CN112194117A - Polymer-assisted separation method for large-diameter semiconductor single-walled carbon nanotubes - Google Patents

Polymer-assisted separation method for large-diameter semiconductor single-walled carbon nanotubes Download PDF

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CN112194117A
CN112194117A CN202011011626.4A CN202011011626A CN112194117A CN 112194117 A CN112194117 A CN 112194117A CN 202011011626 A CN202011011626 A CN 202011011626A CN 112194117 A CN112194117 A CN 112194117A
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walled carbon
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carbon nanotubes
carbon nanotube
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成会明
谢飘
侯鹏翔
刘畅
焦新宇
石超
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Institute of Metal Research of CAS
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Abstract

The invention relates to the field of liquid phase separation of semiconductor single-walled carbon nanotubes, in particular to a polymer auxiliary separation method of a large-diameter semiconductor single-walled carbon nanotube. Firstly, hydrogen peroxide is utilized to pretreat a large-diameter single-walled carbon nanotube prepared by a floating catalyst chemical vapor deposition method (FCCVD), and the end port of the carbon nanotube is selectively functionalized while impurities such as amorphous carbon and the like are removed; and then, performing non-covalent bond modification on the single-walled carbon nanotube by using a polymer, and finally obtaining a high-purity large-diameter semiconductor single-walled carbon nanotube solution through ultrasonic dispersion and centrifugal treatment. The method combines the advantages of nondestructive purification of the large-diameter and high-quality single-walled carbon nanotube grown by the FCCVD method by hydrogen peroxide and good selectivity of a conjugated polymer assisted separation method, successfully realizes the separation of the large-diameter semiconductor single-walled carbon nanotube, and is expected to be applied to the fields of infrared detectors, radio frequency devices and the like.

Description

Polymer-assisted separation method for large-diameter semiconductor single-walled carbon nanotubes
Technical Field
The invention relates to the field of liquid phase separation of semiconductor single-walled carbon nanotubes, in particular to a polymer auxiliary separation method of a large-diameter semiconductor single-walled carbon nanotube.
Background
The carbon nanotube can be regarded as a hollow tubular structure formed by curling two-dimensional graphene sheets, and the unique one-dimensional structure of the carbon nanotube endows the carbon nanotube with a plurality of excellent physical and chemical properties: carrier mobility up to 105cm2V · s; the thermal conductivity is as high as 3500W/(m.K); carrier density up to 109A/cm2. Furthermore, single-walled carbon nanotubes have unique electrical properties, i.e., structurally dependent metallic or semiconducting. The electrical structure of a single-walled carbon nanotube is determined by the way in which the graphene sheets constituting the nanotube are curled, i.e., the chiral indices (n, m). When n-m is 3j, the single-walled carbon nanotube is metallic; when n-m is 3j ± 1, the single-walled carbon nanotube is semiconducting. Single-walled carbon nanotubes are typically prepared as a mixture of-1/3 metallic and-2/3 semiconducting. The metallic single-walled carbon nanotube can be used for high-frequency wires, transparent conductive films and the like, and the semiconductor single-walled carbon nanotube has a huge application prospect in the field of electronic devices such as transistors, photoelectric detectors, solar cells and the like. The large-diameter semiconductor single-walled carbon nanotube is expected to play an important role in the application aspect of short-wave (1-3 mu m) near-infrared detectors due to the advantages of narrow band gap, difficulty in causing exciton trap and the like.
