CN103407983A - Separation method for single-walled carbon nano-tubes with special chirality - Google Patents
Separation method for single-walled carbon nano-tubes with special chirality Download PDFInfo
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- CN103407983A CN103407983A CN2013102981553A CN201310298155A CN103407983A CN 103407983 A CN103407983 A CN 103407983A CN 2013102981553 A CN2013102981553 A CN 2013102981553A CN 201310298155 A CN201310298155 A CN 201310298155A CN 103407983 A CN103407983 A CN 103407983A
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- walled carbon
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Abstract
The invention relates to a separation method for single-walled carbon nano-tubes with special chirality. According to the separation method, interaction of an organic solvent and ultrasonic wave is adopted to separate tube bundles of single-walled carbon nano-tubes into the single carbon nano-tube, centrifugation is performed to separate the carbon nano-tubes dispersed in the solvent from the precipitate to obtain a single-walled carbon nano-tube solution, an organic amine is added to the solution, the organic amine and the dispersed single carbon nano-tube are subjected to absorption through an ultrasonic effect, the metallic single-walled carbon nano-tubes have strong amine absorption ability, and are stable in the solution, high-speed centrifugation is performed to remove the semiconducting carbon nano-tubes so as to obtain a metallic carbon nano-tube solution, a 0.22 mum microporous filtration membrane is adopted to filter the supernatant, and ethanol is adopted to wash the organic amine absorbed on the carbon nano-tubes to obtain the metallic carbon tubes. According to the present invention, the ultrasound-centrifugation process is only required to be repeated twice to obtain the metallic carbon tubes so as to break through the bottleneck of the original separation method, achieve a purpose of large-scale separation of metallic carbon tubes, and achieve the magnitude of g or more.
Description
Technical field
The present invention relates to a kind of separation method with Single Walled Carbon Nanotube of particular chiral.Particularly from the solution of Single Walled Carbon Nanotube, isolating the method for the metallic single-wall carbon nano-tube with specific electrical properties.
Background technology
Its structure of Single Walled Carbon Nanotube, close to desirable soccerballene, is the same cylinder sealing that individual layer is arranged between two ends, and synthetic carbon nanotubes in 1991 are exactly the carbon nanotube of single wall.There is the structure of three types in Single Walled Carbon Nanotube at present, is divided into the handrail-type carbon nanotube, Zigzag carbon nanotubes and Chiral carbon nanotube.Armchair is metallic entirely, and prionodont and spiral type have 1/3 to be metallic carbon nanotube.The formation of the carbon nanotube of these types depends on the hexagonal lattice two-dimension graphite sheet of carbon atom is how " curling " forms columnar.
The character of carbon nanotube and its structure are closely related.Because the structure of carbon nanotube is identical with the laminated structure of graphite, so have good electric property.Its conductivity of theoretical prediction depends on the helix angle of its caliber and tube wall.Work as CNT
SCaliber while being greater than 6mm, conductivity just descends; When caliber is less than 6mm, CNT
SCan be seen as the One-dimensional Quantum wire with excellent conductive performance.
Carbon nanotube has unique electrical properties, and this is that the effective motion of electronics can only be along the axial direction due of carbon nanotube in the mono-layer graphite sheet due to due to the quantum confinement of electronics, and radial motion is restricted, so their wave vector is vertically.Calculating shows: the electrical properties of Single Walled Carbon Nanotube is relevant with its chiral vector, and the constant m in chiral vector and n meet
|?m?-?n?|?=?3?k? (?k?=?0?,1?,2?·?·?·)
The time, carbon nanotube is metallic, the Single Walled Carbon Nanotube of other type is semiconductive.For the direction of n=m, carbon nanotube shows good electroconductibility, and specific conductivity can reach 10,000 times of copper usually.Therefore, if metallic from Single Walled Carbon Nanotube, isolating, can further improve its specific conductivity.
