CN102019224A - Separation method of metallic carbon nanotubes and semiconducting carbon nanotubes - Google Patents
Separation method of metallic carbon nanotubes and semiconducting carbon nanotubes Download PDFInfo
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Abstract
The invention relates to a separation method of metallic carbon nanotubes and semiconducting carbon nanotubes. The method comprises the following steps: dispersing a carbon nanotube sample in dispersion, adding the mixture in a chromatographic column filled with filler matrix, then adding the selected eluent in the chromatographic column, separately collecting metallic and semiconducting carbon nanotube accumulated eluates which flow from the chromatographic column, according to the difference of the retention times of the metallic carbon nanotubes and the semiconducting carbon nanotubes in the chromatographic column to separate the metallic and semiconducting carbon nanotubes. The separation method adopts cheap equipment and simple process and can separate the metallic and semiconducting carbon nanotubes from crude carbon nanotubes largely, effectively and cheaply in a short time; and the separated carbon nanotube samples have stable states and no new impurities. By adopting the method in the invention, the accurate separation and recycling of the metallic and semiconducting carbon nanotubes can be realized more easily; and the method can become an effective way of separating the carbon nanotubes largely and meet the demands of the industrial production and applications.
Description
Technical field
The present invention relates to the separation method of a kind of CNT (CNT), relate in particular to a kind of efficient from CNT, simple and easy, the metallic carbon nanotubes that low-cost separation goes out single conduction property and the method for semiconductive carbon nano tube.
Background technology
SWCN (SWCNT) has great application prospect with its excellent chemical stability, mechanical property and the electricity that can modulate and optical property at aspects such as high-performance, low-cost micro-nano photoelectric device and film photoelectric devices.SWCN can be regarded the seamless hollow pipe that is curled and form by certain helical angle around central shaft by the mono-layer graphite layer as.The different SWCNs that make of caliber and spiral angle present the electric property that can modulate.
But, comprise that in view of present conventional means the prepared CNT of methods such as electric arc, laser ablation and chemical vapour deposition (CVD) all is the mixture of metallicity and semiconductive carbon nano tube, the existence of semiconductive carbon nano tube can to a certain degree reduce the electric conductivity of carbon nano-tube film, and the existence of metal mold CNT then can reduce the transistor characteristic of carbon pipe.Therefore, the carbon nanotube separation technology becomes the focus that recent people pay close attention to and study.
In recent years, people have developed the direct preparation technology of multiple single conductive properties CNT and the preparation post processing isolation technics of different conductive properties SWCNs in succession, wherein, the preparation technology of existing single conductive properties CNT comprises that the plasma enhanced chemical vapor deposition method directly prepares the technology of semiconductor type carbon nano-tube, adopts the single hydroxyl alcohol compounds as the grow technology etc. of high metal mold CNT of the direct CVD of carbon source feed, but this type of technology implements very difficulty, wayward, and efficient is very low.The diameter of the post processing isolation technics general using SWCN of existing different conductive properties SWCNs, the difference of character such as chirality and electronic structure, realize the Selective Separation of part single-wall carbon tube and the separation of conductive properties thereof, remove the technology of metal mold CNT as big electric current ablation method, utilize selective oxidation reaction to eliminate the technology of metal mold CNT, based on the ultrahigh speed centrifugation technique or based on the metallicity of electrophoretic techniques and semiconductive CNT separating technology etc., but these technologies or the enrichment that can not realize two kinds of carbon pipes simultaneously with separate, or equipment is required high, technology is consuming time long, or separating medium costliness, the cost height, or the single conductive properties CNT purity of separating, separating medium is difficult to eliminate, and therefore all can't satisfy low cost, the requirement of large-scale production.
