WO2011108666A1 - カーボンナノチューブの分離回収方法及びカーボンナノチューブ - Google Patents
カーボンナノチューブの分離回収方法及びカーボンナノチューブ Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/17—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/172—Sorting
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/46—Flow patterns using more than one column
- G01N30/461—Flow patterns using more than one column with serial coupling of separation columns
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/8859—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample inorganic compounds
- G01N2030/8863—Fullerenes
Definitions
- the present invention relates to a method for efficiently separating metal-type carbon nanotubes and carbon nanotubes (CNTs) containing semiconductor-type carbon nanotubes, and separating semiconductor-type CNTs for each structure, and carbon nanotubes obtained thereby .
- CNTs metal-type carbon nanotubes and carbon nanotubes
- CNT has excellent properties such as its electrical characteristics and mechanical strength, and research and development is being conducted vigorously as the ultimate new material.
- This CNT is synthesized by various methods such as a laser evaporation method, an arc discharge method, and a chemical vapor deposition method (CVD method).
- CVD method chemical vapor deposition method
- any synthesis method can be used only in the form of a mixture of metal-type CNTs and semiconductor-type CNTs.
- Non-Patent Document 1 a method of dielectrophoresis of CNT dispersed with a surfactant on a microelectrode (Non-Patent Document 1), a method using amines as a dispersant in a solvent (Non-Patent Documents 2 and 3), hydrogen peroxide
- Non-patent Document 4 a method of selectively burning semiconductor-type CNTs (Non-patent Document 4).
- these problems are particularly limited to metal-type CNTs, and the recovery rate is low. The problem has not been resolved.
- a method of separating a semiconductor-type CNT by dispersing a mixture of the semiconductor-type CNT and the metal-type CNT in a liquid, selectively bonding the metal-type CNT to particles, and removing the metal-type CNT bonded to the particles (Patent Document) 1) After the CNTs are treated with a nitronium ion-containing solution, filtration and heat treatment are performed to remove metal-type CNTs contained in the CNTs to obtain semiconductor-type CNTs (Patent Document 2), and a method using sulfuric acid and nitric acid ( Patent Document 3), and a method (Patent Document 4) for obtaining a semiconductor-type CNT with a narrow electric conductivity range by selectively moving and separating CNTs by applying an electric field.
- Non-patent Document 5 There is a method of separating CNT dispersed with a surfactant into metallic CNT and semiconductor CNT by density gradient ultracentrifugation (Non-patent Document 5).
- This method uses a very expensive device called an ultracentrifuge, the ultracentrifugation operation requires a long time, and the size of the ultracentrifuge itself is limited, and multiple ultracentrifuges are installed in parallel. There was a problem that it would be difficult to perform automation and other processing.
- Patent Document 5 There is a method in which a CNT-nucleic acid complex composed of CNTs bonded to nucleic acid molecules is produced and separated by ion exchange chromatography.
- Patent Document 5 There are problems that an expensive synthetic DNA is necessary and that the separation rate is not so high and the recovery rate and purity are not good.
- Patent Document 6 In addition, by adjusting the pH and ionic strength of the CNT solution dispersed with the surfactant, protonation of a different degree occurs depending on the type of CNT, and an attempt is made to separate the metal type and the semiconductor type by applying an electric field. Although there is a report (Patent Document 6), this method requires a step of pretreating the pH and ionic strength of the suspended nanotube mixture with a strong acid prior to separation, and strict process control for that purpose. In the end, separation of metal-type and semiconductor-type CNTs has not been achieved (Patent Document 6, Example 4).
- the diameter separation and the structure separation of the semiconductor-type CNT have the same problems as the separation of the metal-type and semiconductor-type CNT.
- Non-Patent Document 5 Non-Patent Document 5
- Patent Document 7 It has been reported that the CNT-nucleic acid complex is separated from the CNT structure by ion exchange chromatography (Patent Document 7). However, this method has problems that it is necessary to prepare a specific synthetic DNA for CNTs having individual structures, and that the synthetic DNA is very expensive.
