CN101185913A - Method for separating metallicity and semiconductivity nano-tube from single wall carbon nano-tube - Google Patents
Method for separating metallicity and semiconductivity nano-tube from single wall carbon nano-tube Download PDFInfo
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Abstract
The invention discloses a method for separating enriching metallic and semiconductor carbon nanometer tubes from single-walled carbon nanometer tubes The method of the invention is that: first, purified carbon nanometer tubes of 1 weight account that waits for separation and 0.05 to 2 weight accounts of separating accelerator are taken to be added into organic solvent for ultrasonic mixing and lead the separating accelerator to sufficiently adsorb the specific carbon nanometer tube, then liquid and sediments are separated, carbon tubes that are suspended in the liquid are separated, and products of enriching metallic carbon-tubes are acquired; next, 1 weight account of sediment and 0.05 to 2 weight accounts of the separating accelerator are taken to be added into the organic solvent for ultrasonic mixing processing, then sediments and liquid are separated, carbon tubes that are suspended in the liquid are separated, and products of enriching semiconductor carbon tubes are acquired.
Description
Technical field
The present invention relates to a kind of method of from SWCN, isolating CNT, particularly isolate the method for enriched in metals and semiconductive carbon nano tube from SWCN with particular chiral.
Background technology
CNT has many excellent characteristic, make it at composite reinforcing material such as high draw ratio, high strength, high tenacity, good chemical stability and heat endurance and special electrical properties etc., nano electron device, field emission electrode, various fields such as energy and material have obtained paying attention to widely and research.
The electrical properties of SWCN is to be controlled by the caliber of carbon pipe and configuration.The configuration of CNT usually with two chirality characteristic parameters (n m) represents, when m=n, chiral angle θ=30 °, CNT at this moment is called handrail type CNT (Armchair); (θ=0 °) CNT is called zigzag nanotubes (Zigzag) when m=0 or n=0; CNT when m, n during for other value (0＜θ＜30 °) this moment is called chirality type (or screw type Chiral) CNT.Wherein, (n is that Armchair type carbon pipe all is metallic n); For (n, 0) be the Zigzag type when n is 3 multiple, CNT is metallic, otherwise is exactly semiconductive; (n m), when (2n+m)/3 are metallicity during for integer, otherwise is a semiconductive for the chiral carbon pipe.So obviously (n is n-1) with (n, n-2) the chiral carbon pipe of type is semi-conductor type.In addition, the electrical properties of carbon pipe also can be subjected to the influence of external environment and self deformation.
One of the research that is used for photoelectric device at CNT still an open question is to the not fractionation of the carbon pipe of isomorphism type.If desired CNT is integrated in following nano-device, just necessarily requires to know definitely the configuration of CNT in the obtained device.For example, semiconductor carbon nanometer tube is used for memory device, sensor etc., and metallic carbon nanotubes is used for the electrode material of battery, electromagnetic protection layer etc.The research of CNT optical property is found that also interaction with metallicity carbon pipe also can make the near-infrared fluorescent generation cancellation of semiconductor carbon pipe, limited its application [M.J.O ' Connell aspect nanocomposite optical, S.M.Bachilo, R.E.Smalley Science 2002 297:593-596].
Therefore, need a kind of method that can optionally prepare metallicity and semiconductive carbon pipe, perhaps the method for from mixture, the carbon nanotube separation with particular chiral being come out.At present the carbon pipe prepared of conventional method all is the mixture of isomorphism type carbon pipe not, and directly preparing highly purified metallicity or semiconductive carbon pipe in a large number, to obtain the possibility that breaks through in a short time little.Therefore the separation after the carbon pipe is produced in batches just becomes the means of present unique reality.
The chemical modification of CNT is a kind of to receiving the effective means that tubular construction (diameter, helicity, chirality) sieves, and to developing its potential performance (energy storage, gas storage and catalytic performance), exploitation relevant nano-device (nano-reactor, gas sensor, electronic component etc.), new material (biomaterial, electrode material) very big realistic meaning is arranged all.
Usually, when carrying out the separation of carbon pipe in the prior art, when particularly the carbon pipe that contains impurity being separated, need in advance the carbon pipe powder is carried out purification process, its way roughly is that just carbon nanotube powder is put into concentrated hydrochloric acid or the concentrated sulfuric acid or red fuming nitric acid (RFNA), perhaps in the concentrated acid of mixture of the concentrated sulfuric acid and red fuming nitric acid (RFNA) and so on, again carbon nanotube powder is put into and wherein carried out ultrasonic processing, leave standstill then and treat that the complete post precipitation of carbon pipe separates it and wash with water to neutrality, again the carbon pipe powder is carried out annealing in process.
