CN101229918A - Oxidation modifying method for carbon nano-tube - Google Patents
Oxidation modifying method for carbon nano-tube Download PDFInfo
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Abstract
The invention relates to an oxidization modifying method of a carbon nano-tube which is that multi-walled carbon nano-tube or single-walled carbon nano-tube are mixed with oxidant and deionized water; under the condition of stirring and heating, the carbon nano-tube reacts with the oxidant which are separated, washed and dried to obtain the target products.. The method can obtain the carbon nano-tube in which the surface containsa large amount of hydroxyl and carbonyl; The modified carbon nano-tube can be dispersed into the polar solvents such as the water or dimethylformamide and so on. When the reaction temperature is relatively high and the oxidant concentration is relatively large, the carbon nano-tube can be oxidized and fractured into a short nano-tube. The method does not use the unfriendly environmental substances such as strong acid, strong alkali as well as strong oxidant and also does not adopt the organic matters as the reaction medium; the thickness of the carbon nano-tube is relatively high in the reaction system under the moderate reaction condition awith easy production in large scale.
Description
Technical field;
The present invention relates to a kind of novel water carbon nano tube surface oxidation modifying method, this method can obtain the carbon nanotube that great amount of hydroxy group and carbonyl are contained in the surface, and carbon nano tube modified can be dispersed in water or the dimethyl formamide isopolarity solvent.Higher when temperature of reaction, when oxidant concentration was big, carbon nanotube can oxidizedly break to form the short carbon nanometer tube that blocks.
Background technology:
Carbon nanotube is a kind of novel nano-material of finding by 1991, this material has good mechanics, electricity, heat-conductive characteristic and good biocompatibility, so carbon nanotube is at electronic devices and components, strongthener, biosensor, hydrogen storage material, catalystic material, stealth material, there is potential application foreground widely in fields such as battery material.Yet, because the ∏-∏ overlapping effect between the carbon nanotube molecule and the big L/D ratio of molecule itself, make carbon nanotube have can't in solvent, to dissolve, the shortcoming of, poor processability poor with the consistency of other material, thereby limited the application of carbon nanotube.In order to improve the performance of carbon nanotube, expand the application of carbon nanotube in biological medicine, life science, matrix material, carbon nanotube polymer compound film, molecular electronic component such as nanometer pliers and the medium field of nano bearing, since nineteen ninety-eight, progressively launch about the research that improves the carbon nanotube performance, comprise length-to-diameter ratio of the solvability that improves carbon nanotube, consistency, reduction carbon nanotube or the like.The preparation of water-soluble carbon nanometer tube is exactly the research field of one of them awfully hot door.Usually the method for preparing water-soluble carbon nanometer tube has two kinds, the one, the non covalent bond method, polymer is as poly-nitrogen vinyl pyrrolidone, sodium polystyrene sulfonate, styrene-maleic anhydride alternating copolymer after the hydrolysis, dna molecular, polyvinyl alcohol and polyoxyethylene etc. can be coated on carbon nano tube surface and it is dispersed in the aqueous solution.Other small molecules tensio-active agent such as sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, hexadecyl trimethyl ammonium bromide etc. also can be dispersed in carbon nanotube in the aqueous solution.The advantage of these class methods is that the surface tissue of carbon nanotube is not damaged, and shortcoming is must contain in the solution a large amount of polymers or tensio-active agent exists and the solvability of carbon nanotube is subjected to other factors such as pH value, and the interference of ionic strength is bigger.The another kind of method for preparing water-soluble carbon nanometer tube then is that the chemical modification by carbon nano tube surface makes it be easy to be dispersed in the water.At document one: J.AM.CHEM.SOC.2002,124, adopt the water-soluble carbon nanometer tube of the mixture process Single Walled Carbon Nanotube acquisition of the vitriol oil and hydrogen peroxide among the 12418-12419 to the pH value sensitivity.At document two: Chem.Mater.2006,18, the Single Walled Carbon Nanotube that adopts concentrated acid sulfonation to be grafted with phenyl ring among the 1520-1524 also can obtain water-soluble carbon nanometer tube.Document three: Nano Lett.2003,3,29-32 makes the chemical modification method of exerting oneself obtain water-soluble carbon nanotube alcohol, and this carbon nanotube alcohol can self-assembly form array structure.The advantage of aforesaid method is the solubility property that can be good at improving carbon nanotube; Yet its shortcoming is: (1) these class methods can use strong acid usually in a large number, highly basic, strong oxidizer, perhaps price costliness and the disagreeableness material of environment such as organic solvent; (2) reaction process relative complex need be by special equipment, perhaps by polystep reaction to obtain the soluble carbon nanotube; (3) most of chemical modification methods only are applicable to Single Walled Carbon Nanotube or multi-walled carbon nano-tubes, and lacking can be with the universal method of two kinds of carbon nanotubes modification simultaneously; (4) common chemical modification method can only be introduced the solvophilic group in carbon nano tube surface, can't change the length of carbon nanotube by reaction.(5) carbon nanotube concentration is lower usually in the reaction system.