- none of the conventional methods can overcome the above-mentioned problems, and a method of separating metal-type CNT and semiconductor-type CNT from CNT based on a new concept, and a semiconductor having a specific structure Development of a method for separating type CNTs has been desired.
- Patent Documents 9, 10, 11, 12 The present inventors started a novel metal-type CNT and semiconductor-type CNT separation method different from the conventional methods, and completed the following inventions (Patent Documents 9, 10, 11, 12).
- the invention is such that when a combination of a specific type of dispersant and gel is used, the semiconductor CNT can be selectively adsorbed on the gel and can be separated from the metal CNT. In the separation, the semiconductor CNT adsorbed on the gel and the non-adsorbed CNT are separated by electrophoresis (Patent Documents 9 and 10), centrifugation, freeze pressing, diffusion, infiltration, etc. (Patent Document 11). These methods can obtain both metal-type CNTs and semiconductor-type CNTs, can be separated in a short time with a high recovery rate, and can be easily processed in large quantities with inexpensive equipment. It is excellent.
- Patent Document 12 a method for recovering semiconductor CNT adsorbed on the gel using an appropriate eluate was completed (Patent Document 12).
- the method of passing the CNT dispersion liquid through the gel to adsorb the semiconductor CNTs onto the gel, eluting and separating the unadsorbed metal CNTs, and recovering the semiconductor CNT adsorbed on the gels with the eluate It can be used repeatedly and can be automatically separated, which is an excellent technique for industrially mass-producing metal-type and semiconductor-type CNTs.
- Patent Document 12 a method was also invented, in which metal / semiconductor CNTs were separated by adjusting the concentration of the eluate by the same method, and at the same time, CNTs could be separated by diameter. This method can obtain CNTs with different diameters at the same time as separation of metal-type CNT and semiconductor-type CNT.
- high-yield, short-time, and inexpensive equipment can be used for mass processing and automatic processing. It is also very good possible.
- JP 2007-31238 A Japanese Patent Laid-Open No. 2005-325020 JP 2005-194180 A JP 2005-104750 A JP 2006-512276 A JP 2005-527455 A JP 2004-142972 A JP 2006-282418 A JP 2008-285386 A JP 2008-285387 A International Publication WO2009 / 075293 Pamphlet Japanese Patent Application No. 2009-147557 Advanced Materials 18, (2006) 1468-1470 J. Am. Chem. Soc. 127, (2005) 10287-10290 J. Am. Chem. Soc. 128, (2006) 12239-12242 J. Phys. Chem. B 110, (2006) 25-29 Nature Nanotechnology 1, (2006) 60-65 Nano Letters 9, (2009) 1497-1500 NATURE 460, (2009) 250-253
- the present invention has been made in view of the above circumstances, a method for separating metal-type and semiconductor-type CNTs, and also accurately separating semiconductor-type CNTs having different structures, and carbon nanotubes obtained thereby. Is intended to provide.
- a single-type semiconductor CNT can be separated by applying a large excess of CNT dispersion to a small amount of gel. Furthermore, by connecting a plurality of columns filled with gel in series and adding a large excess of CNT dispersion, semiconductor-type CNTs with different structures can be adsorbed to each column, and separated and recovered at once. It is possible (FIG. 1).
- the sample addition amount is less than the binding capacity of the carrier, or the separation amount is aimed to be improved.
- the separation accuracy is improved by deliberately increasing the amount of the sample added in a completely opposite way of thinking, and it can be said that this is an original novel separation method.
- high-accuracy separation is achieved by first binding only those having high affinity to the carrier and separating them from the remaining substances.
- the present invention has been made based on such novel findings.
- An excessive amount of the carbon nanotube dispersion liquid is allowed to act on the gel packed in the column to adsorb carbon nanotubes having a strong adsorptive power to the gel.
- a carbon nanotube characterized in that a solution containing adsorbed carbon nanotubes and a gel adsorbing carbon nanotubes are separated, and an eluent is allowed to act on the gel after the separation, whereby the carbon nanotubes adsorbed on the gel are taken out. Separation and recovery method.
