CN1594211A - Cobaltosic oxide nano-crystalline coated carbon nano-tube composite powder and preparation method thereof - Google Patents
Cobaltosic oxide nano-crystalline coated carbon nano-tube composite powder and preparation method thereof Download PDFInfo
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- CN1594211A CN1594211A CN 200410025518 CN200410025518A CN1594211A CN 1594211 A CN1594211 A CN 1594211A CN 200410025518 CN200410025518 CN 200410025518 CN 200410025518 A CN200410025518 A CN 200410025518A CN 1594211 A CN1594211 A CN 1594211A
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Abstract
The invention provides a method of nano cobaltosic oxide magnetic material in-situ encapsulation for carbon nano tube, which consists of using cobalt nitrate hexahydrate as raw material, n-hexyl alcohol as solvent, conducting in-situ encapsulation of carbon nano tube at the counterflow condition at 140-180 deg. C, subjecting the carbon nano tube to acid-treatment, and introducing reactive groups such as -OH, -COOH, -CO, thus absorbing the cobalt ions in-situ onto the surface of the carbon nano tube, Co(NO#-[3])#-[2]*6H#-[2]O is decomposed into cobaltosic oxide, thus encapsulating the nano cobaltosic oxide uniformly onto the carbon nano tube surface.
Description
Technical field
The present invention relates to brilliant original position parcel carbon nano-tube composite powder of a kind of cobaltosic oxide nano and preparation method, belongs to field of nanocomposite materials.
Background technology
Since S.Iijima in 1991 found carbon nanotube, carbon nanotube had caused that people pay close attention to greatly.It has unique metal or semi-conductive electroconductibility, high physical strength, toughness, bigger specific surface area (120-300m
2/ g), better adsorption capability, catalysis characteristics and stronger microwave absorption capacity and unique vestibule structure, can be widely used in various high-tech areas, be a kind of new-type functional material and structured material.But, its a lot of performances, it is very big influenced by its surface tissue as electricity, mechanics and optical property etc., in order to improve the carbon nano tube surface structure, the general surface modification method that adopts, thereby improve or change carbon nanotube dispersiveness, stability and and other materials between consistency, give its new physics, chemistry, mechanical property and new function.Recently, not only organic decoration is modified or is wrapped up carbon nanotube with inorganic species and also caused people's very big concern, carbon nanotube is coated last layer organic or inorganic functive and is had more wide application prospect (Lei Fu later on, Zhimin Liu, Yunqi Liu, Buxing Han, Jiaqiu Wang, Pingqn Hu, Lingchao Cao and Daoben Zhu, Adv.Mater.2004,16 (2), p350-352).
Tricobalt tetroxide is a kind of important P-type semiconductor magneticsubstance, is widely used in aspects such as solid state sensor, catalyzer, sun power sorbent material, lithium cell, beramic color.Its application prospects makes the tricobalt tetroxide of preparation nanoscale become one of current research focus (Xu.R.; Zeng, H.C.J.Phys.Chem.B 2003,107, p926).But the report that does not still have tricobalt tetroxide/carbon pipe matrix material at present.The carbon nanotube complex function powder of nano-cobaltic-cobaltous oxide parcel will have broad application prospects aspect heterogeneous catalysis, sun power sorbent material, ultra-capacitor and the lithium cell.And carbon nanotube/tricobalt tetroxide is expected to become the novel magnetic matrix material with high electric property.
Summary of the invention
The object of the present invention is to provide brilliant original position enveloping carbon nanotube composite powder of a kind of cobaltosic oxide nano and preparation method.The present invention is by the acidification carbon nanotube, make its surface produce electronegative active group, utilize the consistency and the electrostatic attraction effect of the active group and the cobalt ion of carbon nano tube surface, make the cobalt ion original position be adsorbed in carbon nano tube surface, and then form the composite granule of the nanocrystalline original position parcel of nano-cobaltic-cobaltous oxide carbon nanotube.The method that is provided is simple, and is easy to operate, do not need special equipment, and realized combining closely of cobaltosic oxide nano crystalline substance and carbon nanotube, is the effective way of preparation carbon nanotube/tricobalt tetroxide complex function powder.
