CN109809392B - Method for purifying semiconductor single-walled carbon nanotube by solution layering - Google Patents
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Abstract
The disclosure provides a purification method for realizing semiconductor single-walled carbon nanotubes by solution layering, which comprises the following steps: adding a polymer dispersant or a small molecule dispersant of a carbon nanotube to an organic solvent in which semiconducting single-walled carbon nanotubes are dispersed to form a solution, and making the concentration of the polymer dispersant or the small molecule dispersant in the organic solvent greater than or equal to the concentration at which the solution can be delaminated by a treatment of a centrifugal delamination step; and (3) centrifugal layering: carrying out centrifugal layering treatment on the solution, wherein the temperature of the centrifugal layering treatment is less than or equal to the temperature for layering the solution subjected to the centrifugal layering treatment; and a layered extraction step: and (3) layering the solution subjected to centrifugal layering treatment, and extracting an upper layer solution, wherein the upper layer solution is a purified semiconductor single-walled carbon nanotube solution.
Description
Technical Field
The present disclosure relates to a method for purifying semiconducting single-walled carbon nanotubes, and more particularly, to a method for purifying semiconducting single-walled carbon nanotubes by solution layering.
Background
The semiconductor single-walled carbon nanotube has huge application potential in the semiconductor industries such as sensing, integrated circuits and the like. However, how to obtain ultra-high purity semiconducting single-walled carbon nanotubes has been a hot spot of research.
In the existing purification method of the semiconductor single-walled carbon nanotube, the purity of the semiconductor single-walled carbon nanotube is often determined by the type of the selected conjugated polymer. In addition, in the existing purification process, the purity of the obtained semiconductor single-walled carbon nanotube is limited, the purity of the obtained semiconductor single-walled carbon nanotube can reach 99.9 percent at most, and a space for improving the purity is difficult to be provided.
Disclosure of Invention
According to one aspect of the present disclosure, there is provided a purification method for semiconducting single-walled carbon nanotubes by solution layering, comprising an addition step, a centrifugal layering step, and a layering extraction step, wherein,
an adding step: adding a polymer dispersant or a small molecule dispersant of a carbon nanotube to an organic solvent in which semiconducting single-walled carbon nanotubes are dispersed to form a solution, and making the concentration of the polymer dispersant or the small molecule dispersant in the organic solvent greater than or equal to the concentration at which the solution can be delaminated by a treatment of a centrifugal delamination step;
and (3) centrifugal layering: carrying out centrifugal layering treatment on the solution, wherein the temperature of the centrifugal layering treatment is less than or equal to the temperature for layering the solution subjected to the centrifugal layering treatment; and
layered extraction: and (3) layering the solution subjected to centrifugal layering treatment, and extracting an upper layer solution, wherein the upper layer solution is a purified semiconductor single-walled carbon nanotube solution.
According to another aspect of the present disclosure, there is provided a purification method for semiconducting single-walled carbon nanotubes by solution layering, characterized by comprising an addition step, a centrifugal layering step, and a layering extraction step, wherein,
an adding step: adding a polymer dispersant or a small molecule dispersant of a carbon nano tube into an organic solvent in which a semiconductive single-walled carbon nano tube is dispersed to form a solution, wherein the concentration of the polymer dispersant or the small molecule dispersant in the organic solvent is more than or equal to 2 mg/ml;
and (3) centrifugal layering: carrying out centrifugal layering treatment on the solution, wherein the temperature of the centrifugal layering treatment is less than or equal to 15 ℃; and
layered extraction: and (3) layering the solution subjected to centrifugal layering treatment, and extracting an upper layer solution, wherein the upper layer solution is a purified semiconductor single-walled carbon nanotube solution.
