CN112812507B - Single chiral carbon nanotube-thiophene polymer composite material and preparation method thereof - Google Patents

Single chiral carbon nanotube-thiophene polymer composite material and preparation method thereof Download PDF

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CN112812507B
CN112812507B CN202110018486.1A CN202110018486A CN112812507B CN 112812507 B CN112812507 B CN 112812507B CN 202110018486 A CN202110018486 A CN 202110018486A CN 112812507 B CN112812507 B CN 112812507B
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CN112812507A (en
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洪流
朱海标
马乐
杨成
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Jiangnan University
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Abstract

The invention discloses a single chiral carbon nanotube-thiophene polymer composite material and a preparation method thereof, and belongs to the field of carbon nanomaterials. The thiophene polymer/(6, 5) SWCNT nano composite containing the high-purity single chiral carbon nano tube is successfully prepared by using the specific thiophene polymer to replace PFO-BPy on PFO-BPy/(6,5) SWCNT, and the problems of metal carbon nano tube residue and poor chiral selectivity of the carbon nano tube after the thiophene polymer directly disperses the carbon nano tube are solved.

Description

Single chiral carbon nanotube-thiophene polymer composite material and preparation method thereof
Technical Field
The invention relates to a single chiral carbon nanotube-thiophene polymer composite material and a preparation method thereof, belonging to the field of carbon nanomaterials.
Background
The carbon nano tube is a one-dimensional nano material, has excellent electronic characteristics and is a potential ideal material for electronic devices. The performance of the semiconductor type carbon nano tube is superior to that of the traditional silicon-based semiconductor material, and the semiconductor type carbon nano tube has a great application prospect in the aspect of electronic devices. However, almost all the carbon nanotubes commercialized at present are mixtures of metal type and semiconductor type, and the presence of the metal type carbon nanotubes seriously affects the performance of electronic devices. It is therefore the focus of research to achieve an efficient separation of metallic and semiconducting carbon nanotubes. The most ideal method at present is to carry out non-covalent modification by conjugated polymers, which not only can separate metal type and semiconductor type carbon nanotubes, but also has the characteristics of simple operation and realization of large-scale application. However, most polymers, such as thiophene conjugated polymers, directly modify the coated carbon nanotubes, which results in a large amount of metallic carbon nanotube residues, so that single chiral carbon nanotubes cannot be obtained, and the performance of the organic photovoltaic device is seriously affected.
At present, it has been reported that separation of metallic-type and semiconducting-type carbon nanotubes and single chiral selective enrichment of (6,5) SWCNTs can be achieved using poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co-bipyridine ] (PFO-BPy) as a polymer for dispersing carbon nanotubes. However, the PFO-BPy has a larger band gap and the small-diameter carbon nanotubes (such as (6,5) SWNTs) form I-type heterojunction, which is directly used for electronic devices and is not beneficial to improving the performance of the devices.
Disclosure of Invention
In order to solve the problems, the invention finds that the pi-pi acting force of thiophene conjugated polymers, such as PBTTT-C12 and PBTTT-C14 is larger than the pi-pi acting force between PFO-BPy and a carbon nano tube, PFO-BPy/(6,5) PFO-BPy in SWCNT nano composite can be replaced, and thiophene conjugated polymer modified composite materials which do not contain metal carbon nano tubes and only contain single chiral carbon nano tubes, such as PBTTT-C12/(6,5) SWCNT, PBTTT-C14/(6,5) SWCNT and other nano composites, can realize further improvement of organic solar photovoltaic performance of the carbon nano tubes.
The invention provides a method for constructing a thiophene polymer/(6, 5) SWCNT composite material of a single chiral carbon nanotube, which is based on the principle that acting forces between different polymers and the carbon nanotube are different, and PBTTT-C12 and PBTTT-C14 of thiophene polymers are used for replacing PFO-BPy originally on (6,5) SWCNT, so that nanocomposites of PBTTT-C12/(6,5) SWCNT, PBTTT-C14/(6,5) SWCNT and the like only containing the single chiral carbon nanotube are prepared.
