KR20100072864A - Method for preparing carbon nanotube/tungsten oxide nanocomposite powders and the carbon nanotube/tungsten oxide nanocomposite powders thereof - Google Patents
Method for preparing carbon nanotube/tungsten oxide nanocomposite powders and the carbon nanotube/tungsten oxide nanocomposite powders thereof Download PDFInfo
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- KR20100072864A KR20100072864A KR1020080131397A KR20080131397A KR20100072864A KR 20100072864 A KR20100072864 A KR 20100072864A KR 1020080131397 A KR1020080131397 A KR 1020080131397A KR 20080131397 A KR20080131397 A KR 20080131397A KR 20100072864 A KR20100072864 A KR 20100072864A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 95
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 95
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 34
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000843 powder Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000003657 tungsten Chemical class 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 3
- YXPHMGGSLJFAPL-UHFFFAOYSA-J tetrabromotungsten Chemical compound Br[W](Br)(Br)Br YXPHMGGSLJFAPL-UHFFFAOYSA-J 0.000 claims description 3
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 3
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 claims description 3
- RJNBTFHJYBHWCU-UHFFFAOYSA-L Cl[W](Cl)(=O)=O Chemical compound Cl[W](Cl)(=O)=O RJNBTFHJYBHWCU-UHFFFAOYSA-L 0.000 claims description 2
- 230000021523 carboxylation Effects 0.000 abstract description 4
- 238000006473 carboxylation reaction Methods 0.000 abstract description 4
- 150000007942 carboxylates Chemical class 0.000 abstract 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract 1
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 that is Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
Abstract
Description
본 발명은 텅스텐산화물에 탄소나노튜브가 균일하게 분산된 탄소나노튜브/텅스텐산화물 나노복합분말의 제조방법 및 그 방법에 의해 제조된 탄소나노튜브/텅스텐산화물 나노복합분말에 관한 것이다.The present invention relates to a method for producing a carbon nanotube / tungsten oxide nanocomposite powder in which carbon nanotubes are uniformly dispersed in tungsten oxide, and to a carbon nanotube / tungsten oxide nanocomposite powder prepared by the method.
물 보다 19배 이상 무거운 텅스텐소재 내에 초미세 입자를 균일하게 분산시키면 기계적 강도를 크게 높일 수 있다. 이와 같이 기계적 강도가 높은 복합분말은 다양한 분야에서 사용될 수 있으므로, 이에 대한 연구, 개발이 활발히 진행되고 있다.By uniformly dispersing ultrafine particles in a tungsten material 19 times heavier than water, the mechanical strength can be greatly increased. Since the composite powder having high mechanical strength can be used in various fields, research and development on this is being actively conducted.
C. Balazsi et al.(Sensors and Actuators B 133 (2008) 15155) 및 S. Wang et al.(Journal of Physics and Chemistry of Solids(Article in Press))등의 논문 에서는 탄소나노튜브와 텅스텐산화물 나노분말을 용매에 첨가 및 교반하여 탄소나노튜브-텅스텐산화물 복합분말을 제조하는 방법에 관하여 제시하고 있다. 또한 그 방법으로 제조된 탄소나노튜브-텅스텐산화물 복합분말의 광촉매 특성 및 이산화질소 가스탐지의 특징을 보여주고 있다.C. Balazsi et al. (Sensors and Actuators B 133 (2008) 15155) and S. Wang et al. (Journal of Physics and Chemistry of Solids (Article in Press)), et al. Is added to the solvent and stirred to prepare a carbon nanotube-tungsten oxide composite powder. In addition, the photocatalyst characteristics and nitrogen dioxide gas detection characteristics of the carbon nanotube-tungsten oxide composite powder prepared by the method are shown.