According to still another aspect of the present disclosure, there is provided a purification method for semiconducting single-walled carbon nanotubes by solution stratification, comprising a mixing step, a dispersion forming step, a centrifugation step, an addition step, a centrifugation stratification step, and a stratification extraction step, wherein,
mixing: mixing a conjugated polymer or a conjugated small molecule and a carbon nano tube raw material in an organic solvent for purifying a semiconducting carbon nano tube;
a dispersion forming step: forming a carbon nanotube dispersion;
a centrifugation step: centrifuging the carbon nano tube dispersion liquid to obtain a supernatant;
an adding step: adding a polymer dispersant or a small molecule dispersant of the carbon nanotube to the supernatant to form a solution, and making the concentration of the polymer dispersant or the small molecule dispersant in the supernatant to be greater than or equal to the concentration at which the solution can be stratified by the treatment of the centrifugal stratification step;
and (3) centrifugal layering: carrying out centrifugal layering treatment on the solution, wherein the temperature of the centrifugal layering treatment is less than or equal to the temperature for layering the solution after the centrifugal layering treatment; and
layered extraction: and (3) layering the solution subjected to centrifugal layering treatment, and extracting an upper layer solution, wherein the upper layer solution is a purified semiconductor single-walled carbon nanotube solution.
According to still another aspect of the present disclosure, there is provided a purification method of semiconducting single-walled carbon nanotubes by solution layering, characterized by comprising a mixing step, a dispersion forming step, a centrifugation step, an addition step, a centrifugation layering step, and a layering extraction step, wherein,
mixing: mixing a conjugated polymer or a conjugated small molecule and a carbon nano tube raw material in an organic solvent for purifying a semiconducting carbon nano tube;
a dispersion forming step: forming a carbon nanotube dispersion;
a centrifugation step: centrifuging the carbon nano tube dispersion liquid to obtain a supernatant;
an adding step: adding a polymer dispersant or a small molecule dispersant of the carbon nano tube into the supernatant to form a solution, wherein the concentration of the polymer dispersant or the small molecule dispersant in the supernatant is more than or equal to 2 mg/ml;
and (3) centrifugal layering: carrying out centrifugal layering treatment on the solution, wherein the temperature of the centrifugal layering treatment is less than or equal to 15 ℃; and
layered extraction: and (3) layering the solution subjected to centrifugal layering treatment, and extracting an upper layer solution, wherein the upper layer solution is a purified semiconductor single-walled carbon nanotube solution.
According to one embodiment of the above aspect of the present disclosure, the polymer dispersant or the small molecule dispersant is at least one of a conjugated polymer or a conjugated small molecule capable of dispersing the carbon nanotube in an organic solvent, and a polymer or a small molecule capable of dissolving in an organic solvent, respectively.
According to an embodiment of the above aspect of the present disclosure, the organic solvent is at least one of toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, azomethylpyrrolidone, and dimethylsulfoxide.
According to one embodiment of the above aspect of the present disclosure, the conjugated polymer is at least one of polythiophene, polycarbazole, and polyfluorene.
According to one embodiment of the above aspect of the present disclosure, after the centrifugal stratification step and the stratified extraction step are performed, the centrifugal stratification step and the stratified extraction step are performed more than once.
According to one embodiment of the above aspect of the present disclosure, the centrifugation speed of the centrifugal stratification process is 2000g to 1000000 g.
According to one embodiment of the above aspect of the present disclosure, the time of the centrifugal stratification process is 0.5 to 20 hours.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.
Fig. 1 is a schematic flow diagram of a method according to an embodiment of the present disclosure.
Fig. 2 is a schematic flow diagram of a method according to another embodiment of the present disclosure.
Fig. 3 is a graph of the detection results of a stratified solution according to the methods of the present disclosure.
Detailed Description
The present disclosure is described in further detail below with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant disclosure and not restrictive of the disclosure. It should be further noted that, for the convenience of description, only the portions relevant to the present disclosure are shown in the drawings.
It should be noted that, in the present disclosure, the embodiments and features of the embodiments may be combined with each other without conflict. The present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
In a first embodiment of the present disclosure, a method of purifying semiconducting single-walled carbon nanotubes by solution layering is provided. Wherein, the purification method utilizes a solution layering technology to further improve the purity of the semiconductor single-walled carbon nanotube.
