be expected that the photovoltaic efficiency and light conversion efficiency of the dye-sensitized solar cell photoelectrode can be improved by simultaneously using the improved electron transfer rate and the improved surface area as compared with the conventional titanium dioxide nanofiber And reached the present invention.
본 발명은 이산화티타늄 나노섬유에 그래핀을 도입한 이산화티타늄-그래핀 다공성 나노섬유를 제조함으로써, 기존의 이산화티타늄 나노섬유에 비해 향상된 전자 전달 속도와 넓어진 표면적을 통해 광전극의 염료 흡착량을 늘려 염료감응형 태양전지에 적용시 광전환 효율의 향상을 기대할 수 있게 하였다.The present invention provides titanium dioxide-graphene porous nanofibers with graphene incorporated into titanium dioxide nanofibers, thereby increasing the amount of dye adsorbed on the photoelectrode through improved electron transfer rate and wider surface area compared to conventional titanium dioxide nanofibers It is possible to expect an improvement in light conversion efficiency when applied to a dye-sensitized solar cell.
본 발명은The present invention
(A) 이산화티타늄 전구체, 고분자, 아세트산, 산화그래핀 혼합 용액을 만드는 단계; 및,(A) preparing a mixed solution of a titanium dioxide precursor, a polymer, acetic acid, and an oxidized graphene; And
(B) 상기 혼합 용액을 전기 방사를 이용하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유를 제조하는 단계; 및,(B) preparing a titanium dioxide precursor-oxidized graphene-polymer nanofiber by electrospinning the mixed solution; And
(C) 상기 이산화티타늄 전구체-산화그래핀-고분자 나노섬유의 대기중 수분에 의한 가수분해 및 산화그래핀에서의 축합반응에 의한 추가적인 결정핵 생성을 유도하여 티타늄-산소-티타늄 공유결합을 형성하는 단계; 및,(C) forming a titanium-oxygen-titanium covalent bond by inducing additional crystal nucleation by hydrolysis of the titanium dioxide precursor-oxidized graphene-polymer nanofiber by moisture in the air and condensation reaction in the graphene oxide step; And
(D) 상기 공유결합이 형성된 아산화티타늄-산화그래핀-고분자 나노섬유를 열처리 과정을 통해 anatase 결정성을 가지게 하여 전자 전달 속도가 우수하고 표면적이 증대된 이산화티타늄-그래핀 다공성 나노섬유를 제조하는 단계로 구성되어진다.(D) fabricating titanium dioxide-graphene nanoparticles having an anatase crystallinity through the heat treatment to form the covalently bonded titanium dioxide-oxidized graphene-polymer nanofibers and having increased electron transfer rate and increased surface area .
본 발명에 따른 그래핀이 도입된 이산화티타늄-그래핀 다공성 나노섬유는 이제껏 보고된 바가 없는 전혀 새로운 방법으로써, 이산화티타늄 나노섬유의 크기와 구조로 인한 빛의 산란 효과가 일어나며, 이산화티타늄 나노섬유에 도입된 그래핀으로 인해 전자 전달 속도가 증가할 뿐만 아니라, 기존의 이산화티타늄 나노섬유에 비해 산화그래핀에서의 추가적인 결정핵 생성으로 인해서 표면적이 향상되어 염료의 흡착량이 증가한다. 이러한 이산화티타늄-그래핀 다공성 나노섬유를 염료감응형 태양전지용 광전극에 도입함으로써 일반적인 이산화티타늄 나노섬유로 구성된 광전극에 비해 향상된 전자 수집 효율을 가지고 광전환 효율이 높은 염료감응형 태양전지를 제조할 수 있다.