The technical scheme of the invention is as follows:
a method of making a single chiral carbon nanotube ((6,5) SWCNT) -thiophene-based polymer composite, the method comprising the steps of:
(1) dispersing PFO polymers and carbon nanotubes in a solvent, and uniformly mixing to obtain a dispersion liquid;
(2) centrifuging the dispersion liquid obtained in the step (1), collecting supernatant, adding the thiophene polymer, and uniformly mixing to form a mixed liquid;
(3) and (3) filtering the mixed solution obtained in the step (2) by using a filter membrane, placing the filtered filter membrane in an organic solvent, taking out the filter membrane after filter residues on the filter membrane are completely dispersed in the organic solvent, and collecting the dispersion.
In one embodiment of the present invention, the PFO-based polymer in step (1) comprises: poly (9, 9-dioctylfluorene-2, 7-diyl) (PFO), poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co-benzothiadiazole ] (PFO-BT), poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co-bipyridine ] (PFO-BPy).
In one embodiment of the present invention, the solvent in step (1) comprises toluene, chlorobenzene, o-xylene, m-xylene, o-dichlorobenzene.
In one embodiment of the present invention, the mass concentration of PFO-BPy in the dispersion in step (1) is 1:1-1: 3 (mg/mL); preferably 1:1 mg/mL.
In one embodiment of the present invention, the mass-to-volume ratio of the carbon nanotubes to the solvent in the dispersion in step (1) is 1 (3-6) (mg/mL).
In one embodiment of the present invention, the mass ratio of the PFO-BPy to the carbon nanotubes in the dispersion in step (1) is 3: (1-6).
In one embodiment of the present invention, the thiophene polymer in step (2) is selected from any one or more of: p3HT (poly (3-hexylthiophen-2, 5-diyl)), PBTTT-C12 (poly [2, 5-bis (3-dodecylthiophen-2-yl) thieno [3,2-b ] thiophene ]), PBTTT-C14 (poly [2, 5-bis (3-tetradecylthiophen-2-yl) thieno [3,2-b ] thiophene ]). Further preferred are PBTTT-C12 and PBTTT-C14.
In one embodiment of the present invention, the mass ratio of the addition amount of the thiophene polymer to the originally dispersed carbon nanotubes in step (2) is 1:1 to 1: 2.
In one embodiment of the present invention, the rotation speed of the centrifugation in the step (2) is 17000rpm, and the centrifugation time is 20 min.
In one embodiment of the present invention, the organic solvent in step (3) is selected from any one or more of the following: toluene, chlorobenzene, o-xylene, m-xylene, o-dichlorobenzene.
In one embodiment of the present invention, the pore size of the filter in step (3) is 0.22. mu.m.
In one embodiment of the invention, a method for polymer exchange enrichment of single chiral (6,5) SWCNTs, comprises the steps of:
(1) adding PFO-BPy and carbon nano tubes into a toluene solvent, mixing and then carrying out water bath ultrasonic dispersion;
(2) performing centrifugal separation, taking supernatant, adding thiophene polymers, and performing water bath ultrasound;
(3) and (3) carrying out suction filtration on the PTFE filter membrane, directly placing the filter membrane loaded with the polymer/carbon nanotube composite material in toluene after filtration for water bath ultrasonic dispersion, and taking out the filter membrane after the polymer/carbon nanotube composite material is completely dispersed in the toluene.
In one embodiment, the concentration of PFO-BPy is 1 mg/mL; the ratio of the mass of the carbon nanotubes to the volume of the solvent is 1:3, i.e., 1mg of carbon nanotubes corresponds to 3mL of solvent.
In one embodiment, in the step (1), it is preferable that: the mass of PFO-BPy was 6mg, the volume of toluene was 6mL, and the mass of carbon nanotubes was 2 mg.
In one embodiment, in the step (1), the water bath ultrasound time is 4 h.
In one embodiment, in the step (2), the mass of the thiophene polymer is 3 mg.
In one embodiment, in the step (2), the time of the water bath ultrasound is 30 min.
In one embodiment, in step (3), the pore size of the filter is 0.22 μm.
In one embodiment, in the step (3), the water bath ultrasound time is 30 min.
The second purpose of the invention is to provide a single chiral carbon nanotube ((6,5) SWCNT) -thiophene polymer composite material by using the method.
The third purpose of the invention is to apply the single chiral carbon nanotube ((6,5) SWCNT) -thiophene polymer composite material to the preparation of electronic devices.
The invention has the beneficial effects that:
the P3HT/(6,5) SWCNT, PBTTT-C12/(6,5) SWCNT and PBTTT-C14/(6,5) SWCNT nanocomposite material containing only one chiral carbon nanotube can be prepared by a simple means without the need of carrying out complex design on the structures of a copolymerization unit and a side chain of a polymer.