The method for purifying the semiconducting single-walled carbon nanotube will be described in detail with reference to fig. 1.
In step S10 of fig. 1, a polymer dispersant or a small molecule dispersant of carbon nanotubes is added to an organic solvent in which semiconducting single-walled carbon nanotubes are dispersed to form a solution, and the concentration of the polymer dispersant or the small molecule dispersant in the organic solvent is made greater than or equal to the concentration at which the solution can be delaminated by the treatment of step S11 described below.
In step S10, the organic solvent in which the semiconducting single-walled carbon nanotubes are dispersed may be a pretreated organic solvent in which the semiconducting single-walled carbon nanotubes are dispersed, for example, an organic solvent in which the semiconducting single-walled carbon nanotubes are contained and which has a high purity, or an organic solvent in which the semiconducting single-walled carbon nanotubes are dispersed and which requires further purification.
Preferably, the organic solvent may be at least one of all organic solvents that can be used to purify semiconducting single-walled carbon nanotubes, such as organic solvents like toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, azomethylpyrrolidone, and dimethylsulfoxide.
The polymer dispersant or the small molecule dispersant of the carbon nano tube is a polymer or a small molecule which can disperse the carbon nano tube. In the above-described method of the present disclosure, the kind of the polymer or the small molecule is not strictly required as long as it can disperse the carbon nanotube. In a preferred embodiment of the present disclosure, the polymer dispersant is at least one of a conjugated polymer that can disperse carbon nanotubes in an organic solvent, and a polymer that can be dissolved in an organic solvent, for example, the conjugated polymer may be at least one of polythiophene, polycarbazole, and polyfluorene. In a preferred embodiment of the present disclosure, the small molecule dispersant is at least one of a conjugated small molecule capable of dispersing the carbon nanotube in an organic solvent and a small molecule soluble in an organic solvent, and is, for example, a polymer or a small molecule soluble in an organic solvent such as toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, N-methylpyrrolidone, and dimethyl sulfoxide.
In the present disclosure, the concentration of the above-mentioned polymeric dispersant or small molecule dispersant in the organic solvent is made to be greater than or equal to the concentration at which the solution can be stratified by the treatment of the centrifugal stratification step, so that a better stratification phenomenon can be formed.
In a preferred embodiment of the present disclosure, the concentration of the above-mentioned polymeric dispersant or small molecule dispersant in the organic solvent is greater than 2mg (mg)/ml (ml).
In step S11, the solution obtained in step S10 is subjected to centrifugal stratification. The speed of the centrifugation treatment may be 20000g to 1000000 g. The time for the centrifugation treatment may be set to 0.5 to 20 hours. In order to allow the centrifuged solution to be significantly delaminated, in a preferred embodiment of the present disclosure, the temperature of the centrifugation is less than or equal to the temperature at which the centrifuged solution is delaminated. In a more preferred embodiment, the temperature may be set to 15 ℃ or less. Upon centrifugation, the solution undergoes a stratification phenomenon, such as the solution becoming darker from top to bottom.
In step S12, the uppermost layer solution of the solution obtained in step S11 is extracted to obtain a semiconducting carbon nanotube solution with further improved purity.
In a preferred embodiment of the present disclosure, if it is desired to further improve the purity of the semiconducting carbon nanotube solution, the steps S11 and S12 may be repeated, that is, after the steps S11 and S12 are performed once, the steps S11 and S12 may be performed once or twice or more. By repeated execution, the purity of the semiconducting carbon nanotubes can be infinitely increased, thereby better meeting industrial requirements.
Example 1
Adding polythiophene into toluene dispersed with semiconductor single-walled carbon nanotubes, adjusting the concentration of the polythiophene in the toluene to be 2%, carrying out centrifugal treatment at the temperature of 15 ℃, wherein the speed of the centrifugal treatment is 50000g (gravity acceleration) and the time is 0.5 h, taking out the solution after the centrifugal treatment, and taking out the uppermost layer solution after layering.