The graphene-introduced grafted titanium dioxide-graphene nanofibers according to the present invention are completely new methods that have not been reported so far, and the light scattering effect is caused by the size and structure of the titanium dioxide nanofibers, Not only the electron transfer rate is increased due to the introduced graphene but also the surface area is increased due to the additional nucleation at the oxide graphene compared to the conventional titanium dioxide nanofibers, thereby increasing the adsorption amount of the dye. By introducing such titanium dioxide-graphene porous nanofiber into a photoelectrode for a dye-sensitized solar cell, a dye-sensitized solar cell having improved photoelectric conversion efficiency and improved electron collection efficiency as compared with a photoelectrode composed of general titanium dioxide nanofibers can be manufactured .
도 1은 본 발명의 실시예 1에서 제조된 전기 방사 후 500 ℃ 열처리한 이산화티타늄-그래핀 다공성 나노섬유의 투과전자현미경 사진이고;
도 2는 본 발명의 실시예 1에서 제조된 전기 방사 후 500 ℃ 열처리한 이산화티타늄-그래핀 다공성 나노섬유의 주사전자현미경 사진이다.FIG. 1 is a transmission electron micrograph of titanium dioxide-graphene porous nanofiber heat-treated at 500 ° C. after electrospinning according to Example 1 of the present invention; FIG.
2 is a scanning electron microscope (SEM) image of titanium dioxide-graphene porous nanofiber prepared by heat treatment at 500 ° C. after electrospinning according to Example 1 of the present invention.
본 발명은 이산화티타늄 전구체-산화그래핀-고분자 나노섬유에서 500 나노미터의 직경을 가진 이산화티타늄-그래핀 다공성 나노섬유를 전기방사를 통해 제조하는 것을 내용으로 한다. 단계 (A)에서 사용되는 그래핀은 공지된 방법, 예를 들면 기존문헌 (X. L. Li, X. R. Wang, L. Zhang, S. W. Lee, H. J. Dai, Science 2008, 319, 1229-1232.) 등에 개시된 제조방법을 통해 산화그래핀 형태로 제조한 후 단계 (D)에서의 열처리 과정을 통해 그래핀으로 환원되는 과정을 거친다. 산화그래핀의 부가량은 단계 (A)에서의 혼합 용액 100 중량부에 대하여 0.1 내지 ~ 1 중량부이나 이로 한정되지 않는다.The present invention relates to the preparation of titanium dioxide-graphene porous nanofibers having a diameter of 500 nanometers in a titanium dioxide precursor-oxidized graphene-polymer nanofiber through electrospinning. Graphene is a known method used in the step (A), for example, the literature (Li XL, XR Wang, L. Zhang, Lee SW, HJ Dai, Science 2008 , 319 , 1229-1232), and the like, and then subjected to a heat treatment process in step (D) to be reduced to graphene. The addition amount of the graphene oxide is not limited to 0.1 to 1 part by weight based on 100 parts by weight of the mixed solution in the step (A).
단계 (A) 에서 고분자를 녹인 용매에 있어서 고분자의 종류는 특별히 한정되는 것은 아니며, 유기용매에 녹는 폴리스티렌, 폴리메틸메타아크릴레이드, 셀룰로오스 아세테이트, 폴리비닐피롤리돈, 폴리카프로락톤, 폴리에틸렌옥사이드 등의 고분자가 바람직하다.In the solvent in which the polymer is dissolved in the step (A), the kind of the polymer is not particularly limited. Examples of the polymer include polystyrene, polymethylmethacrylate, cellulose acetate, polyvinylpyrrolidone, polycaprolactone, polyethylene oxide Polymers are preferred.
고분자를 용매에 녹일 때, 고분자의 부가량은 고분자를 녹이는 용매 100 중량부에 대하여 1 내지 30 중량부이고, 온도는 30 내지 80 ℃가 바람직하나, 이에 국한되는 것은 아니며, 고분자의 종류에 따라서 상기범위보다 높거나 낮을 수 있다.When the polymer is dissolved in a solvent, the addition amount of the polymer is 1 to 30 parts by weight based on 100 parts by weight of the solvent for dissolving the polymer, and the temperature is preferably 30 to 80 DEG C, but the present invention is not limited thereto. Range. ≪ / RTI >
이산화티타늄 전구체의 종류는 특정 종류에 한정된 것이 아니며 티타늄 테트라아이소프로폭사이드, 티타늄 부톡사이드, 티타늄 에톡사이드, 티타늄 옥시설페이트, 티타늄 클로라이드가 사용될 수 있다.The type of the titanium dioxide precursor is not limited to a specific type, and titanium tetraisopropoxide, titanium butoxide, titanium ethoxide, titanium oxysulfate, and titanium chloride may be used.