Drawings
FIG. 1 is an absorption spectrum of PFO-BPy dispersed carbon nanotubes in toluene.
FIG. 2 is a Raman spectrum of PFO-BPy dispersed carbon nanotubes in toluene.
FIG. 3 is a diagram showing the absorption spectrum of the carbon nanotubes after PFO-BPy replacement by P3 HT; wherein the insets are S of P3HT for replacing (6,5) carbon nanotubes before and after PFO-BPy11Calculating the peak area.
FIG. 4 is a diagram showing the absorption spectrum of carbon nanotubes after PBTTT-C12 replaces PFO-BPy; wherein the insets are S of PBTTT-C12 carbon nanotubes before and after (6,5) replacement of PFO-BPy11Calculating the peak area.
FIG. 5 is a diagram showing the absorption spectrum of the carbon nanotubes after PBTTT-C14 replaces PFO-BPy; wherein the insets are S of PBTTT-C14 carbon nanotubes before and after (6,5) replacement of PFO-BPy11Calculating the peak area.
FIG. 6 is a Raman spectrum of various composites; wherein, FIG. 6a is a Raman spectrum of the carbon nanotube after P3HT replaces PFO-BPy; FIG. 6b is a Raman spectrum of carbon nanotubes after replacement of PFO-BPy by PBTTT-C12; FIG. 6C is a Raman spectrum of carbon nanotubes after PBTTT-C14 replacing PFO-BPy.
FIG. 7 is an absorption spectrum of different composite materials; wherein, figure 7a is a carbon nanotube absorption spectrum of P3HT for removing the redundant polymer by filtration after replacing PFO-BPy, the insert is an absorption spectrum of PFO-BPy dissolved in toluene, figure 7b is a carbon nanotube absorption spectrum of PBTTT-C12 for removing the redundant polymer by filtration after replacing PFO-BPy, and the insert is an absorption spectrum of PFO-BPy dissolved in toluene; FIG. 7C is the absorption spectrum of carbon nanotubes after replacement of PFO-BPy by PBTTT-C14 and filtration to remove excess polymer, the inset is the absorption spectrum of PFO-BPy dissolved in toluene.
FIG. 8-1a is an Atomic Force Microscope (AFM) view of PFO-BPy dispersed carbon nanotubes, and FIG. 8-1b is a height analysis view of PFO-BPy dispersed carbon nanotubes; FIG. 8-2a is the AFM graph of carbon nanotubes after P3HT has replaced PFO-BPy, and FIG. 8-2b is the height analysis graph of carbon nanotubes after P3HT has replaced PFO-BPy; FIG. 8-3a is an AFM graph of carbon nanotubes after PBTTT-C12 replaces PFO-BPy, and FIG. 8-3b is a height analysis graph of carbon nanotubes after PBTTT-C12 replaces PFO-BPy; FIG. 8-4a is AFM graph of carbon nanotubes after PBTTT-C14 replaces PFO-BPy, FIG. 8-4b is height analysis graph of carbon nanotubes after PBTTT-C14 replaces PFO-BPy, and the inset shows absorption graph of PFO-BPy dissolved in toluene.
Fig. 9 is a raman spectrum of P3HT dispersed carbon nanotubes alone.
Fig. 10 is an absorption spectrum of P3HT dispersed carbon nanotubes alone.
FIG. 11 is a Raman spectrum of PBTTT-C12 dispersed carbon nanotubes alone.
FIG. 12 is the absorption spectrum of PBTTT-C12 dispersed carbon nanotubes alone.
FIG. 13 is a Raman spectrum of PBTTT-C14 dispersed carbon nanotubes alone.
FIG. 14 is the absorption spectrum of PBTTT-C14 dispersed carbon nanotubes alone.
FIG. 15 is a graph of absorption spectra for different carbon nanotube materials; wherein, fig. 15a is a absorption spectrum of the P3HT single dispersed carbon nanotubes after PFO-BPy is added; FIG. 15b is a diagram showing the absorption spectrum of PBTTT-C12 single dispersed carbon nanotubes after PFO-BPy addition; FIG. 15C is the absorption spectrum of PBTTT-C14 dispersed carbon nanotubes after PFO-BPy addition.
