CN104118857B - Method used for automatic continuous chromatographic separation of single-walled carbon nanotubes - Google Patents
Method used for automatic continuous chromatographic separation of single-walled carbon nanotubes Download PDFInfo
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- CN104118857B CN104118857B CN201310149284.6A CN201310149284A CN104118857B CN 104118857 B CN104118857 B CN 104118857B CN 201310149284 A CN201310149284 A CN 201310149284A CN 104118857 B CN104118857 B CN 104118857B
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Abstract
The invention relates to a method used for automatic continuous chromatographic separation of single-walled carbon nanotubes; according to the method, a uniquely designed chromatographic column is used, chromatographic column packing materials with different aperture sizes and heights are selected, different moving phases are used for separation of the metallic and semiconductive single-walled carbon nanotubes. The uniquely designed chromatographic column is designed as follows: a soft filter screen and a hard filter screen are additionally designed at two openings of a conventional chromatographic column respectively, so that single-walled carbon nanotubes of different concentrations can successfully pass through a sample inlet and a sample outlet without accumulation or blocking the openings of the chromatographic column when flowing in and flowing out, and the purpose of automatic continuous chromatographic separation of the single-walled carbon nanotubes can be achieved. The soft filter screen is manufactured by a polymer or carbon fiber material, and the hard filter screen is manufactured by a metal material with a certain aperture size; the aperture size of the soft filter screen is 100-1000 microns, and the aperture size of the hard filter screen is 50-800 microns; the thickness of the soft filter screen is 1-5 cm, and the thickness of the hard filter screen is 3-5 microns.
Description
Art
The present invention relates to a kind of method for automating continuous chromatography separating single-wall CNT, more particularly to automatically
Change is continuously isolated clear and legible from SWCN, structure is single and electrical properties are stable SWCN
Straightforward procedure.
Background technology
Lijima in 1991 has found that CNT is after C60It was found that since carbon geochemistry field it is another catch people's attention it is great
It was found that.CNT (carbon nanotubes abbreviation CNTs) can regard the graphene sheet layer curling of hexatomic ring composition as and form
Seamless, hollow tube.This unique architectural feature makes it have special electrical properties and superpower mechanical property, in electronics
The aspects such as device, composite, hydrogen storage material, chemistry and biology sensor show good application prospect.
But these researchs and application face the separation that huge challenge is exactly CNTs.Because existing technology of preparing is obtained
To be all that the CNTs mixtures of structure and the polydisperse CNTs of performance, various structures and performance strongly limit it in molecule
The further research and application in the field such as electronics and photoelectricity.
In order to realize the application based on SWCN electrology characteristic and the accurate protection of biological toxicity performance, close the most
The task of key is to find a kind of straightforward procedure that can automate, be continuously separated CNTs.In order to break through this problem, researchers
Employ various methods to separate the CNT for growing, such as：Atom conductance is separated, selective oxidation is separated, electronics
Puncture, ultracentrifuge is separated and field flow instrument is separated, chromatography is separated.Patent CN200610113211.1 is existed using photoetching method
Gold electrode is prepared on silica containing substrate, several gaps is carved on electrode using focused ion beam and is immersed in single wall carbon
In the DMF solution of nanotube, under the electric field action that 2～8V, frequency are 1～10Hz, by metallicity and semi-conductive single-walled carbon
Nanotube separated in synchronization.In patent CN200710159924.6, mainly by CNT Jing chemistry or the modified dispersion of biological method
In media as well, then using adsorbent by the carbon nanotube separation of particular modification.Patent CN200910182678.5 using electrophoresis, from
The heart or the method for freezing extruding, separation medium and metallicity or the Selective adsorption and enrichment of semiconductive carbon nano tube
Form semiconductive carbon nano tube and metallic carbon nanotubes enrichment region, realize metallicity and semiconductive carbon nano tube point
From.
Tanaka【Takeshi Tanaka, Yasuko Urabe, Daisuke Nishide, Hiromichi
Kataural, Continuous Separation of Metallic and Semiconducting Carbon
Nanotubes Using Agarose Gel, Applied Physics Express2 (2009) 125002】It is solidifying using agarose
Glue isolates metal as chromatographic column filler and nonmetallic SWCN is the most close with the inventive method principle.This side
Method is filled with the high gels of 3-5cm in syringe, is manually added mobile phase.But this method be using syringe as point
From the carrier of instrument, because syringe can not be closed, mobile phase can not continue, addition uninterruptedly, at the uniform velocity controllable, on the other hand
Syringe post journey highly only has 4cm-10cm, and separating carbon nano-tube amount is few, far can not meet separation needs；Separation process in addition
Middle employing is manually added mobile phase, it is impossible to which automation is carried out continuously CNTs separation..
Chromatographic column separation method is that a kind of ripe business separates macromolecular material method, but is not suitable for CNTs point
From.Because although CNTs diameters only have 1-2nm, length can reach micron, it is impossible to image height molecular material it is like that swelling
In solvent, and can only disperse in the solution.CNTs is not directly entered chromatographic column by buffering, filtration, it will blocking chromatographic column, makes
Chromatographic column fails.