그러나, 상기의 논문에 게재된 방법들은 탄소나노튜브와 텅스텐산화물 나노분말의 단순 혼합수준에 그치고 있어서, 상기의 방법을 사용할 경우, 탄소나노튜브가 응집하는 현상이 발생하여 탄소나노튜브-텅스텐산화물 복합분말의 전기적자기적열적기계적 특성을 떨어뜨리는 문제점이 발생한다. However, the methods described in the above papers are only a simple level of mixing of carbon nanotubes and tungsten oxide nanopowder, and the carbon nanotube agglomeration occurs when the above method is used. Problems deteriorating the electromagnetic, thermomechanical properties of the powder occur.
따라서, 균질한 상태의 탄소나노튜브/텅스텐산화물 복합분말을 제조하려면, 탄소나노튜브가 응집하는 현상, 즉, 분산성을 개선시킬 필요가 있다.Therefore, in order to manufacture the carbon nanotube / tungsten oxide composite powder in a homogeneous state, it is necessary to improve the phenomenon that the carbon nanotubes aggregate, that is, dispersibility.
본 발명은 탄소나노튜브의 분산성을 개선하여, 탄소나노튜브가 균일하게 분산된 탄소나노튜브/텅스텐산화물 나노복합분말을 제조하는 방법 및 그 방법에 의해 제조된 탄소나노튜브/텅스텐산화물 나노복합분말을 제공하고자 한다.The present invention improves the dispersibility of carbon nanotubes, a method for producing a carbon nanotube / tungsten oxide nanocomposite powder in which carbon nanotubes are uniformly dispersed and a carbon nanotube / tungsten oxide nanocomposite powder prepared by the method To provide.
상기의 목적을 달성하기 위하여, 본 발명은 (a) 탄소나노튜브를 카르복실화 하는 단계, (b) 상기 카르복실화된 탄소나노튜브를 분산용매에 분산시키는 단계, (c) 상기 분산용액에 텅스텐염을 혼합하는 단계, (d) 상기 혼합용액을 건조 및 하소하는 단계를 포함하는 탄소나노튜브/텅스텐산화물 나노복합분말의 제조방법을 제공한다. In order to achieve the above object, the present invention comprises the steps of (a) carboxylating carbon nanotubes, (b) dispersing the carboxylated carbon nanotubes in a dispersion solvent, (c) in the dispersion solution Mixing a tungsten salt, (d) provides a method for producing a carbon nanotube / tungsten oxide nanocomposite powder comprising the step of drying and calcining the mixed solution.
본 발명의 방법에 의해서 분산성이 향상된 탄소나노튜브를 제조함으로써, 텅스텐산화물에 탄소나노튜브가 균질하게 분산된 탄소나노튜브/텅스텐산화물 나노복합분말을 제조할 수 있다. 개선된 분산성을 가진 탄소나노튜브/텅스텐산화물 나노복합분말은 광촉매 제품, 광촉매 코팅제, 가스검출용 나노센서, 태양에너지 소자, 디스플레이 소자 등의 소재로 다양하게 사용될 수 있다.By producing carbon nanotubes having improved dispersibility by the method of the present invention, carbon nanotubes / tungsten oxide nanocomposite powders in which carbon nanotubes are uniformly dispersed in tungsten oxide can be prepared. Carbon nanotube / tungsten oxide nanocomposite powder with improved dispersibility can be used in various materials as photocatalyst products, photocatalyst coating agents, gas detection nanosensors, solar energy devices, display devices, and the like.
본 발명은 탄소나노튜브/텅스텐산화물 나노복합분말의 제조방법을 제공한다.The present invention provides a method for preparing carbon nanotube / tungsten oxide nanocomposite powder.
상기 제조방법은 (a) 탄소나노튜브를 카르복실화 하는 단계, (b) 상기 카르복실화된 탄소나노튜브를 분산용매에 분산시키는 단계, (c) 상기 분산용액에 텅스텐염을 혼합하는 단계, (d) 상기 혼합용액을 건조 및 하소하는 단계를 포함한다.The preparation method comprises the steps of (a) carboxylating carbon nanotubes, (b) dispersing the carboxylated carbon nanotubes in a dispersion solvent, (c) mixing a tungsten salt in the dispersion solution, (d) drying and calcining the mixed solution.