The Separation Research of relevant CNT is at the early-stage, has obtained some initial achievements, and representational method has: (1) is carried out original position and is separated in the process of preparation nanometer electronic device.IBM seminar [P.G.Collins, M.S.Arnold, P.Avouris, Science.2001,292,706] utilizes the electric conductivity difference of these two kinds of carbon pipes, under bigger energy interelectrode metallicity carbon pipe is burnt, and only stays semiconductive carbon pipe.Krupke[R.Krupke, F.Hennrich, M.M.Kappes, Science.2003,301,344] etc. utilize two kinds of dielectric constants that the carbon pipe is different, make metallicity carbon pipe polarization back preferential deposition on electrode with the alternating-current bidirectional electrophoretic techniques.The method of this original position device preparation is had relatively high expectations to equipment, and can only be applied to the preparation of small number of devices.(2) the auxiliary separation of large biological molecule such as DNA.[M.Zheng such as Zheng, A.Jagota, M.S.Strano, E.D.Semke, M.Usrey, D.J.Walls, Science.2003,302,1545] reported and utilize DNA to be wrapped on the different carbon pipes effectively linear charge density difference, separated thereby vary in size with the cationic ion-exchange resin adhesion.The method significant disadvantage the most is that cost is too high, and is difficult to DNA is removed, and therefore lacks practicality.(3) method of little molecular chemistry modification: existing existing report adopts bromine [Z.Chen, X.Du, M.Du, A.G.Rinzler, Nano Lett.2003,3,1245-1249], porphyrin [H.Li, B.Zhou, Y.Lin, L.F.Allard, Y.Sun, J.Am.Chem.Soc.2004,126,1014-1015] and octadecylamine [Y.Maeda, S.Kimura, H.Tokumoto, R.Saito, J.Am.Chem.Soc.2005,127,10287-10290] etc. after non-covalent technology modifies the carbon pipe, specific carbon pipe is suspended in the solution, and nonspecific carbon Guan Ze precipitates in solution, adopt proper method again isolating post precipitation, as adopt the isolation technics of centrifugal or coarse filtration, the enrichment semiconductive or the metallicity carbon pipe that are suspended in the solution are separated.Little molecular chemistry method of modifying has significant deficiency, and is lower as the efficient that adopts bromine to separate with porphyrin.Reported and adopted the octadecylamine separating for several times metallicity carbon pipe can be enriched to 87%.Yet, be unfavorable for the performance of nanometer electronic device because octadecylamine originally as the insulating properties molecule, can constitute the electric transmission potential barrier between carbon pipe and the electrode that is connected.In addition, octadecylamine belongs to the surfactant quasi-molecule, is easy to device is polluted.
Learn that by aforementioned content because the difference of SWCN chiral angle θ, the electrical properties that it showed is also different.Isolated metallicity of prior art or semiconductive carbon pipe often are the sub-fraction in the raw material.After using prior art and isolating a certain type CNT, the surplus a large amount of carbon pipe of institute still is that different chiral angles are the mixture of different electrical properties carbon pipes.Split by its chiral angle as the carbon pipe is carried out, then both can repeatedly extract the waste that overcomes raw material in batches, separation and the extraction for single chiral angle carbon pipe provides the basis again.The carbon pipe does not provide way in the prior art by the partition of its chiral angle.
Therefore, from the application point of nano electron device, remarkable advantages will be arranged if can separate to the carbon pipe of different chiral angles.
Summary of the invention
The invention provides a kind of method of from SWCN, isolating different chiral angle carbon pipes successively, particularly the method for separation and enriched in metals and semiconductor carbon pipe.
Method of the present invention is: at first get the CNT to be separated of purified processing of 1 weight portion and the separation promoter of 0.05～2 weight portion, the two is added in the organic solvent, system is carried out ultrasonic mixing, make separation promoter fully adsorb the particular carbon nanotube, remove the precipitation liquid hold-up then, the carbon pipe that will be suspended in again in the liquid is separated, and removes the separation promoter of carbon elimination Guan Shangwei absorption with organic solvent washing, obtains the product of enriched in metals carbon pipe;
The separation promoter of separating obtained precipitation 1 weight portion of the last process of learning from else's experience and 0.05～2 weight portion, the two is added in the organic solvent, system is carried out ultrasonic mixed processing, remove the precipitation liquid hold-up, the carbon pipe that will be suspended in again in the liquid is separated, remove the separation promoter that carbon Guan Shangwei is adsorbed with solvent wash, can obtain enrichment semiconductive carbon pipe product.