Detailed Description
The carbon nanotubes used in the present invention were purchased from Sigma-Aldrich, and the polymers PFO-BPy, P3HT, PBTTT-C12, PBTTT-C14 were purchased from Taiwan optical science and technology, China.
Example 1
The method for constructing the thiophene polymer/(6, 5) SWCNT composite material of the single chiral carbon nanotube comprises the following steps:
(1) preparation of PFO-BPy/(6,5) SWCNT nanocomposites: adding 6mg of PFO-BPy and 2mg of carbon nano tubes into 6mL of toluene solvent, and carrying out water bath ultrasound for 4h to obtain a mixed system;
(2) preparing P3HT/(6,5) SWCNT, PBTTT-C12/(6,5) SWCNT, PBTTT-C14/(6,5) SWCNT nano-complex: centrifuging the mixed system obtained in the step (1) for 20min at the rotating speed of 17000rpm, and taking the centrifuged supernatant; adding 3mg of P3HT or PBTTT-C12 or PBTTT-C14 into 6mL of supernatant, and performing water bath ultrasound for 30 min;
(3) performing vacuum filtration on a PTFE filter membrane with the pore diameter of 0.22 μm; and re-dispersing the filtered filter cake in 6mL of toluene solvent, and collecting the dispersion liquid to obtain the thiophene polymer/(6, 5) SWCNT composite material.
Structural characterization of the composite:
1. performing ultraviolet-visible-near infrared absorption spectrum test on the carbon nano tube after PFO-BPy dispersion:
and (3) testing an absorption spectrum of the dispersed sample by using a UV-3600plus ultraviolet-visible near-infrared spectrophotometer. The absorption spectrum is shown in FIG. 1, where S is present in the carbon nanotube11Almost only the absorption peak of (6,5) SWCNT in the characteristic peak area indicates that the PFO-BPy has single chiral selectivity to (6,5) SWCNT. Meanwhile, no obvious peak appears in the characteristic peak area of the 400-500nm metal type carbon nano tube, which indicates that the PFO-BPy dispersed carbon nano tube does not contain metal type.
2. Performing Raman spectrum test on the PFO-BPy single dispersed carbon nano-tubes:
raman spectroscopy was performed using a confocal microscopy raman spectrometer and the resulting raman spectrum is shown in fig. 2. In FIG. 2, the characteristic peak area of the metal-type carbon nanotube is 150-240cm-1Almost no obvious Raman peak appears, which indicates that the PFO-BPy dispersed carbon nano-tube has strong selectivity to the semiconductor type carbon nano-tube.
3. Performing ultraviolet-visible-near infrared absorption spectrum test on the carbon nanotubes after PBTTT-C12, PBTTT-C14 and P3HT replace PFO-BPy:
and testing the absorption spectrum of the sample after replacing the PFO-BPy by PBTTT-C12, PBTTT-C14 and P3HT by using a UV-3600plus ultraviolet visible near infrared spectrophotometer. The absorption spectra are shown in FIGS. 3-5. As can be seen from FIGS. 3, 4, 5, after adding P3HT (or PBTTT-C12, PBTTT-C14) to a sample of PFO-BPy dispersed carbon nanotubes and sonicating, (6,5) S of SWCNT11The absorption peak positions are red-shifted from original 999nm to 1015nm, 1010nm and 1012nm respectively, and the positions are dispersed with P3HT, PBTTT-C12 and PBTTT-C14 separately (6,5) S of SWCNT11The positions of absorption peaks are the same, which shows that P3HT, PBTTT-C12 and PBTTT-C14 successfully replace the polymer PFO-BPy on the surface of the original carbon nanotube to form a new nanocomposite P3HT/(6,5) SWCNT, PBTTT-C12/(6,5) SWCNT and PBTTT-C14/(6,5) SWCNT.
Meanwhile, S of PBTTT-C12/(6,5) SWCNT, PBTTT-C14/(6,5) SWCNT in FIGS. 4 and 511The absorption peak intensity was hardly changed compared to PFO-BPy/(6,5) SWCNT, indicating that no loss of (6,5) SWCNT occurred during the displacement. However, in FIG. 3, after P3HT replaced PFO-BPy in PFO-BPy/(6,5) SWCNT, the absorption peak of the formed P3HT/(6,5) SWCNT is obviously reduced, and it can be seen that carbon nanotube agglomeration occurs during the P3HT replacement of PFO-BPy, resulting in the loss of a certain amount of (6,5) SWCNT.