Example 2
Adding polycarbazole into xylene dispersed with semiconductor single-walled carbon nanotubes, adjusting the concentration of polycarbazole in xylene to 2.5%, centrifuging at 10 deg.C at 20000g for 20 hr, taking out the centrifuged solution, and taking out the uppermost solution after layering.
Example 3
Adding polyfluorene into chloroform dispersed with semiconductor single-walled carbon nanotube, adjusting the concentration of polyfluorene in chloroform to 2.7%, centrifuging at 5 deg.C at 1000000g for 10 hr, taking out centrifuged solution, and layering to obtain the uppermost layer solution.
Example 4
Adding polythiophene into cyclohexane dispersed with semiconductor single-walled carbon nanotubes, adjusting the concentration of polythiophene in cyclohexane to 3%, centrifuging at 12 deg.C at 100000g for 20 hr, taking out centrifuged solution, and taking out the uppermost layer solution after layering.
Example 5
Adding polythiophene into methylcyclohexane dispersed with semiconductor single-walled carbon nanotubes, adjusting the concentration of polythiophene in methylcyclohexane to be 2%, performing centrifugal treatment at 15 ℃ at the speed of 50000g for 0.5 hour, taking out the centrifuged solution, and taking out the uppermost layer solution after layering. Then, the solution was centrifuged again at 15 ℃ for 0.5 hour at 50000g, and the uppermost layer was separated after delamination.
Example 6
Adding polythiophene into ethylcyclohexane dispersed with semiconductor single-walled carbon nanotubes, adjusting the concentration of polythiophene in ethylcyclohexane to 3%, centrifuging at 10 deg.C at 20000g for 20 hr, taking out centrifuged solution, and taking out the uppermost layer solution after layering. Then, the solution was centrifuged again at a speed of 50000g for 0.5 hours at a temperature of 10 ℃ and the uppermost layer solution was taken out after the separation. Then, the solution was centrifuged again at a speed of 50000g for 0.5 hours at a temperature of 10 ℃ and the uppermost layer solution was taken out after the separation.
Example 7
Adding polythiophene into azomethyl pyrrolidone dispersed with semiconductor single-walled carbon nanotubes, adjusting the concentration of polythiophene in azomethyl pyrrolidone to 3%, centrifuging at 10 deg.C at 100000g for 0.5 hr, taking out centrifuged solution, and taking out the uppermost layer solution after layering. Then, the solution was centrifuged again at a speed of 50000g for 0.5 hours at a temperature of 10 ℃ and the uppermost layer solution was taken out after the separation. Then, the solution was centrifuged again at 15 ℃ for 10 hours at a speed of 2000g, and the uppermost layer was taken out after separation.
From the results of the above examples 1 to 7, it can be measured that the purity of the obtained semiconducting single-walled carbon nanotubes is further improved.
In a second embodiment of the present disclosure, a method of purifying semiconducting single-walled carbon nanotubes is provided. And will be described with particular reference to figure 2.
In step S21 of fig. 2, a conjugated polymer or a conjugated small molecule is mixed with a carbon nanotube raw material in an organic solvent for purifying semiconducting carbon nanotubes.
The conjugated polymer or the conjugated small molecule is a conjugated polymer or a conjugated small molecule capable of dispersing the carbon nanotube in an organic solvent, for example, the conjugated polymer may be at least one of polythiophene, polycarbazole or polyfluorene.
The carbon nanotube material may be carbon nanotubes grown in any manner or pretreated carbon nanotubes.
The organic solvent used to purify the semiconducting carbon nanotubes described above may be any organic solvent that can be used to purify semiconducting carbon nanotubes. The organic solvent may be at least one of toluene, xylene, cyclohexane, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, N-methylpyrrolidone, and dimethyl sulfoxide.
In a preferred embodiment of the present disclosure, the conjugated polymer or the conjugated small molecule and the carbon nanotube raw material are placed in an organic solvent at a mass ratio of 0.1:1 to 20: 1.
For example, 100mg (milligrams) of the conjugated polymer and 100mg of the carbon nanotube raw material are put into 100ml (milliliters) of the above organic solvent and mixed.