As to repeatedly repeating above-mentioned processing procedure again through the separating obtained precipitation of pre-treatment process, can further isolate the CNT of different electrical properties, alternately obtain the product of enriched in metals or semiconductive carbon pipe.For example, from the precipitation of the described separation and concentration processing of the preceding paragraph gained, take out 1 weight portion again, the separation promoter of itself and 0.05～2 weight portion is added in the organic solvent, system is carried out ultrasonic mixed processing, isolate precipitation then, from resulting liquid, isolate the solid of suspension, remove on the gained solid the not separation promoter of absorption with solvent wash again, the metallicity carbon pipe that can obtain enrichment.Get the carbon pipe product that semiconductive was handled and can be obtained to its precipitation again.
Used separation promoter is the compound with linear condensed-nuclei aromatics structure in the above process, and its condensed-nuclei aromatics partly contains at least three aromatic rings.
The present invention can adopt any organic solvent, but preferably use can be good to the separation promoter dissolubility, and CNT is had the organic solvent of better dispersibility.The organic solvent that the present invention recommends to use is chloroform, perhaps adopt oxolane, perhaps adopt the N-N-methyl-2-2-pyrrolidone N-, perhaps adopt N, dinethylformamide perhaps adopts N, the N-dimethylacetylamide, perhaps being dimethyl sulfoxide (DMSO), perhaps is the mixed solvent that diethyl sulfoxide or employing contain aforementioned solvents.
When adopting method of the present invention to separate the carbon pipe,, can make carbon pipe to be separated pure, more help separating if earlier CNT is carried out preliminary treatment.Its preprocess method is: the carbon nanotube powder of 1 weight portion is put into the concentrated acid that is added with 0.1～10 weight portion anion surfactant carry out ultrasonic processing, the carbon pipe is separated, wash with water to neutrality and carry out annealing in process.
The used separation promoter of the present invention can be that anthracene or general formula are:
Compound, R should be and can improve the deliquescent group of condensed-nuclei aromatics in its formula.For example R can be alkyl, perhaps is the trimethyl silicane alkynyl, perhaps triisopropyl silicon alkynyl.In the used in the present invention separation promoter, the carbon in the skeleton of its linear condensed-nuclei aromatics part can also be replaced by hetero atom.
The theoretical analysis shows that with corresponding experiment method of the present invention can effectively be isolated metallicity and semiconductive carbon nano tube from SWCN, and the method for separating is comparatively simple, practical.Adopt the compound of resultant condensed-nuclei aromatics molecule of the inventive method and CNT that special using value is being arranged aspect photoelectric device and the solar cell in addition.
The method of the invention provides can effectively be separated and the enriched in metals CNT.Through separate, the carbon pipe of the semi-conductor type of enrichment (comprises optical sensor and biology at memory device, sensor, chemical sensor), opto-electronic device, nano-machine parts, transistor, there are very high using value or application prospect in aspects such as diode and life science.The carbon pipe that separates the metal mold enrichment that obtains through the present invention will be at battery, the electrode material of electromagnetic protection etc. and electronic device lead, and the SPM needle point, aspects such as capacitor are widely used.
The present invention adopt the condensed-nuclei aromatics molecular separation not the CNT of isomorphism type following advantage is arranged: at first, this method itself is simple to operate, and cost is low, helps widespread adoption; Secondly, compare with the method in the background introduction, expensive single-wall carbon tube raw material is not loss almost; And the condensed-nuclei aromatics molecule that will have fluorescence activity is that the separation promoter in this patent is modified the carbon tube-surface, can realize easily the fluorescence labeling of SWNT and the fluorescent visual of carbon pipe are handled.Moreover, modify the carbon pipe with shla molecule the dispersiveness of carbon pipe in multiple medium improved greatly, for the approach that provides is provided in the ordering of carbon pipe.
Description of drawings
Fig. 1. the flow chart of embodiment of the invention separating metallic and semiconductive carbon pipe.
Fig. 2. the explanation schematic diagram of operation principle of the present invention.Last figure: linear condensed-nuclei aromatics molecule passes through face-to-face pattern and Armchair, Chiral, and Zigzag carbon pipe π-π interacts.When the matching degree of face-to-face pattern was consistent, the tension force of Molecular Adsorption on the carbon pipe was along with carbon pipe chirality changes to the zigzag type and increasing from the armchair type.Figure below: carbon pipe chirality changing features schematic diagram.