The SWNTs that commercialization is at present produced is the mixture of M-SWNTs and S-SWNTs, and wherein the former accounts for 33%, and the latter accounts for 67%.Separate and caused concern widely, and become one of focus of carbon nanotube research.The researchist will find the method for high efficiency separation M-SWNTs and S-SWNTs on the one hand, also will utilize on the other hand the difference of two class SWNTs on the performances such as light, electricity and magnetic, and development detection method easily and effectively characterizes the effect of separating with detection means.Existing SWNTs separation method press separation agent whether with carbon pipe generation chemical reaction, can be divided into fractionation and physical partition method.Fractionation is mainly to reach the purpose of separating by with M-SWNTs, optionally chemical reaction occurring.H for example
2O
2, O
SO
4And HNO
3/ H
2SO
4Deng can selective oxidation M-SWNTs making it water-soluble and remove; Diazonium salt only reacts with M-SWNTs, makes its rate of migration in electrophoresis liquid larger than S-SWNTs, namely separable through electrophoresis.Newest research results shows, available gas phase SO under hot conditions
3Etching S-SWNTs and obtain M-SWNTs.Physical partition method can produce permanent damage to a certain class SWNTs wherein according to whether can be divided into null method and non-covalent partition method.Wherein, null method is to utilize M-SWNTs to separate with S-SWNTs photostabilization or stable on heating difference, as large pulsed current ablation and radiation-selective null method; And non-covalent law of segregation is mainly to utilize the difference of secondary valence bond reactive force between separation agent and two class SWNTs to separate.Fractionation can change the electronic structure of SWNTs and make its degradation, and often take and consume M-SWNTs and be cost; Physics null method required equipment costliness, also need to consume M-SWNTs, causes waste; And non-covalent partition method can not destroyed the electronic structure of two kinds of SWNTs, can realize reversible separation, therefore become class methods of current most study.
Summary of the invention
The purpose of this invention is to provide a kind of easy method, directly from the separation method of the Single Walled Carbon Nanotube with particular chiral of isolating metallic single-wall carbon nano-tube the solution of the Single Walled Carbon Nanotube without modification.
The separation method of the Single Walled Carbon Nanotube with particular chiral that the present invention proposes, concrete steps are as follows:
(1) preparation of Single Walled Carbon Nanotube solution: Single Walled Carbon Nanotube is dissolved in organic solvent, and ultrasonic concussion 4 ~ 12h, be separated into single carbon nanotube by the tube bank of Single Walled Carbon Nanotube; High speed centrifugation 1 ~ 2h again, the carbon nanotube that makes to be dispersed in organic solvent separates with throw out, obtains the solution of Single Walled Carbon Nanotube;
(2) preparation of metallic single-wall carbon nano-tube solution: in step (1), add the 3.0-5.0M organic amine in resulting solution, ultrasonic concussion 2 ~ 3h, make it and be dispersed into single carbon nanotube and adsorb; The carbon nanotube of the semiconductive that will precipitate by high speed centrifugation 12 ~ 24h is removed, and obtains the solution of metallic carbon nanotubes;
(3) preparation of metallic single-wall carbon nano-tube: by the solution of gained metallic carbon nanotubes in step (2) with 0.22 micron filtering with microporous membrane, and with ethanol, wash away the organic amine be adsorbed on carbon nanotube, after drying, obtain the product of Concentration of Gold attribute carbon pipe.
The present invention can adopt any organic solvent to prepare the dispersion liquid of carbon nanotube, and it is good preferably to use the solvability of organic amine, and carbon nanotube is had to the solvent of better dispersive ability.The solvent that the present invention uses is the mixed solvent of tetrahydrofuran (THF) and normal hexane.
Centrifugal impurity and the decolorizing carbon that makes to be dissolved in solvent by the short period of time precipitates, and obtains pure carbon pipe solution to be separated.After step (1) finishes, the gained Single Walled Carbon Nanotube is reacted to 20min at 70 ℃ of temperature, to improve carbon nanotube concentration, be conducive to improve separation efficiency.
In the present invention, the organic amine used in step (2) can be octylame, Tri N-Propyl Amine, Isopropylamine or the amine aqueous solution that is mixed in proportion.
In the present invention, the high speed centrifugation rotating speed described in step (1) and step (2) is 15000rpm.
Beneficial effect of the present invention is:
1. method is simple, only needs twice ultrasonic-centrifugal process of repetition just can obtain the product of Concentration of Gold attribute carbon pipe.
2. break through the bottleneck of original separation method, reach the purpose of extensive separating metallic carbon pipe, can reach the above order of magnitude of gram and gram.
3. when obtaining metallicity carbon pipe, be expected to obtain simultaneously semiconductive carbon pipe.
