CN1794372A - Magnetic composite powder for ferroferric oxide nanometer crystal modified carbon nanometer pipe and its preparation method - Google Patents
Magnetic composite powder for ferroferric oxide nanometer crystal modified carbon nanometer pipe and its preparation method Download PDFInfo
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- CN1794372A CN1794372A CN 200510030919 CN200510030919A CN1794372A CN 1794372 A CN1794372 A CN 1794372A CN 200510030919 CN200510030919 CN 200510030919 CN 200510030919 A CN200510030919 A CN 200510030919A CN 1794372 A CN1794372 A CN 1794372A
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Abstract
This invention relates to a magnetic compound powder of Fe3O4 nm grains for the decoration of C nm tubes and its preparation method characterizing in taking multi-wall or single wall C nm tubes, triacetyl-acetonyl or FeCl3 as the raw materials, 2-ketopyrrolidine as the solution to flow back for 0.5-2 hours protected by 240-250deg.C N or Ar, the character of the powder is: Fe3O4 nm particles cover the surface of the multi-wall nm tubes uniformly and most of the Fe3O4 particles of 6-10nm are at the open-end of the single-wall tubes. The magnetic compound powder has ferromagnetism and a trend of directional aggregation and keeps its state after the field is removed.
Description
Technical field:
The present invention relates to the synthetic preparation method of a kind of nano-magnetic composite granule and original position, relate to composite nano-powder and preparation method that the brilliant original position of a kind of ferriferrous oxide nano coats multi-walled carbon nano-tubes and the brilliant in-situ modification Single Walled Carbon Nanotube of ferriferrous oxide nano port or rather, belong to field of nanocomposite materials.
Technical background:
Since S.Iijima in 1991 found carbon nano-tube, carbon nano-tube had caused people's very big concern with its unique one dimension hollow structure and good mechanics, electronics and chemical characteristic.Particularly its significant electric property and good chemical stability make carbon nano-tube have application prospect extensively aspect the microelectronic components such as large scale integrated circuit, a ballistic transistor and molecule diode.At present, the realization of carbon nano-tube large-scale production has promoted the research of carbon nano-tube in field of nanometer devices greatly.But when microelectronic component was used, the subject matter that people face was exactly how by instructions for use " arbitrarily " carbon nano-tube of arranging.
The main method that present people take has oriented growth of carbon nanometer tube, utilizes extra electric field to make carbon nano-tube oriented, biological template guiding method (L.A.Nagahara, I.Amlani, J.Lewenstein, R.K.Tsui, Appl.Phys.Lett, 2002,80,3826; Z.Liu, Z.Shen, T.Zhu, S.Hou, L.Ying, Z.Shi, Z.Gu, Langmuir, 2000,16,3569; H.Xin, A.T.Woolley, J.Am.Chem.Soc.2003,125,8710), and directed research in magnetic field is reported also fewer to carbon nano-tube.Can inventor's imagination wrap up one deck magnetic particle in carbon nano tube surface, makes it have magnetic, thereby can realize carbon nano-tube oriented alignment in magnetic field, therefore visualizes purpose of the present invention.
Summary of the invention:
The object of the present invention is to provide brilliant in-situ modification carbon nano-tube composite powder of a kind of ferriferrous oxide nano and preparation method.The present invention is the acidification by carbon nano-tube at first, make its surperficial possess hydrophilic property, utilize the thermal decomposition in 2-Pyrrolidone of praseodynium base iron or iron chloride to generate water miscible tri-iron tetroxide again, carbon nano-tube is combined by the aqueous favoring capacitive with tri-iron tetroxide, thereby obtain the composite granule of the brilliant in-situ modification carbon nano-tube of ferriferrous oxide nano.The method that is provided is simple, and is easy to operate, do not need special equipment, and the composite granule of gained is the effective way that realizes carbon nano-tube orientation in magnetic field.
Characteristics of the present invention are: with the carbon nano-tube after the acidification, praseodynium base iron (or iron chloride) is raw material, is solvent with the 2-Pyrrolidone, under 240-250 ℃ of nitrogen or argon shield atmosphere backflow 0.5-2 hour.