상기 (a) 단계는 탄소나노튜브를 질산용액에 첨가함으로써, 탄소나노튜브를 카르복실화 할 수 있다. 이에 따라, 탄소나노튜브의 표면에 정전기적 전하를 구현할 수 있게 되어 탄소나노튜브의 분산능이 우수해 지는 것이다.In the step (a), the carbon nanotubes may be carboxylated by adding the carbon nanotubes to the nitric acid solution. Accordingly, it is possible to implement an electrostatic charge on the surface of the carbon nanotubes to be excellent in the dispersion capacity of the carbon nanotubes.
또한, 상기 질산용액에 황산, 염산 및 아세트산으로 구성된 그룹에서 선택된 하나 이상의 용액을 더 첨가하여 사용할 수도 있다. 질산용액 외의 다른 산용액들은, 탄소나노튜브를 정제하고, 분산용매와의 젖음성을 향상시키는 효과를 가져온다.In addition, one or more solutions selected from the group consisting of sulfuric acid, hydrochloric acid and acetic acid may be further added to the nitric acid solution. Acid solutions other than the nitric acid solution have the effect of purifying the carbon nanotubes and improving the wettability with the dispersion solvent.
상기 (b) 단계의 분산용매는, 물, 에탄올, 메탄올, 아세톤, 클로로포름, 에틸아세트산, 에테르, THF, 디클로로메탄, 헥산, 벤젠, 사염화탄소 또는 펜탄을 사용할 수 있다.The dispersion solvent of step (b) may be water, ethanol, methanol, acetone, chloroform, ethyl acetate, ether, THF, dichloromethane, hexane, benzene, carbon tetrachloride or pentane.
상기 (c) 단계의 텅스텐염은, 암모늄 메타텅스테이트(AMT : Ammonium Metatungstate), 암모늄 파라텅스테이트(APT : Ammonium Paratungstate), 염화 텅스텐(Tungsten chloride), 플루오르화 텅스텐(Tungsten Fluoride), 브로민화텅스텐(Tungsten bromide) 또는 텅스텐 디클로라이드 디옥사이드(Tungsten dichloride dioxide)을 사용할 수 있다.The tungsten salt of step (c), ammonium metatungstate (AMT), ammonium paratungstate (APT: Ammonium Paratungstate), tungsten chloride (Tungsten chloride), tungsten fluoride (Tungsten Fluoride), tungsten bromide (Tungsten bromide) or Tungsten dichloride dioxide can be used.
또한, 상기 (c) 단계에서 텅스텐염을 혼합한 분산용액에 초음파를 처리함으로써, 텅스텐염이 분산용액에 분산 및 혼합되는 것을 더욱 촉진시킬 수 있다.In addition, by treating the dispersion solution in which the tungsten salt is mixed in the ultrasonic wave in step (c), it is possible to further promote the dispersion and mixing of the tungsten salt in the dispersion solution.
상기 (d) 단계의 건조는, 80 ~ 300℃의 온도범위에서 1분 ~ 10시간 동안 실행할 수 있다. 상기의 조건에서 건조함으로써 불순물, 즉 탄소나노튜브의 카르복실화를 위하여 사용한 용액 뿐만 아니라, 분산용매에 포함된 수분을 충분히 제거할 수 있다.The drying of the step (d) can be performed for 1 minute to 10 hours in the temperature range of 80 ~ 300 ℃. By drying under the above conditions, not only the solution used for the carboxylation of impurities, that is, carbon nanotubes, but also the water contained in the dispersion solvent can be sufficiently removed.
상기 (d) 단계의 하소는, 300 ~ 600℃의 온도범위에서 10분 ~ 24시간 동안 실행할 수 있다. 상기의 조건에서 하소함으로써 원하는 탄소나노튜브/텅스텐산화물 나노복합분말을 얻을 수 있다.The calcination of step (d) can be performed for 10 minutes to 24 hours in a temperature range of 300 ~ 600 ℃. By calcination under the above conditions, a desired carbon nanotube / tungsten oxide nanocomposite powder can be obtained.