At present, the controllable preparation of the high-purity semiconductor single-walled carbon nanotube is a key point and a difficulty in the research field of the carbon nanotube, and particularly, the separation of the semiconductor single-walled carbon nanotube with large diameter (>1.7nm) is particularly difficult. This makes carbon nanotube-based short-wave near-infrared detectors less studied and perform poorly. There are two current methods for obtaining semiconducting single-walled carbon nanotubes, one is a direct growth method (document 1: Yu, b.; Liu, c.; Hou, p.x.et al. journal of the American Chemical Society 20011,133,5232; document 2: Li, w.s.; Hou p.x.; Liu, c.et al. acs Nano 2013,7, 6831; document 3: Qin, x.; pen, f.; Li, y.et al. Nano Letter 2014,14,512), and the other is a post-treatment separation method (document 4: Ghosh, s.; bachi, s.m.; Weisman, r.b.et al. nature Nano technology 2010,5, 443; document 5: Wang, h.l.; Li, y.x.; Bao, z.a.vaded. Funale., 2017, t.7, t. takt et al, t. 31, t.7, takta., t.7, t. 31, 11, t.s.; l., t. 4: brick, 3, t.t. 3, r.a. The direct growth method can prepare the semiconductor single-walled carbon nanotube, but the obtained material has low purity and poor repeatability, and the application requirement is still difficult to meet; post-treatment processes have succeeded in obtaining semiconducting single-walled carbon nanotubes having a purity as high as 99.99% and a maximum diameter of about 1.5nm by modifying single-walled carbon nanotubes to expand the difference in physical and chemical properties between metallic and semiconducting single-walled carbon nanotubes and then separating them (document 7: Gu, j.; Qiu, s.; Li, q.et al.small 2016,12, 4993). According to theoretical prediction: small diameter (< 1.2nm) semiconducting single-walled carbon nanotubes are suitable for making photovoltaic solar cells (document 8: Koleilat, g.i.; Zhang, y.; Bao, z.et al.acs Nano 2016,10, 11258); large-diameter semiconductor single-walled carbon nanotubes with diameters of 1.2-1.7 nm are suitable for manufacturing transistors (document 9: Lei, T.; Lai, Y. -C.; Bao, Z.et al.Small 2015,11, 2946); while semiconducting single-walled carbon nanotubes with larger diameters (>1.7nm) are suitable for short-wave near-infrared photodetectors and radio-frequency devices. Therefore, in order to meet the application requirements of photodetectors and radio frequency devices, it is necessary to separate and obtain semiconductor single-walled carbon nanotubes with larger diameters (>1.7 nm). At present, no report on the separation and preparation of high-purity large-diameter semiconductor carbon tubes exists. The reason for this is that the difference in electronic structure and chemical properties between metallic and semiconducting single-walled carbon nanotubes decreases with increasing diameter, making separation of the two more difficult.
Disclosure of Invention
The invention aims to provide a polymer auxiliary separation method of a large-diameter (not less than 1.7nm) and semiconducting single-walled carbon nanotube, which is simple, convenient and efficient, has small structural damage to the carbon nanotube, is expected to be produced in batch and is practically applied in the field of near-infrared photoelectric detectors.
The technical scheme of the invention is as follows:
a polymer auxiliary separation method of a large-diameter semiconductor single-walled carbon nanotube comprises the steps of firstly utilizing aqueous hydrogen peroxide to pretreat the single-walled carbon nanotube grown by a floating catalyst chemical vapor deposition method, removing amorphous carbon impurities, and simultaneously carrying out selective functionalization on the end part of the carbon nanotube; then, the polymer is used for carrying out non-covalent bond modification on the single-walled carbon nanotube; and finally obtaining the high-purity large-diameter semiconductor single-walled carbon nanotube solution through ultrasonic dispersion and centrifugal treatment.
The polymer-assisted separation method of the large-diameter semiconductor single-walled carbon nanotube is characterized in that the single-walled carbon nanotube grown by a floating catalyst chemical vapor deposition method has a concentrated oxidation temperature of more than 800 ℃, an average diameter of more than or equal to 1.7nm and a tube bundle size of 5-20 nm.
The polymer-assisted separation method of the large-diameter semiconductor single-walled carbon nanotube comprises the steps of putting the single-walled carbon nanotube into an analytically pure hydrogen peroxide aqueous solution with the concentration of 30 wt%, wherein the treatment temperature of the hydrogen peroxide aqueous solution is room temperature, the treatment time is 48-72 h, and the mass volume ratio of the single-walled carbon nanotube to the hydrogen peroxide aqueous solution is 100mg (100-300) mL.
The polymer auxiliary separation method of the large-diameter semiconductor single-walled carbon nanotube comprises the steps that the polymer is an N-type polymer, the single-walled carbon nanotube and the N-type polymer are dispersed in organic solvent toluene or xylene, and the mass ratio of the single-walled carbon nanotube to the N-type polymer is 1 (1-3).
According to the polymer-assisted separation method of the large-diameter semiconductor single-walled carbon nanotube, the N-type polymer is P (NDI2OD-T2), PDI-2T or PZ 1.