Concrete steps are:
(1) with the carbon nano-tube oven dry, removes the moisture that is contained; General drying time is 20-24 hour; Temperature 120-150 ℃;
(2) dried carbon nano-tube with red fuming nitric acid (RFNA) in 140 ℃ of reflow treatment 5-8 hours carbon nano tube surface introducing-OH ,-the COOH active group, improve its hydrophily, use deionized water cyclic washing, dry for standby then;
(3) praseodynium base iron or iron chloride are dissolved in the 2-Pyrrolidone, form red or orange-red clear solution, its concentration is 0.5M-2M;
(4) with step 2) carbon nano tube modified joined in the above-mentioned solution ultrasonic 15-60 minute;
(5) mixed solution that step 4) is obtained is put into three-necked bottle, under 240-250 ℃ of nitrogen or argon shield atmosphere backflow 0.5-2 hour, praseodynium base iron or iron chloride resolve into tri-iron tetroxide, this tri-iron tetroxide is water miscible, pass through aqueous favoring capacitive principle in-situ deposition on its surface with carbon nano-tube, be cooled to room temperature;
(6) adding volume ratio is 1: 3 methanol mixed liquor, makes the product sedimentation and with acetone washing 3-5 time, promptly obtains the composite granule of tri-iron tetroxide/carbon nano-tube after the drying
The characteristics of the method that nano ferriferrous oxide provided by the invention is carbon nano-tube modified are:
(1) by acidification carbon nano tube surface introduce introducing-OH ,-COOH isoreactivity group, make the carbon nano tube surface possess hydrophilic property.The tri-iron tetroxide that reaction generates and the aqueous favoring capacitive of multi-wall carbon nano-tube tube-surface, make the brilliant in-situ deposition of ferriferrous oxide nano and be coated on the multi-wall carbon nano-tube tube-surface, and then obtain the composite granule of the multi-walled carbon nano-tubes of the brilliant deposition of ferriferrous oxide nano, coating.
(2) to the encapsulation ratio height of multi-walled carbon nano-tubes, can reach more than 98%.
(3) to Single Walled Carbon Nanotube, the active group multidigit that acid treatment is introduced is in its port, so the brilliant multidigit of ferriferrous oxide nano is in its port.
(4) technology is simple, need not special installation.
(5) tri-iron tetroxide/carbon nano-tube composite powder of gained has ferromagnetism, orientable gathering under magnetic field, and after spreading demagnetizing field, can keep its directed state of assembling; The crystallite dimension of ferriferrous oxide nano crystalline substance is 5-10nm.
Description of drawings:
The X-ray diffraction spectrogram of Fig. 1 tri-iron tetroxide/carbon nano-tube composite powder
The transmission electron microscope photo of Fig. 2 tri-iron tetroxide/multi-walled carbon nano-tubes composite granule: being raw material with praseodynium base iron (a), (b) is raw material with iron chloride
The transmission electron microscope photo of Fig. 3 tri-iron tetroxide/Single Walled Carbon Nanotube composite granule
Fig. 4 tri-iron tetroxide/multi-walled carbon nano-tubes composite granule is the directed SEM photo of assembling under magnetic field
Embodiment:
Further specify execution mode and effect with following indefiniteness embodiment, thereby further prove substantive distinguishing features of the present invention and obvious improvement.
Embodiment 1
Multi-walled carbon nano-tubes is put into 140 ℃ baking oven baking 24 hours to remove the moisture of carbon nano-tube, with its reflow treatment 6 hours in red fuming nitric acid (RFNA), use deionized water wash then, dry.0.35g praseodynium base dissolved ferric iron in the 50mL 2-Pyrrolidone, obtains a red clear solution.Carbon nano-tube after the 100mg acid treatment is added in the above-mentioned solution, and ultrasonic dispersion was poured in the three-necked bottle after 30 minutes, and three-necked bottle connects condenser pipe flatly, feeds nitrogen or argon gas flatly, refluxes 0.5 hour in 245 ℃ silicone oil bath, naturally cools to room temperature then.The adding volume ratio is that 1: 3 methanol mixed solution makes the product sedimentation, again with acetone washing 3 times, promptly obtains the composite granule of nano ferriferrous oxide parcel carbon nano-tube after the oven dry.Fig. 1 is the composite granule X-ray diffraction spectrogram of the parcel carbon nano-tube of present embodiment preparation.Except a peak that belongs to the carbon pipe, other are all corresponding to the diffraction maximum of magnetic iron ore tri-iron tetroxide among the figure.The diffraction maximum of tri-iron tetroxide has tangible broadening, shows that the crystallite dimension of tri-iron tetroxide is very little, and according to the Scherrer formula, its crystallite dimension is 10nm.Fig. 2 (a) is the transmission electron microscope photo of the composite granule of tri-iron tetroxide parcel carbon nano-tube, and the tri-iron tetroxide uniform crystal particles covers carbon nano tube surface, and the tri-iron tetroxide crystallite dimension is about 9nm.
