CN109867274A - The method of purification of semi-conductive single-walled carbon nanotubes and its preparation method of film - Google Patents
The method of purification of semi-conductive single-walled carbon nanotubes and its preparation method of film Download PDFInfo
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- CN109867274A CN109867274A CN201711246761.5A CN201711246761A CN109867274A CN 109867274 A CN109867274 A CN 109867274A CN 201711246761 A CN201711246761 A CN 201711246761A CN 109867274 A CN109867274 A CN 109867274A
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- walled carbon
- carbon nanotubes
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Abstract
This disclosure relates to a kind of method of purification of semi-conductive single-walled carbon nanotubes, comprising: dispersing agent and carbon nanometer tube material are put into the organic solvent of cycloalkane and mixed；It is handled to obtain carbon nano tube dispersion liquid；And it handles carbon nano tube dispersion liquid and extracts semi-conductive single-walled carbon nanotubes solution.
Description
Technical field
This disclosure relates to the method for purification of semi-conductive single-walled carbon nanotubes, more particularly to use cycloalkane solvent purifications
The method of semi-conductive single-walled carbon nanotubes.
Background technique
Semi-conductive single-walled carbon nanotubes have huge application potential in semicon industries such as sensing, integrated circuits.Such as
Semi-conductive single-walled carbon nanotubes are dispersed separation by what from impure raw material, are the important research contents in the field.
Currently, in conjugated polymer or conjugation small molecule dispersion, in order to obtain the semiconductive list of high-purity
Wall carbon nano tube, the organic solvent often used are all benzene kind solvent and other toxic solvents, such as toluene, dimethylbenzene, chloroform
Deng.These solvents have apparent carcinogenesis to human body, seriously destroy natural environment, are unfavorable for semi-conductive single-walled carbon nanometer
The industrialization of pipe.
Summary of the invention
In order to solve the above-mentioned technical problem, present disclose provides a kind of method of purification of semi-conductive single-walled carbon nanotubes and
The preparation method of semi-conductive single-walled carbon nanotubes film.
According to one aspect of the disclosure, a kind of method of purification of semi-conductive single-walled carbon nanotubes is provided, comprising:
Dispersing agent and carbon nanometer tube material are put into the organic solvent of cycloalkane and mixed；
It is handled to obtain carbon nano tube dispersion liquid；And
It handles carbon nano tube dispersion liquid and extracts semi-conductive single-walled carbon nanotubes solution.
In one embodiment, the organic solvent of cycloalkane includes: the organic solvent of cyclohexanes.
In another embodiment, organic solvent includes hexamethylene, hexahydrotoluene, ethyl cyclohexane and butyl cyclohexane
At least one of.
In yet another embodiment, organic solvent includes hexamethylene, hexahydrotoluene, ethyl cyclohexane and butyl cyclohexane
In two or more solvents combination, by adjust combination in solvent type and/or ratio, to adjust the boiling of organic solvent
Point.
In yet another embodiment, it handles carbon nano tube dispersion liquid and extracts semi-conductive single-walled carbon nanotubes solution
In step, centrifugal treating is carried out to carbon nano tube dispersion liquid, and extract the supernatant after centrifugal treating, i.e., it is semi-conductive single-walled
Carbon nano-tube solution.
In yet another embodiment, dispersing agent is at least one of conjugated polymer and conjugation small molecule.
According to another aspect of the present disclosure, a kind of preparation method of semi-conductive single-walled carbon nanotubes film is provided,
It is characterized in that, comprising:
Dispersing agent and carbon nanometer tube material are put into organic solvent and mixed；
It is handled to obtain carbon nano tube dispersion liquid；
Carbon nano tube dispersion liquid is handled, and extracts semi-conductive single-walled carbon nanotubes solution；And
Semi-conductive single-walled carbon nanotubes film is prepared by the semi-conductive single-walled carbon nanotubes solution of extraction,
Wherein, organic solvent includes two or more in hexamethylene, hexahydrotoluene, ethyl cyclohexane and butyl cyclohexane
The combination of solvent, by adjusting the type and/or ratio of the solvent in combination, to adjust the boiling point of organic solvent.