The polymer-assisted separation method of the large-diameter semiconductor single-walled carbon nanotube comprises the following steps of: firstly, carrying out water bath ultrasound for 2-5 min, and then carrying out ultrasonic treatment for 20-40 min by using an ultrasonic cell crusher; or, only adopting water bath ultrasound for 1-3 h.
The polymer auxiliary separation method of the large-diameter semiconductor single-walled carbon nanotube comprises the following steps of: the centrifugal force is as follows: 30000 g-60000 g and 2-4 h of centrifugation time.
According to the polymer-assisted separation method of the large-diameter semiconductor single-walled carbon nanotube, the purity of the obtained semiconductor single-walled carbon nanotube is over 95 wt%, and the average diameter of the obtained semiconductor single-walled carbon nanotube is 1.8 nm.
The design idea of the invention is as follows:
the technical key of separating the single-walled carbon nanotubes with different conductive properties by adopting a liquid phase method is how to obtain a monodisperse single-walled carbon nanotube solution with small structural destructiveness; secondly, how to increase the difference of the physicochemical properties of the large-diameter metallic single-walled carbon nanotube and the semiconductor single-walled carbon nanotube so as to realize separation. Aiming at the two problems, firstly, the end part of the single-walled carbon nanotube is selectively functionalized by adopting the weak-oxidizing aqueous hydrogen peroxide solution, the process has little damage and destruction to the carbon nanotube, and the introduced functional group can weaken the Van der Waals force among the single-walled carbon nanotubes due to the mutual repulsion, thereby being beneficial to the later ultrasonic treatment to obtain the monodisperse single-walled carbon nanotube solution. On the other hand, the invention adopts the electron-accepting type (N type) conjugated polymer to increase the difference of the physicochemical properties of the metallic and semi-conductive single-walled carbon nanotubes, compared with the common electron-donating type (P type) polymer, the electron-accepting type conjugated polymer has deeper LUMO energy level, and further has stronger action with the metallic single-walled carbon nanotubes. In addition, the large planar conjugated backbone of the N-type polymer can allow the polymer to more effectively wind large-diameter low-curvature carbon nanotubes; the N-type polymer contains more thiophene backbone groups, and after more thiophene units are added, the polymer/single-walled carbon nanotube composite shows stronger interaction. The stronger the polymer interacts with the semiconducting single-walled carbon nanotubes, the higher the dispersion yield, while the stronger the polymer interacts with the metallic single-walled carbon nanotubes, the stronger the charge transfer interaction, the higher the selectivity. And finally, the metallic single-walled carbon nanotubes are deposited under the action of centrifugal force due to the strong plane pi stacking action of the metallic carbon nanotubes and the electron-accepting conjugated polymer, so that the separation of the large-diameter semiconductor single-walled carbon nanotubes is realized.
The invention has the advantages and beneficial effects that:
1. the invention realizes the separation and preparation of the semiconductor single-walled carbon nanotube with the large diameter (not less than 1.7nm) for the first time, and fills the technical blank in the field.
2. The invention adopts hydrogen peroxide aqueous solution to pretreat the single-walled carbon nano-tube, and weakens strong van der Waals force between the tubes through selective functionalization of the tube bundle end part, thereby reducing the later-stage dispersion processing strength so as to keep the intrinsic structure of the carbon nano-tube.
3. The invention can obtain the semiconductor single-walled carbon nanotube with the purity of 98wt percent and the average length of 1 mu m.
4. The method disclosed by the invention is simple to operate, consumes less time, can realize batch production, and has a good industrial application prospect.
Drawings
FIG. 1 shows untreated single-walled carbon nanotubes and H2O2The infrared absorption spectrogram of the treated single-walled carbon nanotube has no C ═ O bond in both the single-walled carbon nanotube, which indicates that H is in room temperature2O2The oxidation to single-walled carbon nanotubes is weak.
Fig. 2 is a thermogram of single-walled carbon nanotubes before hydrogen peroxide treatment. In the figure, Temperature on the abscissa represents Temperature (. degree. C.), Mass on the ordinate represents weight loss (%), and DSC on the ordinate represents power (mW/mg) per mg of sample flowing.
