CN101125649A - Method for separating metallic single-wall carbon nano-tube - Google Patents
Method for separating metallic single-wall carbon nano-tube Download PDFInfo
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Abstract
The invention discloses a method to separate and enrich a metallic carbon tube with special electrical performance from single-walled carbon nanotubes. The method of the invention is that: a right amount of to be separated carbon nano tubes and separating promoter are added into an organic solvent, and the system is ultrasonically mixed, so that the separating promoter can fully absorb specific carbon nano tubes, then precipitation in the solution is removed and the liquid is remained; and then the carbon tubes suspending in the liquid are separated, the organic solvent is used for cleaning the carbon tubes to remove the organic that is not absorbed by the carbon tubes, thus, the product enriched with metallic carbon tubes is prepared. The separating promoter adopted by the invention is a compound with a linear condensed nucleus aromatic hydrocarbon structure, the condensed nucleus part of the compound comprises at least three aromatic rings.
Description
Technical field
The present invention relates to a kind of separation method that is applied to the Single Walled Carbon Nanotube of micro-nano opto-electronic device.Particularly from Single Walled Carbon Nanotube, separate and the metallicity carbon tube side method of enrichment particular electrical character.
Background technology
Carbon nanotube has many excellent characteristic, make it at composite reinforcing material such as high length-to-diameter ratio, high strength, high tenacity, good chemical stability and thermostability 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 Single Walled Carbon Nanotube is to be controlled by the caliber of carbon pipe and configuration.The configuration of carbon nanotube usually with two chirality characteristic parameters (n m) represents, when m=n, chiral angle θ=30 °, carbon nanotube at this moment is called armchair carbon nanotube (Armchair); (chiral angle θ=0 °) carbon nanotube is called zigzag nanotubes (Zigzag) when m=0 or n=0; Carbon nanotube when m, n during for other value (0＜θ＜30 °) this moment is called chirality type or spiral type (Chiral) carbon nanotube.Wherein, (n is that Armchair type carbon pipe all is metallic n); For (n, 0) be the Zigzag type when n is 3 multiple, carbon nanotube 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.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 carbon nanotube still open question is to the not fractionation of the carbon pipe of isomorphism type.If desired carbon nanotube is integrated in following nano-device, just necessarily requires to know definitely the configuration of carbon nanotube in the obtained device.For example, semiconductor carbon nanometer tube is used for memory device, transmitter etc., and metallic carbon nanotubes is used for the electrode materials of battery, electromagnetic protection layer etc.The research of carbon nanotube optical property is found that also interaction with metallicity carbon pipe also can make the near-infrared fluorescent generation cancellation of semi-conductor 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 general 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 at present the means of reality the most.
Usually, when carrying out the separation of carbon pipe in the prior art, when particularly the carbon pipe that contains impurity being separated, 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 vitriol oil or concentrated nitric acid, perhaps in the concentrated acid of mixture of the vitriol oil and concentrated nitric acid and so on, again carbon nanotube powder is put into and wherein carried out supersound process, 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 anneal.
The Separation Research of relevant carbon nanotube 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 study group [P.G.Collins, M.S.Arnold, P.Avouris, Science.2001,292,706] utilizes the electroconductibility 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 specific inductivity that the carbon pipe is different, make metallicity carbon pipe polarization back preferential deposition on electrode with the alternating-current bidirectional electrophoretic technique.The method of this original position device preparation is higher to equipment requirements, and can only be applied to the preparation of small number of devices.(2) the auxiliary separation of biomacromolecule 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 Zeo-karb bonding force.This 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 small molecules chemically modified: 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 stearylamine [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 centrifugal or filtering isolation technique, the enrichment semiconductive or the metallicity carbon pipe that are suspended in the solution are separated.Existing chemical modification method has significant deficiency, and is lower as adopting bromine and porphyrin to carry out isolating efficient.Reported and adopted stearylamine metallicity carbon pipe can be enriched to 87% through separating for several times.Yet, be unfavorable for the performance of nanometer electronic device because stearylamine originally as the insulativity molecule, can constitute the electric transmission potential barrier between carbon pipe and the electrode that is connected.In addition, stearylamine belongs to the tensio-active agent quasi-molecule, might pollute device.
Studies show that in recent years, the chemically modified of carbon nanotube is a kind of effective means that carbon nanotube structure (diameter, spirality, chirality) is sieved, and to develop its potential performance (energy storage, gas storage and catalytic performance), exploitation relevant nano-device (nano-reactor, gas sensor, electronic component etc.), type material (biomaterial, electrode materials) all have very big realistic meaning.
Summary of the invention
The invention provides a kind of prior art deficiency that overcomes, can from Single Walled Carbon Nanotube, effectively isolate the method for metallic carbon nanotubes.