In one embodiment, dispersing agent is at least one of conjugated polymer and conjugation small molecule.
In another embodiment, it handles carbon nano tube dispersion liquid and extracts semi-conductive single-walled carbon nanotubes solution
In step, centrifugal treating is carried out to carbon nano tube dispersion liquid, and extract the supernatant after centrifugal treating, i.e., it is semi-conductive single-walled
Carbon nano-tube solution.
Detailed description of the invention
Attached drawing shows the illustrative embodiments of the disclosure, and it is bright together for explaining the principles of this disclosure,
Which includes these attached drawings to provide further understanding of the disclosure, and attached drawing is included in the description and constitutes this
Part of specification.
Fig. 1 is the flow diagram of an embodiment of the method provided according to the disclosure.
Fig. 2 is the flow diagram of another embodiment of the method provided according to the disclosure.
Fig. 3 is the effect detection figure for the purification semi-conductive single-walled carbon nanotubes that the disclosure provides.
Specific embodiment
The disclosure is described in further detail with reference to the accompanying drawings and examples.It is understood that this place is retouched
The specific embodiment stated is only used for explaining related content, rather than the restriction to the disclosure.It also should be noted that in order to just
Part relevant to the disclosure is illustrated only in description, attached drawing.
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the disclosure can phase
Mutually combination.The disclosure is described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
Present disclose provides a kind of methods using cycloalkane organic solvent purification semi-conductive single-walled carbon nanotubes, use
To provide a kind of less toxic or nontoxic, high-purity semi-conductive single-walled carbon nanotubes separation scheme.
Embodiment of the present disclosure is described in detail below with reference to Fig. 1.
In the first embodiment of the disclosure, the method for purifying semi-conductive single-walled carbon nanotubes includes the following steps.
Step S10: dispersing agent and carbon nanometer tube material are put into the organic solvent of cycloalkane and mixed.
In this step, dispersing agent and carbon nanometer tube material are put into organic solvent according to the mass ratio of 0.1:1 to 20:1
In, which is chosen as 1:1 to 10:1, is more chosen as 1:1.
In embodiment of the present disclosure, all can be organic molten for polythiophene, polycarbazole, polyfluorene etc. for above-mentioned dispersing agent
At least one of the conjugated polymer of dispersing Nano carbon tubes or conjugation small molecule in agent.And above-mentioned carbon nanometer tube material includes
The carbon nanotube grown in any method or the carbon nanotube Jing Guo pre-treatment.
In embodiment of the present disclosure, organic solvent is the organic solvent of cycloalkane, and be chosen as cyclohexanes has
Solvent is more chosen as the hydro carbons such as at least one of hexamethylene, hexahydrotoluene, ethyl cyclohexane, butyl cyclohexane etc. and takes
Purification processes are carried out to semiconductor single-walled carbon for cyclohexane solvent.In these solvents, from hexamethylene to butylcyclohexyl
Alkane, toxicity realize good refining effect gradually from low toxicity to nontoxic transformation.
In embodiment of the present disclosure, organic solvent is hexamethylene, hexahydrotoluene, ethyl cyclohexane, butylcyclohexyl
Two or more solvents in alkane etc..And by the type and/or ratio for adjusting the solvent in the combination, described have to adjust
The boiling point of solvent.For example, the boiling point of hexamethylene is 80.7 DEG C, hexahydrotoluene is 100.3 DEG C, ethyl cyclohexane 131.8
DEG C, butyl cyclohexane be 178-180 DEG C, by adjusting the type and ratio of solvent, make any kind and carry out in any proportion
It is used in mixed way, so that the boiling point of organic solvent is adjusted to 80 DEG C to 150 DEG C.In this way, being needed in carbon nano-tube film preparation
When different boiling solvent carries out film preparation, carbon nano-tube film later can be prepared and be of great significance.
Step S11: carbon nano tube dispersion liquid is obtained.