Carbon content determination before and after PBTTT-C12/(6,5) SWCNT, PBTTT-C14/(6,5) SWCNT, P3HT/(6,5) SWCNT in FIGS. 3-5: s of carbon nanotubes before and after the exchange by using Origin mapping software11Integration of peaks to calculate the S of (6,5) carbon nanotubes after replacement of the original PFO-BPy by each thiophene Polymer11The ratio of the area of the peak to the area of the peak before no substitution is the content after the substitution relative to the content before the substitution. With specific values being obtained by calculating the peak areas before and after the substitution, which can be seen in the inset in fig. 3 a-c.
As a result, it was found that the carbon nanotube content after PBTTT-C14 substitution of (6,5) SWCNT was 95% of that before substitution; the carbon nanotube content after PBTTT-C12 replacement of (6,5) SWCNT is 97% of that before replacement; whereas the carbon nanotube content after the P3HT replacement of the (6,5) SWCNTs was only 83% before the replacement.
4. The Raman spectrum test is carried out on the carbon nanotubes after P3HT, PBTTT-C12 and PBTTT-C14 replace PFO-BPy:
raman spectroscopy was performed using DXR2xi confocal microscopy raman spectroscopy, and the resulting raman spectra are shown in fig. 6a, 6b and 6 c. In FIGS. 6a, 6b and 6c, the characteristic peak area of the metallic carbon nanotube is 150-240cm-1No obvious Raman peak appears, which indicates that P3HT/(6,5) SWCNT, PBTTT-C12/(6,5) SWCNT and PBTTT-C14/(6,5) SWCNT nanocomposites formed after P3HT, PBTTT-C12 and PBTTT-C14 replace PFO-BPy do not contain metallic carbon nanotubes.
5. Samples of P3HT (or PBTTT-C12, PBTTT-C14) after replacement of the PFO-BPy and filtration to remove excess polymer were subjected to UV-VIS-NIR absorption Spectroscopy:
UV-visible-near infrared absorption spectroscopy was performed on samples of P3HT, PBTTT-C12, PBTTT-C14 displaced PFO-BPy and filtered to remove excess polymer using a UV-3600plus UV-visible near infrared spectrophotometer, the results are shown in FIGS. 7a, 7b and 7C. The insets of figures 7a, 7b and 7C show the absorption peak of PFO-BPy at 360nm, whereas in the figures of figures 7a, 7b and 7C the characteristic absorption peak of PFO-BPy is completely disappeared, indicating that PFO-BPy is completely replaced by P3HT, PBTTT-C12, PBTTT-C14, thus verifying the high purity of P3HT/(6,5) SWCNT, PBTTT-C12/(6,5) SWCNT, PBTTT-C14/(6,5) SWCNT nanocomposites.
6. AFM tests were carried out on samples which had been filtered to remove excess polymer after P3HT (or PBTTT-C12, PBTTT-C14) had replaced the PFO-BPy:
PFO-BPy/(6,5) SWNTs and P3HT, PBTTT-C12, PBTTT-C14 carbon nanotubes that were filtered to remove excess polymer after PFO-BPy replacement were topographically characterized using a Multimode 8 atomic force microscope, as shown in FIGS. 8-1a, 8-2a, 8-3a, and 8-4 a. FIGS. 8-1b, 8-2b and 8-3b, 8-4b are height views of carbon nanotubes. From FIGS. 8-1b, 8-2b, 8-3b and 8-4b, it can be seen that the heights of the PFO-BPy/(6,5) SWCNT, P3HT/(6,5) SWCNT, PBTTT-C12/(6,5) SWCNT and PBTTT-C14/(6,5) SWCNT are 1.75nm, 1.8nm, 2.0nm and 1.7nm, respectively, and the differences in the heights are almost the same, which indicates that the substituted carbon nanotubes are single-layer polymer-wrapped instead of two-polymer double-layer wrapped structures, and further indicates that P3HT, PBTTT-C12 and PBTTT-C14 replace PFO-BPy in PFO-SWBPy/(6, 5) CNT.
Comparative example 1
P3HT direct dispersion of carbon nanotubes:
6mg of P3HT and 2mg of carbon nano tube are added into 6mL of chlorobenzene solvent, and water bath ultrasound is carried out for 4 h; centrifuging at 17000rpm for 20min, and collecting supernatant to obtain P3HT directly dispersed carbon nanotube composite material.