상기 텅스텐산화물은 WO2, WO3, 또는 W2O3 이 될 수 있다.The tungsten oxide may be WO 2 , WO 3 , or W 2 O 3 .
또한, 본 발명은 상기의 방법에 의해서 제조된 탄소나노튜브/텅스텐산화물 나노복합분말을 제공한다.The present invention also provides a carbon nanotube / tungsten oxide nanocomposite powder prepared by the above method.
이하에서, 본 발명의 바람직한 실시예를 참조하여 상세히 설명한다. 아래의 실시예는 본 발명의 내용을 이해하기 위해 제시된 것일 뿐이며 당해 분야에서 통상의 지식을 가진 자라면 본 발명의 기술적 사상 내에서 많은 변형이 가능할 것이다. 따라서 본 발명의 권리범위가 이러한 실시예에 한정되는 것으로 해석되어서는 안 된다.Hereinafter, with reference to a preferred embodiment of the present invention will be described in detail. The following examples are only presented to understand the content of the present invention, and those skilled in the art will be capable of many modifications within the technical spirit of the present invention. Therefore, the scope of the present invention should not be construed as limited to these examples.
<실시예 1> : 탄소나노튜브의 카르복실화 Example 1 Carboxylation of Carbon Nanotubes
탄소나노튜브/텅스텐산화물 나노복합분말을 제조하기 위한 첫 단계로서, 탄소나노튜브의 카르복실화를 실시하였다. As a first step for preparing carbon nanotube / tungsten oxide nanocomposite powder, carboxylation of carbon nanotubes was performed.
질산과 황산의 혼합용액에 다중벽 탄소나노튜브(직경: 약 10∼15nm, 길이: 10∼20㎛, 제조사: (주)일진나노텍)를 첨가하면, 탄소나노튜브에 카르복실 그룹이 부착된다. 이와 같은 결과는 XPS 결과로 확인할 수 있으며, 도 1에 나타냈다. 도 1의 그래프 중 빨간 선으로 나타낸 그래프를 통해서, -CO-O- 의 존재를 확인할 수 있다.When a multi-walled carbon nanotube (diameter: about 10-15 nm, length: 10-20 μm, manufacturer: Iljin Nanotech Co., Ltd.) is added to the mixed solution of nitric acid and sulfuric acid, a carboxyl group is attached to the carbon nanotube. These results can be confirmed by the XPS results, shown in FIG. The graph represented by the red line in the graph of Figure 1, it can be confirmed the presence of -CO-O-.
<실시예 2> : 탄소나노튜브/AMTExample 2 Carbon Nanotubes / AMT
실시예 1에서 제조된 카르복실화된 탄소나노튜브를 분산용매인 물에 분산시켰다. 상기 분산용액에, 텅스텐염으로서 AMT(Ammonium Metatungstate)를 첨가하였다. 콜파머(Cole-Parmer)社의 08893-16 초음파 세척장치를 이용하여 10시간 동안 초음파 처리를 하였다. 이를 통해서, 물에 AMT와 탄소나노튜브가 고르게 분산되었으며, 이러한 결과는 도 2a에 나타냈다. 도 2a에서도 볼 수 있듯이, 탄소나노튜브끼리 응집되지 않았으며, 텅스텐염(AMT)과 함께 탄소나노튜브가 고르게 분산되어 있음을 확인 할 수 있었다. 또한, 도 2b의 XRD 분석을 통해서, 탄소나노튜브와 텅스텐염(AMT)의 존재를 확인할 수 있었다. 즉, (002) 피크는 탄소나노튜브를 나타내고, (111) 피크 및 (600) 피크는 AMT를 나타내는 바, 도 2a의 고르게 분산된 상태를 고려하면, 탄소나노튜브와 AMT가 화학결합하고 있음을 확인할 수 있었다. The carboxylated carbon nanotubes prepared in Example 1 were dispersed in water as a dispersion solvent. AMT (Ammonium Metatungstate) was added to the dispersion solution as a tungsten salt. Ultrasonic treatment was performed for 10 hours using Cole-Parmer's 08893-16 ultrasonic cleaner. Through this, AMT and carbon nanotubes were evenly dispersed in water, and these results are shown in FIG. 2A. As can be seen in Figure 2a, the carbon nanotubes were not aggregated with each other, it was confirmed that the carbon nanotubes are evenly dispersed with the tungsten salt (AMT). In addition, through the XRD analysis of Figure 2b, it was confirmed the presence of carbon nanotubes and tungsten salt (AMT). That is, the (002) peak represents carbon nanotubes, and the (111) peak and (600) peak represent AMT. Considering the evenly dispersed state of FIG. 2A, the carbon nanotubes and the AMT are chemically bonded. I could confirm it.
