CN101638228B - Method for truncating length-controlled carbon nanotubes - Google Patents
Method for truncating length-controlled carbon nanotubes Download PDFInfo
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- CN101638228B CN101638228B CN2008100125660A CN200810012566A CN101638228B CN 101638228 B CN101638228 B CN 101638228B CN 2008100125660 A CN2008100125660 A CN 2008100125660A CN 200810012566 A CN200810012566 A CN 200810012566A CN 101638228 B CN101638228 B CN 101638228B
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Abstract
The invention provides a method for truncating length-controlled carbon nanotubes, which can control to truncate and obtain the carbon nanotubes with required lengths, and comprises the following steps: loading metal catalyst particles with catalytic oxidation performance on the carbon nanotubes; performing oxidation treatment at an atmosphere with certain oxygen content; and enabling the positions of the carbon nanotubes where the metal particles fall off to generate catalytic oxidation reaction so as to truncate the carbon nanotubes. The carbon nanotubes with different length distribution can be obtained by controlling the loading quantity and dispersion of the metal catalyst. The method has the characteristics of mild operation conditions, controllable lengths of the carbon nanotubes and high yield.
Description
Technical field
The present invention relates to the controlled method for truncating of carbon nanotube, the chemical oxidation method for truncating under specifically a kind of mild conditions belongs to the preparation field of nano catalytic material.
Background technology
Carbon nanotube is a kind of novel carbon material with many unusual characteristics, as high strength, and low density, strong conductive capability, therefore high specific areas etc. have broad application prospects in fields such as catalysis, material engineering, electronics.Yet, all long to the hundreds of micron with the length of carbon nanotube that the method for CVD or arc-over makes tens, when in these fields, using, how all to relate to, thereby bring into play the problem of the excellent properties of carbon nanotube better the carbon nanotube brachymemma.
On the document, the method for truncating of carbon nanotube is mainly contained two kinds of chemical process and physical methods, perhaps two kinds of methods of compound employing simultaneously.
Chemical process mainly is to adopt oxygenant oxidation carbon tube wall to reach the purpose of brachymemma, comprises two kinds of concentrated acid and oxidizing gas processing.3: 1 vitriol oils that adopted as (Science, 1998,280,1253) such as Liu and the miscellany of concentrated nitric acid are handled Single Walled Carbon Nanotube at 70 ℃, can obtain the carbon nanotube that most length are lower than 400 nanometers.The characteristics of this method are that acid casts the first stone the wall defects place, as manage defective on top and the tube wall, if oxidisability is enough strong, then all tube walls are carried out oxidation simultaneously, acid treatment is very serious for the corrosion of tube wall, makes the performance perameters such as physical strength of carbon pipe reduce greatly, and the smaller carbon nanotube of diameter is often eroded fully, the carbon nanotube yield that this method obtains is also lower, has only 30% or lower for the single-walled pipe yield.The method that oxidizing gas is handled is as described in patent WO2003086969, US2003010940 and the CN1628075A, with fluorizating agent and carbon tube reaction, thereby with the brachymemma of carbon pipe, this treatment process is the same with the processing of employing concentrated acid, exists the carbon tube wall to destroy serious and the low problem of yield equally.
Document (Journal of materials chemistry, 2006,16,4231) has adopted a kind of method of phase oxidative reaction to come shortening carbon nano-tube.This method supports the Ni particle on carbon nanotube earlier, 400 ℃ of oxide treatment 2 hours in air then, and then in He gas, be heated to 900 ℃, obtain the carbon nanotube of brachymemma.Yet the treatment temp of this method is very high, and the loading of Ni is up to 50%, the Ni particle is the surface of coated carbon nanotube almost completely, long-time oxidation must be accompanied by a large amount of mass losses in air, so yield can be lower, and the length that obtains carbon nanotube can't be controlled effectively.
