CN105329881A - Method for separating single-walled carbon nanotubes of different sizes by utilizing centrifugal speed variation method - Google Patents
Method for separating single-walled carbon nanotubes of different sizes by utilizing centrifugal speed variation method Download PDFInfo
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- CN105329881A CN105329881A CN201510828967.3A CN201510828967A CN105329881A CN 105329881 A CN105329881 A CN 105329881A CN 201510828967 A CN201510828967 A CN 201510828967A CN 105329881 A CN105329881 A CN 105329881A
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Abstract
The invention provides a method for separating single-walled carbon nanotubes (SWCNTs) of different sizes. The method comprises the steps: under the cooperation of ultrasonic wave and a polymer as a dispersion aid matter, dispersing the SWCNTs in an organic solvent, and then centrifuging the SWCNTs to separate small-size SWCNTs/polymer solution from precipitates (large-size SWCNTs/polymer), thereby obtaining a compound solution formed by the small-size SWCNTs; removing excess polymer by using a THF solvent to wash for many times; acidizing the compound by utilizing trifluoroacetic acid to separate the SWCNTs of different sizes; under the neutralization function of Na2CO3 saturated solution, deionized water is utilized to remove generated salt, thereby obtaining the excess polymer and small content of SWCNTs with different sizes and different responsibility. The method for separating the SWCNTs of different sizes has the advantages that operations are simple and convenient, devices are low-cost, low-cost separation of a large number of SWCNTs is easy to achieve, and the method is an effective way for separating the SWCNTs. The accompanying diagrams mainly show dissolution of the polymer in the organic solvent, successful compound of the polymer and the SWCNTs, and a separation situation of the acidized SWCNTs.
Description
Technical field
The present invention relates to a kind of method of change centrifugation rate method separation different size Single Walled Carbon Nanotube, is a kind of method it be separated according to different size by polymer-modified Single Walled Carbon Nanotube and with the easy operation such as centrifugal.
Background technology
Single Walled Carbon Nanotube has good electric property and the incomparable excellent properties of traditional fibre, such as, low density, high tensile, high elastic coefficient, excellent snappiness, good thermostability and chemical stability, the excellent properties of carbon nanotube has evoked many chemists in worldwide, physicist and the great interest of material scholar, starts the upsurge of one carbon nanotube research.
In recent years, by Single Walled Carbon Nanotube (SWCNTs) the technology development of various method separation different size, become the study hotspot in current SWCNTs practical application, but, under modification condition by dispersion body aids such as polymkeric substance, obtain the SWCNTs of different size and the research of its chemical property aspect rarely has report, therefore, after compound, be separated into one of new means promoting SWCNTs chemical property.
The present invention utilizes polymer-modified effect to be successfully compounded with SWCNTs/ polymer complex and lock out operation after carrying out compound, has focused on the performance variation of different size SWCNTs, has ultimately provided the SWCNTs with better electric property corresponding size.
Summary of the invention
Poly-[the 2-aminopyrimidine-9 of the present invention, 9-dioctyl fluorene] be dispersion body aid, adopt the means such as ultrasonic, centrifugal, filtration, successful be separated different size SWCNTs and adopt the means of testing such as UV-vis, Raman, TG, CV to study it, inquire into its performance variation and confirm the SWCNTs size that best electric property responds.
Goal of the invention
An object of the present invention is to provide a kind of polymkeric substance by SWCNTs degree of scatter and shows the modification of this polymkeric substance.
Two of object of the present invention is to provide a kind of method of separation different size SWCNTs.Although it is more to be separated the research of SWCNTs size aspect, under the modification condition by dispersion body aid, obtain the different SWCNTs of size and the research of its chemical property aspect rarely has report.So this research has potential application prospect.
Three of object of the present invention is to provide the corresponding size of the SWCNTs with better chemical property.