In step S22, the mixture of step S21 is formed into a carbon nanotube dispersion. Specifically, it can be performed using a nano-pulverization dispersion apparatus. For example, an ultrasonic cell disruptor, an ultrasonic water bath, or a stirring device is used. .
In step S23, the carbon nanotube dispersion liquid obtained in step S22 is subjected to a first centrifugation process. The first centrifugation may be performed at a centrifugation speed of 3000rpm (revolutions per minute) to 100000 rpm. And the time for the centrifugal treatment may be 0.5 to 300 hours.
By the processing of step S23, the supernatant liquid is taken out from the resulting solution for use in step S24. The supernatant fluid contains semiconducting carbon nanotubes suspended therein, and the purity of the semiconducting carbon nanotubes is determined by the type of the polymer and the charge ratio.
In step S24, a polymer dispersant or a small molecule dispersant of carbon nanotubes is added to an organic solvent in which semiconducting single-walled carbon nanotubes are dispersed to form a solution, and the concentration of the polymer dispersant or the small molecule dispersant in the organic solvent is made greater than or equal to the concentration at which the solution can be layered by the process of step S25 described below.
In step S24, the organic solvent in which the semiconducting single-walled carbon nanotubes are dispersed may be a pretreated organic solvent in which the semiconducting single-walled carbon nanotubes are dispersed, for example, an organic solvent in which the semiconducting single-walled carbon nanotubes are contained and which has a high purity, or an organic solvent in which the semiconducting single-walled carbon nanotubes are dispersed and which requires further purification.
Preferably, the organic solvent may be at least one of all organic solvents that can be used to purify semiconducting single-walled carbon nanotubes, such as organic solvents like toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, azomethylpyrrolidone, and dimethylsulfoxide.
The polymer dispersant or the small molecule dispersant of the carbon nano tube is a polymer or a small molecule which can disperse the carbon nano tube. In the above-described method of the present disclosure, the kind of the polymer or the small molecule is not strictly required as long as it can disperse the carbon nanotube. In a preferred embodiment of the present disclosure, the polymer dispersant is at least one of a conjugated polymer that can disperse carbon nanotubes in an organic solvent, and a polymer that can be dissolved in an organic solvent, for example, the conjugated polymer may be at least one of polythiophene, polycarbazole, and polyfluorene. In a preferred embodiment of the present disclosure, the small molecule dispersant is at least one of a conjugated small molecule capable of dispersing the carbon nanotube in an organic solvent and a small molecule soluble in an organic solvent, and is, for example, a polymer or a small molecule soluble in an organic solvent such as toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, N-methylpyrrolidone, and dimethyl sulfoxide.
In the present disclosure, the concentration of the above-mentioned polymeric dispersant or small molecule dispersant in the organic solvent is made to be greater than or equal to the concentration at which the solution can be stratified by the treatment of the centrifugal stratification step, so that a better stratification phenomenon can be formed.
In a preferred embodiment of the present disclosure, the concentration of the above-mentioned polymeric dispersant or small molecule dispersant in the organic solvent is greater than 2mg (mg)/ml (ml).
In step S25, the solution obtained in step S24 is subjected to centrifugal stratification. The speed of the centrifugation treatment may be 20000g to 1000000 g. The time for the centrifugation treatment may be set to 0.5 to 20 hours. In order to allow the centrifuged solution to be significantly delaminated, in a preferred embodiment of the present disclosure, the temperature of the centrifugation is less than or equal to the temperature at which the centrifuged solution is delaminated. In a more preferred embodiment, the temperature may be set to 15 ℃ or less. Upon centrifugation, the solution undergoes a stratification phenomenon, such as the solution becoming darker from top to bottom.
In step S26, the uppermost layer solution of the solution obtained in step S25 is extracted to obtain a semiconducting carbon nanotube solution with further improved purity.