Fig. 3 is a thermogram of single-walled carbon nanotubes after hydrogen peroxide treatment. In the figure, Temperature on the abscissa represents Temperature (. degree. C.), Mass on the ordinate represents weight loss (%), and DSC on the ordinate represents power (mW/mg) per mg of sample flowing.
Fig. 4 is a uv-vis-nir absorption spectrum of semiconducting single-walled carbon nanotubes isolated from polymer J61 (left) and polymer J61 (right). In the figure, the abscissa Raman shift represents the Raman shift (cm)-1) The ordinate Intensity represents the relative Intensity (a.u.).
FIG. 5(a) is a 532nm Raman spectrum of crude single-walled carbon nanotubes treated with hydrogen peroxide. In the figure, the abscissa Raman shift represents the Raman shift (cm)-1) The ordinate Intensity represents the relative Intensity (a.u.).
FIG. 5(b) is a 633nm Raman spectrum of raw single-walled carbon nanotubes treated with hydrogen peroxide. In the figure, the abscissa Raman shift represents the Raman shift (cm)-1) The ordinate Intensity represents the relative Intensity (a.u.).
FIG. 5(c) is a semiconducting single-walled carbon separated with Polymer J61532nm Raman spectrum of the nanotube. In the figure, the abscissa Raman shift represents the Raman shift (cm)-1) The Normalized Intensity is represented by the ordinate.
FIG. 5(d) is a 633nm Raman spectrum of semiconducting single-walled carbon nanotubes isolated with Polymer J61. The abscissa Raman shift represents the Raman shift (cm)-1) The Normalized Intensity is represented by the ordinate.
FIGS. 6(a) - (b) are AFM images of semiconducting single-walled carbon nanotubes isolated with polymer J61. Wherein FIG. 6(a) is an absorption spectrum of polymer J61; fig. 6(b) is a liquid phase absorption spectrum of the semiconducting single-walled carbon nanotube and the original single-walled carbon nanotube separated from the polymer J61, wherein the abscissa Wavelength represents the Wavelength (nm) and the ordinate Abs represents the relative intensity.
FIG. 7(a) is an AFM image of isolated semiconducting single-walled carbon nanotubes of J61; fig. 7(b) is a height diagram of selected semiconducting single-walled carbon nanotubes therein.
Detailed Description
The invention takes the large-diameter single-walled carbon nanotubes prepared by the patent technology of 'macro and controllable preparation method of large-diameter and narrow-diameter distribution single-walled carbon nanotubes' in the previous period of the inventor (publication No. CN110357072A) as a raw material, and the single-walled carbon nanotubes grown by a floating catalyst chemical vapor deposition method (FCCVD) have the advantages of high crystallinity, good quality (the concentrated oxidation temperature is higher than 800 ℃), large diameter (the average diameter is more than or equal to 1.7nm), and 5-20 nm of tube bundle size. The polymer-assisted separation method is adopted, and the specific implementation steps comprise the following two steps:
(1) pretreatment of single-walled carbon nanotubes
Putting 100mg of raw material single-walled carbon nanotubes and 200ml of 30 wt% aqueous hydrogen peroxide (analytically pure) into a beaker, and magnetically stirring for a certain time (48-72 h) at room temperature; then, carrying out vacuum filtration on the dispersion liquid, and repeatedly washing with deionized water; and finally, drying the obtained carbon nano tube filter cake in a vacuum drying oven.
(2) Polymer-assisted separation method for preparing large-diameter semiconductor single-walled carbon nanotube
The pretreated single-walled carbon nanotubes and polymer J61 were weighed into a toluene solution and the resulting solution was first heated in a water bath until polymer J61 was completely dissolved. After fully cooling, carrying out ultrasonic dispersion treatment: firstly, performing water bath ultrasound for 2-5 min, and then dispersing under the condition of using an ultrasonic cell crusher (200W/30min) (or only performing water bath ultrasound for 1-3 h); finally, carrying out centrifugal treatment: the separation is finished under the centrifugal force of 30000g/2 h-60000 g/2h, and the supernatant is removed and stored to obtain the semiconductor single-walled carbon nanotube solution.
The present invention will be described in more detail below with reference to examples.
Example 1:
in this example, 100mg of large-diameter single-walled carbon nanotubes were treated in step (1), wherein the concentration of the aqueous hydrogen peroxide solution was analytically pure and the treatment time was 72 hours. As shown in fig. 1, the infrared absorption spectrum indicates that no C ═ O bond was detected in the sample before and after the treatment with the aqueous hydrogen peroxide solution, indicating that the oxidation of the single-walled carbon nanotubes by hydrogen peroxide was weak at room temperature.