이산화티타늄 전구체의 부가량은 고분자 용액 100 중량부에 대하여 10 내지 30 중량부까지 첨가 가능하며 이산화티티늄 전구체 중량부가 10 이상이면 열처리 과정을 거친 후 섬유가 잘 형성되는 것을 관찰할 수 있으나 10 미만이면 나노섬유를 형성하는데 있어서 문제가 발생한다.The addition amount of the titanium dioxide precursor may be 10 to 30 parts by weight with respect to 100 parts by weight of the polymer solution. If the titanium dioxide precursor weight part is 10 or more, it can be observed that the fibers are well formed after the heat treatment, Problems arise in forming nanofibers.
아세트산 용액의 부가량은 단계 (A)에서의 전체 혼합용액 100 중량부에 대하여 10 중량부 내지 30 중량부인 것이 바람직하다. 아세트산의 부가량이 30 중량부 이상이면 혼합용액은 점도가 낮아 구슬모양을 가지는 불규칙적이게 섬유가 형성된다.The amount of the acetic acid solution added is preferably 10 parts by weight to 30 parts by weight based on 100 parts by weight of the total mixed solution in the step (A). When the addition amount of acetic acid is 30 parts by weight or more, the mixed solution has a low viscosity and irregularly shaped fibers having a bead shape are formed.
단계 (B)에서 전기 방사법은 고분자를 녹일 수 있는 용매에 상용 고분자를 녹여 상기 고분자 용액을 전기 방사하여 고분자 나노섬유를 제조하는 것을 말하며, 사용되는 상용 분자의 분자량 범위는 9,000 내지 1,300,000 이 바람직하다.In the step (B), the electrospinning means preparing a polymer nanofiber by dissolving a commercial polymer in a solvent capable of dissolving the polymer and electrospinning the polymer solution, and the molecular weight of the commercial molecule used is preferably 9,000 to 1,300,000.
전기 방사시, 전자기장의 세기는 1 kV 내지 60 kV 이며, 1 kV 보다 낮은 전압에서는 고분자 용액의 고유한 표면장력보다 낮아 고분자 섬유가 형성되지 않고 방울 형태로 고분자가 사출되며, 60 kV 보다 높은 전압에서는 높은 전압으로 인하여 제조되는 고분자 나노섬유가 연속성이 없거나 엉기거나 형태가 불규칙적이다. In the case of electrospinning, the intensity of the electromagnetic field is 1 kV to 60 kV. At a voltage lower than 1 kV, the polymer is lower than the inherent surface tension of the polymer solution, so that the polymer is injected in the form of droplets without forming polymer fibers. Polymer nanofibers produced by high voltage are non-continuous, coarse, or irregular in shape.
전기 방사를 통해 제조되는 고분자 나노섬유는 용매의 농도, 점도, 가해지는 전압의 크기의 변수에 의해서 10 나노미터에서 수 마이크로미터 범위로 직경을 조절할 수 있다. 고분자의 부가량은 용매 100 중량부에 대하여 1 내지 30 중량부이다.Polymer nanofibers produced by electrospinning can be controlled in diameter from 10 nanometers to several micrometers depending on the concentration of the solvent, the viscosity, and the magnitude of the applied voltage. The added amount of the polymer is 1 to 30 parts by weight based on 100 parts by weight of the solvent.