<실시예 3> : 탄소나노튜브/텅스텐산화물 나노복합분말Example 3 Carbon Nanotube / Tungsten Oxide Nanocomposite Powder
실시예에서 제조된 탄소나노튜브/AMT의 용액을 80 ~ 300℃의 온도에서 건조하고, 공기 중에서 300 ~ 600℃의 온도에서 하소시켰다. 이를 통해서, AMT에 탄소나노튜브가 고르게 분산된 탄소나노튜브/텅스텐산화물 나노복합분말을 얻었으며, 이러한 결과는 도 3a에 나타냈다. 또한, 도 3b의 XRD 분석을 통해서, 탄소나노튜브와 텅스텐산화물(WO3)의 존재를 확인할 수 있었다. 즉, (002) 피크는 탄소나노튜브를 나타내고, (001), (200), (111), (220), (121), (140), (401) 피크는 모두 WO3를 나타내는 바, 도 3a의 고르게 분산된 상태를 고려하면, 탄소나노튜브와 WO3가 화학결합하고 있음을 확인할 수 있었다. The solution of carbon nanotubes / AMT prepared in Example was dried at a temperature of 80 ~ 300 ℃, and calcined at a temperature of 300 ~ 600 ℃ in air. Through this, a carbon nanotube / tungsten oxide nanocomposite powder in which carbon nanotubes were evenly dispersed in AMT was obtained, and these results are shown in FIG. 3A. In addition, through the XRD analysis of Figure 3b, it was confirmed the presence of carbon nanotubes and tungsten oxide (WO 3 ). That is, the (002) peak represents carbon nanotubes, and the (001), (200), (111), (220), (121), (140), and (401) peaks all represent WO 3 . Considering the evenly dispersed state of 3a, it was confirmed that the carbon nanotubes and WO 3 are chemically bonded.
도 4에서는 상기의 탄소나노튜브/텅스텐산화물 나노복합분말을 개념도로 나타냈다. 즉, 다결정에 속하는 텅스텐산화물은, 현미경적 크기의 작은 결정인 결정립들로 구성되어 있고, 상기의 결정립들 사이의 계면인 결정립계를 가지고 있으며, 본 발명은 이러한 텅스텐산화물에 탄소나노튜브가 고르게 분산되어 있는 탄소나노튜브/텅스텐산화물 나노복합분말이다.In FIG. 4, the carbon nanotube / tungsten oxide nanocomposite powder is shown in a conceptual diagram. That is, the tungsten oxide belonging to the polycrystal is composed of grains which are small crystals of microscopic size, and has a grain boundary which is an interface between the crystal grains. Carbon nanotube / tungsten oxide nanocomposite powder.
<비교예 1> : 카르복실화된 탄소나노튜브의 분산 정도<Comparative Example 1> Degree of dispersion of carboxylated carbon nanotubes
본 발명의 방법으로 제조된 카르복실화된 탄소나노튜브가 용액에서 고르게 분산되어 있음을 확인하기 위하여, 카르복실화되지 않은 탄소나노튜브와 비교하는 실험을 하였다.In order to confirm that the carboxylated carbon nanotubes prepared by the method of the present invention are evenly dispersed in the solution, an experiment was compared with the uncarboxylated carbon nanotubes.
