CN101164873B - Method for cutting carbon nano pipe by Fenton reaction - Google Patents
Method for cutting carbon nano pipe by Fenton reaction Download PDFInfo
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- CN101164873B CN101164873B CN2007100468825A CN200710046882A CN101164873B CN 101164873 B CN101164873 B CN 101164873B CN 2007100468825 A CN2007100468825 A CN 2007100468825A CN 200710046882 A CN200710046882 A CN 200710046882A CN 101164873 B CN101164873 B CN 101164873B
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- carbon nanotube
- carbon nano
- fenton reaction
- tube
- brachymemma
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Abstract
This invention relates to a method for cutting carbon nanometer tube by utilizing Fenton reaction. First, single-layer wall or multiple layer wall carbon nanometer tubes are acidized to make the surface of said nanometer tubes forming defects, then being coated with transition metal oxides by impregnation. Said carbon nanometer tubes are put into aromatic contaminant solution, together with hydrogen peroxide, so the produced free hydroxide radical attacks the defects and finally cutting said carbon nanometer tubes. The advantages of this invention are: no production of additional defects about the carbon nanometer tubes after being cut; and no environmental pollution.
Description
Technical field
The present invention relates to adopt Fenton reaction shortening carbon nano-tube, the later carbon nanotube of brachymemma is expected to be used widely at aspects such as nano-device, matrix materials.Belong to the brachymemma technical field.
Background technology
Carbon nanotube has the mechanics of many excellences as monodimension nanometer material, electricity and chemical property.Carbon nanotube is used for nano-device, Field Emission Display, and energy storage material, the biomolecule carrier material, aspects such as matrix material exist great potential.But what worth people noted is before these potentiality are achieved, must solve the technical barrier of carbon nanotube brachymemma.Carbon nanotube has several to dozens of microns long usually, and to tens nanometers, high length-to-diameter ratio makes its specific surface energy very big to diameter from several, forms big tube bank thereby cause carbon nanotube to interact, and twines bending mutually.Yet many material engineering and technical field but require the long single-root carbon nano-tube of hundreds of nanometers.Such as, in the process of making electron device, requirement can be operated appointed positions accurately with the carbon nanotube of certain-length.(K.J.Zieger, Z.Gu, H.Peng, E.L.Flor, R.H.Hauge, R.E.Smalley, J.Am.Chem.Soc., 2005,127,1541) so, the brachymemma of carbon nanotube further is applied to every field to carbon nanotube very important meaning.At present, there are many physics, chemistry and mechanical means that carbon nanotube is carried out brachymemma.Yet some needs special equipment in these methods, as utilizes photoetching process that carbon nanotube is carried out brachymemma (S.R.Lustig, E.D.Boyes, R.H.French, T.D.Gierke, M.A.Harmer, P.B.Hietpas, A.Jagota, R.S.McLean, G.P.Mitchell, G.B.Onoa, K.D.Sams, Nano Lett.2003,3,1007); Some expends lot of energy, as ball milling brachymemma (L.Chen, X.Pang, Q.Zhang, Z.Yu, Mater.Lett.2006,60,241); It is not only dangerous in operation that some uses the acid of strong oxidizing property that carbon nanotube is carried out brachymemma, and depleted acid is to environment unfavorable (J.Liu, A.G.Rinzler, H.Dai, J.H.Hafner, R.K.Bradley, P.J.Boul, A.Lu, T.Iverson, K.Shelimov, C.B.Huffman, F.Rodriguez-Macias, Y.Shon, T.R.Lee, D.T.Colbert, R.E.Smalley, Science 1998,280, and 1253).Therefore, study that a kind of simple effectively energy consumption is low, eco-friendly method shortening carbon nano-tube has significance to the application that promotes carbon nanotube.
Summary of the invention
The object of the present invention is to provide a kind of method of the simple and effective Fenton of utilization reaction shortening carbon nano-tube.Fenton reaction is a kind of by the degrade green high-level oxidation technology of aromatic series organic pollutant of the hydroxyl radical free radical that produces the high oxidation gesture.
The objective of the invention is to implement: carbon nanotube is carried out acidification, make it the surface and produce a large amount of defectives by following manner; Carbon pipe external parcel transition metal oxide after acidifying; In aromatic pollution solution, add carbon nanotube and a small amount of hydrogen peroxide that transition metal oxide is modified, make it to produce hydroxyl radical free radical and attack the carbon nanotube fault location, obtain the carbon nanotube of brachymemma.The method that is provided has easy, practical characteristics, does not need special equipment, environmental friendliness, and effective shortening carbon nano-tube has great importance to the further application of carbon nanotube.
The invention is characterized in the fault location of the hydroxyl radical free radical attack carbon nanotube that adopts Fenton reaction generation, make the carbon nanotube brachymemma.