The method of physics mainly is that the wall that adopts means such as ball milling, high-power ultrasonic, extra-high pressure to destroy the carbon pipe is realized the brachymemma to the carbon pipe.Adopt (Chemical Physics Letters, 2001,335,1) such as the method for ball milling such as Pierard, and carbon nanotube and high-intensity abrasive is mixed, carries out long ball milling then with the carbon nanotube brachymemma in ball mill.The yield of this method for truncating carbon nanotube is higher.But the often needed time of the treatment process of ball milling is long, and as what report in (Chemical Physics Letters, 2001,335,1), the carbon pipe that obtains about 500 nanometers needed ball milling 120 hours.In addition, the carbon nanotube that prescinds is mixed in abrasive, is difficult to separate.The method of high-power ultrasonic and extra-high pressure such as document (carbon, 1996,34,814) and document (US2007119372-A1) described, these two kinds of methods are only limited to handles the purpose that micro-carbon nanotube is used to study, and then lacks realistic meaning for large-scale application.
Summary of the invention
The invention provides the carbon nanotube method for truncating of length controlled under a kind of mild conditions.Compare with method for truncating in the aforesaid document, the advantage of this method is the treatment condition gentleness, the length of carbon nanotube can control and yield higher, can be used for large-scale brachymemma and handle.
Carbon nanotube method for truncating provided by the invention is as described below: carbon nano tube surface is carried out wetting ability handle, then metal catalyst is dispersed in the carbon tube-surface, carry out oxide treatment by conditions such as concentration of oxygen in the controlled atmosphere and flow velocity, oxidizing temperature, oxidization times, finally obtain the carbon nanotube of brachymemma.
According to the present invention, the concrete operations step can be divided into: carbon nano tube surface hydrophilic treatment, loaded metal, oxidation brachymemma.Details are as follows respectively:
(1). the purifying of carbon nanotube, surface hydrophilic are handled
Carbon nanotube is mixed under the stirring velocity of 240～480r/min with rare nitric acid, is heated to 50～110 ℃ and under this temperature, kept 0.5～5 hour then,, obtain carbon nanotube purifying, surface hydrophilic.
Described carbon nanotube comprises Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes.
Described rare nitric acid is according to 7: 1～2: 1 (V with 68% nitric acid and water
H2O/ V
HNO3, volume ratio) mixed obtain.
The proportional range of described rare nitric acid and carbon nanotube is 20～50 (ml/g).
(2). loaded metal
The carbon nanotube that metal salt solution and step 1 are obtained is according to 0.005～0.5 mixed, then under 25-80 ℃, with 120～240r/min stir speed (S.S.), be stirred to anhydrous state, after 100-150 ℃ of oven dry, be heated to 300-500 ℃ of carbon nanotube that obtains loaded metal in the mobile gas phase, transmission electron microscope shows that metal nanoparticle is scattered in the surface of carbon nanotube equably.
Metal salt solution of the present invention comprises Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, all soluble salts of Au element.
The ratio of described metal salt solution and carbon nanotube is meant the ratio of metal quality contained in the metal salt solution and carbon nanotube quality.
The concentration of described metal salt solution is 0.01～0.2mol/L.
Described gas phase can be a kind of rare gas element such as N
2, He, Ar, Kr, Xe etc., also can be a kind of gas such as H of reductibility
2, CO etc.
(3). the oxidation brachymemma
The load that step 2 is obtained has the carbon nanotube of metal to place 1%～80%O
2Be heated to 100-700 ℃ in the mixed air of rare gas element and keep the carbon nanotube that obtained brachymemma in 5～200 minutes.
Described rare gas element can be N
2, any gas among He, Ar, Kr, the Xe or the mixture of two kinds and two or more rare gas elementes wherein.
The present invention has following advantage:
1. mild condition is not used acid or gas with severe corrosive.
2. can control condition, make oxidation only occur in the position that metallics supports, there is not the position of metallics oxidation can not take place, therefore can keep the original appearance and the physical property of carbon nanotube preferably.