단계 (C) 에서 전기 방사로 제조된 이산화티타늄 전구체-산화그래핀-고분자 나노섬유는 대기 중의 수분과 반응하여 이산화티타늄 전구체가 가수분해된다. 이때 형성된 수산기들의 축합반응에 의해 티타늄-산소-티타늄 공유결합이 형성되면서 나노 섬유 내 전반에 걸쳐서 결정핵이 생성되고 이 결정핵이 공유결합이 계속 진행됨에 따라 이산화티타늄 낱알이 된다. 이 때 산화그래핀의 수산기, 카르복실기는 이산화티타늄 나노섬유에서만 생성되는 결정핵 이외에도 추가적인 결정핵 생성 위치로 작용한다. (X. Li, W. Qi, D. Mei, M. L. Sushko, I. Aksay, J. Liu, Advanced Materials, 2012, 24, 5136-5141.) 이로 인해 이산화티타늄-그래핀 다공성 나노섬유는 그래핀이 없는 이산화티타늄 나노섬유보다 공기 중에서 가수분해 및 축합반응 시 결정핵이 더 많이 존재하게 된다. 그로 인해 나노섬유 내 한정된 이산화티타늄 전구체 하에서 이산화티타늄의 낱알 개수는 늘어나지만 낱알 크기가 더 작아지게 되어 결국 나노섬유의 표면적이 더 넓어지게 된다.In step (C), the titanium dioxide precursor-oxidized graphene-polymer nanofiber prepared by electrospinning reacts with moisture in the atmosphere to hydrolyze the titanium dioxide precursor. The titanium-oxygen-titanium covalent bonds are formed by the condensation reaction of the hydroxyl groups formed to form crystal nuclei throughout the entire nanofiber, and the crystal nuclei become titanium dioxide particles as the covalent bond proceeds. At this time, the hydroxyl group and the carboxyl group of the graphene oxide act as additional crystal nucleation sites in addition to the crystal nuclei generated only in the titanium dioxide nanofibers. (X. Li, W. Qi, D. Mei, ML Sushko, I. Aksay, J. Liu, Advanced Materials, 2012, 24, 5136-5141) This titanium dioxide-graphene porous nanofibers is graphene is no titanium dioxide is the hydrolysis and condensation reaction of nucleation exists in the air more than the nanofiber. As a result, under a limited titanium dioxide precursor in the nanofiber, the number of grain of titanium dioxide increases but the grain size becomes smaller, resulting in a wider surface area of the nanofiber.
이때 가수분해 및 축합반응은 상온이 바람직하나, 이에 국한되는 것은 아니며, 이산화티타늄 전구체의 종류에 따라서 상기 범위보다 높거나 낮아질 수 있다. 가수분해 및 축합반응 시간은 특별히 제한적이지 않으나 30분 내지 3 시간 동안 진행된다. At this time, the hydrolysis and condensation reaction is preferably performed at room temperature, but is not limited thereto, and may be higher or lower than the above range depending on the type of the titanium dioxide precursor. The hydrolysis and condensation reaction time is not particularly limited, but is carried out for 30 minutes to 3 hours.
단계 (D)에서 이산화티타늄-그래핀-고분자 나노섬유를 공기에서 열처리시 이산화티타늄은 anatase의 결정구조를 형성하게 되어 광 활성을 갖게 되며, 산화그래핀은 열처리시 그래핀으로 환원된다. 이산화티타늄-그래핀 다공성 나노섬유의 열처리의 온도는 400 내지 550 ℃ 가 바람직하나, 이보다 높거나 낮을 수 있다. 열처리 시간은 2시간 내지 8 시간이 바람직하다.In the step (D), when the titanium dioxide-graphene-polymer nanofiber is heat-treated in the air, the titanium dioxide forms an anatase crystal structure and becomes photoactive, and the oxidized graphene is reduced to graphene at the time of heat treatment. The temperature of the heat treatment of the titanium dioxide-graphene porous nanofiber is preferably 400 to 550 ° C, but may be higher or lower. The heat treatment time is preferably 2 hours to 8 hours.
이하, 본 발명에 따르는 실시예를 통하여 본 발명을 보다 상세히 설명하나, 본 발명의 범위가 하기 제시된 실시예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited by the following examples.
