CN101774573A - Method for amination of carbon nano tube - Google Patents
Method for amination of carbon nano tube Download PDFInfo
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- CN101774573A CN101774573A CN201010301340A CN201010301340A CN101774573A CN 101774573 A CN101774573 A CN 101774573A CN 201010301340 A CN201010301340 A CN 201010301340A CN 201010301340 A CN201010301340 A CN 201010301340A CN 101774573 A CN101774573 A CN 101774573A
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Abstract
The invention discloses a method for amination of a carbon nano tube, relating to a method for amination and solving the problems of complicated process and low nitrogenous functional group introduction efficiency of the existing method for modification of the carbon nano tube. The method is as follows: first, putting the pre-treated carbon nano tube into a supercritical reactor for reaction; and second, washing the products from the first step through distilled water and then vacuum drying under 55-65 DEG C. In this way, an aminated carbon nano tube can be prepared. The method is simple in process, and the analysis of the infrared spectrum diagram and infrared X-ray electron spectrum diagram of the aminated carbon nano tube prepared through the method shows that the nitrogenous functional group introduction efficiency through the method is high.
Description
Technical field
The present invention relates to a kind of amidized method.
Background technology
Carbon nanotube (CNT) is just found a kind of novel carbon structure in 1991, and it is seamless, the hollow tube body that is rolled into by the Graphene lamella that carbon atom forms.Generally can be divided into Single Walled Carbon Nanotube (SWCNT), double-walled carbon nano-tube (DWCNT) and multi-walled carbon nano-tubes (MWCNT).At present, be modification or functionalization to the research direction emphasis of carbon nanotube in the world at carbon nanotube.
Carbon nanotube has a lot of peculiar physical propertiess and grabs unique characteristic of semiconductor, high physical strength, specific surface, excellent adsorptive power etc. greatly.Important application prospects is arranged in a lot of fields, as nano electron device, reinforced fiber, biological/chemical sensor, nano-probe storage hydrogen, energy storage material, support of the catalyst etc., is 21 century one of the most promising nano material.But, because stronger adsorptive power effect between the carbon nanotube tube and tube, make carbon nanotube be difficult to water-soluble and organic solvent and bunchy are difficult to disperse.In addition, the carbon nano pipe purity of various prepared is not very high, and homogeneity is poor, and these have limited application and the research of carbon nanotube in every field greatly.Existing studies show that, there are many defective bit in the sidewall of the carbon nanotube that actual production is come out or pipe end, is can produce valence electron or active centre fully at these positions by means such as chemical reaction or electron impacts, and therefore purity and the homogeneity that improves carbon nanotube by the modification to carbon nanotube is fully feasible.Mostly carbon current nanotube method of modifying is to adopt means such as supercutical fluid, condensing agent method to make carbon nanotube connect nitrogen-containing functional group, with purity and the homogeneity of improving carbon nanotube, but this method complex process, waste time and energy, and the content of nitrogen-atoms only can reach about 1% in carbon nanotube, the efficient of introducing nitrogen-containing functional group is also lower, has limited the use of carbon nanotube.
Summary of the invention
The objective of the invention is in order to solve existing carbon nano-tube modification method complex process, to introduce the inefficient problem of nitrogen-containing functional group, and a kind of method of amination of carbon nano tube is provided.
The method of amination of carbon nano tube of the present invention is carried out according to following steps: one, 0.2～0.5g's in pretreated carbon nanotube is put into the supercritical reaction still, add the ammoniacal liquor of 20～24ml or the quadrol of 20～24ml then, the temperature of control supercritical reaction still is 340～350 ℃, pressure is 6～11MPa, reaction times is 2～4min, uses the water cooling reactor; Two, the reacted product of step 1 cleans back vacuum-drying under 55～65 ℃ of conditions with distilled water, promptly obtains the carbon nanotube after the amination.
Method technology of the present invention is simple, and the carbon nanotube after the present invention is aminated has on infrared spectrogram significantly-CH at carbon nanotube through infrared spectra as can be known
2,-C=O ,-absorption peak of C-N-H, can infer that thus amido is grafted on the carbon nanotube, and the carbon nanotube of the present invention after aminated is by red x-ray photoelectron spectroscopy as can be known, N occurred in red x-ray photoelectron spectroscopy figure
1sThe peak this shows that nitrogen-atoms has been introduced on the surface of carbon nanotube, and the content of nitrogen-atoms has reached more than 3% the efficient height of the nitrogen-containing functional group that the inventive method is introduced in the carbon nanotube that obtains of the inventive method.