Charge capacity by regulating metal, control its dispersity, can regulate the quantity of the position of carbon nano tube surface generation oxidizing reaction, thereby obtain the different carbon nanotube of length distribution scope.
4. the yield height of carbon nanotube.
In a word, the invention provides a kind of carbon nanotube method for truncating of length controlled, it can control the carbon nanotube that brachymemma obtains desired length, detailed process is: the metal catalyst particle load that will have catalytic oxidation performance is on carbon nanotube, oxide treatment in the oxygen atmosphere of certain content, make carbon nanotube catalytic oxidation take place in the fall place of position of metallics, thereby with the carbon nanotube brachymemma.By the charge capacity and the dispersion of control metal catalyst, can obtain the carbon nanotube that different lengths distributes.
Present method has the operational condition gentleness, length of carbon nanotube is controlled and yield than higher characteristics.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the carbon nanotube behind the rare nitric acid purifying of process in the embodiment of the invention 1;
One of transmission electron microscope photo of the carbon nanotube of the brachymemma that Fig. 2 obtains for the embodiment of the invention 1;
Two of the transmission electron microscope photo of the carbon nanotube of the brachymemma that Fig. 3 obtains for the embodiment of the invention 1.
Embodiment
Do a detailed explanation below by embodiment for whole process, but claim scope of the present invention is not subjected to the restriction of these embodiment.Simultaneously, embodiment has just provided the partial condition of realizing this purpose, but and does not mean that must satisfy these conditions just can reach this purpose.
Embodiment 1
1. get carbon nanotube 3 grams and put into Florence flask, add 2: 1 (V
H2OThe V of/mass concentration 68%
HNO3, volume ratio) rare nitric acid 120ml, then in oil bath 110 ℃ refluxed 5 hours, use the deionized water filtering and washing at last, 100 ℃ of oven dry 2 hours, obtain the hydrophilic carbon nanotube in purifying rear surface, its transmission electron microscope photo is seen accompanying drawing 1.By the transmission electron microscope photo as seen, can not be after rare nitric acid treatment with the multi-walled carbon nano-tubes brachymemma, most length are all more than 3 microns.
2. get carbon nanotube 1 gram that obtains in 1, add the silver nitrate solution 23.1ml of 0.02mol/L, add entry 10ml again, thorough mixing is even.Speed with 160r/min is stirred to dried in 80 ℃ of water-baths then.In 100 ℃ of baking ovens, dried 2 hours at last.
3. be cooled to room temperature after the sample that obtains in 2 being heated to 300 ℃ with the speed of 2K/min in the He gas that flows, switch to 5%O then
2/ He (V/V, volumn concentration) gas mixture is heated to 300 ℃ and keep oxidation 105 minutes under this temperature with the speed of 2K/min, is cooled to room temperature at last, obtains the carbon nanotube of brachymemma.The overall yield of carbon nanotube is 70%.The transmission electron microscope photo of the carbon nanotube after the brachymemma and length distribution statistics are seen accompanying drawing 2,3 and subordinate list 1.By accompanying drawing 2 as seen, carbon nanotube is by brachymemma, and the silver-colored particle that works the effect of blocking is still stayed the section part of carbon nanotube.Accompanying drawing 3 shows, only takes place and produces breach in the fall ground aerobic reaction just now of position of silver particles.By subordinate list 1 as seen, the length distribution scope of the carbon nanotube of brachymemma is narrower, and about 87% carbon length of tube is lower than 500 nanometers.
Embodiment 2
1. get carbon nanotube 4 grams and put into Florence flask, add 2: 1 (V
H2OThe V of/mass concentration 68%
HNO3) rare nitric acid 200ml, then in oil bath 110 ℃ refluxed 5 hours, use the deionized water filtering and washing at last, 100 ℃ of oven dry 2 hours.