Characteristics of the present invention are: with the Cobaltous nitrate hexahydrate is raw material, is solvent with the n-hexyl alcohol, original position parcel carbon nanotube under reflux conditions between 140-180 ℃.
Concrete steps are:
(1) with the carbon nanotube oven dry, removes the moisture that is contained;
(2) dried carbon nano-tube with concentrated nitric acid in 140 ℃ of reflow treatment 6-8 hours carbon nano tube surface introducing-OH ,-COOH or-the CO active group, use deionized water wash, dry for standby then;
(3) Cobaltous nitrate hexahydrate is dissolved in the n-hexyl alcohol, forms red clear solution, Cobaltous nitrate hexahydrate concentration is 0.02-0.08M in its solution;
(4) step (2) carbon nano tube modified is joined in the above-mentioned solution ultrasonic 15-60 minute; The mixing solutions that step (4) obtains is put into three-necked bottle, in 140-180 ℃ silicone oil bath backflow 5-10 hour, be adsorbed on the Co (NO of carbon nano tube surface
3)
26H
2O resolves into tricobalt tetroxide, thus the carbon nanotube dust of the synthetic tricobalt tetroxide parcel of reaction in.
(5) product respectively washs 2-5 time through hexanaphthene, dehydrated alcohol, promptly obtains the composite granule of the brilliant parcel of cobaltosic oxide nano carbon nanotube after the drying.
The three-necked bottle experimental installation that the present invention uses is successively by three-necked bottle (round-bottomed flask), drying tube and prolong, has 4A type molecular sieve to be used for absorbing moisture content (Fig. 1) in the drying tube.
The characteristics of the method for nano-cobaltic-cobaltous oxide parcel carbon nanotube provided by the invention are:
(1) by acidification carbon nano tube surface introduce introducing-OH ,-COOH ,-CO isoreactivity group, and make the carbon nano tube surface bear.Electrostatic interaction and aqueous favoring capacitive by reactive ion and active group make the cobalt ion original position cover carbon nano tube surface, and then cover one deck cobaltosic oxide nano crystalline substance in carbon nano tube surface.
(2) realized the full coating of carbon nanotube, coating thickness is the 15-20 nanometer.The particle diameter of tricobalt tetroxide is 5-10nm, and mean sizes is 8nm.Parcel back carbon nanotube diameter is 90nm, and length is 500nm-1um.
(3) technology is simple, need not specific installation; And need not add any tensio-active agent.
Description of drawings
The synoptic diagram of the three-necked bottle experimental installation that Fig. 1 the present invention uses
The X-ray diffraction spectrogram of the brilliant parcel of Fig. 2 cobaltosic oxide nano carbon nano-tube composite powder
The composite granule transmission electron microscope photo of the brilliant parcel of Fig. 3 cobaltosic oxide nano carbon nanotube
Patent working
Further specify embodiment and effect with following indefiniteness embodiment:
Embodiment 1
Carbon nanotube is put into 140 ℃ baking oven baking 24 hours to remove the moisture of carbon nanotube, with its reflow treatment 6 hours in concentrated nitric acid, use deionized water wash then, dry.0.5gCo (NO
3)
26H
2O is dissolved in the 40mL n-hexyl alcohol, obtains a red clear solution.Carbon nanotube after the 150mg acid treatment is added in the above-mentioned solution, and ultra-sonic dispersion is poured into after 45 minutes in the experimental installation shown in Figure 1 and to be mixed above-mentioned mixing solutions and refluxed 10 hours in 160 ℃ silicone oil bath, naturally cools to room temperature then.The product that obtains respectively washs three times through hexanaphthene, dehydrated alcohol, promptly obtains the composite granule of nano-cobaltic-cobaltous oxide parcel carbon nanotube after the oven dry.Fig. 2 is the composite granule X-ray diffraction spectrogram of the parcel carbon nanotube of present embodiment preparation.Except a peak that belongs to the carbon pipe, other are all corresponding to the diffraction peak of tricobalt tetroxide among the figure.The diffraction peak of tricobalt tetroxide has tangible broadening, shows that the grain-size of tricobalt tetroxide is very little, and according to the Scherrer formula, its grain-size is 8nm.Fig. 3 is the transmission electron microscope photo of the composite granule of tricobalt tetroxide parcel carbon nanotube, and the tricobalt tetroxide uniform crystal particles covers carbon nano tube surface, and the tricobalt tetroxide grain-size is about 8nm, and cover thickness is 20nm.