- n columns in series (n ⁇ 2, n is a natural number)
- an excess amount of carbon nanotube dispersion is allowed to act on the gel packed in the first column
- the n th The first to n-th adsorptive power adsorbed on the gel of each n-stage column is strong by allowing the carbon nanotube dispersion liquid to act on the first-stage column until the carbon nanotubes are adsorbed on the gel of the above-mentioned column.
- ⁇ 4> The method for separating and recovering carbon nanotubes according to ⁇ 1> or ⁇ 2>, wherein semiconductor-type carbon nanotubes having a specific structure having a strong adsorptive power are taken out from the gel after separation.
- ⁇ 5> The method for separating and collecting carbon nanotubes according to ⁇ 4>, wherein semiconductor-type carbon nanotubes having a specific diameter as a specific structure are taken out from the gel after separation.
- ⁇ 7> The method for separating and collecting carbon nanotubes according to ⁇ 4>, wherein semiconductor-type carbon nanotubes having a specific local radius of curvature are extracted as a specific structure from the separated gel.
- concentration of the carbon nanotube dispersion liquid acting on the gel packed in the n-th column is made lower than the concentration of the carbon nanotube dispersion liquid acting on the gel packed in the n-1 st column.
- ⁇ 2> The method for separating and collecting carbon nanotubes according to ⁇ 2>.
- the present invention it is possible to separate the metal CNT and the semiconductor CNT simultaneously, and at the same time, the semiconductor CNT can be separated due to the difference in structure. Similarly, it is also possible to separate those having a specific structure from a mixture of semiconducting CNTs. In addition to continuous separation using a column, it can also be applied to a batch system. A plurality of types of semiconductor-type CNTs having a specific structure can be obtained with high accuracy at a time. As described above, in the method of separating single-structure semiconductor CNTs using expensive synthetic DNA (Non-patent Document 7), it is necessary to prepare synthetic DNA having a specific sequence for CNTs having individual structures.
- the same reagent may be used to separate the semiconductor CNTs of any structure, which is very excellent in terms of operability and cost.
- the equipment is inexpensive and can be separated with high accuracy, the column can be used repeatedly, and can be separated by automation. From these advantages, the separation cost can be greatly reduced. It can be said that the semiconductor type CNT can be separated according to the structure, and the metal type CNT and the semiconductor type CNT can be separated at the same time.
- the fluorescence intensity of the fluorescence wavelength (horizontal axis) with respect to the excitation wavelength (vertical axis) is shown by a contour map. It shows that the intensity increases in the order of the darkness of the spot that appears brighter and the spot that appears darker than the dark background (see the scale on the right).
- the main spot shows a chiral index aside. It is a light absorption spectrum (CoMoCAT-CNT) of a separated sample. It is the result (unseparated sample, CoMoCAT-CNT) of a fluorescence spectrum measurement. It is a result of a fluorescence spectrum measurement (separated sample, CoMoCAT-CNT). It is a photograph (CoMoCAT-CNT) of a separated sample.
- the carbon nanotubes having a “specific structure” separated and recovered in the present invention have an ultraviolet-visible-near-infrared in a specific structure defined by a diameter, chirality, local radius of curvature, and a combination thereof. From the light absorption spectrum measurement, the fluorescence spectrum measurement, the Raman spectrum measurement, etc., the features based on the structure can be clearly identified when compared with those before the separation operation. Therefore, the carbon nanotube having a specific structure after separation and recovery is a mixture in which two or more kinds of specific structures are extracted as well as those having a single structure. Also good.
- the carbon nanotube having such a specific structure is a mixture containing a small amount of any other structure within a range where it can be discriminated that the carbon nanotube is selectively separated and recovered based on the above measurement. There may be.
- the present invention is directed to a mixture of metal-type CNT and semiconductor-type CNT (hereinafter also simply referred to as CNT) or a mixture of semiconductor-type CNTs having different structures, and is separated into metal-type CNTs and semiconductor-type CNTs and semiconductors having different structures
- CNT metal-type CNT
- the present invention relates to a method for separating CNTs or a method for separating CNTs having different structures.
- an excessive amount of the CNT dispersion liquid obtained as described above is added to the gel packed in the column to separate and purify only a part of the CNTs having strong adsorptive power. It is to do.