The accompanying drawing explanation
Fig. 1 is the ultraviolet-visible-near-infrared absorption spectrum of carbon pipe solution to be separated.Can see the transition of electron of first band of the transition of electron of the 3rd band of semi-conductive single-walled carbon nanotubes and metallic single-wall carbon nano-tube, on figure, show as the S at 600nm place
33The M at characteristic peak and 700nm place
11Characteristic peak.
Fig. 2 is the ultraviolet-visible-near-infrared absorption spectrum of the carbon nanotube after Tri N-Propyl Amine is processed.
Fig. 3 is the ultraviolet-visible-near-infrared absorption spectrum of the carbon nanotube after Isopropylamine is processed.The S at 600nm place
33Characteristic peak has disappeared, and illustrates that the carbon nanotube of semiconductive after ultrasonic-centrifugal process has been removed.The M at 700nm place
11Characteristic peak is enhanced, and illustrates and has obtained metallic carbon nanotube.
Embodiment
The present invention is described in detail with concrete embodiment below in conjunction with accompanying drawing.
Embodiment 1:
The carbon nanotube of one weight part was dissolved in the ten weight part tetrahydrofuran solutions that are added with two weight part normal hexanes to ultrasonic concussion four hours.Under supercentrifuge 15000rpm rotating speed centrifugal one hour, obtain upper solution, in 70 ℃ of baking ovens, to process after 20min standbyly, the ultraviolet-visible-near-infrared absorption spectrum of this solution refers to Fig. 1.In figure, can find out the S that represents semiconductive carbon nano tube
33Absorption peak and the M that represents metallic carbon nanotubes
11Absorption peak.
In gained solution, add the ultrasonic concussion of 5.0M Tri N-Propyl Amine two hours, then centrifugal 12h under the 15000rpm rotating speed, obtain supernatant liquor and precipitation.
Finally use 0.22 micron filtering with microporous membrane supernatant liquor, with ethanol, wash away the organic amine be adsorbed on carbon nanotube, after drying, obtain the product of Concentration of Gold attribute carbon pipe.Ultraviolet-visible-near-infrared absorption spectrum refers to Fig. 2.In figure, there is no S
33Absorption peak, only have the M of the metallic carbon nanotubes of representing
11Absorption peak, illustrate successfully and separate and obtained metallic single-wall carbon nano-tube.
Embodiment 2:
The carbon nanotube of one weight part was dissolved in the ten weight part tetrahydrofuran solutions that are added with two weight part normal hexanes to ultrasonic concussion four hours.Under supercentrifuge 15000rpm rotating speed centrifugal two hours, obtain upper solution, in 70 ℃ of baking ovens, to process after 20min standbyly, the ultraviolet-visible-near-infrared absorption spectrum of this solution refers to Fig. 1.In figure, can find out the S that represents semiconductive carbon nano tube
33Absorption peak and the M that represents metallic carbon nanotubes
11Absorption peak.
In gained solution, add the ultrasonic concussion of 3.0M Isopropylamine two hours, then centrifugal 20h under the 15000rpm rotating speed, obtain supernatant liquor and precipitation.
Finally use 0.22 micron filtering with microporous membrane supernatant liquor, with ethanol, wash away the organic amine be adsorbed on carbon nanotube, after drying, obtain the product of Concentration of Gold attribute carbon pipe.Ultraviolet-visible-near-infrared absorption spectrum refers to Fig. 3.In figure, there is no S
33Absorption peak, only have the M of the metallic carbon nanotubes of representing
11Absorption peak, illustrate successfully and separate and obtained metallic single-wall carbon nano-tube.
Claims (5)
1. separation method with Single Walled Carbon Nanotube of particular chiral is characterized in that concrete steps are as follows:
(1) preparation of Single Walled Carbon Nanotube solution: Single Walled Carbon Nanotube is dissolved in organic solvent, and ultrasonic concussion 4 ~ 12h, be separated into single carbon nanotube by the tube bank of Single Walled Carbon Nanotube; High speed centrifugation 1 ~ 2h again, the carbon nanotube that makes to be dispersed in organic solvent separates with throw out, obtains the solution of Single Walled Carbon Nanotube;
(2) preparation of metallic single-wall carbon nano-tube solution: in step (1), add the organic amine of 3.0-5.0M in resulting solution, ultrasonic concussion 2 ~ 3h, make it and be dispersed into single carbon nanotube and adsorb; The carbon nanotube of the semiconductive that will precipitate by high speed centrifugation 12 ~ 24h is removed, and obtains the solution of metallic carbon nanotubes;
(3) preparation of metallic single-wall carbon nano-tube: by the solution of gained metallic carbon nanotubes in step (2) with 0.22 micron filtering with microporous membrane, and with ethanol, wash away the organic amine be adsorbed on carbon nanotube, after drying, obtain the product of Concentration of Gold attribute carbon pipe.