Fig. 3 and Fig. 4 modify the Raman spectrogram of separation and Extraction gained first and second batch of separating obtained supernatant carbon pipe sample for anthracene of the present invention and pentacene derivative: wherein: sample 2 (A) among sample 1 and the embodiment 5 among the embodiment 3, sample 2 (B) Raman spectrogram-ring breathing zone (RBM) zone among sample 1 and the embodiment 4 among the embodiment 2.
Fig. 5. anthracene is modified separation and Extraction gained two and is pulled on clear liquid sample Raman spectrogram among the present invention: sample 2 Raman spectrogram among sample 1 and the embodiment 5 among the embodiment 3-G band.The semiconductor peak feature of the both shoulders peak of the tangible metallicity of example 3 supernatant samples and example 5 supernatant samples as can be seen.
The specific embodiment
Used condensed-nuclei aromatics compound with special geometric configuration is the condensed-nuclei aromatics that a class has linear rigid structure among the present invention, as anthracene, and solubility pentacene derivative etc.Condensed-nuclei aromatics and the interactional preferential conformation of CNT π-π are face-to-face pattern (as shown in Figure 2).According to this point as can be seen, along with carbon pipe chiral angle from 30 ° (armchair) to 0 ° (zigzag), because the curvature of carbon pipe and the rigidity of aromatic hydrocarbon molecule, this type of aromatic hydrocarbon molecule and the interactional tension force of carbon pipe are increasing, thereby make that the energy of adsorption of aromatic hydrocarbon molecule on the carbon pipe is more and more littler.This shows that linear condensed-nuclei aromatics molecule will be preferentially adsorbed on the armchair metallic carbon nanotubes, is the chirality semiconductor carbon nanometer tube secondly, energy of adsorption minimum on (n, 0) type ziagzag pipe.In this case, if employing has fine deliquescent condensed ring molecular selectivity and is adsorbed on the different carbon pipes, make different chiral carbon pipes that different dispersivenesses be arranged in solvent, adopt simple dispersion-centrifugal method can realize extraction in batches and enrichment different chiral carbon pipes.
We adopt Density functional (DFT) method to simulate the absorption situation of a series of condensed-nuclei aromatics molecules on metallicity (Armchair) (7,7) and semiconductor (Zigzag) (13,0) single-walled pipe (SWNT).The result of calculation of DFT shows pentacene and (7,7) SWNT binding energy ratio and high about 29% of (13,0) SWNT.Referring to table 1.
Table 1
By calculating, further specify the following feature that is adsorbed with that the present invention plants aromatic hydrocarbon molecule and carbon pipe: (1) condensed-nuclei aromatics is at the bigger energy of adsorption of (7,7) metal mold carbon Guan Shangyou, and promptly this quasi-molecule is more prone to preferential adsorption (7,7) metal mold carbon tube-surface.(2) aromatic hydrocarbon molecule is along with the proportional increase of energy of adsorption on (7,7) metal mold carbon pipe of being increased in of number of rings, and on (13,0), because tension force or not matching of face-to-face binding mode make that the energy of adsorption increasing degree is very little.(3) structure of condensed-nuclei aromatics is the key factor that influences itself and two kinds of carbon pipe active force difference.The number of rings of condensed-nuclei aromatics is many more, and the difference of the energy of adsorption on two kinds of carbon pipes is big more, and promptly the separating effect to two kinds of carbon pipes is good more.Carbon is also had the ability of certain separating metal carbon pipe on the skeleton by the condensed-nuclei aromatics that hetero atom replaced.
On the basis of above theory analysis, carry out actual separation test.It below is the example that adopts condensed-nuclei aromatics compound-pentacene derivative to separate.The separation method that test is adopted is referring to accompanying drawing 1.
Embodiment 1: the purifying of carbon pipe
Because the used carbon pipe powder of experiment itself has certain impurity, therefore be necessary it is carried out preliminary treatment, i.e. purification process, this can make thereafter separation more effective, reliably.If employed carbon pipe powder itself is comparatively pure, also can not adopt the purification process of present embodiment.