In a preferred embodiment of the present disclosure, if it is desired to further improve the purity of the semiconducting carbon nanotube solution, the steps S25 and S26 may be repeated, that is, after the steps S11 and S12 are performed once, the steps S25 and S26 may be performed once or twice or more. By repeated execution, the purity of the semiconducting carbon nanotubes can be infinitely increased, thereby better meeting industrial requirements.
Example 8
100mg of polythiophene and 100mg of carbon nanotube material were mixed with 100ml of toluene. The dispersion was sonicated for 30 minutes at 150W using a sonicator, and the dispersion was taken out and centrifuged at 8000rpm for 2 hours. After centrifugation, the supernatant was taken out, polythiophene was added to the supernatant, the concentration of polythiophene in the supernatant was adjusted to 2%, centrifugation was carried out at 15 ℃ at 50000g (gravitational acceleration) for 0.5 hour, the centrifuged solution was taken out, and after layering, the uppermost layer solution was taken out.
Example 9
10mg of polycarbazole and 100mg of carbon nanotube material were mixed with 100ml of xylene. The dispersion was sonicated for 300 minutes at 20W using a sonicator cell disruptor, and centrifuged at 1000000rpm for 0.5 hour. Centrifuging, taking out supernatant, adding polycarbazole into the supernatant, adjusting the concentration of the polycarbazole in the supernatant to be 2.5%, centrifuging at the temperature of 10 ℃, wherein the speed of the centrifuging is 20000g, the time is 20 hours, taking out the centrifuged solution, and taking out the uppermost layer solution after layering.
Example 10
500mg of polyfluorene and 100mg of carbon nanotube material were mixed with 100ml of chloroform. The dispersion was sonicated for 100 minutes at 100W using a sonicator and centrifuged at 50000rpm for 1 hour. Centrifuging, taking out supernatant, adding polyfluorene into the supernatant, adjusting the concentration of polyfluorene in the supernatant to 2.7%, centrifuging at 5 deg.C at 1000000g for 10 hr, taking out centrifuged solution, and layering to obtain the uppermost layer solution.
Example 11
1000mg of polythiophene and 100mg of carbon nanotube material were mixed with 100ml of tetrahydrofuran. Performing ultrasonic treatment at 500W for 5 min with ultrasonic cell disruptor, and centrifuging at 5000rpm for 100 hr. Centrifuging, taking out supernatant, adding polythiophene into the supernatant, adjusting the concentration of polythiophene in the supernatant to 3%, centrifuging at 12 deg.C at 100000g for 20 hr, taking out centrifuged solution, and layering to obtain the uppermost layer solution.
Example 12
100mg of polythiophene and 100mg of carbon nanotube material were mixed with 100ml of toluene. The dispersion was sonicated for 30 minutes at 150W using a sonicator, and the dispersion was taken out and centrifuged at 8000rpm for 2 hours. And after centrifugation, taking out supernatant, adding polythiophene into the supernatant, adjusting the concentration of the polythiophene in the supernatant to be 2%, carrying out centrifugation treatment at the temperature of 15 ℃, wherein the speed of the centrifugation treatment is 50000g, the time is 0.5 h, taking out the centrifuged solution, and taking out the uppermost layer solution after layering. Then, the solution was centrifuged again at 15 ℃ for 0.5 hour at 50000g, and the uppermost layer was separated after delamination.
Example 13
1000mg of polythiophene and 100mg of carbon nanotube material were mixed with 100ml of toluene. Performing ultrasonic treatment at 1500W for 5 min with ultrasonic cell disruptor, and centrifuging at 8000rpm for 300 hr. Centrifuging, taking out supernatant, adding polythiophene into the supernatant, adjusting the concentration of polythiophene in the supernatant to 3%, centrifuging at 10 deg.C at 20000g for 20 hr, taking out centrifuged solution, and layering to obtain the uppermost layer solution. Then, the solution was centrifuged again at a speed of 50000g for 0.5 hours at a temperature of 10 ℃ and the uppermost layer solution was taken out after the separation. Then, the solution was centrifuged again at a speed of 50000g for 0.5 hours at a temperature of 10 ℃ and the uppermost layer solution was taken out after the separation.