Accompanying drawing explanation
Fig. 1: the ultraviolet-visible light spectrogram of mixture;
Fig. 2: the Single Walled Carbon Nanotube thermogravimetric analysis figure departed from when pure Single Walled Carbon Nanotube, polymkeric substance, mixture and centrifugation rate 500rpm/min;
Fig. 3: the Raman spectrogram (a) of the Single Walled Carbon Nanotube departed from when pure Single Walled Carbon Nanotube, mixture and centrifugation rate 5000rpm/min and Raman spectrum expanded view (b);
Fig. 4: SEM figure (amplification range is 1um, 500nm, 200nm) of the Single Walled Carbon Nanotube (d – f) departed from when pure Single Walled Carbon Nanotube (a – c) and centrifugation rate 5000rpm/min;
Fig. 5: Single Walled Carbon Nanotube (b-d) TEM departed from when pure Single Walled Carbon Nanotube (a) and centrifugation rate 500rpm/min, 3000rpm/min, 5000rpm/min schemes.
Embodiment
Below in conjunction with accompanying drawing, the present invention is elaborated:
(1) synthesis of body aid is disperseed
In 100ml polymerization bottle, pass into argon gas, under stirring, add 2-amino-4,6-bis-iodine pyrimidine (0.4160mmol successively, 144.31mg), 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxaborinate-2-base)-9,9-dioctyl fluorene (0.4160mmol, 267.31mg), cesium carbonate Cs
2cO
3(2.08mmol, 676.0mg), then add 20.8mLDME and 10.4ml deionized water, pass into argon gas 15min under induction stirring, add zero valent palladium catalyst Pd (PPh
3)
4(0.0208mmol; 23.9mg); under argon shield; reflux reaction system at 58-60 DEG C 48h; reactant cool to room temperature, resultant uses methyl alcohol, distilled water wash successively, chloroform/methanol recrystallization 3 times, again with 50 DEG C of vacuum-drying 48h after methanol wash; can obtain 138mg pale yellow powder thing, yield is 69%.
(2) by 3:2:1 ratio, dissolve completely in 20mlTHF solvent with 30mg polymkeric substance respectively, this liquid centrifugal (8000rpm), get supernatant liquid and wherein add 10mgHipcoSWCNT, ultrasonic 1h, obtain the three bottles of polymkeric substance/SWCNTs complex solution of better dispersion, the successful preparation of mixture as shown in Figure 1.
(3) these three bottles of complex solutions, centrifugal 20min under room temperature, rotating speed is respectively 500,3000,5000rpm/min, obtain the different mixture dispersion liquid of supernatant liquid and it takes out from top portion batch.
(4) each upper liquid is filtered respectively by the teflon membrane filter of aperture 200nm, add 25mlTHF stirring solvent washing 4h successively to refilter, this operation repetition 5 times, substantially that removed excess polymer, that granular size is different mixture, Fig. 2 represents polymkeric substance and SWCNTs success compound, and the polymer content in mixture is 62.7%.
(5) 1.2ml trifluoroacetic acid to add in above-mentioned mixture and it stirs 30min respectively, by this operation, SWCNTs is departed from from mixture, obtain 500 respectively, 3000,5000rpm/min from the SWCNTs of speed process, as shown in Figure 3, the successful disengaging of SWCNTs.
(6) add 2mlTHF respectively in the different SWCNTs obtained from speed and filter with teflon membrane filter, using Na successively
2cO
3saturated solution (neutralization) and deionized water filter (going out to desalt), obtain granular size different SWCNTs(Fig. 4 and Fig. 5).
Claims (5)
1. the present invention is a kind of method of change centrifugation rate method separation different size Single Walled Carbon Nanotube, and it is characterized in that, described method comprises:
1). synthesize the polymkeric substance as dispersion body aid, synthetic route is as follows:
2). dispersion body aid is put into tetrahydrofuran (THF) (THF) solvent, obtain the polymers soln of CL through excusing from death.
3). raw material Single Walled Carbon Nanotube (SWCNTs) is put into resulting polymers solution, by ultrasonic acquisition homodisperse SWCNTs/ polymkeric substance (all saying mixture below) mixed solution.
4). by the mixed solution of ultrasonic gained, it is 25 DEG C in temperature, rotating speed is respectively 500,3000,5000rpm/min, time is centrifugal under the condition of 20 minutes, obtain a kind of mixture dispersion liquid according to particle size dispersion, taken out from top portion batch by the dispersion liquid obtained, for obtaining different size, nano particle of different nature is laid a solid foundation.