Description of drawings
Fig. 1 is the infrared spectrogram of aminated back carbon nanotube in the embodiment seven; Fig. 2 is the x-ray photoelectron spectroscopy figure of aminated back carbon nanotube in the embodiment seven; Fig. 3 is the infrared spectrogram of aminated back carbon nanotube in the embodiment eight; Fig. 4 is the x-ray photoelectron spectroscopy figure of aminated back carbon nanotube in the embodiment eight.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for present embodiment amination of carbon nano tube is carried out according to following steps: one, 0.2～0.5g's in pretreated carbon nanotube is put into the supercritical reaction still, add the ammoniacal liquor of 20～24ml or the quadrol of 20～24ml then, the temperature of control supercritical reaction still is 340～350 ℃, pressure is 6～11MPa, reaction times is 2～4min, uses the water cooling reactor; Two, the reacted product of step 1 cleans back vacuum-drying under 55～65 ℃ of conditions with distilled water, promptly obtains the carbon nanotube after the amination.
The method technology of present embodiment is simple, and the carbon nanotube after present embodiment is aminated has on infrared spectrogram significantly-CH at carbon nanotube through infrared spectra as can be known
2,-C=O ,-absorption peak of C-N-H, can infer that thus amido is grafted on the carbon nanotube, and the carbon nanotube of present embodiment after aminated is by red x-ray photoelectron spectroscopy as can be known, N occurred in red x-ray photoelectron spectroscopy figure
1sThe peak this shows that nitrogen-atoms has been introduced on the surface of carbon nanotube, and the content of nitrogen-atoms has reached more than 3% the efficient height of the nitrogen-containing functional group that the inventive method is introduced in the carbon nanotube that obtains of present embodiment.
Embodiment two: what present embodiment and embodiment one were different is: pretreated method adopts purification process in the step 1, concrete operations are: with carbon nanotube calcination 5～7h under 300～400 ℃ of conditions, promptly obtain pretreated carbon nanotube.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment and embodiment one to two were different is: acid-treated method is adopted in the carbon nanotube pre-treatment in the step 1, and concrete operations are: a, carbon nanotube calcination 5～7h under 300～400 ℃ of conditions; It is that 80～100Hz, temperature are ultrasonic 5～7h under 45～55 ℃ the condition that b, the carbon nanotube after the step 1 of the nitration mixture of 250ml and 0.3～0.6g handled are blended in frequency, and wherein nitration mixture is by dense H
2SO
4With dense HNO
3Form according to 3: 1 volume ratio; C, ultrasonic back are cleaned with distilled water, use 0.45 μ m millipore filtration suction filtration then, suction filtration obtains is deposited in that the vacuum-drying sky promptly obtains pretreated carbon nanotube under 55～65 ℃ of conditions, and wherein the distilled water wash number is 3～5 times, and each time of repose that cleans is 22～26h.Other step and parameter are identical with embodiment one to two.
Embodiment four: what present embodiment and embodiment one to three were different is: the temperature of control supercritical reaction still is 345 ℃ in the step 1, and pressure is 8MPa, and the reaction times is 3min.Other step and parameter are identical with embodiment one to three.
Embodiment five: what present embodiment and embodiment one to four were different is: the distilled water wash number is 3～5 times in the step 2, and each time of repose that cleans is 22～26h.Other step and parameter are identical with embodiment one to four.
Embodiment six: the method for present embodiment amination of carbon nano tube is carried out according to following steps: one, 0.3g's in pretreated carbon nanotube is put into the supercritical reaction still, the ammoniacal liquor that adds 20ml then, the temperature of control supercritical reaction still is 346 ℃, pressure is 10MPa, reaction times is 3min, uses the water cooling reactor; Two, the reacted product of step 1 cleans back vacuum-drying under 60 ℃ of conditions with distilled water, promptly obtains the carbon nanotube after the amination.
Employed reactor is bought by the adjacent plant and instrument of Shanghai moral company limited and is obtained in the present embodiment step 1, and model is R-401 Supercritical Fluid Extraction System.
Pretreated method adopts purification process in the present embodiment step 1, and concrete operations are: with carbon nanotube calcination 6h under 350 ℃ of conditions, promptly obtain pretreated carbon nanotube.