다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경과 주사전자현미경으로 관찰한 결과, 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다. (도 1, 도 2)A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was sprayed at 15 kV through a titanium dioxide precursor- Polymer nanofiber fibers were prepared, hydrolyzed for 30 minutes under the presence of water, and heat - treated at 500 ℃ for 2 hours to prepare titanium dioxide - graphene porous nanofiber. As a result of observation with a transmission electron microscope and a scanning electron microscope, it was confirmed that titanium dioxide-graphene porous nanofiber having a diameter of 150 nm was successfully produced. (Figs. 1 and 2)
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 350,000 의 폴리메틸메타아크릴레이트 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해 및 축합반응한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polymethylmethacrylate having a molecular weight of 350,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was charged in the same manner as in Example 1 at 15 The titanium dioxide precursor-oxidized graphene-polymer nanofiber fiber was prepared through electrospinning in the presence of water and then subjected to hydrolysis and condensation reaction for 30 minutes under the presence of water and then heat-treated at 500 ° C. for 2 hours to obtain titanium dioxide - grafted porous nanofibers were prepared. Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 50,000 의 셀룰로오스 아세테이트 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해 및 축합반응한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of cellulose acetate having a molecular weight of 50,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was charged in the same manner as in Example 1, The titanium dioxide precursor-oxidized graphene-polymer nanofiber fiber was prepared through spinning. After hydrolysis and condensation reaction for 30 minutes under the presence of water and heat treatment at 500 ° C for 2 hours, titanium dioxide-graphene Porous nanofibers were prepared. Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 1,300,000 의 폴리비닐피롤리돈 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해 및 축합반응한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polyvinylpyrrolidone having a molecular weight of 1,300,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was dissolved in 15 The titanium dioxide precursor-oxidized graphene-polymer nanofiber fiber was prepared through electrospinning in the presence of water and then subjected to hydrolysis and condensation reaction for 30 minutes under the presence of water and then heat-treated at 500 ° C. for 2 hours to obtain titanium dioxide - grafted porous nanofibers were prepared. Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 50,000 의 셀룰로오스 아세테이트 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해 및 축합반응한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of cellulose acetate having a molecular weight of 50,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was charged in the same manner as in Example 1, The titanium dioxide precursor-oxidized graphene-polymer nanofiber fiber was prepared through spinning. After hydrolysis and condensation reaction for 30 minutes under the presence of water and heat treatment at 500 ° C for 2 hours, titanium dioxide-graphene Porous nanofibers were prepared. Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 70,000 의 폴리카프로락톤 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해 및 축합반응한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polycaprolactone having a molecular weight of 70,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was prepared in the same manner as in Example 1 at 15 kV The titanium dioxide precursor-oxidized graphene-polymer nanofiber fiber was prepared by electrospinning. Hydrolysis and condensation reaction were performed for 30 minutes under the presence of water and then heat-treated at 500 ° C. for 2 hours to obtain titanium dioxide- Fin porous nanofiber was prepared. Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 70,000 의 폴리에틸렌옥사이드 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해 및 축합반응한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polyethylene oxide having a molecular weight of 70,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was charged in the same manner as in Example 1, The titanium dioxide precursor-oxidized graphene-polymer nanofiber fiber was prepared through spinning. After hydrolysis and condensation reaction for 30 minutes under the presence of water and heat treatment at 500 ° C for 2 hours, titanium dioxide-graphene Porous nanofibers were prepared. Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 부톡사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해 및 축합반응한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 3 g of titanium butoxide, 1 g of acetic acid and 0.05 g of graphene was subjected to the same method as in Example 1, Titanium precursor-oxidized graphene-polymer nanofiber fibers were prepared, hydrolyzed and condensed for 30 minutes under the presence of water, and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 에톡사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해 및 축합반응한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 3 g of titanium ethoxide, 1 g of acetic acid and 0.05 g of graphene was subjected to the same method as in Example 1, Titanium precursor-oxidized graphene-polymer nanofiber fibers were prepared, hydrolyzed and condensed for 30 minutes under the presence of water, and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 옥시설페이트 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해 및 