Summary of the invention:
The carbon nanotube aqueous phase oxidation method of modifying that the purpose of this invention is to provide a kind of gentleness.This method has avoided using the disagreeableness materials of environment such as strong acid and strong base strong oxidizer in reaction system, also do not adopt organism as reaction medium, and carbon nanotube concentration is higher in the reaction system.This method generates the carbon nanotube that the surface is connected with hydroxyl and carbonyl with carbon nanotube and oxygenant effect, and can obtain total length or intercepted short carbon nanometer tube by changing reaction conditions, modified carbon nanotube can be dissolved in water, dimethyl formamide isopolarity solvent.
Key of the present invention is to use the tube wall of water miscible oxidizer oxygen carbon nano tube, its principles of chemistry as Figure 1-1: (1) under the condition of normal temperature or heating, oxidizer oxygen carbon nano tube surface forms the carbon nanotube that contains great amount of hydroxy group and carbonyl.(2) under the reaction conditions of lesser temps and oxygenate content, can obtain the solubility total length carbon nanotube that need not block.(3) higher and oxidant concentration is also under the conditions of higher when temperature of reaction, and carbon nanotube ruptures in oxidized, forms intercepted solubility short carbon nanometer tube.Reaction process is shown in Fig. 1-2.
The oxidation modifying method of carbon nanotube of the present invention, carry out as follows: multi-walled carbon nano-tubes or Single Walled Carbon Nanotube are mixed with oxygenant and deionized water, make carbon nanotube and oxidant reaction under the stirring and the condition of heating, reaction separates, washs, is drying to obtain target product after finishing.
Described oxygenant is water-soluble persulphate or hydrogen peroxide, and water-soluble persulphate is Potassium Persulphate, ammonium persulphate or Sodium Persulfate, initiator system of ammonium persulfate.The quality percentage composition of oxygenant is 0.5% to saturated in the reaction system.The quality percentage composition 0.03-20% of carbon nanotube; For Single Walled Carbon Nanotube, its quality percentage composition in system is 0.03-15%, and that preferable is 0.5-2%; For its quality percentage composition in system of multi-walled carbon nano-tubes is 0.03-20%, and that preferable is 0.5-2%.Carbon nanotube and oxidant reaction condition are that reaction is 0.25-120 hour under 20-90 ℃ temperature.
When preparing the solubility total length carbon nanotube that need not block, suitable oxygenant quality percentage composition is 0.5-5%; Suitable reaction conditions is 20-90 ℃ of reaction 0.25-120 hour, and reaction conditions preferably is 20-50 ℃ of reaction 12-120 hour.
When solubility short carbon nanometer tube that preparation is blocked, suitable oxygenant quality percentage composition is 5-30%, is preferably 20-30%.Suitable reaction conditions is 50 ℃-80 ℃ reactions 0.25-24 hour, and reaction conditions preferably is 70-80 ℃ of reaction 1-5 hour.
For difficult dispersive single-walled nanotube system, before reaction, can make its preliminary dispersion by ultrasonic, ultrasonic time is within 10 hours, and ultrasonic power is 100W-250W.
Described separation method can adopt centrifugation; Also can adopt millipore filtration to separate, the base material of millipore filtration can be base materials such as PTFE or polysulfones, the aperture between 0.1-1um, preferred 0.20-0.45um.