The used purification treating method of present embodiment is: at first, with 1 weight portion CNT be added with in the 10 weight portion concentrated hydrochloric acid solutions of 4 weight portion lauryl sodium sulfate or dodecyl sodium sulfate, behind ultrasonic 3～4h, leave standstill, treat that carbon pipe post precipitation inclines the upper strata acid solution and secrete, it is ultrasonic to add the new acid solution that has surfactant again, for fully removing the catalyst granules in the CNT, repeats this step until no longer flavescence of acid solution.Remove solution with 0.45 micron filtering with microporous membrane again.With acid and the surfactant in the pure water flush away solid, use the acetone rinsing solid again.As for 80 ℃ of dryings in the vacuum drying chamber 12 hours, abrasive solid became Powdered with the gained solid.The carbon pipe powder is put into 820 ℃ in tube furnace, and annealing is 2 hours under the high-purity argon gas atmosphere.After the cooling, impurity such as carbon nano-particle were removed in oxidation in 1.5 hours in 550 ℃ of following air fully.As can be seen through after this three steps purifying, obtain purer SWCN on the TEM shape appearance figure.The purity TEM of carbon pipe, SEM, the Raman spectral characterization proves through behind the purifying to obtain pure SWCN.The test contrast shows that adding surfactant in purge process in acid has higher purification efficiency than prior art.
Embodiment 2: condensed-nuclei aromatics compound-6, two (2-(TMS) acetenyl) pentacenes of 13-are modified and first step products of separated
With the good SWCN of 1 weight portion example, 1 gained purifying, with 6 of 0.09 weight portion, two (2-(TMS) acetenyl) pentacenes of 13-mix after ultrasonic 3.5 hours in the N-methyl pyrrolidone under the 200W power, centrifugal under the supercentrifuge 12000rpm rotating speed, collect supernatant and precipitation.With 0.22 micron filtering with microporous membrane supernatant and precipitation, with a large amount of solvent wash to remove 6 of a small amount of not absorption or desorption, two (2-(TMS) acetenyl) pentacenes of 13-.Collect the product on the filter membrane, obtain first separating obtained supernatant and precipitation.Use the mineral wool filtering supernatant again, collect filtrate, obtain sample 1.
The sign of separated product is seen Fig. 3.
Embodiment 3: the modification of condensed-nuclei aromatics compound-anthracene with carry out first time product and separate
With the good SWCN of 1 weight portion example, 1 gained purifying, centrifugal under the supercentrifuge 12000rpm rotating speed with the anthracene of 0.1 weight portion mixes ultrasonic 3.5h under the 200W power in chloroform after, collect supernatant and precipitation respectively.With 0.22 micron filtering with microporous membrane supernatant and precipitation, a large amount of solvent wash are to remove the anthracene of a small amount of not absorption or desorption.Collect the product on the filter membrane, obtain first separating obtained supernatant and precipitation.Use the mineral wool filtering supernatant again, collect filtrate, obtain sample 1.
The sign of separated product is seen Fig. 3, Fig. 4 and Fig. 5.
Embodiment 4: the modification of condensed-nuclei aromatics compound-pentacene derivative with carry out second time product and separate
With 1 weight portion example, 2 gained precipitations, with 6 of 0.07 weight portion, two (2-(TMS) acetenyl) pentacenes of 13-mix in chloroform under the 200W power behind the ultrasonic 3.5h, and are centrifugal under the supercentrifuge 12000rpm rotating speed, collection supernatant and precipitation.With 0.22 micron filtering with microporous membrane supernatant and precipitation, with a large amount of solvent wash to remove 6 of a small amount of not absorption or desorption, two (2-(TMS) acetenyl) pentacenes of 13-.Collect the product on the filter membrane, obtain second batch of separating obtained supernatant and precipitation.Use the mineral wool filtering supernatant again, collect filtrate, obtain sample 2.
The sign of separated product is seen Fig. 3 and Fig. 4.
Embodiment 5: the modification of condensed-nuclei aromatics compound-anthracene with carry out second time product and separate
With 1 weight portion example, 3 gained deposit sample, in chloroform, mix under the 200W power behind the ultrasonic 3.5h with the anthracene of 0.1 weight portion, centrifugal under the supercentrifuge 12000rpm rotating speed, collect supernatant and precipitation respectively.With 0.22 micron filtering with microporous membrane supernatant and precipitation, with a large amount of solvent wash to remove the anthracene of a small amount of not absorption or desorption.Collect the product on the filter membrane, obtain second batch of separating obtained supernatant and precipitation.Use the mineral wool filtering supernatant again, collect filtrate, obtain sample 2.
The sign of separated product is seen Fig. 3, Fig. 4.
