CN104118857A - 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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- CN104118857A CN104118857A CN201310149284.6A CN201310149284A CN104118857A CN 104118857 A CN104118857 A CN 104118857A CN 201310149284 A CN201310149284 A CN 201310149284A CN 104118857 A CN104118857 A CN 104118857A
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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
Affiliated field
The present invention relates to a kind of method for automatization continuous chromatography separating single-wall carbon nanotube, particularly relate to the simple method of the Single Walled Carbon Nanotube that automatization is isolated clear and legiblely continuously from Single Walled Carbon Nanotube, structure is single and electrical properties is stable.
Background technology
Lijima in 1991 finds that carbon nanotube is the C that continues
60the another great discovery catching people's attention in carbon geochemistry field since discovery.Carbon nanotube (carbon nanotubes is called for short CNTs) can be regarded curling seamless, the hollow tube forming of graphene sheet layer that six-ring forms as, the constitutional features of this uniqueness makes it have special electrical properties and superpower mechanical property, at aspects such as electron device, matrix material, hydrogen storage material, chemistry and biosensors, demonstrates good application prospect.
It is exactly the separated of CNTs that yet these researchs face a huge challenge with application.Because that existing technology of preparing obtains is all the polydisperse CNTs of structure and performance, the CNTs mixture of various structures and performance has limited its further research and application in fields such as molectronics and photoelectricities widely.
So, in order to realize application based on Single Walled Carbon Nanotube electrology characteristic and the accurate protection of biological toxicity performance, the most key task be find a kind of can automatization, continuous separate is from the simple method of CNTs.In order to break through this problem, investigators have adopted several different methods to carry out separation to the carbon nanotube of growth, such as, atom electricity is led separation, selective oxidation separation, electron puncture, and ultracentrifuge is separated separated with field flow instrument, chromatography is separated.Patent CN200610113211.1 adopts photoetching method to prepare gold electrode on silica containing substrate, utilize focused ion beam on electrode, to carve in the DMF solution that several gaps are immersed in Single Walled Carbon Nanotube, under the electric field action that is 1～10Hz in 2～8V, frequency, by metallicity and semi-conductive single-walled carbon nanotubes separated in synchronization.In patent CN200710159924.6, mainly carbon nanotube is dispersed in medium through chemistry or biological method modification, then adopts sorbent material by the carbon nanotube separation of particular modification.Patent CN200910182678.5 adopts electrophoresis, centrifugal or freeze the method for extruding, the separated Selective adsorption with medium and metallicity or semiconductive carbon nano tube and inrichment form semiconductive carbon nano tube and metallic carbon nanotubes enrichment region, realize the separated of metallicity and semiconductive carbon nano tube.
Tanaka[Takeshi Tanaka, Yasuko Urabe, Daisuke Nishide, Hiromichi Kataura l, Continuous Separation of Metallic and Semiconducting Carbon Nanotubes Using Agarose Gel, Applied Physics Express 2 (2009) 125002] to adopt sepharose to isolate metal and nonmetallic Single Walled Carbon Nanotube and the inventive method principle as chromatographic column filler the most close.This method has been filled the high gel of 3-5cm in syringe, manually adds moving phase.But this method is a kind of manual methods, in sepn process, can not automatization carry out continuously CNTs separation, because syringe can not seal, moving phase can not continue, uninterruptedly, at the uniform velocity controlled adding, syringe post journey height only has 4cm-10cm on the other hand, can not meet separated needs far away.
In addition, chromatographic column separation method is a kind of separated macromolecular material method of business of maturation, but is not suitable for CNTs separation because CNTs can not the such swelling of image height molecular material in solvent, can directly introduce in chromatographic column by pump.Although and CNTs diameter only has 1-2nm, length can reach micron, can only be dispersed in solution.CNTs introduces chromatographic column by pump, pump can be stopped up; CNTs does not enter chromatographic column by buffering, filtration, chromatographic column can be stopped up yet, and chromatographic column was lost efficacy.
Summary of the invention
This patent as separating tool, meets carbon nanotube separation demand by filling the different fillers of different heights by unique design chromatographic column.In two ports of conventional chromatogram post, increase respectively soft filter net and hard filtering net, play buffering and filteration, make different concns Single Walled Carbon Nanotube smoothly by injection port and the outlet of chromatographic column, and do not accumulate or blocked sample flows to and flows out chromatographic column port, reach the object of automatization continuous chromatography separating single-wall carbon nanotube.
The present invention realizes like this.