Carbon nano tube modified is adopted high-resolution-ration transmission electric-lens (HRTEM) respectively, transmission electron microscope (TEM), Fourier absorbs infrared spectra (FTIR), Raman spectrum (Raman), absorption spectrum (UV-vis-NIR), x-ray photoelectron power spectrum (XPS), atomic force microscope (AFM) characterizes.
There is one among the FTIR of Fig. 2 and is positioned at 3417cm
-1The hydroxyl absorption peak, exist one to be in 1710cm simultaneously
-1Carbonyl absorption peak.Be in 1323cm in the Raman spectrum of Fig. 3
-1Irregular mould (disorder mode) obviously strengthen, and be in 1580cm
-1Represent the G peak area of SP2 hydridization carbon atom then obviously to descend.These presentation of results hydrophilic radical such as hydroxyls, carbonyl is a large amount of is connected to carbon nano tube surface.
HRTEM spectrogram by Fig. 4 can be observed, and the modification Single Walled Carbon Nanotube of embodiment 1 preparation is dispersed into single or diameter is the pencil thing of several nanometers; And the structural pipe wall of carbon nanotube is not destroyed.
AFM spectrogram by Fig. 5, Fig. 7 can draw, and the modification Single Walled Carbon Nanotube of embodiment 1 preparation is blocked into the short tube about nanometer to surplus in the of 100 micron; The modification multi-wall carbon nano-tube of embodiment 2 preparation is blocked into the short tube about hundreds of to a micron.
Fig. 6 has provided the Cls swarming spectrogram of modification Single Walled Carbon Nanotube among the embodiment 1.XPS result has provided the atomic percent carbon that is connected with hydroxyl and carbonyl on carbon-to-oxygen ratio and the carbon nanotube.Measurement result is mainly determined based on the swarming to Cls.
Carbon nano tube modified can be used for the matrix material of polymer-based or other base materials of various carbon nanotube enhanced, also can be used for can also being applied to fields such as catalyst cupport in various biosystems and the biosensor.
The invention has the beneficial effects as follows: (1) the present invention proposes a kind of simple and easy to do aqueous phase oxidation carbon nanotube method.This method of modifying does not need special reaction unit and equipment, does not need violent reaction conditions to realize the modification of carbon nanotube yet, therefore can produce on a large scale through simple improvement.(2) the present invention does not need the high organic solvent of strong acid and strong base used in the traditional method or price as reaction carriers, is a kind of eco-friendly carbon nanotube oxidation modifying method.(3) concentration of carbon nanotube helps effective utilization of reactor oxygenant etc. apparently higher than traditional method of modifying in reaction system.(4) can be by changing solubility total length carbon nanotube or two kinds of different reaction product of intercepted solubility short carbon nanometer tube that the reaction conditions acquisition need not be blocked.(5) modified product of the present invention can be water-soluble, dimethyl formamide (DMF), and tetrahydrofuran (THF) intensive polar solvents such as (THF) is insoluble to benzene, toluene, normal hexane, non-polar solvents such as hexanaphthene.This product is that carbon nanotube is laid a good foundation in the application aspect biological chemistry and the biological medicine.
Description of drawings
Fig. 1: modified carbon nano-tube preparation process reaction mechanism synoptic diagram.
The FTIR spectrogram of modification Single Walled Carbon Nanotube among Fig. 2: the embodiment 1.
The Raman spectrogram of modification Single Walled Carbon Nanotube among Fig. 3: the embodiment 1.
The HRTEM spectrogram of modification Single Walled Carbon Nanotube derivative among Fig. 4: the embodiment 1.
The atomic power spectrogram of modification Single Walled Carbon Nanotube among Fig. 5: the embodiment 1.
The XPS swarming spectrogram of modification Single Walled Carbon Nanotube among Fig. 6: the embodiment 1.
The atomic power spectrogram of modification multi-walled carbon nano-tubes among Fig. 7: the embodiment 2.
The atomic power spectrogram of modification Single Walled Carbon Nanotube among Fig. 8: the embodiment 3.