The method technology of present embodiment is simple, and the carbon nanotube after present embodiment is aminated has on infrared spectrogram significantly-CH at carbon nanotube through infrared spectra as can be known
2,-C=O ,-absorption peak of C-N-H, can infer that thus amido is grafted on the carbon nanotube, and the carbon nanotube of present embodiment after aminated is by red x-ray photoelectron spectroscopy as can be known, N occurred in red x-ray photoelectron spectroscopy figure
1sThe peak this shows that nitrogen-atoms has been introduced on the surface of carbon nanotube, and the content of nitrogen-atoms has reached 3.5%, the efficient height of the nitrogen-containing functional group that the inventive method is introduced in the carbon nanotube that obtains of present embodiment.
Embodiment seven: the method for present embodiment amination of carbon nano tube is carried out according to following steps: one, 0.3g's in pretreated carbon nanotube is put into the supercritical reaction still, the quadrol that adds 20ml then, the temperature of control supercritical reaction still is 346 ℃, pressure is 10MPa, reaction times is 3min, uses the water cooling reactor; Two, the reacted product of step 1 cleans back vacuum-drying under 60 ℃ of conditions with distilled water, promptly obtains the carbon nanotube after the amination.
Employed reactor is bought by the adjacent plant and instrument of Shanghai moral company limited and is obtained in the present embodiment step 1, and model is R-401 Supercritical Fluid Extraction System.
The method of purification process is adopted in the carbon nanotube pre-treatment in the present embodiment step 1, and concrete operations are: carbon nanotube is calcination 6h under 350 ℃ of conditions, promptly obtains the carbon nanotube behind the purifying.
The distilled water wash number is 3 times in the present embodiment step 2, each time of repose that cleans is 24h, wherein clean, to precipitate concrete operations as follows: the beaker of earlier the reacted product of step 1 being put into 500ml, then distilled water is filled it up with beaker, seal the beaker mouth with aluminium foil again, leave standstill 24h, remove supernatant liquor again, again distilled water is filled it up with beaker, mix, seal the beaker mouth with aluminium foil again, leave standstill 24h, and then remove supernatant liquor, and again distilled water is filled it up with beaker, mix, seal the beaker mouth with aluminium foil again, leave standstill 24h, remove supernatant liquor, promptly clean and finish.
Use Nicolet-Nexus 670 infrared spectrometers, the carbon nanotube to present embodiment after aminated characterizes and analyzes, infrared spectrogram as shown in Figure 1, as can be seen from the figure at 1515cm
-1Corresponding is-NH flexural vibration absorption peak that the method for present embodiment that hence one can see that is grafted to quadrol and contains nitrogen-atoms on the carbon nanotube with amide group.Use the PHI5700ESCA x-ray photoelectron spectroscopy, the carbon nanotube to present embodiment after aminated characterizes and analyzes, x-ray photoelectron spectroscopy figure as shown in Figure 2, as can be seen from the figure except C occurring at 284eV electron binding energy place
LsThe peak, O appears in the 532eV electron binding energy
1sOutside the peak, also at 399eV electron binding energy place N appears
1sThe peak, this explanation nitrogen-atoms has been introduced on the surface of carbon nanotube, by analyze among the figure quadrol as can be known handle 350 ℃, the high-temperature high-voltage reaction condition of 6.28MPa to make a large amount of-OH and-COOH chain rupture and decomposition, and a part of carboxyl is transformed into acid amides, thereby greatly reduce surface oxygen content, and improved the efficient of introducing nitrogen-containing functional group.Wherein present embodiment obtains that the C atom content is 94.11% in the carbon nanotube, and the O atom content is 2.65%, and the N atom content is 3.24%, N atom content height in the carbon nanotube after present embodiment is aminated.
Embodiment eight: what present embodiment and embodiment six were different is: the temperature of control supercritical reaction still is 350 ℃ in the step 1, and pressure is 6.28MPa.Other steps and parameter are identical with embodiment six.
Acid-treated method is adopted in the carbon nanotube pre-treatment in the present embodiment step 1, and concrete operations are: a, carbon nanotube calcination 6h under 80 ℃ of conditions; It is that 90Hz, temperature are ultrasonic 6h under 50 ℃ the condition that b, the carbon nanotube after the step 1 of the nitration mixture of 250ml and 0.3～0.6g handled are blended in frequency, and wherein nitration mixture is by dense H
2SO
4With dense HNO
3Form according to 3: 1 volume ratio; C, ultrasonic back are cleaned with distilled water, use 0.45 μ m millipore filtration suction filtration then, and suction filtration obtains is deposited in that the vacuum-drying sky promptly obtains acid-treated carbon nanotube under 60 ℃ of conditions, and wherein the distilled water wash number is 3 times, and each sedimentation time is 24h.