2. the separation method with Single Walled Carbon Nanotube of particular chiral according to claim 1, is characterized in that organic solvent described in step (1) selects the mixed solvent of tetrahydrofuran (THF) and normal hexane.
3. the separation method with Single Walled Carbon Nanotube of particular chiral according to claim 1, after it is characterized in that step (1) finishes, react the gained Single Walled Carbon Nanotube to 20min at 70 ℃ of temperature, to improve carbon nanotube concentration.
4. the separation method with Single Walled Carbon Nanotube of particular chiral according to claim 1, is characterized in that the organic amine used in step (2) is octylame, Tri N-Propyl Amine, Isopropylamine or the amine aqueous solution that is mixed in proportion.
5. the separation method with Single Walled Carbon Nanotube of particular chiral according to claim 1, is characterized in that step (1) and step (2) high speed centrifugal rotational speed are 15000rpm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229771A (en) * | 2014-09-05 | 2014-12-24 | 西安医学院 | Preparation method of carbon nanotubes (8, 8) most characterized by metal properties |
| RU2709890C1 (en) * | 2019-06-11 | 2019-12-23 | Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" | Method for chromatographic separation of single-layer carbon nanotubes by chirality |
| CN110885076A (en) * | 2019-12-23 | 2020-03-17 | 哈尔滨工业大学 | Method for efficiently, continuously and selectively separating carbon nanotubes in gas phase |
| CN111747399A (en) * | 2019-03-26 | 2020-10-09 | 中国科学院物理研究所 | Separation method of carbon nano tube |
| CN115676807A (en) * | 2021-09-30 | 2023-02-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Echelon ultrahigh-speed centrifugal purification method of single-chiral carbon nanotube |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101018738A (en) * | 2004-08-02 | 2007-08-15 | 国立大学法人筑波大学 | Method of carbon nanotube separation, dispersion liquid and carbon nanotube obtained by the separation method |
| CN101125649A (en) * | 2007-09-22 | 2008-02-20 | 兰州大学 | Method for separating metallic single-wall carbon nano-tube |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101018738A (en) * | 2004-08-02 | 2007-08-15 | 国立大学法人筑波大学 | Method of carbon nanotube separation, dispersion liquid and carbon nanotube obtained by the separation method |
| CN101125649A (en) * | 2007-09-22 | 2008-02-20 | 兰州大学 | Method for separating metallic single-wall carbon nano-tube |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229771A (en) * | 2014-09-05 | 2014-12-24 | 西安医学院 | Preparation method of carbon nanotubes (8, 8) most characterized by metal properties |
| CN104229771B (en) * | 2014-09-05 | 2016-01-20 | 西安医学院 | A kind of preparation method of carbon nanotube (8,8) of most metallic character |
| CN111747399A (en) * | 2019-03-26 | 2020-10-09 | 中国科学院物理研究所 | Separation method of carbon nano tube |
| CN111747399B (en) * | 2019-03-26 | 2021-11-23 | 中国科学院物理研究所 | Separation method of carbon nano tube |
| RU2709890C1 (en) * | 2019-06-11 | 2019-12-23 | Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" | Method for chromatographic separation of single-layer carbon nanotubes by chirality |
| CN110885076A (en) * | 2019-12-23 | 2020-03-17 | 哈尔滨工业大学 | Method for efficiently, continuously and selectively separating carbon nanotubes in gas phase |
| CN110885076B (en) * | 2019-12-23 | 2021-05-25 | 哈尔滨工业大学 | Method for efficiently, continuously and selectively separating carbon nanotubes in gas phase |
| CN115676807A (en) * | 2021-09-30 | 2023-02-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Echelon ultrahigh-speed centrifugal purification method of single-chiral carbon nanotube |
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