Method of the present invention is: get the carbon nanotube to be separated of 1 weight part and the separation promoter of 0.05～2 weight part, 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 retaining liquid then, the carbon pipe that will be suspended in again in the liquid is separated, remove carbon elimination Guan Shangwei adsorbed organic matter with organic solvent washing, obtain the product of enriched in metals carbon pipe, used separation promoter is the compound with linear condensed-nuclei aromatics structure, 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 solvability, and carbon nanotube is had the organic solvent of better dispersive ability.The organic solvent that the present invention recommends to use is chloroform, perhaps adopts tetrahydrofuran (THF), perhaps adopts the N-N-methyl-2-2-pyrrolidone N-, perhaps adopts N, and dinethylformamide perhaps adopts N,N-dimethylacetamide, perhaps adopts the mixed solvent that contains aforementioned solvents.
When adopting method of the present invention to separate the carbon pipe,, can make carbon pipe to be separated pure, help improving separation efficiency if earlier carbon nanotube is carried out purifying.Purification process of the present invention is: with anion surfactant by the carbon pipe: the mass ratio of tensio-active agent is that 1: 0.1～10 anion surfactant is dissolved in the concentrated acid, again carbon nanotube powder is put into concentrated acid and carry out supersound process, leave standstill then and treat that the carbon pipe precipitates fully, again the carbon pipe is separated, washed with water to neutrality and under inert atmosphere, carry out anneal.
The used separation promoter of the present invention can be an anthracene, or general formula is:
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 heteroatoms.
The theoretical analysis shows that with corresponding experiment method of the present invention can effectively be isolated metallic carbon nanotubes from Single Walled Carbon Nanotube, and isolating method is comparatively simple, practical.
The method of the invention provides can effectively be isolated metallic carbon nanotubes.The carbon pipe that separates the metal mold enrichment that obtains through the present invention will be at battery, the electrode materials of electromagnetic protection etc. and electron device lead, and the SPM needle point, aspects such as electrical condenser are widely used.Adopt the mixture of resultant condensed-nuclei aromatics molecule of the inventive method and carbon nanotube that special using value is being arranged aspect photoelectric device and the solar cell in addition.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) picture, wherein: (A) the purified Single Walled Carbon Nanotube pattern that obtains, (B) be the pattern of the metallicity carbon pipe that adopts method of the present invention to carry out to leach in the supernatant liquor of resulting separation, (C) for after separating in precipitation the pattern of the semi-conductor carbon pipe of enrichment.
Fig. 2 is the Raman spectrogram in ring breathing zone (RBM) zone of the carbon pipe that leaches through the isolating gained supernatant liquor of method of the present invention.
Fig. 3 is the Raman spectrogram through ring breathing zone (RBM) zone of the isolating gained deposit sample of method of the present invention.M represents metallicity carbon pipe The corresponding area among the figure, and S represents semiconductive carbon pipe The corresponding area.
Fig. 4 is the Raman spectrogram G band with the present invention isolating carbon pipe product, and as can be seen from the figure tangible both shoulders peak in the supernatant samples meets the feature of metal carbon pipe.Simultaneously, deposit sample demonstrates the characteristic peak of tangible semi-conductor carbon pipe.
Embodiment
Relative theory analysis is provided below the present invention, and tests accordingly and measured result.
Metallicity of the present invention and the characteristics of the separation method of semiconductive carbon nano tube have been to introduce the notion of the different electrical properties carbon of condensed-nuclei aromatics molecular separation pipe, have proposed the thought by π-π interaction differential liberation.Used condensed-nuclei aromatics compound with special geometric configuration is the condensed-nuclei aromatics that a class has linear rigid structure, as anthracene, and tetracene (naphthacene), pentacene and derivative thereof are referring to table 1.
We adopt Density functional (DFT) method to simulate the absorption situation of condensed ring aromatic molecules on metal mold (7,7) and semi-conductor type (13,0) single-walled pipe (SWNT).The insider can understand, the combination of the two best Orbit Matching be each phenyl ring in the condensed ring aromatic molecules and the six-membered ring structure on the SWNT by the face-to-face pattern match to reach maximum π-π stacking reactive force.Because the remarkable curvature of carbon nanotube and the rigidity of condensed ring aromatic molecules, the π-π matching degree of condensed ring aromatic molecules on (13,0) carbon pipe is not as going up fully in (7,7).The calculation result of DFT shows condensed-nuclei aromatics compound and the height of (7,7) SWNT bound energy ratio with (13,0) SWNT.Referring to table 1.
