CN1184140C - Preparation method of carbon nano pipe filled with organic solvent - Google Patents

Preparation method of carbon nano pipe filled with organic solvent Download PDF

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Publication number
CN1184140C
CN1184140C CNB021067252A CN02106725A CN1184140C CN 1184140 C CN1184140 C CN 1184140C CN B021067252 A CNB021067252 A CN B021067252A CN 02106725 A CN02106725 A CN 02106725A CN 1184140 C CN1184140 C CN 1184140C
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carbon nanotube
organic solvent
preparation
carbon nano
carbon
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CN1442359A (en
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刘云圻
王贤保
韩布兴
刘志敏
胡安平
朱道本
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Institute of Chemistry CAS
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Abstract

The present invention discloses a method for preparing a carbon nano-pipe filled with an organic solvent by a supercritical fluid technique for the first time, concretely the carbon nano-pipe with a single wall or multiple walls, and the carbon nano-pipe is filled with a polarity or nonpolarity organic solvent such as benzene, toluene, pentane, isoprene, tetrachlormethane, methanol, alcohol, acetonitrile, etc., and has the diameter of 1 to 200 nanometers and the length of 0.01 to 50 micrometers. The practical and feasible method has the advantages of high filling efficiency and convenient and controllable operation. By the method, a large amount of nanometer fluid is effectively obtained, which opens up an extensive clew for implementing the nanometer chemical experiment. At the same time, the method lays the foundation for exploring the unique performance of the carbon nano-pipe filled with an organic solvent and carrying out the nanometer chemical reaction.