The TEM spectrogram of modification multi-walled carbon nano-tubes among Fig. 9: the embodiment 4.
The TEM spectrogram of modification multi-walled carbon nano-tubes among Figure 10: the embodiment 5.
The TEM spectrogram of modification multi-walled carbon nano-tubes among Figure 11: the embodiment 6.
Embodiment
Embodiment 1
Take by weighing Single Walled Carbon Nanotube (available from Chengdu Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) 50mg respectively, ammonium persulphate 4.28g joins in the 10ml deionized water, ultra-sonic dispersion placed 75 ℃ of water bath with thermostatic control reactions 4 hours with reaction solution after (power 250w) in 1 hour, and to follow stirring, rotating speed be 2000r/min.Reaction finishes the back discharging, and separates the acquisition solid product with whizzer.Add deionized water centrifuge dripping again in centrifugal barrel, operate 4 times to remove oxygenant more than repeating, products therefrom is dried in vacuum drying oven, can obtain the Single Walled Carbon Nanotube of functionalization.
XPS characterizes demonstration, and the carbon-to-oxygen ratio of product carbon nanotube is 4.5 to 1, and the result is as shown in the table for carbon ls swarmming.Products therefrom carbon nanotube solubleness in water is about 1.5mg/ml.
The XPS spectrum figure Cls swarmming of oxide/carbon nanometer tube table as a result among the embodiment 1
| The peak | Center (ev) | Point out | Peak width at half height | Normal area | Atomic percent |
| Cls Cls Cls Cls | 284.59 286.14 287.58 289.26 | Graphite C C-OH C=O COOH | 1.58 1.7 1.72 2.3 | 33849.62 17403.17 11494.71 7253.9 | 48.35％ 24.86％ 16.42％ 10.36％ |
Can draw according to last table on 24.86% the carbon and be connected with hydroxyl, be connected with carbonyl on 16.42% the carbon.Wherein be connected with carboxyl on 10.36% the carbon, carboxyl is that the carbon nanotube before the modification produces in purge process, and is irrelevant with this reaction.
This oxide/carbon nanometer tube is carried out high resolution transmission electron microscopy and atomic force microscope sign, accompanying drawing 4 has provided the Electronic Speculum picture of Single Walled Carbon Nanotube, this caption modified carbon nanotube well scatter and tube wall is not subjected to too havoc, accompanying drawing 5 has provided the atomic power spectrogram of single-walled nanotube, and this figure illustrates that the length of carbon nanotube is truncated to about hundreds of nanometers to 1 micron.
Embodiment 2
Take by weighing multi-walled carbon nano-tubes (available from Chengdu Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) 50mg respectively, ammonium persulphate 4.28g joins in the 10ml deionized water, behind ultra-sonic dispersion half an hour (power 250w) reaction solution is placed 90 ℃ of water bath with thermostatic control reactions 1 hour, mixing speed is 1000r/min.Reaction finishes the back discharging, and separates the acquisition solid product with whizzer.With PTFE filtering with microporous membrane products therefrom, and with water wash 3 to 4 times to remove oxygenant, products therefrom is dried in vacuum drying oven.
The XPS characterization result shows that the carbon-to-oxygen ratio of product carbon nanotube is 5.85 to 1, and the result is as shown in the table for carbon ls swarmming.Products therefrom carbon nanotube solubleness in water is about 2mg/ml.
The XPS spectrum figure Cls swarmming of oxide/carbon nanometer tube table as a result among the embodiment 2
| The peak | Center (ev) | Point out | Peak width at half height | Normal area | Atomic percent |
| Cls Cls Cls Cls | 284.49 285.92 287.18 288.97 | Graphite C C-OH C=O COOH | 1.32 1.47 1.64 2.9 | 46894.71 15733.99 7329.726 8797.838 | 59.54％ 19.98％ 9.3％ 11.17％ |
Can draw according to last table on 19.98% the carbon and be connected with hydroxyl, be connected with carbonyl on 9.3% the carbon.Wherein be connected with carboxyl on 11.17% the carbon, carboxyl is that the carbon nanotube before the modification produces in purge process, and is irrelevant with this reaction.