Table 1
By calculating, illustrate that the present invention plants the following feature that is adsorbed with of aromatic hydrocarbon molecule and carbon pipe: condensed-nuclei aromatics is more prone to be adsorbed onto (7,7) metal mold carbon tube-surface, forms π-π stacking mixture; The structure of condensed-nuclei aromatics is the important factor that influences itself and nanotube effect.The number of rings of linear condensed-nuclei aromatics (anthracene, pentacene) is many more, and its absorption difference on these two types of carbon pipes is just big more.Theoretical analysis and calculating show that the number of rings of linear condensed-nuclei aromatics (anthracene, pentacene) is many more, and its absorption difference on these two types of carbon pipes is just big more, and this indicates that also its isolating effect will be better.In addition, carbon is also had the ability of certain separating metal carbon pipe on the skeleton by the condensed-nuclei aromatics that heteroatoms replaced.
On the basis of above theoretical analysis, carried out actual separation test, and with this result who comes proof theory to analyze.Below for adopting condensed-nuclei aromatics compound-pentacene and anthracene to carry out isolating example.In the actual separation test, resulting sample is adopted UV-Vis-NIR, Raman spectral evaluation separation efficiency, the pattern of product and dispersiveness etc. after TEM investigates and separates.
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 purification process, the treatment process that for example adopts prior art to provide, this can make separation thereafter more effective, reliable.If employed carbon pipe powder itself is comparatively pure, also can not adopt purification step.
The used purification process of present embodiment is: at first, with 1 weight part carbon nanotube be added with in the 10 weight part concentrated hydrochloric acid solutions of 4 weight part sodium lauryl sulphate or sodium laurylsulfonate, behind ultrasonic 3～4h, leave standstill, treat to remove the upper strata acid solution after the sedimentation of carbon pipe, it is ultrasonic once more to add the new acid solution that has tensio-active agent, for fully removing the granules of catalyst in the carbon nanotube, should repeat this step to acid solution color and no longer change, remove solution with 0.45 micron filtering with microporous membrane again.Pure water rinsing leaches thing to neutral (common pH test paper test), uses the acetone rinsing solid again.As for 80 ℃ of dryings in the vacuum drying oven 12 hours, abrasive solid became Powdered with the gained solid.The carbon pipe powder is put into tube furnace, and annealing is 2 hours under 820 ℃ of high-purity argon gas atmosphere.Slowly after the cooling, impurity such as carbon nano-particle were removed in 550 ℃ of following oxidations in 1.5 hours in air.The purity TEM of carbon pipe, SEM, the Raman spectral characterization proves through behind the purifying to obtain purified Single Walled Carbon Nanotube.Simultaneous test shows that adding tensio-active agent in purge process in acid has higher purification efficiency than prior art.
Embodiment 2: with 6, two (2-(TMS) ethynyl) pentacenes of 13-are modified and product separation
With the good Single Walled Carbon Nanotube of 1 weight part example, 1 gained purifying, with 6 of 0.1 weight part, two (2-(TMS) ethynyl) pentacenes of 13-mix ultrasonic 3.5 hours in chloroform after, centrifugal under the supercentrifuge 12000rpm rotating speed, collect supernatant liquor and precipitation.Be precipitated as enrichment semiconductive carbon pipe product.With 0.22 micron filtering with microporous membrane supernatant liquor, adopt a large amount of solvent washs subsequently to remove 6 of a small amount of not absorption or desorption, two (2-(TMS) ethynyl) pentacenes of 13-.Collect the product on the filter membrane, obtain enriched in metals carbon pipe product.
The sign of separated product is seen Fig. 1, Fig. 2, Fig. 3 and Fig. 4.
Embodiment 3: modify and product separation with anthracene
With the good Single Walled Carbon Nanotube of 1 weight part example, 1 gained purifying, centrifugal under the supercentrifuge 12000rpm rotating speed with the anthracene of 0.1 weight part mixes ultrasonic 3.5 hours in chloroform after, collect supernatant liquor and precipitation respectively.Be precipitated as enrichment semiconductive carbon pipe product.With 0.22 micron filtering with microporous membrane supernatant liquor, remove and to desolvate, with a large amount of solvent washs to remove a small amount of absorption or the anthracene of desorption.Collect the product on the filter membrane, obtain enriched in metals carbon pipe product.
The sign of separated product is seen Fig. 3.