Embodiment 6: pentacene derivative is modified repeatedly " ultrasonic dispersion-centrifugation " process of carbon pipe
The pentacene derivative that adds 0.02～0.1 mole part in the N-methyl pyrrolidone solution with N the separating obtained deposit sample of 1 mole part, under the 200W power behind the ultrasonic 3.5h, centrifugal under the supercentrifuge 12000rpm rotating speed, collect supernatant and precipitation respectively.The N+1 that obtains pentacene derivative modification carbon pipe criticizes separating obtained supernatant and precipitation.Use the mineral wool filtering supernatant again, collect filtrate, obtain sample N+1.
Embodiment 7: anthracene is modified repeatedly " ultrasonic dispersion-centrifugation " process of carbon pipe
The anthracene that adds 0.02～0.1 mole part in the N-methyl pyrrolidone solution with N the separating obtained deposit sample of 1 mole part, behind the ultrasonic 3.5h, centrifugal under the supercentrifuge 12000rpm rotating speed under the 200W power, collect supernatant and precipitation respectively.The N+1 that obtains anthracene modification carbon pipe criticizes separating obtained supernatant and precipitation.Use the mineral wool filtering supernatant again, collect filtrate, obtain sample N+1.
The caliber that by optical maser wavelength is the sample that obtains in the Raman scattering spectrum test case 2 of 532nm and the example 3 distributes and the chirality distribution, and the content of metal tube content and semiconductor carbon nanometer tube in each sample.Experimental result is shown in Fig. 3, among Fig. 4.With reference to Fig. 3, example 3 gained supernatants are the 215～290cm of sample 1 at ring breathing zone (RBM) as can be seen
-1The peak that the metallicity district is obviously strong than the carbon Guan Yougeng of purifying, and example 5 gained supernatants are that sample 2 is at 160～215cm
-1With 290～340cm
-1The characteristic of semiconductor district is slightly stronger than the peak of the carbon pipe of purifying.This trend is for example 2 and example 4 gained supernatants more obvious (Fig. 3).As can be seen from Figure 3, embodiment 2 gained supernatants are that the content of metal carbon pipe in the sample 1 is very high; For embodiment 4 supernatants is sample 2, and the content of semiconductive carbon pipe has very significant increase than raw material (being the carbon pipe of purifying).With reference to Fig. 4, embodiment 3 demonstrates very strong metallicity carbon pipe feature peak shape and characteristic of semiconductor peak shape with the supernatant (promptly being respectively sample 1 and sample 2) that embodiment 5 obtains respectively at the G-band.Therefore, just can conclude,, can separate a large amount of metallicity and semiconductive carbon nano tube efficiently in batches according to the method for the embodiment of the invention.
For the first time separation and Extraction goes out metallicity carbon pipe and extracts semi-conductive single-walled this embodiment result of carbon pipe for the second time, has verified when the condensed-nuclei aromatics Molecular Adsorption is on the carbon pipe dependence and this operation principle of the present invention of selectivity to carbon pipe chirality.Pentacene derivative has better separating effect than anthracene.This is also consistent with separating mechanism of the present invention: when the π-π of linear condensed ring molecule and carbon pipe mates absorption, because carbon pipe curvature, take all factors into consideration two factors of contact area of π-π coupling and tension force influence, make the acene molecular selectivity of rigidity be adsorbed on the armchair type carbon pipe.The caliber unanimity of carbon pipe, the difference of long so more rigidity and the benzene molecular energy of adsorption on metallicity armchair and semiconductive zigzag carbon pipe is just big more.But what should consider is, big more linearity and benzene molecular, and dissolubility is just poor more, and is unfavorable to separating.Because added the hydrotropy group, then there is not this problem in acene molecule derivant through modifying.
Adopt anthracene, reach other use general formula and be:
The thick aromatic hydrocarbons of ring (R in the formula is an alkyl, perhaps is the trimethyl silicane alkynyl, perhaps triisopropyl silicon alkynyl), and the assorted pentacene compound of N etc. carries out separating experiment, its result and accord with theoretical analysis.
In related experiment of the present invention, the separation promoter that uses in separating for the first time, i.e. anthracene or pentacene derivative, its addition is in 0.05～2 weight portion scope; The promotes dosage that uses in separating for the second time is 0.05～1.5 weight portion, and its result is all similar with the disclosed embodiments.
Also adopted chloroform respectively in the present invention's experiment, oxolane, the N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N, the N-dimethylacetylamide, perhaps being dimethyl sulfoxide (DMSO), perhaps is that diethyl sulfoxide or the mixed solvent that contains aforementioned solvents substitute chloroform or the N-N-methyl-2-2-pyrrolidone N-in the previous embodiment, obtains similar result equally.