Summary of the invention
The objective of the invention is to propose the separation method of a kind of metallicity and semiconductive carbon nano tube, it can isolate metallic carbon nanotubes and semiconductive carbon nano tube in the rough CNT efficiently, at low cost in batches, thereby overcomes deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
The separation method of a kind of metallicity and semiconductive carbon nano tube, it is characterized in that, this method is: after the CNT sample dispersion is in dispersion liquid, be added in the chromatographic column that is filled with filler matrix, in chromatographic column, add the selected washing lotion of taking off again, thereafter the difference of retention time in chromatographic column according to metallic carbon nanotubes and semiconductive carbon nano tube, collect the metallic carbon nanotubes rich stream fluid and the semiconductive carbon nano tube rich stream fluid that from chromatographic column, flow out in batches, realize separating of metallic carbon nanotubes and semiconductive carbon nano tube;
Described separation filler matrix is any one or the two or more combination in polysaccharide, protein, high molecular polymer and inorganic or the organic elastomeric polymer gel;
Described wash-out leacheate is any one or the two or more combination in anion surfactant, cationic surfactant, amphoteric surfactant and the non-ionic surface active agent.
Say that further this method comprises the steps:
I, in chromatographic column, add filler matrix;
II, with the CNT ultrasonic dissolution in dispersion liquid, and the CNT dispersion liquid added in the chromatographic column;
III, in chromatographic column, add the wash-out leacheate, the difference of retention time in chromatographic column according to metallic carbon nanotubes and semiconductive carbon nano tube is collected metallic carbon nanotubes rich stream fluid and semiconductive carbon nano tube rich stream fluid at the chromatographic column end in batches;
IV, finish the separating of metallic carbon nanotubes and semiconductive carbon nano tube after, with the wash-out leacheate chromatographic column is carried out drip washing repeatedly, so that carry out the separation of next batch CNT;
V, repetition above-mentioned steps I～IV realize that the batch of CNT separates.
Described CNT is to be prepared by laser evaporation method, arc discharge method or chemical vapour deposition technique, contains the SWCN of metallic carbon nanotubes and semiconductive carbon nano tube.
Described inorganic or organic elastomeric polymer gel is any one or the two or more combination in glucan series, agarose series, agarose-glucan series, polyacrylamide series, glucan-polyacrylamide series, polyvinyl alcohol series, polystyrene series and the polymethylacrylic acid hydroxyl second fat gel.
Contain surfactant in described filler matrix and/or the dispersion liquid.
Described surfactant is any one or the two or more combination in anion surfactant, cationic surfactant, amphoteric surfactant and the non-ionic surface active agent.
Described surfactant is an amphiphilic compound, and described amphiphilic compound is any one or the two or more combination in DNA, high molecular polymer and the protein.
Described wash-out leacheate is any one or the two or more combination in anion surfactant, cationic surfactant, amphoteric surfactant and the non-ionic surface active agent.
Described anion surfactant is the straight-chain alkyl sulfate of carbochain 10～14; Perhaps, described anion surfactant is any one or the two or more combination in lauryl sodium sulfate, sodium taurocholate and the NaTDC.
In this method, adopt lauryl sodium sulfate and NaTDC anion surfactant any one or two kinds of combinations wash-out leacheate as metallic carbon nanotubes and semiconductive carbon nano tube.
Can't prepare the metallicity or the semiconductive carbon nano tube of complete single character down in view of present preparation condition, and existing carbon nanotube separation technology is difficult to carry out the industry application, thereby the defective that the restriction CNT is used at many sciemtifec and technical spheres, this case inventor is through studying for a long period of time and putting into practice, based on following design, the present invention is proposed, that is: utilize based on the filler matrix of chromatographic column difference with both retention times in chromatographic column that cause by the different suction-operateds of the metallicity of dispersant dispersion and semiconductive carbon nano tube, and collect metallicity and semiconductive carbon nano tube respectively by the drip washing eluent, realize separating of metallicity and semiconductive carbon nano tube.