축합반응한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 3 g of titanium oxysulfate, 1 g of acetic acid and 0.05 g of graphene was treated at 15 kV by the same method as in Example 1, Titanium precursor-oxidized graphene-polymer nanofiber fibers were prepared, hydrolyzed and condensed for 30 minutes under the presence of water, and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 클로라이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해 및 축합반응한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 3 g of titanium chloride, 1 g of acetic acid and 0.05 g of graphene was applied at 15 kV, Precursor-oxidized graphene-polymer nanofiber fibers were prepared, hydrolyzed and condensed for 30 minutes under the presence of water, and then heat-treated at 500 ° C for 2 hours to prepare titanium dioxide-graphene porous nanofibers Respectively. Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 테트라아이소프로폭사이드 3.5 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 200 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다. A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 3.5 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was subjected to electrospinning at 15 kV using the same method as in Example 1 Titanium dioxide precursor-oxidized graphene-polymer nanofiber fibers were prepared and hydrolyzed in the presence of water for 30 minutes and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy confirmed that titanium dioxide-graphene nanoparticles of 200 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 테트라아이소프로폭사이드 4 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 250 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 4 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was subjected to electrospinning at 15 kV using the same method as in Example 1 Titanium dioxide precursor-oxidized graphene-polymer nanofiber fibers were prepared and hydrolyzed in the presence of water for 30 minutes and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy confirmed that titanium dioxide-graphene nanoparticles of 250 nm diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 150 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was subjected to electrospinning at 15 kV using the same method as in Example 1 Titanium dioxide precursor-oxidized graphene-polymer nanofiber fibers were prepared and hydrolyzed in the presence of water for 30 minutes and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy revealed that titanium dioxide-graphene nanoparticles of 150 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 3 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 200 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 3 g of polystyrene having a molecular weight of 35,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was subjected to electrospinning at 15 kV using the same method as in Example 1 Titanium dioxide precursor-oxidized graphene-polymer nanofiber fibers were prepared and hydrolyzed in the presence of water for 30 minutes and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy confirmed that titanium dioxide-graphene nanoparticles of 200 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 3 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 200 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 3 g of polystyrene having a molecular weight of 35,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was subjected to electrospinning at 15 kV using the same method as in Example 1 Titanium dioxide precursor-oxidized graphene-polymer nanofiber fibers were prepared and hydrolyzed in the presence of water for 30 minutes and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy confirmed that titanium dioxide-graphene nanoparticles of 200 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 4 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1.25 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 250 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 4 g of polystyrene having a molecular weight of 35,000, 3 g of titanium tetraisopropoxide, 1.25 g of acetic acid and 0.05 g of graphene was subjected to electrospinning at 15 kV using the same method as in Example 1 Titanium dioxide precursor-oxidized graphene-polymer nanofiber fibers were prepared and hydrolyzed in the presence of water for 30 minutes and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy confirmed that titanium dioxide-graphene nanoparticles of 250 nm diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1.5 g, 그래핀 0.05 g 의 혼합용액을 15 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 100 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 3 g of titanium tetraisopropoxide, 1.5 g of acetic acid and 0.05 g of graphene was subjected to electrospinning at 15 kV using the same method as in Example 1 Titanium dioxide precursor-oxidized graphene-polymer nanofiber fibers were prepared and hydrolyzed in the presence of water for 30 minutes and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy confirmed that titanium dioxide-graphene nanoparticles of 100 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 10 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 200 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was subjected to electrospinning at 10 kV using the same method as in Example 1 Titanium dioxide precursor-oxidized graphene-polymer nanofiber fibers were prepared and hydrolyzed in the presence of water for 30 minutes and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy confirmed that titanium dioxide-graphene nanoparticles of 200 nanometers in diameter were successfully fabricated.