Example 14
100mg of polythiophene and 100mg of carbon nanotube material were mixed with 100ml of toluene. The dispersion was sonicated for 30 minutes at 150W using a sonicator, and the dispersion was taken out and centrifuged at 8000rpm for 2 hours. Centrifuging, taking out supernatant, adding polythiophene into the supernatant, adjusting the concentration of polythiophene in toluene to be 3%, centrifuging at 10 deg.C at 100000g for 0.5 hr, taking out centrifuged solution, and taking out uppermost layer solution after layering. Then, the solution was centrifuged again at a speed of 50000g for 0.5 hours at a temperature of 10 ℃ and the uppermost layer solution was taken out after the separation. Then, the solution was centrifuged again at 15 ℃ for 10 hours at a speed of 2000g, and the uppermost layer was taken out after separation.
Comparative example 1
10mg of polythiophene and 5mg of carbon nanotube raw material were put into 25ml of toluene and mixed, and subjected to ultrasonic treatment at 525W for 30 minutes by an ultrasonic cell disruptor, and the obtained carbon nanotube dispersion was centrifuged at 42000g for 150 minutes. Taking out supernatant obtained by centrifugal treatment to obtain the semiconductor single-walled carbon nanotube solution.
The results of comparing examples 8-14 of the present disclosure with comparative example 1 are shown in table 1.
TABLE 1 comparison results of inventive examples 8-14 with comparative example 1
| Comparison table | Purification effect |
| Comparative example 1 | The purity of the semiconductive single-walled carbon nanotube can reach 99.9 percent at most |
| Examples 8 to 14 | The purity of the semiconductive single-walled carbon nanotube can be more than 99.999 percent |
According to experimental results, the purity of the semiconductor single-walled carbon nanotube can be more than 99.999% by the method of the embodiment 8-14 of the disclosure, and the application requirements of all electronic fields are met.
FIG. 3 shows the results of the examination of the layered solution. Fig. 3 shows the relationship between the wavelength and the absorbance of the carbon nanotube, and in fig. 3, the upper, middle and lower solutions of the layered solution were analyzed, and the result showed that the purity of the semiconducting single-walled carbon nanotube was the highest in the upper solution.
In the method disclosed by the invention, the type of the polymer or the micromolecule is not strictly required, and the purity of the semiconductive carbon nanotube can reach 99.999 percent or above. And the purity can be infinitely improved by repeating the purification process for a plurality of times.
The semiconductor single-walled carbon nanotube obtained by the method has high purity and is suitable for industrial production; the method has wide application prospect in the fields of semiconductor devices, integrated circuits, display drivers, transparent conductive films, biological/chemical sensing, infrared detection, infrared thermotherapy and the like.
It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.
Claims (10)
1. A purification method for realizing semiconductor single-walled carbon nanotubes by solution layering is characterized by comprising a mixing step, a dispersion forming step, a centrifuging step, an adding step, a centrifuging and layering step and a layering and extracting step, wherein,
the mixing step comprises the following steps: mixing a conjugated polymer or a conjugated small molecule and a carbon nano tube raw material in an organic solvent for purifying a semiconducting carbon nano tube;
the dispersion forming step: forming a carbon nanotube dispersion;
the centrifugation step comprises: centrifuging the carbon nano tube dispersion liquid to obtain a supernatant;
the adding step comprises: adding a polymer dispersant or a small molecule dispersant of carbon nanotubes to the supernatant to form a solution, and allowing the concentration of the polymer dispersant or the small molecule dispersant in the supernatant to be greater than or equal to a concentration at which the solution can be stratified by the treatment of the centrifugal stratification step;
the centrifugal layering step: subjecting the solution to centrifugal layering at a temperature less than or equal to a temperature at which the solution is layered after the centrifugal layering, wherein the temperature is set so that the solution can be separated into an upper layer, an intermediate layer and a lower layer; and
the layered extraction step comprises: and layering the solution subjected to centrifugal layering treatment, and extracting an upper layer solution, wherein the upper layer solution is a purified semiconductor single-walled carbon nanotube solution.