Raman spectroscopy was performed on P3HT carbon nanotubes dispersed alone:
raman spectroscopy was performed using DXR2xi confocal microscopy raman spectroscopy, and the resulting raman spectrum is shown in fig. 9. In FIG. 9, the characteristic peak area of the metal-type carbon nanotube is 150-240cm-1AppearThe obvious raman peak indicates that the P3HT carbon nanotubes dispersed alone will contain metallic carbon nanotubes.
The ultraviolet-visible-near infrared absorption spectrum test is carried out on the carbon nano tube dispersed by the P3HT alone:
a UV-3600plus ultraviolet-visible near-infrared spectrophotometer is used for testing the absorption spectrum of a sample with a slit width of 1nm, wherein the sample is prepared by singly dispersing the carbon nanotubes of P3HT, PBTTT-C12 and PBTTT-C14. The absorption spectrum is shown in FIG. 10. As can be seen from FIG. 10, S in the carbon nanotube11In the characteristic absorption peak area, a plurality of chiral carbon nanotubes mainly including (6,5), (7,6), (9,1) and the like appear, which indicates that the P3HT directly dispersing the carbon nanotubes can not realize single chiral selection of the (6,5) SWCNT. Also, S of P3 HT-encapsulated (6,5) SWCNT can be seen11The characteristic absorption peak position occurs at 1015 nm.
Comparative example 2
PBTTT-C12 direct dispersion of carbon nanotubes:
adding 6mg of PBTTT-C12 and 2mg of carbon nano tubes into 6mL of toluene solvent, and carrying out water bath ultrasound for 4 h; centrifuging at 17000rpm for 20min, and collecting supernatant.
Raman spectroscopy was performed on PBTTT-C12 carbon nanotubes dispersed alone:
raman spectroscopy was performed using a DXR2xi confocal microscopy raman spectrometer and the resulting raman spectrum is shown in fig. 11. In FIG. 11, the characteristic peak area of the metal-type carbon nanotube is 150-240cm-1Obvious Raman peaks appear, which indicates that the carbon nanotubes dispersed by PBTTT-C12 alone contain metallic carbon nanotubes.
The ultraviolet-visible-near infrared absorption spectrum test is carried out on the carbon nano tube singly dispersed by the PBTTT-C12:
the absorption spectrum of the carbon nanotube sample dispersed solely by PBTTT-C12 was measured by UV-3600plus UV-visible near-IR spectrophotometer, and the absorption spectrum is shown in FIG. 12. As can be seen from FIG. 12, S in the carbon nanotube11The characteristic absorption peak area has a plurality of chiral carbon nanotubes, mainly including (6,5), (7,6), (8,3), (9,1), and the like, which indicates that PBTTT-C12 can not be used for dispersing carbon nanotubes directlyNow single chiral selection for (6,5) SWCNTs. S of PBTTT-C12-wrapped (6,5) SWCNT11The characteristic absorption peak position occurs at 1012 nm.
Comparative example 3
PBTTT-C14 direct dispersion of carbon nanotubes:
adding 6mg of PBTTT-C14 and 2mg of carbon nano tubes into 6mL of toluene solvent, and carrying out water bath ultrasound for 4 h; centrifuging at 17000rpm for 20min, and collecting supernatant.
The Raman spectrum of the PBTTT-C14 single dispersed carbon nanotubes was tested:
raman spectroscopy was performed using DXR2xi confocal microscopy raman spectroscopy, and the resulting raman spectrum is shown in fig. 13. In FIG. 13, the characteristic peak area of the metal-type carbon nanotube is 150-240cm-1Obvious Raman peaks appear in the PBTTT-C14, and the carbon nanotubes dispersed alone contain metallic carbon nanotubes.
The ultraviolet-visible-near infrared absorption spectrum test is carried out on the carbon nano tube singly dispersed by the PBTTT-C12:
the sample of PBTTT-C14 dispersed carbon nanotubes alone was subjected to absorption spectrum measurement using UV-3600plus UV-visible near infrared spectrophotometer, and the absorption spectrum is shown in FIG. 14. As can be seen from FIG. 14, S in the carbon nanotube11The characteristic absorption peak area shows carbon nanotubes with various chiralities, mainly including (6,5), (7,6), (8,3), and (9,1), etc., which indicates that when PBTTT-C14 disperses the carbon nanotubes alone, the single chirality selection of (6,5) SWCNT cannot be realized. S of PBTTT-C14-wrapped (6,5) SWCNT11The position of the characteristic absorption peak appears at 1012 nm.