5). filtered by the supernatant liquor teflon membrane filter obtained, add 25mlTHF successively and filter, this operation repetition 5 times, is not comprised the mixture of excess polymer.
6). trifluoroacetic acid is added in above-mentioned mixture, through this operation, SWCNTs is departed from from mixture, obtain the SWCNTs. processed
7). SWCNTs teflon membrane filter obtained above is filtered, uses Na successively
2cO
3saturated solution and THF filter, the processed SWCNTs with different electrical characteristic of the nano particle that obtains varying in size.
2. the method for a kind of change centrifugation rate method separation different size Single Walled Carbon Nanotube according to claims 1, its characteristic feature is: the diameter of SWCNTs is less, that disperses in dispersion body aid solution is better, and this result shows that polymkeric substance and the less SWCNTs of diameter are easier to form dispersed soluble complex preferably.
3. the method for a kind of change centrifugation rate method separation different size Single Walled Carbon Nanotube according to claims 1, its characteristic feature is: the lock out operation that the present invention utilizes is easy, experiment required time brief (ultrasonic disperse time used is 1h, and centrifugation time is 20min).
4. the method for a kind of change centrifugation rate method separation different size Single Walled Carbon Nanotube according to claims 1, its characteristic feature is: by removing the mixture be centrifugation down, obtain comprising the mixture that the size of SWCNTs is less, finally obtain the processed SWCNTs that size is different with response performance.
5. the method for a kind of change centrifugation rate method separation different size Single Walled Carbon Nanotube according to claims 1, its characteristic feature is: by present method, can draw the conclusion that the less chemical property of diameter is better.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017215358A1 (en) * | 2016-06-12 | 2017-12-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Selective separation method for semiconducting carbon nanotubes and separating reagent therefor |
Citations (4)
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|---|---|---|---|---|
| CA2283502A1 (en) * | 1997-03-07 | 1998-09-11 | William Marsh Rice University | Carbon fibers formed from singlewall carbon nanotubes |
| CN101830454A (en) * | 2009-03-10 | 2010-09-15 | 国家纳米科学中心 | Selective separation method of diameter of single-wall carbon nano tube |
| CN103112839A (en) * | 2013-02-22 | 2013-05-22 | 复旦大学 | Separation method of single chiral single-walled carbon nanotubes applied to field effect transistor |
| CN103112840A (en) * | 2012-12-24 | 2013-05-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Selective separation method of semiconductor CNT (Carbon Nano Tube) in commercial large pipe diameter CNT and application of selective separation method |
-
2015
- 2015-11-25 CN CN201510828967.3A patent/CN105329881B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2283502A1 (en) * | 1997-03-07 | 1998-09-11 | William Marsh Rice University | Carbon fibers formed from singlewall carbon nanotubes |
| CN101830454A (en) * | 2009-03-10 | 2010-09-15 | 国家纳米科学中心 | Selective separation method of diameter of single-wall carbon nano tube |
| CN103112840A (en) * | 2012-12-24 | 2013-05-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Selective separation method of semiconductor CNT (Carbon Nano Tube) in commercial large pipe diameter CNT and application of selective separation method |
| CN103112839A (en) * | 2013-02-22 | 2013-05-22 | 复旦大学 | Separation method of single chiral single-walled carbon nanotubes applied to field effect transistor |
Non-Patent Citations (3)
| Title |
|---|
| FUMING CHEN ET AL.,: "Toward the Extraction of Single Species of Single-Walled Carbon Nanotubes Using Fluorene-Based Polymers", 《NANO LETTERS》 * |
| 刘丹等，: "单壁碳纳米管的分离方法", 《科学通报》 * |
| 赛亚尔•斯迪克等，: "含嘧 啶与芴 结构单元 共聚物 的 合成及性能", 《功能高分子学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017215358A1 (en) * | 2016-06-12 | 2017-12-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Selective separation method for semiconducting carbon nanotubes and separating reagent therefor |
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