Claims (5)
1. the brilliant original position parcel of a cobaltosic oxide nano carbon nano-tube composite powder is characterized in that the brilliant original position of cobaltosic oxide nano evenly covers the multi-wall carbon nano-tube tube-surface, and cover thickness is about 15-20nm.
2. by the composite granule of the brilliant parcel of the described cobaltosic oxide nano of claim 1 carbon nanotube, the particle diameter that it is characterized in that tricobalt tetroxide is 5-10nm, and particle mean size is 8nm.Carbon nanotube diameter behind the parcel is about 90nm, and length is 500nm-1 μ m.
3. press the preparation method of the composite granule of the described nano-cobaltic-cobaltous oxide parcel of claim 1 carbon nanotube, it is characterized in that: by the acidification carbon nanotube, make its surface produce electronegative active group, utilize the consistency and the electrostatic attraction effect of the active group and the cobalt ion of carbon nano tube surface, make the cobalt ion original position be adsorbed in carbon nano tube surface, and then form the composite granule of the nanocrystalline original position parcel of nano-cobaltic-cobaltous oxide carbon nanotube.
4. by the preparation method of the brilliant parcel of the described cobaltosic oxide nano of claim 3 carbon nano-tube composite powder, it is characterized in that concrete steps are:
(a) with the carbon nanotube oven dry, remove the moisture that is contained;
(b) dried carbon nano-tube with concentrated nitric acid in 140 ℃ of reflow treatment 6-8 hours, carbon nano tube surface introducing-OH ,-COOH or-the CO active group, use deionized water repetitive scrubbing, dry for standby then;
(c) Cobaltous nitrate hexahydrate is dissolved in the n-hexyl alcohol, forms red clear solution, Cobaltous nitrate hexahydrate concentration is 0.02-0.08M in its solution;
(a) step (b) carbon nano tube modified is joined in the above-mentioned solution ultrasonic 15-60 minute;
(e) mixing solutions that step (d) is obtained is put into three-necked bottle, in 140-180 ℃ silicone oil bath backflow 5-10 hour, is adsorbed on the Co (NO of carbon nano tube surface
3)
26H
2O resolves into tricobalt tetroxide, thus the carbon nanotube dust of the synthetic tricobalt tetroxide parcel of reaction in.
(f) product promptly obtains the composite granule of the brilliant parcel of cobaltosic oxide nano carbon nanotube through hexanaphthene, each washing of dehydrated alcohol after the drying.
5. by the preparation method of the brilliant parcel of the described cobaltosic oxide nano of claim 4 carbon nano-tube composite powder, it is characterized in that the reaction in synthetic time is 5-20 hour.