Among the present invention as the CNT of separate object, all be suitable for as long as comprise the CNT of metallic carbon nanotubes (metallicity CNT) and semiconductive carbon nano tube (semiconductive CNT), be not subjected to the restriction of its preparation method, caliber, pipe range and carbon tubular construction (single wall and Duo Bi).And it is prepared that CNT can be laser evaporation method, arc discharge method, chemical vapour deposition technique and other any methods.
Usually, represent the direction of atomic arrangement on the CNT, wherein Ch=na with circumference (chirality) the vector Ch of CNT
1+ ma
2, be designated as the helix-coil vector (n, m).a
1And a
2Represent two basic vectors of graphite linings hexagonal gridding respectively, n and m are integer, represent all possible helical vector.。(n, m) closely related with the electric conductivity of CNT, according to the electronics band structure, (n m) will determine the conductive properties of SWCN to index to helical vector.。Given (n, CNT m) is when (n, when m) satisfying the relation (wherein q is an integer) of 2n+m=3q, SWCN is a metallicity, otherwise is exactly semiconductive for one.The SWCN with " armchair " (arm chair) structure for the direction of n=m all is a metal mold, shows good electrical conductivity, and electrical conductivity can reach 10,000 times of copper usually.And " sawtooth pattern " (zigzag, n=0) and " screw type " (chiral) the carbon pipe of structure have 1/3 to be metal mold, remaining 2/3 is semi-conductor type.
According to method separating carbon nano-tube of the present invention, one of more important operation is with CNT dissolving and evenly dispersion with suitable dispersion liquid.Dispersion liquid is generally the appropriate solvent that contains surfactant or dispersant.Preferably, described solvent adopts water.
Above-mentioned surfactant can be any one or the two or more combinations in anion surfactant, cationic surfactant, amphoteric surfactant and the non-ionic surface active agent.Suitable surfactant is that carbochain is 10～14 straight-chain alkyl sulfate series, and especially preferably adopting carbochain is 12 lauryl sodium sulfate (SDS), and comparatively suitable also have sodium taurocholate (SC) etc.These surfactants not only can mix use, and can be with other surfactants and with using.Spendable in addition surfactant except that anion, cation, both sexes and non-ionic surface active agent, also can be amphiphilic compounds such as DNA, high molecular polymer and protein.Be solubility or the static stability that promotes above-mentioned CNT dispersion liquid, through integration test and consider, also can in the dispersion process of CNT, be aided with ultrasonic wave and handle that effect is better like this.Utilize this kind method can prepare the CNT dispersion liquid of 1 μ g/ml～10mg/ml.
The present invention utilizes in the chromatographic column filler matrix absorption and separating metallic and semiconductive carbon nano tube, the adsorbing separation filler matrix that uses be any one or two or more combinations in polysaccharide, protein, high molecular polymer and inorganic or the organic elastomeric polymer gel.Optimum filler matrix is a high-molecular gel.According to the strength difference of high-molecular gel, can select to use any one or two or more combinations in commercially available and homemade glucan series, agarose series, agarose-glucan series, polyacrylamide series, glucan-polyacrylamide series, polyvinyl alcohol series, polystyrene series and the polymethylacrylic acid hydroxyl second fat gel to the selective absorption effect of metallicity and semiconductive carbon nano tube.Preparing gel technology can adopt the method that is cooled to glue behind the heating and melting, perhaps adds polymerization and begins the method that agent becomes glue.And, also can use the gel that adds surfactant or dispersant, so, gel can be used as chromatographic column filler and is repeatedly used after reducing through the drip washing eluent.
(1) preparation of CNT dispersion liquid
Because metallicity among the prepared CNT of present stage and semiconductive CNT, be in from tens to the hundreds of root be wound in the pencil attitude, need before CNT separates, it be dispersed into single CNT.Thereby, be necessary the metallicity and the semiconductive that add surfactant are mixed carbon nano-tube solution, implement sufficient ultrasonic processing, isolated and dispersion CNT.Comprise the CNT of single dispersion in this dispersion liquid and do not formed the CNT of bunchy by single dispersion and the CNT preparation process in accessory substance such as the amorphous carbon that generated and metallic catalyst.To carry out centrifugation through the CNT after the ultrasonic dispersion, after precipitating and removing fasciculation CNT, amorphous carbon and metallic catalyst etc., can obtain containing the single dispersion CNT solution of surfactant.This solution becomes the initial soln that separates in chromatographic column.