실시예 1과 마찬가지의 방법을 이용하여 다이메틸포름아마이드 4 g, 분자량 35,000 의 폴리스티렌 2 g, 티타늄 테트라아이소프로폭사이드 3 g, 아세트산 1 g, 그래핀 0.05 g 의 혼합용액을 20 kV 에서 전기방사를 통하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유 섬유를 제조하였으며, 수분이 존재하는 대기 하에서 30 분 동안 가수분해한 뒤, 500 ℃ 에서 2 시간 열처리를 함으로써, 이산화티타늄-그래핀 다공성 나노섬유를 제조하였다. 투과전자현미경으로 관찰한 결과 직경 100 나노미터의 이산화티타늄-그래핀 다공성 나노섬유가 성공적으로 제조된 것을 확인하였다.A mixed solution of 4 g of dimethylformamide, 2 g of polystyrene having a molecular weight of 35,000, 3 g of titanium tetraisopropoxide, 1 g of acetic acid and 0.05 g of graphene was subjected to electrospinning at 20 kV using the same method as in Example 1 Titanium dioxide precursor-oxidized graphene-polymer nanofiber fibers were prepared and hydrolyzed in the presence of water for 30 minutes and then heat-treated at 500 ° C for 2 hours to obtain titanium dioxide-graphene porous nanofibers . Transmission electron microscopy confirmed that titanium dioxide-graphene nanoparticles of 100 nanometers in diameter were successfully fabricated.
상기 실시예 1에서 제시된 방법에 따라서 제조된 이산화티타늄-그래핀 다공성 나노섬유와 이산화티타늄 나노섬유의 표면적 BET 분석을 통해을 비교해본 결과, 이산화티타늄-그래핀 다공성 나노섬유가 이산화티타늄 나노섬유에 비해 표면적이 83.4 %증가했음을 확인하였다. (표 1)As a result of a surface area BET analysis of titanium dioxide-graphene porous nanofibers and titanium dioxide nanofibers prepared according to the method described in Example 1 above, it was found that the titanium dioxide-graphene porous nanofiber had a surface area Of the total population increased by 83.4%. (Table 1)
(m2/g)BET surface area
(m 2 / g)
(nm)Average pore diameter
(nm)
(cm3/g)Total void volume
(cm < 3 > / g)
없음.none.
Claims (10)
(B) 상기 혼합 용액을 전기 방사를 이용하여 이산화티타늄 전구체-산화그래핀-고분자 나노섬유를 제조하는 단계; 및,
(C) 상기 이산화티타늄 전구체-산화그래핀-고분자 나노섬유의 대기중 수분에 의한 가수분해 및 산화그래핀에서의 축합반응에 의한 추가적인 결정핵 생성을 유도하여 티타늄-산소-티타늄 공유결합을 형성하는 단계; 및,
(D) 상기 공유결합이 형성된 아산화티타늄-산화그래핀-고분자 나노섬유를 열처리 과정을 통해 anatase 결정성을 가지게 하여 전자 전달 속도가 우수하고 표면적이 증대된 이산화티타늄-그래핀 다공성 나노섬유 제조방법.(A) preparing a mixed solution of a titanium dioxide precursor, a polymer, acetic acid, and an oxidized graphene;
(B) preparing a titanium dioxide precursor-oxidized graphene-polymer nanofiber by electrospinning the mixed solution; And
(C) forming a titanium-oxygen-titanium covalent bond by inducing additional crystal nucleation by hydrolysis of the titanium dioxide precursor-oxidized graphene-polymer nanofiber by moisture in the air and condensation reaction in the graphene oxide step; And
(D) a process for producing titanium dioxide-graphene nanoparticles having an anatase crystallinity through heat treatment to form the covalently bonded titanium dioxide-oxidized graphene-polymer nanofibers, thereby increasing the electron transfer rate and increasing the surface area.
The process for producing a titanium dioxide-graphene porous nanofiber according to claim 1, wherein the range of the heat treatment temperature is 400 ° C to 550 ° C.
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