Specifically, carbon nanotube can be made in the mixed liquor of step S10 by modes such as ultrasound, oscillation, stirrings
Dispersion liquid.For example, the step can be realized by all nanometer pulverization dispersing apparatus.In an optional embodiment, lead to
Cross Ultrasonic cell smash 20W (watt) to 1500W power, 100W to 1000W can be selected in power, can more be selected in 150W
Power under ultrasound 5 to 300 minutes, be chosen as 30 to 100 minutes, be more chosen as 30 minutes.Certain those skilled in the art
It should be appreciated that the dispersion liquid can also be obtained under suitable conditions using other modes in addition to ultrasound.
In step s 12, it manages the carbon nano tube dispersion liquid and extracts semi-conductive single-walled carbon nanotubes solution.
Specifically, carrying out centrifugal treating to the carbon nano tube dispersion liquid that step S11 is obtained, the speed of the centrifugal treating can
Think 3000rpm to 100000rpm, is chosen as 5000rpm to 50000rpm, is more chosen as 8000rpm, and centrifugal treating
Time can be 0.5 to 300 hour, be chosen as 2 to 100 hours, more be chosen as 2 hours.Supernatant after extracting centrifugal treating,
That is semi-conductive single-walled carbon nanotubes solution.Wherein, semi-conductive single-walled carbon nanotubes are suspended in the supernatant.
According to the second embodiment of the disclosure, a kind of preparation side of semi-conductive single-walled carbon nanotubes film is provided
Method further includes step S13 after step S10~S12 of first embodiment.
In step s 13, semi-conductive single-walled carbon nanometer is prepared by the semi-conductive single-walled carbon nanotubes solution of extraction
Pipe film.
In an embodiment of the disclosure, due to the boiling point of the organic solvent in step S10 be it is adjustable, because
This, according to the boiling point needed when prepared by carbon nano-tube film, can type to organic solvent and ratio correspondingly adjusted
Section.
, can be before step S10~S13 in an embodiment of the disclosure, including prejudge carbon nanotube
The step of boiling point needed when film preparation, by judging required boiling point, in step slo adjust organic solvent type and
Ratio.
The specific embodiment of the disclosure is given below.
Embodiment 1
It will be mixed in the polythiophene of 100mg and the ethyl cyclohexane of the carbon nanometer tube material of 100mg investment 100ml.With super
Sound wave cell pulverization instrument ultrasound 5 minutes at 1500W.Take out dispersion liquid centrifugation, centrifugal speed 3000rpm, centrifugation time 300h.
After centrifugation, supernatant is taken, is suspended with semi-conductive single-walled carbon nanotubes in supernatant.
Embodiment 2
It will be mixed in the polythiophene of 100mg and the butyl cyclohexane of the carbon nanometer tube material of 5mg investment 100ml.With ultrasound
Wave cell pulverization instrument ultrasound 300 minutes at 20W.Take out dispersion liquid centrifugation, centrifugal speed 100000rpm, centrifugation time 0.5h.
After centrifugation, supernatant is taken, is suspended with semi-conductive single-walled carbon nanotubes in supernatant.
Embodiment 3
It will be mixed in the polycarbazole of 100mg and the hexahydrotoluene of the carbon nanometer tube material of 1000mg investment 100ml.With super
Sound wave cell pulverization instrument ultrasound 30 minutes at 150W.Take out dispersion liquid centrifugation, centrifugal speed 8000rpm, centrifugation time 2h.From
After the heart, supernatant is taken, is suspended with semi-conductive single-walled carbon nanotubes in supernatant.
Embodiment 4
It will be mixed in the polyfluorene of 100mg and the carbon nanometer tube material of 10mg investment 100ml hexamethylene.With supersonic cell powder
The ultrasound taking-up dispersion liquid centrifugation in 100 minutes at 100 of broken instrument, centrifugal speed 50000rpm, centrifugation time 100 hours.Centrifugation
Afterwards, supernatant is taken, is suspended with semi-conductive single-walled carbon nanotubes in supernatant.
Embodiment 5
It will be mixed in the polyfluorene of 100mg and the ethyl cyclohexane of the carbon nanometer tube material of 100mg investment 100ml.With ultrasound
Wave cell pulverization instrument 30 minutes of ultrasound at 1000W take out dispersion liquid centrifugation, centrifugal speed 5000rpm, centrifugation time 2h.From
After the heart, supernatant is taken, is suspended with semi-conductive single-walled carbon nanotubes in supernatant.