Embodiment 2
Multi-walled carbon nano-tubes is put into 140 ℃ baking oven baking 24 hours to remove the moisture of carbon nano-tube, with its reflow treatment 6 hours in red fuming nitric acid (RFNA), use deionized water wash then, dry.0.35g iron chloride is dissolved in the 50mL 2-Pyrrolidone, obtains a transparent salmon solution.Carbon nano-tube after the 100mg acid treatment is added in the above-mentioned solution, and ultrasonic dispersion was poured in the three-necked bottle after 60 minutes, and three-necked bottle connects condenser pipe flatly, feeds nitrogen or argon gas flatly, refluxes 3 hours in 245 ℃ silicone oil bath, naturally cools to room temperature then.The adding volume ratio is that 1: 3 methanol mixed solution makes the product sedimentation, again with acetone washing 5 times, promptly obtains the composite granule of nano ferriferrous oxide parcel carbon nano-tube after the oven dry.Fig. 2 (b) is the transmission electron microscope photo of the composite granule of tri-iron tetroxide parcel carbon nano-tube, and the tri-iron tetroxide uniform crystal particles covers carbon nano tube surface, and the tri-iron tetroxide crystallite dimension is about 7nm.
Embodiment 3
Change the multi-walled carbon nano-tubes among the embodiment 1 into Single Walled Carbon Nanotube, other condition is constant, can obtain tri-iron tetroxide/Single Walled Carbon Nanotube composite granule.Fig. 3 is the transmission electron microscope photo of the typical tri-iron tetroxide/Single Walled Carbon Nanotube composite material of gained, and as can be seen, ferriferrous oxide nano-particle is not wrapped on the Single Walled Carbon Nanotube tube wall, but accumulates in mouth of pipe place, and its particle size is about 7nm.This structure is the ideal structure that Single Walled Carbon Nanotube is used for electronic device, because tri-iron tetroxide only is positioned at its port, only plays the physical property that directed guide effect does not influence body itself.
Embodiment 4
The composite granule that obtains among the embodiment 1 is distributed in the ethanolic solution, drips one and drip on the slide, this slide is placed horseshoe magnet, find that composite powder cognition moves along magnetic direction is directed.After treating the ethanol volatilization, this slide is taken observation under the field emission scanning electron microscope.Fig. 4 is tri-iron tetroxide/multi-walled carbon nano-tubes composite granule directed SEM photo of assembling under magnetic field, can know and see that this composite granule has the formula that becomes of directional profile.Fig. 4 (b) is the SEM photo than high-amplification-factor, can see the oriented alignment of single-root carbon nano-tube along magnetic direction.
Claims (7)
1, the magnetic composite powder of ferroferric oxide nanometer crystal modified carbon nanometer pipe is characterized in that the brilliant in-situ deposition of ferriferrous oxide nano, is coated on the surface of multi-walled carbon nano-tubes; For Single Walled Carbon Nanotube, the ferriferrous oxide nano crystalline substance is positioned at its port.
2, by the magnetic composite powder of the described ferroferric oxide nanometer crystal modified carbon nanometer pipe of claim 1, the crystallite dimension that it is characterized in that described ferriferrous oxide nano crystalline substance is 5-10nm.
3, the method for the magnetic composite powder of preparation ferroferric oxide nanometer crystal modified carbon nanometer pipe as claimed in claim 1, it is characterized in that: by the acidification carbon nano-tube, make its surperficial possess hydrophilic property, utilize praseodynium base iron or iron chloride in 2-Pyrrolidone, to decompose again and obtain the ferriferrous oxide nano crystalline substance, carbon nano-tube is combined with the ferriferrous oxide nano crystalline phase, thereby obtain the composite granule of the brilliant in-situ modification carbon nano-tube of ferriferrous oxide nano.
4, press the preparation method of the magnetic composite powder of the described ferroferric oxide nanometer crystal modified carbon nanometer pipe of claim 3, it is characterized in that concrete steps are:
(a) with the carbon nano-tube oven dry, remove the moisture that is contained;
(b) dried carbon nano-tube with red fuming nitric acid (RFNA) in 140 ℃ of reflow treatment 5-8 hours carbon nano tube surface introducing-OH ,-the COOH active group, use deionized water cyclic washing, oven dry then;
(c) praseodynium base iron or iron chloride are dissolved in the 2-Pyrrolidone, form redness or transparent salmon solution, the concentration of solution is 0.5M-2M;
(d) step (b) carbon nano tube modified is joined in the solution of step (c) preparation ultrasonic 15-60 minute;
(e) mixed solution that step (d) is obtained is put into three-necked bottle, under 240-250 ℃ of nitrogen or argon shield atmosphere backflow 0.5-2 hour, praseodynium base iron or iron chloride resolve into tri-iron tetroxide, pass through aqueous favoring capacitive principle in-situ deposition on the surface with carbon nano-tube, are cooled to room temperature;
(f) the adding volume ratio is 1: 3 a methanol mixed liquor, makes the product sedimentation, and washs with acetone, promptly obtains the composite granule of tri-iron tetroxide/carbon nano-tube after the oven dry.