The present invention is a kind of method for automatization continuous chromatography separating single-wall carbon nanotube, it is characterized in that:
Described method is by the chromatographic column of unique design, selects the chromatographic column filler of different pore size and height, adopt different moving phase, by Single Walled Carbon Nanotube length distribution, realize the separated of metallicity and semi-conductive single-walled carbon nanotubes.
In concrete enforcement,
Described unique design chromatographic column is for increasing respectively design soft filter net and hard filtering net in two ports of conventional chromatogram post, make different concns Single Walled Carbon Nanotube smoothly by injection port and outlet, and do not accumulate or blocked sample flows to and flows out chromatographic column port, reach the object of automatization continuous chromatography separating single-wall carbon nanotube.
Described soft filter net is employing polymer materials or carbon fibre material manufacture soft filter net that form, that have certain pore size, aperture size 100 μ m-1000 μ m, and thickness is 1-5cm.There is the flow through speed of chromatographic column port of buffering Single Walled Carbon Nanotube, avoid Single Walled Carbon Nanotube in the accumulation of port;
Described hard filtering net is the hard filtering net that the manufacture of employing metallic substance formed, had certain pore size, aperture size 50 μ m-800 μ m, and thickness is 3-5 μ m.There is the flow through speed of chromatographic column port of buffering Single Walled Carbon Nanotube, play and support soft filter net, avoid the distortion of soft filter net and in the accumulation of port;
Described different chromatographic column fillers are the filler of the biologies such as sepharose, dextrane gel, polyacrylic acid amide and macromolecular material, and filler aperture is 45-200 μ m, preferred 60-165 μ m, and packing height is 5-25cm, preferred 10-20cm; Described chromatographic column is normal pressure or the medium pressure chromatography post of mm of (200-300) mm * (8-20).
Described separation method specifically can comprise lower step:
Adopting the anion surfactant of 0.5-3wt% is moving phase, and flow rate pump 0.1mL/min-0.5mL/min, rinses populated gel chromatographic columns 1-2 hour; Then in gel chromatographic columns, add 0.2mL-5mL and disperse the carbon nanotube mother liquor obtaining, adopting the anion surfactant of 0.5-3wt% is moving phase, flow rate pump 0.1-0.5mL/min, collect at set intervals sample, collect 0.5-3 hour, obtain the carbon nanotube of different lengths and semiconductive.
Key point of the present invention is:
The aperture size of the thickness of soft filter net and aperture control and stopping composition.Not only to control
(1) thickness of soft filter net and aperture, make it play buffering and filteration, and
(2) to control filler even, consistent distribution in chromatographic column, the more important thing is
(3) to guarantee in chromatographic column, there is no bubble.
Innovative point of the present invention:
1) in conventional chromatogram post, unique design increases soft filter net, makes its stopping property that neither affects chromatographic column, again carbon nanotube separation is played to buffering and filteration, has protected the effect of chromatographic column;
2) by unique design, transform conventional chromatogram post, in carbon nanotube chromatographic separation process, neither stop up chromatographic column, affect chromatographic column effect, can make again carbon nanotube chromatographic separation become automatization, continuous separate from simple method.
Accompanying drawing explanation
Fig. 1. the present invention makes the schematic diagram of chromatographic column by oneself
In figure: 1: lock screw; 2: nut; 3: Glass tubing; 4: moving phase; 5: kapillary; 6: seal washer; 7: soft filter net; 8: hard filtering net
Embodiment:
Chromatographic column of the present invention is filled as shown in Figure 1.Different fillers are tamped and reach chromatographic column packing height and without bubble, by soft filter net 7, hard filtering net 8, seal washer 6, seal two ends, fastening nut and lock screw, standby.
Disjunctive path of the present invention:
Adopting the anion surfactant of 0.5-3wt% is moving phase, and flow rate pump 0.1mL/min-0.5mL/min, rinses populated gel chromatographic columns 1-2 hour; Then in gel chromatographic columns, add 0.2mL-5mL and disperse the carbon nanotube mother liquor obtaining, adopting the anion surfactant of 0.5-3wt% is moving phase, flow rate pump 0.1-0.5mL/min, collect at set intervals sample, collect 0.5-3 hour, obtain the carbon nanotube of different lengths and semiconductive.
Embodiment 1
A: configuration 1wt%DOC solution is as moving phase.
B: take 0.0021g Single Walled Carbon Nanotube and join ultrasonic dispersion 10 hours high speed centrifugation 15min in the 10mL 1wt%DOC aqueous solution, get upper strata centrifugate, obtain Single Walled Carbon Nanotube mother liquor.