The content of the invention
This patent is used as separating tool by unique design chromatographic column, and by filling the different fillers of differing heights carbon is met
Nanotube separates demand.Main inventive is to increase soft filter net and hard filtration respectively in two ports of conventional chromatogram post
Net, plays buffering and filtration, makes variable concentrations SWCN pass through the injection port and outlet of chromatographic column, and
Do not accumulate or blocked sample flows in and out chromatographic column port, reach the mesh of automation continuous chromatography separating single-wall CNT
's.
What the present invention was realized in.
The present invention is a kind of method for automating continuous chromatography separating single-wall CNT, it is characterised in that：
The chromatographic column that described method passes through unique design, selects the chromatographic column filler of different pore size and height, using not
With mobile phase, by SWCN distribution of lengths, realize the separation of metallicity and semi-conductive single-walled carbon nanotubes.
In being embodied as,
Described unique design chromatographic column be two ports of conventional chromatogram post increase respectively design soft filter net and
Hard screen pack, makes variable concentrations SWCN pass through injection port and outlet, and does not accumulate or blocked sample stream
Enter and flow out chromatographic column port, reach the purpose of automation continuous chromatography separating single-wall CNT.
Described soft filter net is being fabricated by using polymeric material or carbon fibre material, with certain pore size
Soft filter net, 100 μm -1000 μm of aperture size, thickness is 1-5cm.Chromatogram styletable is flowed through with buffering SWCN
The speed of mouth, it is to avoid accumulation of the SWCN in port.
Described hard screen pack be fabricated by using metal material, the hard screen pack with certain pore size, aperture
50 μm -800 μm of size, thickness is 3-5 μm.The speed of chromatographic column port is flowed through with buffering SWCN, support is played
Soft filter net, avoid soft filter net deform and in the accumulation of port.
Described different chromatographic column fillers are the biology such as Ago-Gel, sephadex, polyacrylic acid amide and high score
The filler of sub- material, filler aperture is 45-200 μm, preferred 60-165 μm, and packed height is 5-25cm, preferred 10-20cm；Institute
The chromatographic column stated is the normal pressure or medium pressure chromatography post of (200-300) mm × (8-20) mm.
Described separation method can specifically include lower step：
The anion surfactant of 0.5-3wt% is adopted for mobile phase, flow rate pump 0.1mL/min-0.5mL/min, punching
Wash populated gel chromatographic columnses 1-2 hours；Then the CNT that 0.2mL-5mL dispersions are obtained is added in gel chromatographic columnses
Mother liquor, adopts the anion surfactant of 0.5-3wt% for mobile phase, flow rate pump 0.1-0.5mL/min, at set intervals
Sample is collected, 0.5-3 hours are collected, the CNT of different length and semiconductive is obtained.
The present invention key point be：
The thickness and pore size control and the aperture size of inserts of soft filter net.Not only to control
(1) thickness of soft filter net and aperture so as to play buffering and filtration, and
(2) uniform in chromatographic column, the consistent distribution of filler is controlled, it is often more important that
(3) to ensure in chromatographic column without bubble.
The innovative point of the present invention：
1) unique design increases soft filter net in conventional chromatogram post so as to neither affect the sealing of chromatographic column, and
Buffering and filtration are played to carbon nanotube separation, effect of chromatographic column is protected；
2) conventional chromatogram post is transformed by unique design, in CNT chromatographic separation process, neither blocks chromatographic column,
Affect chromatographic column effect, the straightforward procedure that CNT chromatographic isolation can be made to become automation, be continuously separated again.
Description of the drawings
Fig. 1. the schematic diagram of present invention self-control chromatographic column
In figure：1：Lock screw；2：Nut；3：Glass tube；4：Mobile phase；5：Capillary；6：Seal washer；7：Soft mistake
Filter screen；8：Hard screen pack
Specific embodiment：
The chromatographic column filling of the present invention is as shown in Figure 1.Different fillers are tamped and reaches chromatographic column packed height and without gas
Bubble, by soft filter net 7, hard screen pack 8, seal washer 6, seals two ends, tightens nut and lock screw, standby.
The disjunctive path of the present invention：
The anion surfactant of 0.5-3wt% is adopted for mobile phase, flow rate pump 0.1mL/min-0.5mL/min, punching
Wash populated gel chromatographic columnses 1-2 hours；Then the CNT that 0.2mL-5mL dispersions are obtained is added in gel chromatographic columnses
Mother liquor, adopts the anion surfactant of 0.5-3wt% for mobile phase, flow rate pump 0.1-0.5mL/min, at set intervals
Sample is collected, 0.5-3 hours are collected, the CNT of different length and semiconductive is obtained.
Embodiment 1
A：Configuration 1wt%DOC solution is used as mobile phase.