The concrete operations step is:
(a) carbon nanotube is carried out acidification.With carbon nanotube at dense HNO
3Ultrasonic or refluxed 5～30 hours in solution or the mixed acid solution, filter washing, drying;
(b) by the carbon nanotube external parcel transition metal oxide of pickling process after acidifying, it is a ferric oxide, cupric oxide a kind of, or both mixtures, and the transition metal oxide of carbon nanotube external parcel and the mass ratio of carbon nanotube are 1: 100～1: 1;
(c) carbon nanotube 0.5～50mg that the transition metal oxide of step (b) gained is modified joins in the aromatic pollution solution of 0.01～1.0g/L, regulate pH value to 2.0～about 6.0, add hydrogen peroxide, carbon nanotube unit mass in the transition metal oxide parcel, add-on is 0.02-0.1ml/mg, be 0.01-5ml, reflux after 2～10 hours, filter, dry, the length distribution of the multi-walled carbon nano-tubes after the brachymemma is in 100nm-500nm, and the length distribution of the Single Walled Carbon Nanotube after the brachymemma is in 0.2 μ m-2 μ m.
Method by Fenton reaction shortening carbon nano-tube provided by the invention has following characteristics:
(1) in the process of purifying carbon nano-tube, the group of introducing not only has certain functional, absorption Fe
3+Thereby generate Fe
2O
3, and can be used as the attack that defective is accepted free radical
(2) Fe of Yin Ruing
2O
3Produce hydroxyl radical free radical, Fe with the hydrogen peroxide reaction
2O
3Naturally consume, do not need extra purification step, can the further application of carbon nanotube not exerted an influence
(3) hydroxyl radical free radical is attacked the carbon nanotube fault location, can not cause new defective.
(4) technology is simple, and environmental friendliness need not specific installation, has universality.
Description of drawings
The original TEM photo of Fig. 1 multi-walled carbon nano-tubes
TEM photo after the brachymemma of Fig. 2 multi-walled carbon nano-tubes and staple diagram (upper right corner)
The original TEM photo of Fig. 3 Single Walled Carbon Nanotube
TEM photo after the brachymemma of Fig. 4 Single Walled Carbon Nanotube and staple diagram (upper right corner)
The TEM photo of the multi-walled carbon nano-tubes after Fig. 5 acidifying
Fig. 6 Fe
2O
3The TEM photo of the multi-walled carbon nano-tubes of parcel
The TEM photo of the Single Walled Carbon Nanotube after Fig. 7 acidifying
Fig. 8 presses the TEM photo of the method for embodiment 1 to Single Walled Carbon Nanotube
The carbon nanotube TEM photo of Fig. 9 brachymemma and staple diagram (upper right corner)
Embodiment
Further specify embodiment and effect with following indefiniteness embodiment
Embodiment 1
With 1g multi-walled carbon nano-tubes ultra-sonic dispersion at 400ml nitration mixture (H
2SO
4: HNO
3=3: 1v/v) in the solution, ultrasonic 5 hours, suction filtration was washed 3 times then, and alcohol is washed 1 time, dried 24 hours for 80 ℃.Carbon nanotube after the acidifying is seen Fig. 5.Get acidifying carbon pipe 0.1g, at 1g/L Fe (NO
3)
3In the solution ultrasonic 5-10 minute,, filter back 60 ℃ of oven dry 12 hours down then 50 ℃ of dippings 36 hours.200 ℃ of down calcinings 4 hours in retort furnace then (heat-up rate is: rise to 100 ℃ from 60 ℃ in 1 hour, rose to 200 ℃ from 100 ℃ in 1 hour again).Fe
2O
3The carbon nanotube of parcel is seen Fig. 6.Get 10mg Fe
2O
3/ MWCNTs ultra-sonic dispersion is used 1M HNO in the phenol solution of 0.1g/L
3Regulate about pH value to 3.5, add the 0.5ml hydrogen peroxide, 80 ℃ of stirring and refluxing are after 6 hours, with the sample suction filtration.The carbon nanotube of resultant brachymemma as shown in Figure 2, length distribution is between 100-500nm.(upper right corner)
Embodiment 2
At the 400mL concentrated nitric acid, 140 ℃ were refluxed 24 hours with 1g Single Walled Carbon Nanotube ultra-sonic dispersion, and suction filtration is washed 3 times then, and alcohol is washed 1 time, dried 24 hours for 80 ℃.Carbon my humble opinion Fig. 7 after the acidifying.Fe
2O
3The method of the carbon nanotube of parcel and Fenton reaction conditions are with embodiment 1.The carbon nanotube of resultant brachymemma as shown in Figure 4, as Fig. 4 upper right corner staple diagram as can be known length distribution between 0.5-2 μ m.