C: gel chromatography separation
Chromatographic column height 9cm, soft filter net thickness 2cm, aperture 800 μ m, sepharose is chromatographic column filler, filler aperture is 60 μ m.
Draw the Single Walled Carbon Nanotube solution 1mL obtaining in B, be injected in populated chromatographic column, using 1wt%DOC as moving phase, the flow velocity 0.2mL/min of pump, collects sample every 2min, collects 1 hour, obtains separated Single Walled Carbon Nanotube.
Embodiment 2
A: configuration 1.5wt%SDS solution is as moving phase.
B: take 0.0040g Single Walled Carbon Nanotube and join ultrasonic dispersion 10 hours high speed centrifugation 15min in the 10mL 1.5wt%SDS aqueous solution, get upper strata centrifugate, obtain Single Walled Carbon Nanotube mother liquor.
C: gel chromatography separation
Chromatographic column height 15cm, soft filter net thickness 3cm, aperture 1000 μ m, dextrane gel is chromatographic column filler, filler aperture is 120 μ m.
Draw the Single Walled Carbon Nanotube solution 2mL obtaining in B, be injected in populated chromatographic column, using 1.5wt%SDS as moving phase, the flow velocity 0.2mL/min of pump, collects sample every 2min, collects 1 hour, obtains separated Single Walled Carbon Nanotube.
Claims (5)
1. for a method for automatization continuous chromatography separating single-wall carbon nanotube, it is characterized in that:
Described method, for passing through unique design chromatographic column as separating tool, meets carbon nanotube separation demand by filling the different fillers of different heights.In two ports of conventional chromatogram post, increase respectively soft filter net and hard filtering net, play buffering and filteration, make different concns Single Walled Carbon Nanotube smoothly by injection port and outlet, and do not accumulate or blocked sample flows to and flows out chromatographic column port, reach the object of automatization continuous chromatography separating single-wall carbon nanotube.
2. according to the method for automatization continuous chromatography separating single-wall carbon nanotube of claim 1, it is characterized in that:
Described unique design chromatographic column is for increasing respectively design soft filter net and hard filtering net in two ports of conventional chromatogram post, make different concns Single Walled Carbon Nanotube smoothly by injection port and outlet, and do not accumulate or blocked sample flows to and flows out chromatographic column port, reach the object of automatization continuous chromatography separating single-wall carbon nanotube.
3. according to the unique design chromatographic column of claim 2, it is characterized in that:
Described soft filter net is employing polymer materials or carbon fibre material manufacture soft filter net that form, that have certain pore size, aperture size 100 μ m-1000 μ m, and thickness is 1-5cm.There is the flow through speed of chromatographic column port of buffering Single Walled Carbon Nanotube, avoid Single Walled Carbon Nanotube in the accumulation of port;
Described hard filtering net is the hard filtering net that the manufacture of employing metallic substance formed, had certain pore size, aperture size 50 μ m-800 μ m, and thickness is 2-5 μ m.There is the flow through speed of chromatographic column port of buffering Single Walled Carbon Nanotube, play and support soft filter net, avoid the distortion of soft filter net and in the accumulation of port.
4. according to the method for automatization continuous chromatography separating single-wall carbon nanotube of claim 1, it is characterized in that:
Described different chromatographic column fillers are the filler of the biologies such as sepharose, dextrane gel, polyacrylic acid amide and macromolecular material, and filler aperture is 60-165 μ m, and packing height is 5-20cm; Described chromatographic column is normal pressure or the medium pressure chromatography post of mm of (200-300) mm * (8-20).
5. according to the method for claim 1～4 automatization continuous chromatography separating single-wall carbon nanotube, it is characterized in that described separation method comprises the steps:
Adopting the anion surfactant of 0.5-3wt% is moving phase, and flow rate pump 0.1mL/min-0.5mL/min, rinses populated gel chromatographic columns 1-2 hour; Then in gel chromatographic columns, add 0.2mL-5mL and disperse the carbon nanotube mother liquor obtaining, adopting the anion surfactant of 0.5-3wt% is moving phase, flow rate pump 0.1-0.5mL/min, collect at set intervals sample, collect 0.5-3 hour, obtain the carbon nanotube of different lengths and semiconductive.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104692358B (en) * | 2015-02-16 | 2019-03-15 | 中国科学院物理研究所 | Carbon nanotube separation method |
Citations (4)
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| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104692358B (en) * | 2015-02-16 | 2019-03-15 | 中国科学院物理研究所 | Carbon nanotube separation method |
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