(2) chromatographic column separation method
In chromatographic column commonly used, add filler, add CNT from the chromatographic column inlet again and disperse initial liquid, utilize the difference of retention time in the chromatographic column of metallicity and semiconductive carbon nano tube, go out metallicity and semiconductive carbon nano tube with surfactant drip washing successively wash-out.Usually, because gel chromatographic columns separates and can separate with the molecular weight size, the present invention is a prerequisite to select suitable gel kind, is not only applicable to metallicity when separating with semiconductive CNT, also applicable to the separation in view of the CNT of pipe range or caliber size.
(3) absorption spectrum test
The ratio analysis of metallicity and semiconductive CNT can utilize the test result of ultraviolet-visible-near-infrared absorption spectrum.With HiPco-CNT separating experiment result represented among Fig. 1 is example, is called M
11Absorbing band (about 400-600nm) be metallicity CNT origin; Be called S
22Absorbing band (about 600-900nm) and be called S
11Absorbing band (about 1000-1200nm) be semiconductive CNT origin.From M
11And S
22The peak value ratio, can infer the ratio of metallicity and semiconductive CNT roughly.Absorbing band (M
11, S
11, S
22) change with the vary in diameter of measuring CNT, when the CNT variation in diameter, move to short wavelength's direction; When the chap of CNT diameter, move to long wavelength's direction.
Absorption spectrum test can be adopted in the container such as quartz ampoule the method for the solution that directly test separates, perhaps the method for directly testing in chromatography column separation.According to for distributing, can infer the absorbing band that metallicity and semiconductive CNT in the CNT diameter that separates.
Compared with prior art, good effect of the present invention is: utilize cheap apparatus and easy operation, realize to isolate in a large number, effectively, at low cost at short notice metallic carbon nanotubes and semiconductive carbon nano tube in the rough CNT, and the CNT sample after separating keeps stable state, do not introduce new impurity in separation and collection process, the precision that helps metallicity and semiconductive carbon nano tube is separated and recovery sample.The present invention is expected to become a kind of effective way of scale separating carbon nano-tube, helps satisfying the needs that suitability for industrialized production is used.
Description of drawings
Fig. 1 is the terminal liquid abosrption spectrogram that flows out of the chromatographic column of the embodiment of the invention 1;
Fig. 2 is the terminal liquid abosrption spectrogram that flows out of the chromatographic column of the embodiment of the invention 2;
Fig. 3 is the terminal liquid abosrption spectrogram that flows out of the chromatographic column of the embodiment of the invention 3.
The specific embodiment
Below in conjunction with accompanying drawing and several preferred embodiments technical scheme of the present invention is elaborated.
(1) preparation of CNT dispersion liquid
Take by weighing 1.2mg HiPco-CNT (Lot number P0276, Unidym.Inc., diameter 1.0 ± 0.3nm) samples, the 1%SDS aqueous solution of adding 4ml.Above-mentioned solution is placed in the water-bath of circulation running water, and behind drill bit formula Ultrasonic Cell Disruptor (Misonix XL2000) continuous ultrasound 2h (level 6), centrifugal 4h gets supernatant, comprises a lot of isolated and monodispersed CNT in this dispersion liquid.
(2) gel chromatographic columns separates
To be filled in the chromatographic column commonly used through the pretreated agarose of drip washing series Sepharose CL-2B gel separation media, with the 1%SDS surfactant solution wetting after, end entrance adds the dispersion liquid of above-mentioned HiPco-CNT on the chromatographic column.Constantly add 1%SDS solution from chromatographic column top, can see that as time passes the CNT dispersion liquid is divided into the almost actionless two parts of part and chromatographic column top that move to the chromatographic column bottom.After the light brown red that chromatographic column outlet collection arrives in advance flowed out liquid, the green outflow liquid that goes out to remain the transfixion part with 0.5%DOC solution drip washing wash-out was also collected.