Description

The preparation method of the carbon nanotube that a kind of organic solvent is filled
Technical field:
The present invention relates to a kind of preparation method of carbon nanotube of organic solvent filling.
Background technology:
Do the nanochemistry reaction of nano-reactor with carbon nanotube, for experiment and understand dimension and size to the key concepts such as influence of chemical property, be extremely important.And to realize the precondition of the chemical reaction in the carbon nanotube, be will find one effectively and the method for system is filled into organic solvent in the carbon nanotube and goes.The method that is used for filling carbon nano-pipe in early days mainly is by capillary action, and it can make some metals (Ajayan, P.M.; Iijima, S.Nature 1993,361, and 333.) and inorganic materials (Tsang, S.C.; Chen, Y.K.; Harris, P.J.F.; Green, M.L.H.Nature 1994,372, and 159.) enter carbon nanotube with molecular form or liquid state.Yet the charging efficiency of this method is low, and is difficult to control.
U.S. scientist Pederson and Broughton are according to computer simulation results, and the just prediction once as far back as 1992 can be by capillary action with liquid filling (Pederson, M.R. in the carbon nanotube of opening; Broughton, J.Q.Phys.Rev.Lett.1992,69,2689).Yet, so far the experiment of organic solvent filling carbon nano-pipe also of no use report, mainly be because in the process of filling by capillary action, its charging efficiency will be filled the influence of various factors such as diameter of surface tension, viscosity, contact angle and the pipe of material.
The invention provides a kind of method of effective filling carbon nano-pipe, this method adopts supercritical fluid technology that organic solvent is filled in the carbon nanotube for the first time and goes.As supercutical fluids such as carbonic acid gas and traditional solvent phase ratio many advantages are arranged: it is not flammable, nontoxic substantially and environmental friendliness, its lower critical temperature (31.1 ℃) and pressure (73.8 crust) are easy to obtain, thereby, many investigators are referred to as a kind of " continuable green solvent " (Cooper, A.I.Adv.Mater.2001,13,1111.).The many liquid solvents of the viscosity ratio of postcritical carbonic acid gas are much lower, surface tension that it is quite low and surface energy, and---even lower than many perfluoro-carbons---makes it have the good wetting property energy.Simultaneously, adopt postcritical carbonic acid gas, product separate easily and purifying, solvent load is few.
Summary of the invention:
The objective of the invention is to adopt supercritical fluid technology, effectively organic solvent is filled in the carbon nanotube, and obtain a large amount of nano-fluids that are sealed in the carbon nanotube, for the nano level chemical reaction that is implemented in the carbon nanotube is laid a solid foundation.
A kind of carbon nanotube that organic solvent is housed provided by the invention, be meant to use and fill as toluene, benzene, pentane, isoprene, tetrachloromethane, methyl alcohol, ethanol, acetonitrile isopolarity or nonpolar organic solvent, diameter be 1-200 nanometer, length be the 0.01-50 micron, single wall or multi-walled carbon nano-tubes.
The carbon nanotube that the present invention prepares the organic solvent filling divided for two steps carried out:
In the 1st step, the purifying of carbon nanotube and processing: it is that sulfuric acid and nitric acid volume ratio are 3: 1 in the mixing acid in the carbon nanotube 500-5000 sulfuric acid and the mixed acid of nitric acid doubly that single wall or multi-walled carbon nano-tubes are joined quality.Ultrasonic 1-5 hour, to use the distilled water diluting after-filtration, and be washed till neutrality, vacuum-drying obtains the carbon nanotube that length is the purifying of 0.01-50 micron.
The 2nd step, the filling of carbon nanotube: after the carbon nanotube after the above-mentioned purified processing and organic solvent joined high pressure vessel by 1: 60 mass ratio, put into Water Tank with Temp.-controlled, when homo(io)thermism at 30-100 ℃, be preferably 30-45 ℃, by pump pressure injecting carbon dioxide or lower carbon number hydrocarbons, make pressure reach 3.0 * 10 5-30 * 10 5Pascal is preferably 11 * 10 5-15 * 10 5Pascal keeps cooling the temperature to room temperature after 2-24 hour, and container decompression emptying after the vacuum-drying of taking-up sample, obtains the carbon nanotube that organic solvent is filled.Observe under transmission electron microscope, its charging efficiency is up to more than 90%.Described organic solvent comprises benzene, toluene, pentane, isoprene, tetrachloromethane, acetone, methyl alcohol, ethanol, acetonitrile isopolarity or nonpolar solvent.Described lower carbon number hydrocarbons comprises that carbonatomss such as methane, ethane, ethene, acetylene, propane, propylene, normal butane, Trimethylmethane are less than 4 hydro carbons.
The carbon nanotube that organic solvent provided by the invention is filled has following feature and advantage:
1. the present invention discloses for the first time by supercritical fluid technology, with the method for organic solvent filling carbon nano-pipe.
2. method disclosed by the invention is compared with traditional kapillary method, has improved charging efficiency greatly, and is practical, easy to operate controlled.Product separate easily and purifying, solvent load is few.
3. the supercritical co of the present invention's employing is safe and reliable, does not burn, and nontoxic pollution-free is a kind of continuable green solvent.
4. method disclosed by the invention can obtain nano-fluid in a large number and effectively, and this is for implementing the nanochemistry experiment, opened up a wide thinking, simultaneously, for exploring the special performance of this carbon nanotube of being filled by organic solvent, carry out the nanochemistry reaction and lay a solid foundation.
Description of drawings:
Fig. 1 is by the apparatus structure synoptic diagram of supercritical co with the organic solvent filling carbon nano-pipe.1-dioxide bottle, 2-syringe pump, 3,5,7-valve, 4-digital altimeter, 6-stainless steel high pressure vessel, 8-tank, 9-temperature controller.
The transmission electron microscope photo of the carbon nanotube that Fig. 2 organic solvent is filled.
Embodiment:
The present invention is described in detail below in conjunction with drawings and Examples.
Embodiment 1 joins 100 milligrams multi-walled carbon nano-tubes in the mixing acid of 20 milliliters sulfuric acid and nitric acid (volume ratio is 3), ultrasonic 2 hours, water dilution after-filtration with 100 milliliters, be washed till neutrality with distilled water again, vacuum-drying, obtain the carbon nanotube that the quilt of purifying prescinds, its diameter is the 50-80 nanometer, and length is the 0.5-5 micron.
As shown in Figure 1, after the toluene of the carbon nanotube after 20 milligrams of purified processing and 1.5 milliliters joined stainless steel high pressure vessel 6, put into Water Tank with Temp.-controlled 8, regulate temperature controller 9, make homo(io)thermism at 40 ℃, open valve 3 and 5, by syringe pump 2 injecting carbon dioxides, when the pressure of weather gauge 4 reaches 1.1 * 10 6Behind the pascal, valve-off 3 keeps this pressure and temperature after 15 hours, cools the temperature to room temperature, opens valve 7 and makes high pressure vessel 6 decompression emptying, after the vacuum-drying of taking-up sample, obtains the carbon nanotube that organic solvent is filled.Observe under transmission electron microscope, obtain electromicroscopic photograph as shown in Figure 2, its filling ratio is up to more than 90%.
Embodiment 2 presses the preparation method of embodiment 1, just toluene is changed to benzene, and the filling ratio of resulting carbon nanotube is equally up to more than 90%.
Embodiment 3 presses the preparation method of embodiment 1, just toluene is changed to pentane, and the filling ratio of resulting carbon nanotube is up to more than 90%.
Embodiment 4 presses the preparation method of embodiment 1, just toluene is changed to tetrachloromethane, and the filling ratio of resulting carbon nanotube is up to more than 90%.
Embodiment 5 presses the preparation method of embodiment 1, just toluene is changed to isoprene, and the filling ratio of resulting carbon nanotube is up to more than 90%.
Embodiment 6 presses the preparation method of embodiment 1, just toluene is changed to methyl alcohol, and the filling ratio of resulting carbon nanotube is up to more than 90%.
Embodiment 7 presses the preparation method of embodiment 1, just toluene is changed to ethanol, and the filling ratio of resulting carbon nanotube is up to more than 90%.
Embodiment 8 presses the preparation method of embodiment 1, just toluene is changed to acetonitrile, and the filling ratio of resulting carbon nanotube is up to more than 90%.
Embodiment 9 presses the preparation method of embodiment 1, just multi-walled carbon nano-tubes is changed to Single Walled Carbon Nanotube, the diameter that obtains carbon nanotube after the purified processing is the 1-1.5 nanometer, and length is the 50-2000 nanometer, fill with toluene, the filling ratio of resulting carbon nanotube reaches more than 70%.
Embodiment 10 presses the preparation method of embodiment 1, just the tank temperature is raised to 60 ℃ from 40 ℃, and the filling ratio of resulting carbon nanotube reaches more than 65%.
Embodiment 11 presses the preparation method of embodiment 1, just with the pressure of stainless steel high pressure vessel from 1.1 * 10 6Pascal reduces to 0.75 * 10 6Pascal, the filling ratio of resulting carbon nanotube is more than 20%.
Embodiment 12 presses the preparation method of embodiment 1, just the time of constant temperature and pressure is reduced to 5 hours from 15 hours, and the filling ratio of resulting carbon nanotube is more than 30%.
Embodiment 13 presses the preparation method of embodiment 1, just carbonic acid gas is changed to ethane, and the filling ratio of resulting carbon nanotube is up to more than 90%.
Embodiment 14 presses the preparation method of embodiment 1, just carbonic acid gas is changed to ethene, and the filling ratio of resulting carbon nanotube is up to more than 90%.
Embodiment 15 presses the preparation method of embodiment 1, just carbonic acid gas is changed to acetylene, and the filling ratio of resulting carbon nanotube is up to more than 90%.