2. get carbon nanotube 0.5 gram that obtains in 1, add the silver nitrate solution 1.16ml of 0.08mol/L, it is even to add entry 20ml thorough mixing again.Speed with 160r/min is stirred to dried in 80 ℃ of water-baths then.In 100 ℃ of baking ovens, dried 2 hours at last.
3. be cooled to room temperature after 2 samples that obtain being heated to 300 ℃ with the speed of 2K/min in the He gas that flows, switch to 5%O then
2/ He (V/V, volumn concentration) gas mixture is heated to 300 ℃ and kept 105 minutes with the speed of 2K/min under this temperature, be cooled to room temperature at last, obtains the carbon nanotube of brachymemma.The overall yield of carbon nanotube is 80%.Transmission electron microscope shows that carbon nanotube is by brachymemma.Its length distribution statistics sees attached list 1.
Embodiment 3
1. get carbon nanotube 4 grams and put into Florence flask, add 2: 1 (V
H2OThe V of/mass concentration 68%
HNO3) rare nitric acid 200ml, then in oil bath 110 ℃ refluxed 5 hours, use the deionized water filtering and washing at last, 100 ℃ of oven dry 2 hours.
2. get carbon nanotube 0.5 gram that obtains in 1, add the silver nitrate solution 0.29ml of 0.08mol/L, it is even to add entry 20ml thorough mixing again.Speed with 160r/min is stirred to dried in 80 ℃ of water-baths then.In 100 ℃ of baking ovens, dried 2 hours at last.
3. be cooled to room temperature after the sample that obtains in 2 being heated to 300 ℃ with the speed of 2K/min in the He gas that flows, switch to 5%O then
2/ He (V/V, volumn concentration) gas mixture is heated to 300 ℃ and kept 105 minutes with the speed of 2K/min under this temperature, be cooled to room temperature at last, obtains the carbon nanotube of brachymemma.The overall yield of carbon nanotube is 93%.Transmission electron microscope shows that carbon nanotube is by brachymemma.Its length distribution statistics sees attached list 1.
Embodiment 4
Oxidizing temperature is 350 ℃, and oxidization time is 13 minutes.Other is with embodiment 1.The overall yield of carbon nanotube is 80%.Transmission electron microscope shows that the carbon nanometer is by brachymemma.About 85% carbon length of tube is lower than 500 nanometers.
Embodiment 5
1. with the step 1 among the embodiment 1.
2. get carbon nanotube 1 gram that obtains in 1, add the Fe (NO of 0.05mol/L
3)
3Solution 17.8ml adds entry 20ml again, and thorough mixing is even.Speed with 160r/min is stirred to dried in 80 ℃ of water-baths then.In 100 ℃ of baking ovens, dried 2 hours at last.
3. be cooled to room temperature after the sample that obtains in 2 being heated to 600 ℃ with the speed of 2K/min in the He gas that flows, switch to 5%O then
2/ He (V/V, volumn concentration) gas mixture is heated to 460 ℃ and kept 30 minutes with the speed of 2K/min under this temperature, be cooled to room temperature at last, obtains the carbon nanotube of brachymemma.The overall yield of carbon nanotube is 78%.Transmission electron microscope shows that carbon nanotube is by brachymemma.Its length distribution statistics sees attached list 1.
The length distribution statistical graph of the carbon nanotube of the brachymemma that subordinate list 1 obtains for embodiment of the invention 1-3, embodiment 5.