(3) absorption spectromtry
Above-mentioned two parts of collecting are respectively flowed out liquid, utilize ultraviolet-visible-near-infrared absorption spectrum instrument (Perkin Elmer Lambda 950) to test its absorption spectrum, its result as shown in Figure 1.The absorption spectrum of the CNT dispersion liquid before separating with chromatographic column is compared the curve of below (among the figure), shows semiconductive CNT origin S from the visual absorption spectrum (curve 1 figure) of confirming as henna outflow liquid
11And S
22Absorption band significantly reduce (, and metallicity CNT origin M
11Absorption band obviously increases.In contrast, absorption spectrum (curve 2 among the figure) result of green outflow liquid shows, the S of corresponding semiconductive CNT
11And S
22Absorption band significantly increases, and the M of corresponding metallicity CNT
11Absorption band reduces on the contrary.
Based on the above results, the conclusion that is drawn is:
Utilize some that often use in the chromatographic column separation method commonly used to separate with filler matrix and metallicity or semiconductive carbon nano tube and have different choice surface suction-operated and cause the difference of both retention times in chromatographic column, the present invention has realized the different time sections outflow and the collection of metallicity and semiconductive carbon nano tube.About this kind segregation phenomenon and effect, do not have any relevant report and report up to now, show that chromatographic column gel filler medium separation method of the present invention is, based on the diverse new separation mechanism of metallicity and semiconductive CNT separation method in the past.
Embodiment 2:
Present embodiment is substantially the same manner as Example 1, and difference is:
Gel filler matrix is with glucan series Sephadex
TMReplace agarose series Sepharose CL-2B.Fig. 2 represents the terminal liquid absorption spectrum test result that flows out of chromatographic column after chromatographic column is separated.The absorption spectrum that separates CNT dispersion liquid before with chromatographic column is compared, and shows semiconductive CNT origin S from the visual absorption spectrum of confirming as henna outflow liquid (lines 1 figure)
11And S
22Absorption band significantly reduces, and metallicity CNT origin M
11Absorption band obviously increases.In contrast, the absorption spectrum result of green outflow liquid (lines 2 among the figure) shows, the S of corresponding semiconductive CNT
11And S
22Absorption band significantly increases, and the M of corresponding metallicity CNT
11Absorption band reduces on the contrary.This result shows, follows agarose series gel filler same, also can isolate metallicity and semiconductive CNT when using glucan series gel filler.
Embodiment 3:
Present embodiment is substantially the same manner as Example 1, and difference is:
Gel filler matrix is with agarose-glucan series Superdex
TMReplace agarose series SepharoseCL-2B.Fig. 3 represents the terminal liquid absorption spectrum test result that flows out of chromatographic column after chromatographic column is separated.The absorption spectrum that separates CNT dispersion liquid before with chromatographic column is compared, and shows semiconductive CNT origin S from the visual absorption spectrum of confirming as henna outflow liquid (lines 1 figure)
11And S
22Absorption band significantly reduces, and metallicity CNT origin M
11Absorption band obviously increases.In contrast, the absorption spectrum result of green outflow liquid (lines 2 among the figure) shows, the S of corresponding semiconductive CNT
11And S
22Absorption band significantly increases, and the M of corresponding metallicity CNT
11Absorption band reduces on the contrary.This result shows, and is same with agarose series gel filler, also can isolate metallicity and semiconductive CNT when using agarose-glucan series gel filler.
More than preferable enforcement example only for the usefulness of explanation technical scheme of the present invention, and should not constitute any restriction to protection scope of the present invention.All employing equivalents or equivalence are replaced and the technical scheme of formation, all should drop within the rights protection scope of patent of the present invention.