As shown in fig. 2 and fig. 3, thermogravimetric/differential thermal analysis curves of the single-walled carbon nanotube before and after the hydrogen peroxide treatment indicate that the content of carbon impurities and the like in the single-walled carbon nanotube after the hydrogen peroxide treatment is greatly reduced, which indicates that the aqueous hydrogen peroxide solution has a strong oxidizing effect on the impurities such as amorphous carbon.
As shown in fig. 4, in the ultraviolet-visible-near infrared absorption spectra of the semiconducting single-walled carbon nanotubes (right) separated from the polymer J61 (left) and the polymer J61, the polymer J61 has no absorption peak in the range of 700-2000 nm, and does not affect the absorption peak of the semiconducting single-walled carbon nanotubes; the pristine single-walled carbon nanotubes were dispersed in sodium dodecyl sulfate (SBS) surfactant and ultracentrifuged to serve as a control. Raman spectra showed that the G/D ratio of the samples after treatment with aqueous hydrogen peroxide decreased slightly compared to the untreated samples, but was still as high as 90 or more.
Weighing 6mg and 12mg of the polymer J61 of the single-walled carbon nanotube sample treated in the step (1), adding into 30ml of toluene solution, and dispersing and separating the semiconductor single-walled carbon nanotubes by adopting the method in the step (2). Wherein the water bath ultrasonic time is 4 minutes, the power of an ultrasonic cell crusher is 200W, the ultrasonic time is 30 minutes, the centrifugal force is 45000g, the centrifugal time is 2 hours, and the structure representation is carried out on the separated supernatant of the single-walled carbon nanotube. As shown in fig. 5(a) - (d), the multi-wavelength raman spectroscopy breath mode, before separation and purification, the single-walled carbon nanotube sample has raman breath mode excited in both metallic and semiconducting intervals (fig. 5a-b), indicating that the original sample is a mixture of metallic and semiconducting single-walled carbon nanotubes. After separation and purification, all the excited raman breathing modes are distributed in the interval of the semiconducting single-walled carbon nanotubes (fig. 5c-d), which shows that the semiconducting single-walled carbon nanotubes are separated and purified. Through counting the Raman breathing mode of the separated carbon nano tube, the purity of the purified semiconductor carbon nano tube can be calculated to be 98 wt% by comparing the corresponding metallic breathing mode and the corresponding semiconductor breathing mode in 532nm and 633 nm.
Referring to FIGS. 6(a) - (b), AFM analysis of semiconducting single-walled carbon nanotubes isolated with polymer J61 showed that most semiconducting single-walled carbon nanotubes had diameters of 1.7nm or more. The content of the semiconductor single-walled carbon nanotubes in the sample is further characterized by utilizing an ultraviolet-visible-near infrared absorption spectrum, and compared with the original sample, the separated and purified sample does not have an absorption peak in a metallic region, which shows that the purified sample has high semiconductor purity.
As shown in fig. 7(a) - (b), the diameters of the separated single-walled carbon nanotubes were characterized using atomic force microscopy, and all single-walled carbon nanotubes were found to be >1.7nm in diameter.
Example 2:
and (2) treating 100mg of large-diameter single-walled carbon nanotubes by using the step (1), wherein the concentration of the aqueous solution of hydrogen peroxide is analytically pure, and the treatment time is 72 hours. The infrared absorption spectrogram shows that C ═ O bonds are not detected in the sample before and after the treatment of the aqueous hydrogen peroxide solution, which indicates that the oxidability of the hydrogen peroxide to the single-walled carbon nanotube is weak at room temperature. The thermogravimetric/differential thermal analysis curve shows that the content of carbon impurities in the single-walled carbon nanotube after hydrogen peroxide treatment is greatly reduced, and the hydrogen peroxide aqueous solution has stronger oxidation effect on amorphous carbon and other impurities; the raman spectrum showed that the G/D ratio of the sample after the treatment with aqueous hydrogen peroxide was slightly lower than that of the original carbon nanotube sample, but still as high as 90 or more.