For the implementation result for verifying disclosed method, absorbance detection, root are carried out to semi-conductive single-walled carbon nanotubes
According to wavelength shown in Fig. 3 (the arc discharge carbon nanotube of polycarbazole separating-purifying in ethyl cyclohexane) and carbon nanotube extinction
Relationship between degree, those skilled in the art it can be found that, the carbon nanotube gone out by three separating-purifying of embodiment in purity and
On yield, preferable result is all reached.Meanwhile the toxicity that has of organic solvent that the present embodiment uses is very low, to environment and
Human injury is small, thus industrially has positive meaning.
The technical effect comparing result of the embodiment of the present disclosure and prior art is as shown in table 1:
1 embodiment of the present disclosure of table and prior art Contrast on effect result
In conclusion the disclosure using cycloalkane organic solvent obtain semi-conductive single-walled carbon nanotubes toxicity it is low,
Purity is high is suitble to industrial production；Have a broad prospect of the use in fields such as semiconductor devices, integrated circuit, film preparations.
Obviously, those skilled in the art can carry out various modification and variations without departing from the essence of the disclosure to the disclosure
Mind and range.In this way, if these modifications and variations of the disclosure belong to the range of disclosure claim and its equivalent technologies
Within, then the disclosure is also intended to include these modifications and variations.
Claims (9)
1. a kind of method of purification of semi-conductive single-walled carbon nanotubes characterized by comprising
Dispersing agent and carbon nanometer tube material are put into the organic solvent of cycloalkane and mixed；
It is handled to obtain carbon nano tube dispersion liquid；And
It handles the carbon nano tube dispersion liquid and extracts semi-conductive single-walled carbon nanotubes solution.
2. the method as described in claim 1, which is characterized in that the organic solvent of the cycloalkane includes: cyclohexanes
Organic solvent.
3. method according to claim 1 or 2, which is characterized in that the organic solvent include hexamethylene, hexahydrotoluene,
At least one of ethyl cyclohexane and butyl cyclohexane.
4. method according to any one of claims 1 to 3, which is characterized in that the organic solvent includes hexamethylene, methyl
The combination of two or more solvents in hexamethylene, ethyl cyclohexane and butyl cyclohexane, by adjusting the solvent in the combination
Type and/or ratio, to adjust the boiling point of the organic solvent.
5. method according to any one of claims 1 to 4, which is characterized in that handle the carbon nano tube dispersion liquid and
In the step of extracting semi-conductive single-walled carbon nanotubes solution, centrifugal treating is carried out to the carbon nano tube dispersion liquid, and mention
Supernatant after taking centrifugal treating, i.e. semi-conductive single-walled carbon nanotubes solution.
6. the method as described in any one of claims 1 to 5, which is characterized in that the dispersing agent is for conjugated polymer and altogether
At least one of yoke small molecule.
7. a kind of preparation method of semi-conductive single-walled carbon nanotubes film characterized by comprising
Dispersing agent and carbon nanometer tube material are put into organic solvent and mixed；
It is handled to obtain carbon nano tube dispersion liquid；
The carbon nano tube dispersion liquid is handled, and extracts semi-conductive single-walled carbon nanotubes solution；And
Semi-conductive single-walled carbon nanotubes film is prepared by the semi-conductive single-walled carbon nanotubes solution of extraction,
Wherein, the organic solvent includes two or more in hexamethylene, hexahydrotoluene, ethyl cyclohexane and butyl cyclohexane
The combination of solvent, by adjusting the type and/or ratio of the solvent in the combination, to adjust the boiling point of the organic solvent.
8. the method for claim 7, which is characterized in that the dispersing agent is in conjugated polymer and conjugation small molecule
It is at least one.
9. method as claimed in claim 7 or 8, which is characterized in that handle the carbon nano tube dispersion liquid and extract and partly lead
In the step of body single-walled carbon nanotube solution, centrifugal treating is carried out to the carbon nano tube dispersion liquid, and extract at centrifugation
Supernatant after reason, i.e. semi-conductive single-walled carbon nanotubes solution.
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