Comparative example 4
(1) PBTTT-C12, PBTTT-C14 dispersed carbon nanotubes in toluene: adding 6mg of PBTTT-C12 (or PBTTT-C14) and 2mg of carbon nano tubes into 6mL of toluene solvent (or adding 6mg of P3HT and 2mg of carbon nano tubes into 6mL of chlorobenzene solvent), and carrying out water bath ultrasound for 4 h; centrifuging at 17000rpm for 20min, and collecting supernatant;
(2) 6mg of PFO-BPy was added to the above PPBTTT-C12 (or PBTTT-C14, P3HT) dispersed carbon nanotube sample, and subjected to water bath sonication for 30 min.
The sample of P3HT (or PBTTT-C12, PBTTT-C14) dispersed carbon nanotubes added with PFO-BPy was subjected to UV-visible-near infrared absorption spectroscopy:
a sample in which P3HT (or PBTTT-C12, PBTTT-C14) with PFO-BPy added was separately dispersed with a UV-3600plus UV-visible near infrared spectrophotometer to carry out the absorption spectrum test, and the absorption spectrum is shown in FIGS. 15a, 15b, 15C. As can be seen from FIGS. 15a, 15b and 15C, S of (6,5) SWCNT in the dispersed carbon nanotube samples of P3HT, PBTTT-C12 and PBTTT-C14 before and after PFO-BPy addition11The characteristic absorption peak position does not move to 999nm when the PFO-BPy wraps the carbon nano tube, which indicates that the PFO-BPy cannot replace P3HT, PBTTT-C12 and PBTTT-C14 on the surface of the carbon nano tube.
As can be seen from the comparison of example 1 with comparative examples 1, 2, 3 and 4, the method of example 1 is based on the principle that different polymers and carbon nanotubes have different acting forces, and P3HT, PBTTT-C12 and PBTTT-C14 are used to replace PFO-BPy in PFO-BPy/(6,5) SWCNT to successfully prepare P3HT/(6,5) SWCNT, TTPBT-C12/(6, 5) SWCNT and PBTTT-C14/(6,5) SWCNT nanocomposites containing high-purity single chiral carbon nanotubes.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (8)

1. A method for preparing a single chiral carbon nanotube-thiophene polymer composite, comprising the steps of:
(1) dispersing PFO polymers and carbon nanotubes in a solvent, and uniformly mixing to obtain a dispersion liquid;
(2) centrifuging the dispersion liquid obtained in the step (1), collecting supernatant, adding the thiophene polymer, and uniformly mixing to form a mixed liquid;
(3) filtering the mixed solution obtained in the step (2) by using a filter membrane, placing the filtered filter membrane in an organic solvent, taking out the filter membrane after filter residues on the filter membrane are completely dispersed in the organic solvent, and collecting the dispersion liquid;
the PFO polymer in the step (1) comprises: PFO, PFO-BT, PFO-BPy;
the thiophene polymer in the step (2) is selected from any one or more of the following: p3HT, PBTTT-C12 and PBTTT-C14.
2. The method according to claim 1, wherein the mass concentration of the PFO-based polymer in the dispersion in step (1) is mg: mL is 1:1-1: 3.
3. the method according to claim 1, wherein the mass to volume ratio of carbon nanotubes to solvent in the dispersion in step (1) is mg: mL is 1 (3-6).
4. The method according to claim 1, wherein the mass ratio of PFO-BPy to carbon nanotubes in the dispersion in step (1) is 3: (1-6).
5. The method according to claim 1, wherein the mass ratio of the thiophene polymer in step (2) to the carbon nanotubes in step (1) is 1:1 to 1: 2.
6. The method according to any one of claims 1 to 5, wherein the organic solvent in step (3) is selected from any one or more of: toluene, chlorobenzene, o-xylene, m-xylene, o-dichlorobenzene.
7. The single chiral carbon nanotube-thiophene polymer composite prepared by the method of any one of claims 1-6.
8. The use of the single chiral carbon nanotube-thiophene polymer composite of claim 7 in the field of electronic device fabrication.
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