B：Weigh 0.0021g SWCNs and be added to ultrasonic disperse 10 hours and height in the 10mL1wt%DOC aqueous solution
Speed centrifugation 15min, takes upper strata centrifugate, obtains SWCN mother liquor.
C：Gel chromatography separation
Chromatographic column height 9cm, soft filter thickness of net 2cm, 800 μm of aperture, Ago-Gel is chromatographic column filler, filler
Aperture is 60 μm.
The SWCN solution 1mL obtained in B is drawn, in being injected into populated chromatographic column, with 1wt%DOC works
For mobile phase, the flow velocity 0.2mL/min of pump, sample is collected every 2min, collected 1 hour, obtain detached SWCN.
Embodiment 2
A：Configuration 1.5wt%SDS solution is used as mobile phase.
B：Weigh 0.0040g SWCNs and be added in the 10mL1.5wt%SDS aqueous solution ultrasonic disperse 10 hours simultaneously
High speed centrifugation 15min, takes upper strata centrifugate, obtains SWCN mother liquor.
C：Gel chromatography separation
Chromatographic column height 15cm, soft filter thickness of net 3cm, 1000 μm of aperture, sephadex is chromatographic column filler, is filled out
Blanking aperture is 120 μm.
The SWCN solution 2mL obtained in B is drawn, in being injected into populated chromatographic column, with 1.5wt%SDS
As mobile phase, the flow velocity 0.2mL/min of pump, sample is collected every 2min, collected 1 hour, obtain detached single
Pipe.
Claims (3)
1. a kind of method for automating continuous chromatography separating single-wall CNT, it is characterised in that：
Described method is to be used as separating tool by unique design chromatographic column, is met by filling the different fillers of differing heights
Carbon nanotube separation demand, in two ports of conventional chromatogram post soft filter net and hard screen pack are increased respectively, play slow
Punching and filtration, make variable concentrations SWCN pass through injection port and outlet, and do not accumulate or blocked sample
Chromatographic column port is flowed in and out, the purpose of automation continuous chromatography separating single-wall CNT is reached；
Wherein described soft filter net is being fabricated by using polymeric material or carbon fibre material, with certain pore size
Soft filter net, 100 μm -1000 μm of aperture size, thickness is 1-5cm, and with buffering SWCN chromatogram styletable is flowed through
The speed of mouth, it is to avoid accumulation of the SWCN in port；
Described hard screen pack be fabricated by using metal material, the hard screen pack with certain pore size, aperture size
50 μm -800 μm, thickness is 2-5 μm, and with buffering SWCN the speed of chromatographic column port is flowed through, and plays support soft
Screen pack, avoid soft filter net deform and in the accumulation of port.
2. the method for automating continuous chromatography separating single-wall CNT according to claim 1, it is characterised in that：
Described different chromatographic column fillers are the biology such as Ago-Gel, sephadex, polyacrylic acid amide and macromolecule material
The filler of material, filler aperture is 60-165 μm, and packed height is 5-20cm；Described chromatographic column is (200-300) mm × (8-
20) normal pressure of mm or medium pressure chromatography post.
3. according to the method for automating continuous chromatography separating single-wall CNT of claim 1 or 2, it is characterised in that described
Separation method comprises the steps：
Adopt the anion surfactant of 0.5-3wt% for mobile phase, flow rate pump 0.1mL/min-0.5mL/min, flushing is filled out
The gel chromatographic columnses 1-2 hours substituted the bad for the good；Then the CNT mother that 0.2mL-5mL dispersions are obtained is added in gel chromatographic columnses
Liquid, adopts the anion surfactant of 0.5-3wt% for mobile phase, and flow rate pump 0.1-0.5mL/min is received at set intervals
Collection sample, collects 0.5-3 hours, obtains the CNT of different length and semiconductive.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007055027A1 (en) * | 2005-11-14 | 2007-05-18 | Matsushita Electric Industrial Co., Ltd. | Connecting structure for circuit board |
| WO2011124888A1 (en) * | 2010-04-09 | 2011-10-13 | Ucl Business Plc | Separation method |
| CN102219205A (en) * | 2011-03-18 | 2011-10-19 | 中国计量科学研究院 | Separation method for metallic and semiconducting single-walled carbon nanotubes |
| CN102627271A (en) * | 2012-04-27 | 2012-08-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Separating method for metallic carbon nanotube |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007055027A1 (en) * | 2005-11-14 | 2007-05-18 | Matsushita Electric Industrial Co., Ltd. | Connecting structure for circuit board |
| WO2011124888A1 (en) * | 2010-04-09 | 2011-10-13 | Ucl Business Plc | Separation method |
| CN102219205A (en) * | 2011-03-18 | 2011-10-19 | 中国计量科学研究院 | Separation method for metallic and semiconducting single-walled carbon nanotubes |
| CN102627271A (en) * | 2012-04-27 | 2012-08-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Separating method for metallic carbon nanotube |
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