Fig. 7 is the atomic power spectrogram of the multi-walled carbon nano-tubes of this embodiment preparation, and this figure illustrates that the length of carbon nanotube is truncated to about hundreds of nanometers to a micron.
Take by weighing Single Walled Carbon Nanotube (available from Chengdu Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) 50mg respectively, ammonium persulphate 0.526g joins in the 10ml deionized water, ultra-sonic dispersion after 1 hour (power 100w) reaction solution is placed 50 ℃ of waters bath with thermostatic control reaction 24 hours, stir and be rotating speed 1000r/min.Subsequent step is with embodiment 1.Obtain the Single Walled Carbon Nanotube of functionalization.
The XPS characterization result shows that the carbon-to-oxygen ratio of product carbon nanotube is 6.79 to 1, and the result is as shown in the table for carbon ls swarmming.Products therefrom carbon nanotube solubleness in water is about 0.25mg/ml.
The XPS spectrum figure Cls swarmming of oxide/carbon nanometer tube table as a result among the embodiment 3
| The peak | Center (ev) | Point out | Peak width at half height | Normal area | Atomic percent |
| Cls Cls Cls Cls | 284.66 286.04 287.79 289.02 | Graphite C C-OH C=O COOH | 1.28 1.34 1.29 2.18 | 30660.65 13303.75 10965.82 8749.03 | 48.14％ 20.89％ 17.22％ 13.74％ |
Can draw according to last table on 20.89% the carbon and be connected with hydroxyl, be connected with carbonyl on 17.22% the carbon.Wherein be connected with carboxyl on 13.74% the carbon, carboxyl is that the carbon nanotube before the modification produces in purge process, and is irrelevant with this reaction.
Fig. 8 is the atomic power spectrogram of the Single Walled Carbon Nanotube of this embodiment preparation, and this figure illustrates that the length of carbon nanotube still remains on about several microns.
Take by weighing multi-walled carbon nano-tubes (available from Chengdu Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) 50mg respectively, ammonium persulphate 0.526g joins in the 10ml deionized water, reaction solution is placed 50 ℃ of water bath with thermostatic control reactions 24 hours, and mixing speed is 1000r/min.Subsequent step is with embodiment 1.Obtain the multi-walled carbon nano-tubes of functionalization.
The XPS characterization result shows that the carbon-to-oxygen ratio of product carbon nanotube is 8.14 to 1, and the result is as shown in the table for carbon ls swarmming.Products therefrom carbon nanotube solubleness in water is about 0.7mg/ml.
The XPS spectrum figure Cls swarmming of oxide/carbon nanometer tube table as a result among the embodiment 4
| The peak | Center (ev) | Point out | Peak width at half height | Normal area | Atomic percent |
| Cls Cls Cls Cls | 284.53 285.98 287.3 289.08 | Graphite C C-OH C=O COOH | 1.35 1.36 1.42 2.42 | 70118.45 15006.38 5917.706 7647.857 | 71.05％ 15.20％ 5.99％ 7.75％ |
Can draw according to last table on 15.20% the carbon and be connected with hydroxyl, be connected with carbonyl on 5.99% the carbon.Wherein be connected with carboxyl on 7.75% the carbon, carboxyl is that the carbon nanotube before the modification produces in purge process, and is irrelevant with this reaction.
Fig. 9 illustrates that for the TEM figure of the multi-walled carbon nano-tubes of this embodiment preparation, this figure the length of carbon nanotube still remains on about several microns.
Embodiment 5
Take by weighing multi-walled carbon nano-tubes (available from Chengdu Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) 50mg respectively, Potassium Persulphate 0.54g joins in the 10ml deionized water, directly reaction solution is placed 50 ℃ of water bath with thermostatic control reactions 24 hours, mixing speed is 1000r/min.Subsequent step is with embodiment 1.Obtain the multi-walled carbon nano-tubes of functionalization.
The XPS characterization result shows that the carbon-to-oxygen ratio of product carbon nanotube is 7.65 to 1, and the result is as shown in the table for carbon ls swarmming.Products therefrom carbon nanotube solubleness in water is about 0.8mg/ml.