Use Nicolet-Nexus 670 infrared spectrometers, the carbon nanotube to present embodiment after aminated characterizes and analyzes, infrared spectrogram as shown in Figure 3, as can be seen from the figure at 2920cm
-1, 1650cm
-1Be respectively MWNT-Ac-NH
2-CH
2,-C=O stretching vibration absorption peak, 1520cm
-1Corresponding is-C-N-H flexural vibration absorption peak.3300 to 3500cm
-1Between have clearly-the N-H absorption peak, can infer that thus quadrol is grafted on the carbon nanotube with amide group.Use the PHI5700ESCA x-ray photoelectron spectroscopy, the carbon nanotube to present embodiment after aminated characterizes and analyzes, x-ray photoelectron spectroscopy figure as shown in Figure 4, as can be seen from the figure except C occurring at 284eV electron binding energy place
LsThe peak, O appears in the 532eV electron binding energy
1sOutside the peak, also at 399eV electron binding energy place N appears
1sThe peak, this explanation nitrogen-atoms has been introduced on the surface of carbon nanotube, by analyze among the figure quadrol as can be known handle 350 ℃, the high-temperature high-voltage reaction condition of 6.28MPa to make a large amount of-OH and-COOH chain rupture and decomposition, and a part of carboxyl is transformed into acid amides, thereby greatly reduce surface oxygen content, and improved the efficient of introducing nitrogen-containing functional group.Wherein present embodiment obtains that the C atom content is 89.83% in the carbon nanotube, and the O atom content is 3.74%, and the N atom content is 5.66%, N atom content height in the carbon nanotube after present embodiment is aminated.
Claims (5)
1. the method for an amination of carbon nano tube, the method that it is characterized in that amination of carbon nano tube is carried out according to following steps: one, 0.2～0.5g's in pretreated carbon nanotube is put into the supercritical reaction still, add the ammoniacal liquor of 20～24ml or the quadrol of 20～24ml then, the temperature of control supercritical reaction still is 340～350 ℃, pressure is 6～11MPa, reaction times is 2～4min, uses the water cooling reactor; Two, the reacted product of step 1 cleans back vacuum-drying under 55～65 ℃ of conditions with distilled water, promptly obtains the carbon nanotube after the amination.
2. the method for a kind of amination of carbon nano tube according to claim 1, it is characterized in that the pretreated method of carbon nanotube adopts purification process in the step 1, concrete operations are: with carbon nanotube calcination 5～7h under 300～400 ℃ of conditions, promptly obtain pretreated carbon nanotube.
3. the method for a kind of amination of carbon nano tube according to claim 1 is characterized in that acid-treated method is adopted in the carbon nanotube pre-treatment in the step 1, and concrete operations are: a, carbon nanotube calcination 5～7h under 300～400 ℃ of conditions; It is that 80～100Hz, temperature are ultrasonic 5～7h under 45～55 ℃ the condition that b, the carbon nanotube after the step 1 of the nitration mixture of 250ml and 0.3～0.6g handled are blended in frequency, and wherein nitration mixture is by dense H
2SO
4With dense HNO
3Form according to 3: 1 volume ratio; C, ultrasonic back are cleaned with distilled water, use 0.45 μ m millipore filtration suction filtration then, suction filtration obtains is deposited in that the vacuum-drying sky promptly obtains pretreated carbon nanotube under 55～65 ℃ of conditions, and wherein the distilled water wash number is 3～5 times, and each time of repose that cleans is 22～26h.
4. the method for a kind of amination of carbon nano tube according to claim 3 is characterized in that the temperature of control supercritical reaction still in the step 1 is 345 ℃, and pressure is 8MPa, and the reaction times is 3min.
5. according to the method for claim 1,2 or 4 described a kind of amination of carbon nano tube, it is characterized in that the distilled water wash number is 3～5 times in the step 2, each time of repose that cleans is 22～26h.
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| CN102140145A (en) * | 2011-01-24 | 2011-08-03 | 哈尔滨工业大学 | Method for grafting carbon nanotubes by using cyclodextrin |
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