Subordinate list 1
| Embodiment | Length of carbon nanotube distributes |
| Embodiment 1 | About 85% length of carbon nanotube is less than 500 nanometers |
| Embodiment 2 | About 60% length of carbon nanotube greater than 500 nanometers less than 1 micron |
| Embodiment 3 | About 75% length of carbon nanotube greater than 1.5 microns less than 3 microns |
| Embodiment 5 | About 80% length of carbon nanotube is less than 500 nanometers |
Claims (7)
1. the carbon nanotube method for truncating of a length controlled, key step is as follows:
(1). the purifying of carbon nanotube, surface hydrophilic are handled
Carbon nanotube is under agitation mixed with rare nitric acid, be heated to 50～110 ℃ and kept 0.5～5 hour then under this temperature, filtration washing obtains carbon nanotube purifying, surface hydrophilic;
The proportional range of described rare nitric acid and carbon nanotube is 20～50ml/g;
(2). loaded metal
Metal salt solution is mixed with the carbon nanotube that step (1) obtains, the mass ratio that makes final metal and carbon pipe is 0.005～0.5, then under 25-80 ℃, be stirred to anhydrous state with 120～240r/min speed, after in 100-150 ℃ of air, drying, be heated to 300-500 ℃ at mobile gas with the speed of 2-10K/min, obtain the carbon nanotube of loaded metal;
(3). the oxidation brachymemma
The load that step (2) is obtained has the carbon nanotube of metal to place O
2Be heated to 100～700 ℃ of oxidizing temperatures in the gas mixture of rare gas element, and keep the carbon nanotube that oxidation 5～200min obtains brachymemma.
2. method for truncating according to claim 1 is characterized in that: the rare nitric acid described in the step (1) is that the nitric acid with water and mass concentration 68% obtains according to 7: 1～2: 1 mixed of volume ratio.
3. method for truncating according to claim 1 is characterized in that: the metal salt solution described in the step (2) is more than one of soluble salt solution of Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Au element.
4. method for truncating according to claim 1 is characterized in that: the concentration of the metal salt solution described in the step (2) is 0.01～0.2mol/L.
5. method for truncating according to claim 1 is characterized in that: the mobile gas composition described in the step (2) is the gas of rare gas element or reductibility.
6. method for truncating according to claim 1 is characterized in that: the rare gas element described in the step (3) is N
2, more than one rare gas elementes among He, Ar, Kr, the Xe mixture; O
2V/V is 1%～80% with rare gas element blended ratio.
7. method for truncating according to claim 1 is characterized in that: the carbon nanotube that is used for brachymemma described in the step (1) is a Single Walled Carbon Nanotube, double-walled carbon nano-tube and/or multi-walled carbon nano-tubes.
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| US8848183B2 (en) | 2011-07-22 | 2014-09-30 | Hewlett-Packard Development Company, L.P. | Apparatus having nano-fingers of different physical characteristics |
| CN105251488A (en) * | 2015-10-21 | 2016-01-20 | 扬州大学 | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst |
| CN105195147A (en) * | 2015-10-21 | 2015-12-30 | 扬州大学 | Dehydrogenation catalyst with copper nanoparticles loaded inside carbon nano tube and preparation method of dehydrogenation catalyst |
| CN112978717A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Method for shortening carbon nano tube |
| CN114890408B (en) * | 2022-05-12 | 2023-08-22 | 湖南湘投轻材科技股份有限公司 | Preparation method of carbon nano tube with controllable size distribution and preparation method of carbon nano tube reinforced aluminum matrix composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060051290A1 (en) * | 2004-07-13 | 2006-03-09 | William Marsh Rice University | Short carbon nanotubes as adsorption and retention agents |
| CN1807233A (en) * | 2006-01-26 | 2006-07-26 | 上海交通大学 | Chemical shearing method for preparing high dispersion short carbon nanometer tube |
| CN101164873A (en) * | 2007-10-10 | 2008-04-23 | 中国科学院上海硅酸盐研究所 | Method for cutting carbon nano pipe by Fenton reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060051290A1 (en) * | 2004-07-13 | 2006-03-09 | William Marsh Rice University | Short carbon nanotubes as adsorption and retention agents |
| CN1807233A (en) * | 2006-01-26 | 2006-07-26 | 上海交通大学 | Chemical shearing method for preparing high dispersion short carbon nanometer tube |
| CN101164873A (en) * | 2007-10-10 | 2008-04-23 | 中国科学院上海硅酸盐研究所 | Method for cutting carbon nano pipe by Fenton reaction |
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