By optical maser wavelength be the caliber of the sample that obtains in the Raman scattering test case 2 of 532nm and the example 3 distribute and each sample in the content of metal tube content and semiconductor carbon nanometer tube.Experimental result is shown among Fig. 2, Fig. 3 and Fig. 4.With reference to Fig. 2, as can be seen among the embodiment 3 the separating obtained supernatant liquor of anthracene the ring breathing zone (RBM) 210～290cm
-1Obviously there is stronger more peak in the metallicity district than precipitation, proves the method according to the embodiment of the invention, can separate a large amount of metallicity and semiconductive carbon nano tube efficiently.In the example 26, it is more obvious that the auxiliary separating obtained supernatant liquor of two (2-(TMS) ethynyl) pentacenes of 13-and sedimentary Raman spectrum are distinguished, and proves that pentacene derivative has better separating effect than anthracene.Simultaneously, the analysis that G in the Raman spectrum is with can obtain the result consistent with encircling breathing zone, has further proved the enrichment of metallicity carbon pipe in supernatant liquor.G band characteristic peak is shown as the characteristic of semiconductor peak in the purified carbon pipe, change the bimodal peak shape of significant metallicity in supernatant liquor into, and the peak shape at G peak demonstrates the feature peak shape of semiconductive carbon pipe more in precipitation.
Pentacene derivative has this trend of better separating effect consistent with separating mechanism of the present invention than anthracene: when the π-π of linear condensed ring molecule and carbon pipe mates absorption, because the curvature of carbon tube-surface, take all factors into consideration π-π coupling and two factors of contact area, make inflexible condensed-nuclei aromatics molecule (being separation promoter of the present invention) selective adsorption on metal mold carbon pipe.If the caliber of carbon pipe is certain, the difference of the sorptive power of long so more condensed-nuclei aromatics molecule on metallicity and semiconductive carbon pipe is just big more.But what should consider is, big rectilinearity condensed-nuclei aromatics solvability is relatively poor, and is unfavorable to separating, and the introducing of hydrotropy group can address this problem preferably.
The present invention can use any organic solvent, but can solvability preferably be arranged to separation promoter as employed organic solution, and has certain dispersive ability will have effect preferably to carbon nanotube.Also used in the following solvent any in the experiment: tetrahydrofuran (THF), the N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N,N-dimethylacetamide, or the mixture of aforementioned solvents, its effect is identical with chloroform.
As mentioned above, according to embodiments of the invention, can separate and a large amount of highly purified metallic carbon nanotubes of enrichment.This has strengthened the application of carbon nanotube in the micro-nano electron device greatly, for example corresponding devices such as nm-class conducting wire, nanoelectronic element, photoelectric device, transmitter.Compared with prior art, treating processes of the present invention can not introduced too much defective, and modifier 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 ratio is higher.
The present invention adopts the condensed ring aromatic molecules to separate not, and its characteristics of SWNT of isomorphism type also are 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, present method is a nondestructive, 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 fluorescent mark 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 mixture of gained condensed-nuclei aromatics molecule of the present invention and carbon nanotube 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, protection scope of the present invention is not limited in listed examples.Those of ordinary skills should be understood that, under the situation that does not break away from the principle that limited by above claim and scope, can make the various variations on form and the details.
Claims (6)
1. the method for separating metallic single-wall carbon nano-tube, carbon nanotube is carried out chemical molecular to be modified, ultra-sonic dispersion is handled, from remove precipitation gained liquid portion, take out the carbon pipe again, it is characterized in that: get the carbon nanotube to be separated of 1 weight part and the separation promoter of 0.05～2 weight part, 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 retaining liquid then, the carbon pipe that will be suspended in again in the liquid is separated, remove carbon elimination Guan Shangwei adsorbed organic matter with organic solvent washing, obtain the product of enriched in metals carbon pipe, used separation promoter is the compound with linear condensed-nuclei aromatics structure, and its condensed-nuclei aromatics partly contains at least three aromatic rings.
2. the method for separating metallic single-wall carbon nano-tube according to claim 1, it is characterized in that used organic solvent is a chloroform, it perhaps is tetrahydrofuran (THF), it perhaps is the N-N-methyl-2-2-pyrrolidone N-, perhaps be N, dinethylformamide perhaps is N,N-dimethylacetamide or the mixed solvent that contains aforementioned solvents.
3. the method for separating metallic single-wall carbon nano-tube according to claim 1 and 2, it is characterized in that carbon nanotube pretreatment process to be separated is: with anion surfactant by the carbon pipe: the mass ratio of tensio-active agent is that 1: 0.1～10 anion surfactant is dissolved in the concentrated acid, again carbon nanotube powder is put into concentrated acid and carry out supersound process, the carbon pipe is separated, washed with water to neutrality and carry out anneal.
4. the method for separating metallic single-wall carbon nano-tube according to claim 3 is characterized in that used separation promoter is an anthracene.
5. the method for separating metallic single-wall carbon nano-tube according to claim 3 is characterized in that used separation promoter general formula is:
Wherein R is an alkyl, perhaps is the trimethyl silicane alkynyl, perhaps triisopropyl silicon alkynyl.
6. the method for separating metallic single-wall carbon nano-tube according to claim 5 is characterized in that the carbon on the used separation promoter neutral line condensed-nuclei aromatics skeleton partly can be replaced by heteroatoms.
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| 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 |
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