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Cited By (9)
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|---|---|---|---|---|
| CN101161725B (en) * | 2007-09-29 | 2010-09-01 | 复旦大学 | Polyaniline coated magnetic carbon-nano tube composite material and preparation method thereof |
| CN101898134A (en) * | 2010-07-19 | 2010-12-01 | 江南大学 | Liquid phase preparation method for carbon nano tube and cobalt oxide composite structure |
| CN102327782A (en) * | 2011-07-06 | 2012-01-25 | 哈尔滨工业大学 | Preparation method of cobalt nanoparticle/carbon nanotube composite material |
| CN102424430A (en) * | 2011-08-24 | 2012-04-25 | 郑州轻工业学院 | Preparation method for single crystal cobalt oxide nano-sphere/carbon nano-tube composite nano-material |
| CN104167295A (en) * | 2014-04-03 | 2014-11-26 | 杭州电子科技大学 | Carbon nano tube surface loaded nano cobaltosic oxide composite material and preparation method thereof |
| CN106582650A (en) * | 2016-12-21 | 2017-04-26 | 湘潭大学 | Preparation method of Co particle coated CNT (carbon nanotube) catalytic material and application of catalytic material in cyclohexane oxidation reaction |
| CN106669555A (en) * | 2016-12-06 | 2017-05-17 | 深圳市华星光电技术有限公司 | Preparation method of carbon nanotube conductive ball |
| CN108269976A (en) * | 2017-12-19 | 2018-07-10 | 中南大学 | Cobalt-based lithium ion battery negative material preparation method |
| CN114933297A (en) * | 2022-06-14 | 2022-08-23 | 河南农业大学 | Preparation method of nanocrystalline/carbon nano tube composite super microsphere |
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| CN101837287B (en) | 2009-03-21 | 2012-05-30 | 清华大学 | Preparation of carbon nano-tube nano-particle composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101161725B (en) * | 2007-09-29 | 2010-09-01 | 复旦大学 | Polyaniline coated magnetic carbon-nano tube composite material and preparation method thereof |
| CN101898134A (en) * | 2010-07-19 | 2010-12-01 | 江南大学 | Liquid phase preparation method for carbon nano tube and cobalt oxide composite structure |
| CN101898134B (en) * | 2010-07-19 | 2011-12-28 | 江南大学 | Liquid phase preparation method for carbon nano tube and cobalt oxide composite structure |
| CN102327782B (en) * | 2011-07-06 | 2013-01-16 | 哈尔滨工业大学 | Preparation method of cobalt nanoparticle/carbon nanotube composite material |
| CN102327782A (en) * | 2011-07-06 | 2012-01-25 | 哈尔滨工业大学 | Preparation method of cobalt nanoparticle/carbon nanotube composite material |
| CN102424430B (en) * | 2011-08-24 | 2013-08-14 | 郑州轻工业学院 | Preparation method for single crystal cobalt oxide nano-sphere/carbon nano-tube composite nano-material |
| CN102424430A (en) * | 2011-08-24 | 2012-04-25 | 郑州轻工业学院 | Preparation method for single crystal cobalt oxide nano-sphere/carbon nano-tube composite nano-material |
| CN104167295A (en) * | 2014-04-03 | 2014-11-26 | 杭州电子科技大学 | Carbon nano tube surface loaded nano cobaltosic oxide composite material and preparation method thereof |
| CN104167295B (en) * | 2014-04-03 | 2017-02-15 | 杭州电子科技大学 | Carbon nano tube surface loaded nano cobaltosic oxide composite material and preparation method thereof |
| CN106669555A (en) * | 2016-12-06 | 2017-05-17 | 深圳市华星光电技术有限公司 | Preparation method of carbon nanotube conductive ball |
| CN106582650A (en) * | 2016-12-21 | 2017-04-26 | 湘潭大学 | Preparation method of Co particle coated CNT (carbon nanotube) catalytic material and application of catalytic material in cyclohexane oxidation reaction |
| CN108269976A (en) * | 2017-12-19 | 2018-07-10 | 中南大学 | Cobalt-based lithium ion battery negative material preparation method |
| CN114933297A (en) * | 2022-06-14 | 2022-08-23 | 河南农业大学 | Preparation method of nanocrystalline/carbon nano tube composite super microsphere |
| CN114933297B (en) * | 2022-06-14 | 2023-08-18 | 河南农业大学 | Preparation method of nanocrystalline/carbon nanotube composite super microsphere |
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