우선, 카르복실화되지 않은 탄소나노튜브(가)를 물에 넣어 분산시켰다. 도 5의 왼쪽 사진을 보면, 육안으로도 탄소나노튜브들이 물에 균일하게 분산되지 않고, 뭉쳐서 물에 뜨거나 가라앉아 있음을 확인할 수 있었다.First, uncarboxylated carbon nanotubes (A) were dispersed in water. Looking at the left picture of Figure 5, even with the naked eye it can be seen that the carbon nanotubes are not uniformly dispersed in the water, but aggregated and floated or sinked in the water.
또한, 본 발명의 방법에 의해 황산 : 질산 = 3 : 1 의 부피비로 혼합한 용액에 탄소나노튜브를 혼합하여 탄소나노튜브를 카르복실화하였다. 그 후, 상기의 카르복실화된 탄소나노튜브(나)를 물에 넣어 분산시켰다. 도 5의 오른쪽 사진을 보면, 육안으로도 탄소나노튜브들이 물에 균일하게 분산되어, 뭉쳐서 물에 뜨거나 가라앉지 않았음을 확인할 수 있었다. 즉, 상기의 결과들을 통해서, 본 발명의 방법에 의해 제조된 카르복실화된 탄소나노튜브는 분산성을 향상되었음을 확인할 수 있었다.In addition, the carbon nanotubes were carboxylated by mixing the carbon nanotubes in a solution of sulfuric acid: nitric acid = 3: 1 by the method of the present invention. Thereafter, the carboxylated carbon nanotubes (na) were dispersed in water. Looking at the right picture of Figure 5, even with the naked eye, the carbon nanotubes are uniformly dispersed in water, it can be confirmed that the aggregates did not float or sink in the water. That is, through the above results, it was confirmed that the carboxylated carbon nanotubes produced by the method of the present invention improved dispersibility.
<비교예 2> : 탄소나노튜브/AMT의 분산 정도Comparative Example 2 Dispersion Degree of Carbon Nanotubes / AMT
본 발명의 방법으로 제조된 탄소나노튜브/텅스텐염이 분산용매에서 고르게 분산되어 있음을 확인하기 위하여, 카르복실화되지 않은 탄소나노튜브 텅스텐염과 비교하는 실험을 하였다.In order to confirm that the carbon nanotube / tungsten salt prepared by the method of the present invention is uniformly dispersed in the dispersion solvent, an experiment was compared with the uncarboxylated carbon nanotube tungsten salt.
비교예 1의 (가), (나)의 탄소나노튜브를 분산용매(물)에 분산시킨 후, 텅스텐염(AMT)과 혼합하였다. 이를 통해 카르복실화 되지 않은 탄소나노튜브/AMT(다)와 카르복실화된 탄소나노튜브/AMT(라)를 얻었다. (다)의 주사전자현미경 사진을 도 6에 나타냈으며, 이와 비교되는 (라)의 주사전자현미경 사진은 도 2a에 나타냈다. (다)의 경우(도 6 참조)를 보면, 탄소나노튜브들끼리 응집되어 AMT에 균질하지 않은 상태로 분산되어 있는 반면, (라)의 경우(도 2a 참조)를 보면, 탄소나노튜브들이 AMT에 균질하게 분산되어 있음을 확인할 수 있었다. 즉, 상기의 결과들을 통해서, 본 발명의 방법에 따라 제조된 카르복실화된 탄소나노튜브/AMT는 분산용매에서 분산성을 향상되었음을 확인할 수 있었다.Carbon nanotubes of (A) and (B) of Comparative Example 1 were dispersed in a dispersion solvent (water) and then mixed with tungsten salt (AMT). This resulted in uncarboxylated carbon nanotubes / AMT (C) and carboxylated carbon nanotubes / AMT (D). The scanning electron micrograph of (C) is shown in FIG. 6, and the scanning electron micrograph of (D) compared with this is shown in FIG. 2A. In case (c) (see FIG. 6), the carbon nanotubes are aggregated and dispersed in a non-homogeneous state in the AMT, whereas in case of (d) (see FIG. 2a), the carbon nanotubes are AMT It was confirmed that it is homogeneously dispersed in. That is, through the above results, it was confirmed that the carboxylated carbon nanotubes / AMT prepared according to the method of the present invention improved the dispersibility in the dispersion solvent.