Embodiment 3
Method by embodiment 1 is carried out acidification to Single Walled Carbon Nanotube, the carbon my humble opinion Fig. 8 after the acidifying.Fe
2O
3The method of the carbon nanotube of parcel and Fenton reaction conditions are with embodiment 1.The carbon nanotube of resultant brachymemma as shown in Figure 9, as Fig. 9 upper right corner staple diagram as can be known its length distribution between 0.2-1.5 μ m.
Claims (5)
1. adopt the method for Fenton reaction shortening carbon nano-tube, it is characterized in that at first single wall or multi-walled carbon nano-tubes being carried out acidification, make it the surface and produce a large amount of defectives; By pickling process carbon nanotube external parcel transition metal oxide after acidifying; In aromatic pollution solution, add the carbon nanotube and the hydrogen peroxide of transition metal oxide parcel, make it to produce hydroxyl radical free radical and attack the carbon nanotube fault location, obtain the carbon nanotube of brachymemma; The method of described employing Fenton reaction shortening carbon nano-tube, concrete steps are:
(a) carbon nanotube is carried out acidification: with carbon nanotube at dense HNO
3Ultrasonic or refluxed 5～30 hours in solution or the mixed acid solution, filter washing, drying;
(b) by the carbon nanotube external parcel ferric oxide of pickling process after acidifying;
(c) carbon nanotube with the transition metal oxide of step (b) gained parcel joins in the aromatic pollution solution, regulates pH value to 2.0～6.0, again
Add hydrogen peroxide after refluxing, filter and drying;
Wherein, described aromatic pollution concentration is 0.01-1.0g/L;
Described mixed acid solution is H
2SO
4: HNO
3=3: 1v/v;
Described hydrogen peroxide add-on is that add-on is 0.02-0.1ml/mg in the carbon nanotube unit mass of transition metal oxide parcel.
2. by the method for the described employing of claim 1 Fenton reaction shortening carbon nano-tube, it is characterized in that return time is 2-10 hour in the step (c).
3. by the method for the described employing of claim 1 Fenton reaction shortening carbon nano-tube, it is characterized in that described aromatic pollution is a phenol.
4. by the method for the described employing of claim 1 Fenton reaction shortening carbon nano-tube, the length distribution that it is characterized in that the multi-walled carbon nano-tubes after the brachymemma is between 100nm-500nm.
5. by the method for the described employing of claim 1 Fenton reaction shortening carbon nano-tube, the length distribution that it is characterized in that the Single Walled Carbon Nanotube after the brachymemma is between 0.2 μ m-2 μ m.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342493A (en) * | 2018-04-03 | 2019-10-18 | 清华大学 | Transition metal oxide/carbon nano tube compound material and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101638228B (en) * | 2008-07-30 | 2011-09-21 | 中国科学院大连化学物理研究所 | Method for truncating length-controlled carbon nanotubes |
| CN110078056B (en) * | 2019-05-08 | 2021-03-09 | 福州大学 | Carbon nano tube with electrochemiluminescence activity |
| CN111807350A (en) * | 2020-06-15 | 2020-10-23 | 上海大学 | Preparation method of short carbon nano tube with open end |
| CN113479864A (en) * | 2021-08-04 | 2021-10-08 | 岳阳振兴中顺新材料科技有限公司 | Preparation method of coal-based carbon nano tube based on hydrogen peroxide wastewater treatment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696053A (en) * | 2004-05-14 | 2005-11-16 | 中国科学院成都有机化学有限公司 | Method for truncating Nano carbon tubes |
| US20070158622A1 (en) * | 2005-10-18 | 2007-07-12 | Lee Jeong-Hee | Method of cutting carbon nanotubes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696053A (en) * | 2004-05-14 | 2005-11-16 | 中国科学院成都有机化学有限公司 | Method for truncating Nano carbon tubes |
| US20070158622A1 (en) * | 2005-10-18 | 2007-07-12 | Lee Jeong-Hee | Method of cutting carbon nanotubes |
Non-Patent Citations (6)
| Title |
|---|
| Yangqiao Liu et al..A multi-step strategy for cutting and purification of single-walled carbon nanotubes.Carbon45.2007,451972-1978. * |
| 于华荣等.碳纳米管负载纳米Fe2O3的研究.无机化学学报21 11.2005,21(11),1649-1654. |
| 于华荣等.碳纳米管负载纳米Fe2O3的研究.无机化学学报21 11.2005,21(11),1649-1654. * |
| 李明玉等.无机离子对Fenton 试剂降解水中苯胺的影响.化学通报66.2003,661-8. * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342493A (en) * | 2018-04-03 | 2019-10-18 | 清华大学 | Transition metal oxide/carbon nano tube compound material and preparation method thereof |
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