2. A purification method for realizing semiconductor single-walled carbon nanotubes by solution layering is characterized by comprising a mixing step, a dispersion forming step, a centrifuging step, an adding step, a centrifuging and layering step and a layering and extracting step, wherein,
the mixing step comprises the following steps: mixing a conjugated polymer or a conjugated small molecule and a carbon nano tube raw material in an organic solvent for purifying a semiconducting carbon nano tube;
the dispersion forming step: forming a carbon nanotube dispersion;
the centrifugation step comprises: centrifuging the carbon nano tube dispersion liquid to obtain a supernatant;
the adding step comprises: adding a polymer dispersant or a small molecule dispersant of a carbon nano tube into the supernatant to form a solution, and enabling the concentration of the polymer dispersant or the small molecule dispersant in the supernatant to be greater than or equal to 2 mg/ml;
the centrifugal layering step: carrying out centrifugal layering treatment on the solution, wherein the temperature of the centrifugal layering treatment is less than or equal to 15 ℃, so that the solution can be divided into an upper layer, a middle layer and a lower layer; and
layered extraction: and layering the solution subjected to centrifugal layering treatment, and extracting an upper layer solution, wherein the upper layer solution is a purified semiconductor single-walled carbon nanotube solution.
3. The method according to claim 1 or 2, wherein the polymer dispersant or the small molecule dispersant is at least one of a conjugated polymer or a conjugated small molecule capable of dispersing carbon nanotubes in the organic solvent, and a polymer or a small molecule capable of dissolving in the organic solvent, respectively.
4. The method according to claim 1 or 2, wherein the organic solvent is at least one of toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, azomethylpyrrolidone, and dimethylsulfoxide.
5. The method of claim 3, wherein the organic solvent is at least one of toluene, xylene, chloroform, tetrahydrofuran, cyclohexane, methylcyclohexane, ethylcyclohexane, azomethylpyrrolidone, and dimethylsulfoxide.
6. The method of claim 3, wherein the conjugated polymer is at least one of polythiophene, polycarbazole, and polyfluorene.
7. The method of any one of claims 1, 2, 5 and 6, wherein the centrifugation and stratification steps are performed more than once after the centrifugation and stratification steps are performed.
8. The method of claim 3, wherein the centrifuging and layering steps are performed more than once after the centrifuging and layering steps and the layering steps are performed.
9. The method of claim 4, wherein the centrifuging and layering steps are performed more than once after the centrifuging and layering steps are performed.
10. The method according to claim 1 or 2, wherein the time for the centrifugal stratification process is 0.5 to 20 hours.
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| CN105611986A (en) * | 2013-08-20 | 2016-05-25 | 加拿大国家研究委员会 | Process for purifying semiconducting single-walled carbon nanotubes |
| CN105819425A (en) * | 2016-03-30 | 2016-08-03 | 苏州希印纳米科技有限公司 | High-purity semiconductor type carbon nanotubes and batched separation method and application thereof |
| CN105883749A (en) * | 2016-04-12 | 2016-08-24 | 苏州希印纳米科技有限公司 | Single-walled carbon nanotube as well as selective extraction method and application thereof |
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| CN105611986A (en) * | 2013-08-20 | 2016-05-25 | 加拿大国家研究委员会 | Process for purifying semiconducting single-walled carbon nanotubes |
| CN105585000A (en) * | 2015-12-25 | 2016-05-18 | 苏州希印纳米科技有限公司 | Method for preparing dispersant-free semi-conductive single-walled carbon nanotube film |
| CN105819425A (en) * | 2016-03-30 | 2016-08-03 | 苏州希印纳米科技有限公司 | High-purity semiconductor type carbon nanotubes and batched separation method and application thereof |
| CN105883749A (en) * | 2016-04-12 | 2016-08-24 | 苏州希印纳米科技有限公司 | Single-walled carbon nanotube as well as selective extraction method and application thereof |
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