도 1은 실시예 1에 의해 제조된 카르복실화된 탄소나노튜브의 XPS 결과를 나타낸다.Figure 1 shows the XPS results of the carboxylated carbon nanotubes prepared in Example 1.
도 2a는 실시예 2에 의해 제조된 탄소나노튜브/AMT의 주사전자현미경 사진이며, 도 2b는 실시예 2에 의해 제조된 탄소나노튜브/AMT의 XRD 결과를 나타낸다. Figure 2a is a scanning electron micrograph of the carbon nanotubes / AMT prepared by Example 2, Figure 2b shows the XRD results of the carbon nanotubes / AMT prepared by Example 2.
도 3a는 실시예 3에 의해 제조된 탄소나노튜브/텅스텐산화물 나노복합분말의 주사전자현미경 사진이며, 도 3b는 실시예 3에 의해 제조된 탄소나노튜브/텅스텐산화물 나노복합분말의 XRD 결과를 나타낸다. 3A is a scanning electron micrograph of the carbon nanotube / tungsten oxide nanocomposite powder prepared in Example 3, and FIG. 3B shows the XRD results of the carbon nanotube / tungsten oxide nanocomposite powder prepared in Example 3. .
도 4는 탄소나노튜브/텅스텐산화물 나노복합분말의 개념도를 나타낸다.4 shows a conceptual diagram of a carbon nanotube / tungsten oxide nanocomposite powder.
도 5는 카르복실화 되지 않은 탄소나노튜브와 카르복실화된 탄소나노튜브를 물에 분산시킨 후, 이를 비교한 사진을 나타낸다.FIG. 5 shows a photograph comparing the uncarboxylated carbon nanotubes with the carboxylated carbon nanotubes in water and then comparing them.
도 6은 비교예 2의 카르복실화 되지 않은 탄소나노튜브/AMT(다)의 주사전자현미경 사진을 나타낸다. 왼쪽 사진은 20000배율의 주사전자현미경 사진이며, 오른쪽 사진은 50000배율의 주사전자현미경 사진이다.Figure 6 shows a scanning electron micrograph of the non-carboxylated carbon nanotube / AMT (C) of Comparative Example 2. The left picture is a scanning electron microscope picture of 20000 magnification, and the right picture is a scanning electron microscope picture of 50000 magnification.
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| CN101913597A (en) * | 2010-09-14 | 2010-12-15 | 武汉理工大学 | Tungsten oxide nano-wire and porous carbon nano composite structural material and preparation method thereof |
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| KR20190137367A (en) * | 2018-06-01 | 2019-12-11 | 한국생산기술연구원 | TiO2 based oxide composite for lithium secondary battery and manufacturing method the same |
| CN113307326A (en) * | 2021-05-20 | 2021-08-27 | 江西善拓环境科技有限公司 | Preparation of tungsten-based oxide/carbon-based nano composite hydrosol and application of tungsten-based oxide/carbon-based nano composite hydrosol in wastewater treatment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913597A (en) * | 2010-09-14 | 2010-12-15 | 武汉理工大学 | Tungsten oxide nano-wire and porous carbon nano composite structural material and preparation method thereof |
| KR101460756B1 (en) * | 2013-01-28 | 2014-11-14 | 순천대학교 산학협력단 | manufacturing method of tungsten nano fluid using liquid phase plasma reaction |
| KR20190137367A (en) * | 2018-06-01 | 2019-12-11 | 한국생산기술연구원 | TiO2 based oxide composite for lithium secondary battery and manufacturing method the same |
| CN113307326A (en) * | 2021-05-20 | 2021-08-27 | 江西善拓环境科技有限公司 | Preparation of tungsten-based oxide/carbon-based nano composite hydrosol and application of tungsten-based oxide/carbon-based nano composite hydrosol in wastewater treatment |
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