As mentioned above, according to embodiments of the invention, can isolate a large amount of highly purified metallic carbon nanotubes and semiconductor carbon nanometer tube in batches.This has strengthened the application of CNT in the micro-nano electronic device greatly, for example corresponding devices such as nm-class conducting wire, nanoelectronic element, photoelectric device, sensor.Compared with prior art, processing procedure of the present invention can not introduced too much defective, and trim also can be removed by washing or method for calcinating with comparalive ease.Compare with separation method in the past, not only products obtained therefrom purity is higher in the present invention, and the loss of raw material itself is less, and utilization rate is higher.
The present invention adopt the condensed-nuclei aromatics molecular separation not its characteristics of SWNT of isomorphism type also be to have following advantage: at first, this method itself is simple to operate, and cost is low, helps widespread adoption; Secondly, compare with the prior art in the background introduction, this method is a non-destructive, and it is to the almost not loss of expensive single-wall carbon tube raw material; To have photoactive condensed-nuclei aromatics molecular modification to the carbon tube-surface, and might realize the fluorescence labeling of SWNT and the fluorescent visual of carbon pipe are handled.Simultaneously, because the condensed-nuclei aromatics molecule can absorb visible light and shift with carbon pipe generation energy, so the compound of gained condensed-nuclei aromatics molecule of the present invention and CNT is having special using value aspect organic photovoltaic devices and the solar cell.Moreover, modify the carbon pipe with shla molecule the dispersiveness of carbon pipe in multiple medium improved greatly, for the approach that provides is provided in the ordering of carbon pipe.
Though specifically illustrate and described the present invention with reference to exemplary enforcement of the present invention, but those of ordinary skills should be understood that, under the situation that does not break away from the invention spirit and scope that limit by above claim, can make the various variations on form and the details.
Claims (8)
1. the method for separating metallic and semiconductive nanotube from SWCN is carried out chemical molecular modification, ultrasonic dispersion treatment to CNT, takes out the carbon pipe again from remove precipitation gained liquid part, it is characterized in that:
A. get the CNT to be separated of purified processing of 1 weight portion and the separation promoter of 0.05～2 weight portion, the two is added in the organic solvent, system is carried out ultrasonic mixing, make separation promoter fully adsorb the particular carbon nanotube, remove the precipitation liquid hold-up then, the carbon pipe that will be suspended in again in the liquid is separated, and removes the separation promoter of carbon elimination Guan Shangwei absorption with organic solvent washing, obtains the product of enriched in metals carbon pipe;
B. get the separation promoter of 1 weight portion through separating obtained precipitation of a and 0.05～2 weight portion, the two is added in the organic solvent, system is carried out ultrasonic mixed processing, remove the precipitation liquid hold-up, the carbon pipe that will be suspended in again in the liquid is separated, remove the separation promoter that carbon Guan Shangwei is adsorbed with solvent wash, obtain enrichment semiconductive carbon pipe product;
Used separation promoter is the compound with linear condensed-nuclei aromatics structure in above process, and its condensed-nuclei aromatics partly contains at least three aromatic rings.
2. separation method according to claim 1, the separating obtained precipitation of b process in the claim 1 that it is characterized in that learning from else's experience repeats the b process of claim 1 again and handles, and can further isolate the CNT of different electrical properties.
3. separation method according to claim 2 is characterized in that can alternately isolating the CNT of different electrical properties successively to repeatedly repeat the processing procedure of claim 2 through the separating obtained precipitation of preceding process.
According to claim 1 or 2 or 3 described from SWCN the method for separating metallic and semiconductive nanotube, it is characterized in that used organic solvent is a chloroform, it perhaps is oxolane, it perhaps is the N-N-methyl-2-2-pyrrolidone N-, perhaps be N, dinethylformamide perhaps is N, N-dimethylacetylamide or be dimethyl sulfoxide (DMSO) is perhaps for diethyl sulfoxide or contain the mixed solvent of aforementioned solvents.
5. according to claim 4 from SWCN the method for separating metallic and semiconductive nanotube, it is characterized in that CNT purification treating method to be separated is: the carbon nanotube powder of 1 weight portion is put into the concentrated acid that is added with 0.1～10 weight portion anion surfactant carry out ultrasonic processing, the carbon pipe is separated, washed with water to neutrality and carry out annealing in process.
6. according to claim 5 from SWCN the method for separating metallic and semiconductive nanotube, it is characterized in that used separation promoter is an anthracene.