Claims (10)
1. the separation method of metallicity and semiconductive carbon nano tube, it is characterized in that, this method is: after the CNT sample dispersion is in dispersion liquid, be added in the chromatographic column that is filled with filler matrix, in chromatographic column, add the selected washing lotion of taking off again, thereafter the difference of retention time in chromatographic column according to metallic carbon nanotubes and semiconductive carbon nano tube, collect the metallic carbon nanotubes rich stream fluid and the semiconductive carbon nano tube rich stream fluid that from chromatographic column, flow out in batches, realize separating of metallic carbon nanotubes and semiconductive carbon nano tube;
Described separation filler matrix is any one or the two or more combination in polysaccharide, protein, high molecular polymer and inorganic or the organic elastomeric polymer gel;
Described wash-out leacheate is any one or the two or more combination in anion surfactant, cationic surfactant, amphoteric surfactant and the non-ionic surface active agent.
2. the separation method of metallicity according to claim 1 and semiconductive carbon nano tube is characterized in that this method comprises the steps:
I, in chromatographic column, add filler matrix;
II, with the CNT ultrasonic dissolution in dispersion liquid, and the CNT dispersion liquid added in the chromatographic column;
III, in chromatographic column, add the wash-out leacheate, the difference of retention time in chromatographic column according to metallic carbon nanotubes and semiconductive carbon nano tube is collected metallic carbon nanotubes rich stream fluid and semiconductive carbon nano tube rich stream fluid at the chromatographic column end in batches;
IV, finish the separating of metallic carbon nanotubes and semiconductive carbon nano tube after, with the wash-out leacheate chromatographic column is carried out drip washing repeatedly, so that carry out the separation of next batch CNT;
V, repetition above-mentioned steps I～IV realize that the batch of CNT separates.
3. the separation method of metallicity according to claim 1 and 2 and semiconductive carbon nano tube, it is characterized in that: described CNT contains the SWCN of metallic carbon nanotubes and semiconductive carbon nano tube for what prepared by laser evaporation method, arc discharge method or chemical vapour deposition technique.
4. the separation method of metallicity according to claim 1 and semiconductive carbon nano tube is characterized in that: described inorganic or organic elastomeric polymer gel is any one or the two or more combination in glucan series, agarose series, agarose-glucan series, polyacrylamide series, glucan-polyacrylamide series, polyvinyl alcohol series, polystyrene series and the polymethylacrylic acid hydroxyl second fat gel.
5. the separation method of metallicity according to claim 1 and 2 and semiconductive carbon nano tube is characterized in that: contain surfactant in described filler matrix and/or the dispersion liquid.
6. the separation method of metallicity according to claim 5 and semiconductive carbon nano tube is characterized in that: described surfactant is any one or the two or more combination in anion surfactant, cationic surfactant, amphoteric surfactant and the non-ionic surface active agent.
7. the separation method of metallicity according to claim 6 and semiconductive carbon nano tube, it is characterized in that: described surfactant is an amphiphilic compound, and described amphiphilic compound is any one or the two or more combination in DNA, high molecular polymer and the protein.
8. the separation method of metallicity according to claim 1 and semiconductive carbon nano tube is characterized in that: described wash-out leacheate is any one or the two or more combination in anion surfactant, cationic surfactant, amphoteric surfactant and the non-ionic surface active agent.
9. according to the separation method of claim 6 or 8 described metallicity and semiconductive carbon nano tube, it is characterized in that: described anion surfactant is the straight-chain alkyl sulfate of carbochain 10～14; Perhaps, described anion surfactant is any one or the two or more combination in lauryl sodium sulfate, sodium taurocholate and the NaTDC.
10. the separation method of metallicity according to claim 1 and 2 and semiconductive carbon nano tube, it is characterized in that: in this method, adopt the wash-out leacheate of the combination of lauryl sodium sulfate and NaTDC anion surfactant any one or two kinds as metallic carbon nanotubes and semiconductive carbon nano tube.
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