Claims (5)

1. the preparation method of the organic solvent carbon nanotube of filling is characterized in that: carry out according to the following step:
(1) purifying of carbon nanotube and processing: it is in the carbon nanotube 500-5000 sulfuric acid and the mixed acid of nitric acid doubly that single wall or multi-walled carbon nano-tubes are joined quality, the volume ratio of sulfuric acid and nitric acid is 3: 1 in the mixed acid, ultrasonic 1-5 hour, use the distilled water diluting after-filtration, and be washed till neutrality, vacuum-drying obtains the carbon nanotube that length is the purifying of 0.01-50 micron
(2) filling of carbon nanotube: after the carbon nanotube after the above-mentioned purified processing and polarity or non-polar organic solvent joined high pressure vessel by mass ratio at 1: 60, put into Water Tank with Temp.-controlled, behind 30-100 ℃ of constant temperature,, make pressure reach 3.0 * 10 by pump pressure injecting carbon dioxide or lower carbon number hydrocarbons 5-30 * 10 5Pascal keeps cooling the temperature to room temperature after 2-24 hour, and container decompression emptying after the vacuum-drying of taking-up sample, obtains the carbon nanotube that organic solvent is filled.
2. preparation method according to claim 1 is characterized in that: described carbon nanotube be diameter be 1-200 nanometer, length be the 0.01-50 micron, single wall or multi-walled carbon nano-tubes.
3. preparation method according to claim 1 is characterized in that: described nonpolar organic solvent is benzene, toluene, pentane, isoprene or tetrachloromethane.
4. preparation method according to claim 1 is characterized in that: described polar organic solvent is acetone, methyl alcohol, ethanol or acetonitrile.
5. preparation method according to claim 1 is characterized in that: described lower carbon number hydrocarbons is methane, ethane, ethene, acetylene, propane, propylene, normal butane or Trimethylmethane.
CNB021067252A 2002-03-04 2002-03-04 Preparation method of carbon nano pipe filled with organic solvent Expired - Fee Related CN1184140C (en)

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CN100395304C (en) * 2004-08-28 2008-06-18 鸿富锦精密工业（深圳）有限公司 Heat conducting material
CN1309104C (en) * 2005-04-06 2007-04-04 清华大学 Method for increasing electrochemical lithium storage content of nano-carbon tube
CN101391184B (en) * 2008-10-23 2010-04-14 上海交通大学 Preparation method of carbon nano tube drag-reduction nano fluid
CN102198930A (en) * 2010-11-19 2011-09-28 中国科学院高能物理研究所 Supercritical filling method and composite material prepared by same
CN104638252B (en) * 2015-02-13 2017-04-12 深圳市贝特瑞新能源材料股份有限公司 Silicon composited negative electrode material, preparation method of silicon composited negative electrode material and lithium ion battery
CN113548931B (en) * 2021-07-27 2022-03-11 陕西师范大学 Carbon nano tube filled copper acetylacetonate composite burning rate catalyst

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