7. according to claim 5 from SWCN the method for separating metallic and semiconductive nanotube, it is characterized in that used separation promoter general formula is:
Wherein R is for can improve the deliquescent group of condensed-nuclei aromatics.
8. according to claim 7 from SWCN the method for separating metallic and semiconductive nanotube, it is characterized in that the carbon in the skeleton of used separation promoter neutral line condensed-nuclei aromatics part can be replaced by hetero atom.
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Cited By (9)
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| CN101704506A (en) * | 2009-09-18 | 2010-05-12 | 苏州纳米技术与纳米仿生研究所 | Method for separating metal or semiconductive carbon nanotubes |
| CN102320592A (en) * | 2011-08-26 | 2012-01-18 | 复旦大学 | Method for separating carbon nanotubes with different conductive performances |
| CN102557007A (en) * | 2011-05-20 | 2012-07-11 | 上海大学 | Method for separating carbon nanometer tubes by fractional extraction method |
| CN103569994A (en) * | 2012-07-27 | 2014-02-12 | 国家纳米科学中心 | Processing method for single-wall carbon nanotube |
| CN105233968A (en) * | 2015-06-17 | 2016-01-13 | 陶栋梁 | Method for separating nano particles of different particle sizes |
| CN106315559A (en) * | 2016-08-02 | 2017-01-11 | 山东大学 | Large-scale method for selectively separating semi-conductive single-walled carbon nanotube |
| CN107285298A (en) * | 2016-04-01 | 2017-10-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | The method and application of selection separation special diameter and the single-walled carbon nanotube of chirality |
| CN108423652A (en) * | 2018-04-18 | 2018-08-21 | 中国科学院福建物质结构研究所 | A kind of method of semi-conductive single-walled carbon nanotubes separation and concentration |
| CN111573655A (en) * | 2020-06-18 | 2020-08-25 | 江南大学 | Method for enriching single chiral carbon nano tube with high yield |
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| CN102923692A (en) * | 2012-11-21 | 2013-02-13 | 光明乳业股份有限公司 | Method for purifying carbon nano tube |
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| JP4734575B2 (en) * | 2004-08-02 | 2011-07-27 | 国立大学法人 筑波大学 | Carbon nanotube separation method, dispersion, and carbon nanotube obtained by the separation method |
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| CN101704506B (en) * | 2009-09-18 | 2013-08-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for separating metal or semiconductive carbon nanotubes |
| CN101704506A (en) * | 2009-09-18 | 2010-05-12 | 苏州纳米技术与纳米仿生研究所 | Method for separating metal or semiconductive carbon nanotubes |
| CN102557007A (en) * | 2011-05-20 | 2012-07-11 | 上海大学 | Method for separating carbon nanometer tubes by fractional extraction method |
| CN102320592A (en) * | 2011-08-26 | 2012-01-18 | 复旦大学 | Method for separating carbon nanotubes with different conductive performances |
| CN103569994A (en) * | 2012-07-27 | 2014-02-12 | 国家纳米科学中心 | Processing method for single-wall carbon nanotube |
| CN105233968A (en) * | 2015-06-17 | 2016-01-13 | 陶栋梁 | Method for separating nano particles of different particle sizes |
| CN105233968B (en) * | 2015-06-17 | 2017-11-14 | 陶栋梁 | A kind of method for separating different-grain diameter nano-particle |
| CN107285298B (en) * | 2016-04-01 | 2019-12-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | method for selectively separating single-walled carbon nanotubes with specific diameters and chiralities and application |
| CN107285298A (en) * | 2016-04-01 | 2017-10-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | The method and application of selection separation special diameter and the single-walled carbon nanotube of chirality |
| CN106315559A (en) * | 2016-08-02 | 2017-01-11 | 山东大学 | Large-scale method for selectively separating semi-conductive single-walled carbon nanotube |
| CN108423652A (en) * | 2018-04-18 | 2018-08-21 | 中国科学院福建物质结构研究所 | A kind of method of semi-conductive single-walled carbon nanotubes separation and concentration |
| CN108423652B (en) * | 2018-04-18 | 2021-12-14 | 中国科学院福建物质结构研究所 | Method for separating and enriching semiconductor single-walled carbon nanotubes |
| CN111573655A (en) * | 2020-06-18 | 2020-08-25 | 江南大学 | Method for enriching single chiral carbon nano tube with high yield |
| CN111573655B (en) * | 2020-06-18 | 2021-09-28 | 江南大学 | Method for enriching single chiral carbon nano tube with high yield |
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