Weighing 6mg and 12mg of the polymer J61 of the single-walled carbon nanotube sample treated in the step 1, adding the single-walled carbon nanotube sample into 30ml of toluene solution, and dispersing and separating the semiconductor single-walled carbon nanotube by adopting the method in the step 2. Except that only water bath ultrasound is adopted, and the time is 2 h. And carrying out structural characterization on the separated supernatant of the single-walled carbon nanotube. And the multi-wavelength Raman spectrum breathing mode shows that after separation and purification, all the excited Raman breathing modes are distributed in the interval of the semiconductor single-walled carbon nano tubes, and the semiconductor single-walled carbon nano tubes are separated and purified. Through counting the Raman breathing mode of the separated carbon nano tube, the purity of the purified semiconductor carbon nano tube can be calculated to be 96 wt% by comparing the corresponding metallic breathing mode and the corresponding semiconductor breathing mode in 532nm and 633 nm. The diameters of the separated single-walled carbon nanotubes were characterized using an atomic force microscope and all single-walled carbon nanotubes were found to be >1.7nm in diameter.
Comparative example 1:
the single-walled carbon nanotube sample is not pretreated by aqueous hydrogen peroxide, 6mg and 12mg of the polymer J61 of the single-walled carbon nanotube sample are directly weighed and added into 30ml of toluene solution, and the semiconductor single-walled carbon nanotube is dispersed and separated by the method in the step 2. Wherein the water bath ultrasonic time is 4 minutes, the power of an ultrasonic cell crusher is 200W, the ultrasonic time is 30 minutes, the centrifugal force is 45000g, the centrifugal time is 2 hours, and the structure representation is carried out on the separated supernatant of the single-walled carbon nanotube. And the multi-wavelength Raman spectrum breathing mode shows that after separation and purification, all the excited Raman breathing modes are distributed in the interval of the semiconductor single-walled carbon nano tubes, and the semiconductor single-walled carbon nano tubes are separated and purified. Through counting the Raman breathing mode of the separated carbon nano tube, the purity of the purified semiconductor carbon nano tube can be calculated to be 93 wt% by comparing the corresponding metallic breathing mode and the corresponding semiconductor breathing mode in 532nm and 633 nm. The diameters of the separated single-walled carbon nanotubes were characterized using an atomic force microscope and all single-walled carbon nanotubes were found to be >1.7nm in diameter.
Comparative example 2:
and (2) treating 100mg of large-diameter single-walled carbon nanotubes by using the step (1), wherein the concentration of the aqueous solution of hydrogen peroxide is analytically pure, and the treatment time is 72 hours. The infrared absorption spectrogram shows that C ═ O bonds are not detected in the sample before and after the treatment of the aqueous hydrogen peroxide solution, which indicates that the oxidability of the hydrogen peroxide to the single-walled carbon nanotube is weak at room temperature. The thermogravimetric/differential thermal analysis curve shows that the content of carbon impurities in the single-walled carbon nanotube after hydrogen peroxide treatment is greatly reduced, and the hydrogen peroxide aqueous solution has stronger oxidation effect on the amorphous carbon rich in seven-membered rings and five-membered rings; the raman spectrum showed that the G/D ratio of the sample after treatment with aqueous hydrogen peroxide decreased slightly compared to the untreated original carbon nanotube sample, but still was as high as 90 or more.
Weighing 6mg and 12mg of rr-P3DDT polymers of the single-walled carbon nanotube sample treated in the step 1, adding the single-walled carbon nanotube sample into 30ml of toluene solution, and dispersing and separating the semiconductor single-walled carbon nanotube by adopting the method in the step 2. Wherein, the water bath ultrasonic time is 2-5 minutes, the power of the ultrasonic cell crusher is 200W, the ultrasonic time is 30 minutes, the centrifugal force is 45000g, and the centrifugal time is 2 hours. And carrying out structural characterization on the separated supernatant of the single-walled carbon nanotube. The multi-wavelength Raman spectrum breathing mode shows that after separation and purification, all the excited Raman breathing modes are distributed in the interval of the semiconductor single-walled carbon nano-tubes, and the semiconductor single-walled carbon nano-tubes are separated and purified. Through counting the Raman breathing mode of the separated carbon nano tube, the purity of the purified semiconductor carbon nano tube can be calculated to be only about 93 wt% by comparing the corresponding metallic breathing mode and the corresponding semiconductor breathing mode in 532nm and 633 nm. The content of the semiconductor single-walled carbon nanotubes in the sample is roughly characterized by using ultraviolet-visible-near infrared absorption spectrum, and a plurality of smaller metallic single-walled carbon nanotube peaks still exist in a metallic area. The diameters of the separated single-walled carbon nanotubes were characterized using an atomic force microscope and all single-walled carbon nanotubes were found to be >1.7nm in diameter.