5, press the preparation method of the magnetic composite powder of the described ferroferric oxide nanometer crystal modified carbon nanometer pipe of claim 4, it is characterized in that described carbon nano-tube is multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.
6, press the preparation method of the magnetic composite powder of the described ferroferric oxide nanometer crystal modified carbon nanometer pipe of claim 4, it is characterized in that drying time is 20-24 hour, bake out temperature 120-150 ℃.
7, press the preparation method of the magnetic composite powder of the described ferroferric oxide nanometer crystal modified carbon nanometer pipe of claim 4, it is characterized in that the final product that makes it sedimentation with methanol washs 3-5 time with acetone.
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| CN100544823C (en) * | 2007-12-29 | 2009-09-30 | 中国科学院长春应用化学研究所 | A kind of preparation method of nanometer particle carbon nanotube compound catalyst |
| CN101161725B (en) * | 2007-09-29 | 2010-09-01 | 复旦大学 | Polyaniline coated magnetic carbon-nano tube composite material and preparation method thereof |
| CN101940952A (en) * | 2010-08-17 | 2011-01-12 | 复旦大学 | Bimetal nano particle catalyst and preparation method thereof |
| CN101966343A (en) * | 2010-10-11 | 2011-02-09 | 上海师范大学 | Carbon nanotube/magnetic nanoparticle magnetic resonance contrast medium and preparation method thereof |
| CN102391831A (en) * | 2011-12-07 | 2012-03-28 | 复旦大学 | Carbon nanotube composite material modified by magnetic nanoparticles, its preparation method and application |
| CN101695994B (en) * | 2009-10-30 | 2012-08-15 | 江苏大学 | Carbon nano tube-doped ferric oxide three-dimensional nanometer material and preparation method thereof |
| CN102671661A (en) * | 2012-03-20 | 2012-09-19 | 清华大学 | Multi-walled carbon nanotube-loaded nano ferroferric oxide catalyst and preparation method and application thereof |
| CN104393259A (en) * | 2014-10-13 | 2015-03-04 | 同济大学 | Preparation method of porous carbon ball-supported MxOy nanoparticle composite material |
| CN105036115A (en) * | 2015-07-29 | 2015-11-11 | 桂林电子科技大学 | Carbon nanotube uniformly and stably loaded with iron-containing nano particles and preparation method of carbon nanotube |
| 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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| 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 |
| CN100544823C (en) * | 2007-12-29 | 2009-09-30 | 中国科学院长春应用化学研究所 | A kind of preparation method of nanometer particle carbon nanotube compound catalyst |
| CN101695994B (en) * | 2009-10-30 | 2012-08-15 | 江苏大学 | Carbon nano tube-doped ferric oxide three-dimensional nanometer material and preparation method thereof |
| CN101940952A (en) * | 2010-08-17 | 2011-01-12 | 复旦大学 | Bimetal nano particle catalyst and preparation method thereof |
| CN101966343A (en) * | 2010-10-11 | 2011-02-09 | 上海师范大学 | Carbon nanotube/magnetic nanoparticle magnetic resonance contrast medium and preparation method thereof |
| CN101966343B (en) * | 2010-10-11 | 2012-08-01 | 上海师范大学 | Carbon nanotube/magnetic nanoparticle magnetic resonance contrast medium and preparation method thereof |
| CN102391831A (en) * | 2011-12-07 | 2012-03-28 | 复旦大学 | Carbon nanotube composite material modified by magnetic nanoparticles, its preparation method and application |
| CN102671661A (en) * | 2012-03-20 | 2012-09-19 | 清华大学 | Multi-walled carbon nanotube-loaded nano ferroferric oxide catalyst and preparation method and application thereof |
| CN102671661B (en) * | 2012-03-20 | 2014-03-12 | 清华大学 | Multi-walled carbon nanotube-loaded nano ferroferric oxide catalyst and preparation method and application thereof |
| CN104393259A (en) * | 2014-10-13 | 2015-03-04 | 同济大学 | Preparation method of porous carbon ball-supported MxOy nanoparticle composite material |
| CN104393259B (en) * | 2014-10-13 | 2017-01-25 | 同济大学 | Preparation method of porous carbon ball-supported MxOy nanoparticle composite material |
| CN105036115A (en) * | 2015-07-29 | 2015-11-11 | 桂林电子科技大学 | Carbon nanotube uniformly and stably loaded with iron-containing nano particles and preparation method of carbon nanotube |
| 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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