The XPS spectrum figure Cls swarmming of oxide/carbon nanometer tube table as a result among the embodiment 5
| The peak | Center (ev) | Point out | Peak width at half height | Normal area | Atomic percent |
| Cls Cls Cls Cls | 284.54 286 287.35 289.2 | Graphite C C-OH C=O COOH | 1.34 1.36 1.51 2.46 | 68427.99 15208.2 6016.32 7791.92 | 70.22％ 15.60％ 6.17％ 7.99％ |
Can draw according to last table on 15.60% the carbon and be connected with hydroxyl, be connected with carbonyl on 6.17% the carbon.Wherein be connected with carboxyl on 7.99% the carbon, carboxyl is that the carbon nanotube before the modification produces in purge process, and is irrelevant with this reaction.
Accompanying drawing 10 has provided the TEM figure of multi-walled carbon nano-tubes, and this figure illustrates that the length of carbon nanotube is truncated to about hundreds of nanometers to 1 micron.
Embodiment 6
Take by weighing multi-walled carbon nano-tubes (available from Chengdu Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) 50mg respectively, ammonium persulphate 0.526g joins in the 10ml deionized water, reaction solution is placed 25 ℃ of water bath with thermostatic control reactions 120 hours, and mixing speed is 1000r/min.Subsequent step is with embodiment 1.Obtain the multi-walled carbon nano-tubes of functionalization.
Products therefrom carbon nanotube solubleness in water is about 0.5mg/ml.
Accompanying drawing 11 has provided the TEM figure of many walls nanotube, and this figure illustrates that the length of carbon nanotube still remains on about several microns.
Embodiment 7
Take by weighing Single Walled Carbon Nanotube (available from Chengdu Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) 0.2g respectively, ammonium persulphate 4.28g joins in the 10ml deionized water, and reaction solution is placed 90 ℃ of water bath with thermostatic control reactions 4 hours, and mixing speed is 2000r/min.Subsequent step is with embodiment 1.Obtain the Single Walled Carbon Nanotube of functionalization.
The XPS characterization result shows that the carbon-to-oxygen ratio of product carbon nanotube is 6.16 to 1, and the result is as shown in the table for carbon ls swarmming.Products therefrom carbon nanotube solubleness in water is about 0.9mg/ml.
The XPS spectrum figure Cls swarmming of oxide/carbon nanometer tube table as a result among the embodiment 7
| The peak | Center (ev) | Point out | Peak width at half height | Normal area | Atomic percent |
| Cls Cls Cls Cls | 284.73 286.19 287.41 289.08 | Graphite C C-OH C=O COOH | 1.42 1.4 1.39 2.31 | 10570.34 4708.871 2572.429 2229.99 | 52.63％ 23.45％ 12.81％ 11.10％ |
Can draw according to last table on 23.45% the carbon and be connected with hydroxyl, be connected with carbonyl on 12.81% the carbon.Wherein be connected with carboxyl on 11.10% the carbon, carboxyl is that the carbon nanotube before the modification produces in purge process, and is irrelevant with this reaction.
Embodiment 8
Take by weighing Single Walled Carbon Nanotube (available from Chengdu Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) 10mg respectively, ammonium persulphate 4.28g joins in the 10ml deionized water, and reaction solution is placed 80 ℃ of water bath with thermostatic control reactions 4 hours, and mixing speed is 2000r/min.Subsequent step is with embodiment 1.Obtain the Single Walled Carbon Nanotube of functionalization.
The XPS characterization result shows that the carbon-to-oxygen ratio of product carbon nanotube is 4.39 to 1, and the result is as shown in the table for carbon ls swarmming.
The XPS spectrum figure Cls swarmming of oxide/carbon nanometer tube table as a result among the embodiment 8
| The peak | Center (ev) | Point out | Peak width at half height | Normal area | Atomic percent |
| Cls Cls Cls Cls | 284.66 286.04 287.79 289.02 | Graphite C C-OH C=O COOH | 1.34 1.56 1.64 1.88 | 26276.96 16219.41 10863.91 8830.7 | 42.25％ 26.08％ 17.47％ 14.19％ |
Can draw according to last table on 26.08% the carbon and be connected with hydroxyl, be connected with carbonyl on 17.47% the carbon.Wherein be connected with carboxyl on 14.19% the carbon, carboxyl is that the carbon nanotube before the modification produces in purge process, and is irrelevant with this reaction.