The results of the examples and the comparative examples show that the large-diameter single-walled carbon nanotubes prepared by the hydrogen peroxide pretreatment Floating Catalyst Chemical Vapor Deposition (FCCVD) method combine the advantages of hydrogen peroxide on the large-diameter and high-quality single-walled carbon nanotubes grown by the FCCVD method and good selectivity of a conjugated polymer assisted separation method, separation of the large-diameter semiconducting single-walled carbon nanotubes is successfully realized, the purity of the obtained semiconducting single-walled carbon nanotubes can reach 98 wt%, the average diameter is 1.8nm, and the obtained semiconducting single-walled carbon nanotubes with the largest diameter are high-purity semiconducting single-walled carbon nanotubes with the largest diameter at present. The invention not only breaks through the problem of controllable preparation of the current large-diameter semiconductor single-walled carbon nanotube, but also is expected to be applied to the field of infrared detectors and radio frequency devices.

Claims (8)

1. A polymer auxiliary separation method of a large-diameter semiconductor single-walled carbon nanotube is characterized in that firstly, a single-walled carbon nanotube grown by a floating catalyst chemical vapor deposition method is pretreated by aqueous hydrogen peroxide, amorphous carbon impurities are removed, and meanwhile, the end part of the carbon nanotube is selectively functionalized; then, the polymer is used for carrying out non-covalent bond modification on the single-walled carbon nanotube; and finally obtaining the high-purity large-diameter semiconductor single-walled carbon nanotube solution through ultrasonic dispersion and centrifugal treatment.
2. The polymer-assisted separation method of large-diameter semiconducting single-walled carbon nanotubes according to claim 1, characterized in that the single-walled carbon nanotubes grown by the floating catalyst chemical vapor deposition method have a concentrated oxidation temperature of more than 800 ℃, an average diameter of more than or equal to 1.7nm and a tube bundle size of 5-20 nm.
3. The method for polymer-assisted separation of large-diameter semiconducting single-walled carbon nanotubes of claim 1, wherein the single-walled carbon nanotubes are placed in an analytically pure aqueous hydrogen peroxide solution with a concentration of 30 wt%, the treatment temperature of the aqueous hydrogen peroxide solution is room temperature, the treatment time is 48-72 h, and the mass-to-volume ratio of the single-walled carbon nanotubes to the aqueous hydrogen peroxide solution is 100mg (100-300) mL.
4. The polymer-assisted separation method of large-diameter semiconducting single-walled carbon nanotubes according to claim 1, wherein the polymer is an N-type polymer, the single-walled carbon nanotubes and the N-type polymer are dispersed in an organic solvent toluene or xylene, and the mass ratio of the single-walled carbon nanotubes to the N-type polymer is 1 (1-3).
5. The polymer-assisted separation method of large-diameter semiconducting single-walled carbon nanotubes of claim 4, wherein the N-type polymer is P (NDI2OD-T2), PDI-2T or PZ 1.
6. The polymer-assisted separation method of large-diameter semiconducting single-walled carbon nanotubes of claim 1, wherein the ultrasonic dispersion treatment: firstly, carrying out water bath ultrasound for 2-5 min, and then carrying out ultrasonic treatment for 20-40 min by using an ultrasonic cell crusher; or, only adopting water bath ultrasound for 1-3 h.
7. The method of polymer-assisted separation of large diameter semiconducting single-walled carbon nanotubes of claim 1, wherein centrifugation: the centrifugal force is as follows: 30000 g-60000 g and 2-4 h of centrifugation time.
8. The polymer-assisted separation method of large-diameter semiconducting single-walled carbon nanotubes according to any of claims 1 to 7, characterized in that semiconducting single-walled carbon nanotubes are obtained with a purity of more than 95 wt% and an average diameter of 1.8 nm.
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