Embodiment 9
Take by weighing multi-walled carbon nano-tubes (available from Chengdu Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) 0.75g respectively, ammonium persulphate 2.14g joins in the 5ml deionized water, directly reaction solution is placed 80 ℃ of water bath with thermostatic control reactions 4 hours, mixing speed is 1000r/min.Subsequent step is with embodiment 1.Obtain the multi-walled carbon nano-tubes of functionalization.
The XPS characterization result shows that the carbon-to-oxygen ratio of product carbon nanotube is 7.3 to 1, and the result is as shown in the table for carbon ls swarmming.Products therefrom carbon nanotube solubleness in water is about 0.95mg/ml.
The XPS spectrum figure Cls swarmming of oxide/carbon nanometer tube table as a result among the embodiment 9
| The peak | Center (ev) | Point out | Peak width at half height | Normal area | Atomic percent |
| Cls Cls Cls Cls | 284.57 286.09 287.4 289 | Graphite C C-OH C=O COOH | 1.35 1.37 1.51 2.19 | 63572.18 16415.7 7029.44 7831.82 | 67.02％ 17.31％ 7.41％ 8.25％ |
Can draw according to last table on 17.31% the carbon and be connected with hydroxyl, be connected with carbonyl on 7.41% the carbon.Wherein be connected with carboxyl on 8.25% the carbon, carboxyl is that the carbon nanotube before the modification produces in purge process, and is irrelevant with this reaction.
Claims (10)
1. the oxidation modifying method of a carbon nanotube, concrete steps are: multi-walled carbon nano-tubes or Single Walled Carbon Nanotube are mixed with oxygenant and deionized water, make carbon nanotube and oxidant reaction under the stirring and the condition of heating, reaction separates, washs, is drying to obtain target product after finishing.
2. the oxidation modifying method of carbon nanotube according to claim 1 is characterized in that described oxygenant is water-soluble persulphate or hydrogen peroxide; The quality percentage composition of oxygenant is 0.5% to saturated in the reaction system; The quality percentage composition of carbon nanotube is 0.03-20% in the reaction system; Carbon nanotube and oxidant reaction condition are that reaction is 0.25-120 hour under 20-90 ℃ temperature.
3. the oxidation modifying method of carbon nanotube according to claim 1 and 2 is characterized in that described water-soluble persulphate is Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
4. the oxidation modifying method of carbon nanotube according to claim 1 and 2 is characterized in that described oxygenant is an ammonium persulphate.
5. the oxidation modifying method of carbon nanotube according to claim 1 is characterized in that for its quality percentage composition in system of Single Walled Carbon Nanotube be 0.03-15%; For its quality percentage composition in system of multi-walled carbon nano-tubes is 0.03-20%.
6. the oxidation modifying method of carbon nanotube according to claim 1 is characterized in that for Single Walled Carbon Nanotube, and its quality percentage composition in system is 0.5-2%; For its quality percentage composition in system of multi-walled carbon nano-tubes is 0.5-2%.
7. the oxidation modifying method of carbon nanotube according to claim 1 is characterized in that the quality percentage composition of oxygenant is 0.5-5% in the reaction system when preparing the long carbon nanotube of solubility that need not block; Reaction conditions is 20-90 ℃ of reaction 0.25-120 hour.
8. the oxidation modifying method of carbon nanotube according to claim 1 is characterized in that when preparing the long carbon nanotube of solubility that need not block, and reaction conditions is 20-50 ℃ of reaction 12-120 hour.
9. the oxidation modifying method of carbon nanotube according to claim 1 is characterized in that oxygenant quality percentage composition is 5-30% in the reaction system when preparing the solubility weak point nanotube that blocks; Reaction conditions is 50 ℃-80 ℃ reactions 0.25-24 hour.
10. the oxidation modifying method of carbon nanotube according to claim 1 is characterized in that oxygenant quality percentage composition is 20-30% in the reaction system when preparing the solubility weak point nanotube that blocks; Reaction conditions is 70 ℃-80 ℃ reactions 1-5 hour.
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