- the excessive amount of the CNT dispersion is an amount larger than the adsorption capacity of the carbon nanotubes with respect to the gel packed in the column.
- the amount of CNT charged into the column is increased, the CNT that can be adsorbed on the gel is eluted without being adsorbed on the column in the same manner as the CNT that cannot be adsorbed on the gel. It is a quantity.
- the CNTs that are collected without adsorbing to the gel packed in the column are again left in the newly prepared similar column. When this occurs, the amount of CNT initially charged into the column is an excessive amount.
- the principle of binding only CNTs having a specific structure when an excessive amount of CNT dispersion is allowed to act on the gel packed in the column is considered as follows.
- CNTs having a specific structure having a strong adsorptive power with respect to the gel are lower than those with a weak adsorbing power.
- CNTs that are preferentially adsorbed and CNTs having a weak adsorbing power are discharged without being adsorbed on the gel.
- the types of CNTs adsorbed on the gel are limited to those having strong adsorptive power, and only specific types of CNTs can be obtained.
- CNTs used for the separation can be any of the separation targets of the present invention without any problem regarding the production method, shape (diameter or length), or structure (single layer, double layer, etc.).
- CNT the structure of CNT is uniquely defined by a chiral index consisting of a pair of two integers (n, m).
- the synthesized CNTs are usually tens to hundreds of bundles including both metallic CNTs and semiconductor CNTs. Prior to separation of metal-type CNT and semiconductor-type CNT, or separation by the structure of CNT, it is important to disperse and solubilize CNTs that are isolated one by one and to remain stable for a long time.
- CNTs are dispersed and isolated by adding a mixture of CNTs to a solution to which a surfactant is added as a dispersant and sufficiently performing ultrasonic treatment.
- the liquid subjected to the dispersion treatment includes dispersed / isolated CNT, CNT that cannot be dispersed / isolated and remains in a bundle, amorphous carbon, a metal catalyst, and the like as synthesis by-products.
- CNTs, amorphous carbon, and metal catalyst as bundles are precipitated, while isolated CNTs that form micelles with surfactants are used as supernatant. Can be recovered. The obtained supernatant becomes a sample used for separation of CNTs.
- water is most preferable. From this point, water is used for preparing the CNT dispersion.
- any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant can be used.
- alkylsulfuric acid type having 10 to 14 carbon atoms dodecanesulfonic acid, dodecanoyl sarcosine, dodecanoic acid, cholic acid and the like are preferable.
- amphoteric surfactants n-dodecylphosphocholine and the like are preferable. These surfactants can be used in combination, and can also be used in combination with other surfactants.
- the surfactant used in combination may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a dispersing agent such as a polymer, DNA, or protein.
- concentration of the dispersant such as the surfactant varies depending on the type and concentration of the CNT used, the type of the dispersant used, and the like. For example, the final concentration may be 0.01% to 25%.
- the concentration of CNT in the dispersion can be adjusted to 1 ⁇ g / ml to 10 mg / ml, preferably 0.1 mg / ml to 1 mg / ml.
- the amount of sample added varies depending on the number of separated substances contained in the sample and the composition ratio, but can be several times to several tens of times the binding capacity of the gel carrier, for example. .
- the gel to be used is a conventionally known saccharide-based gel, such as dextran-based gel (sephaacryl: allyl dextran and N, N′-methylenebisacrylamide homopolymer, GE Healthcare), agarose gel, starch gel, etc. Acrylamide gel.
- the gel which consists of a mixture of these gels, or the structural component of these gels, and the mixture and compound of another substance may be sufficient.
- the gel concentration is preferably 0.01% to 25% as a final concentration, for example.
- the separation of the present invention is not limited to the column method.
- a small amount of gel is added to a large excess of CNT dispersion, and only a substance having strong adsorptive power is adsorbed on the gel and separated and recovered. It can also be applied to the batch method.
- the liquid can be sent to the column by a method of sending the solution by gravity drop of a solvent using an open column or a method of sending the solution by a pump to a sealed column.
- a method of sending the solution by gravity drop of a solvent using an open column or a method of sending the solution by a pump to a sealed column.
- the separation using a pump it is possible to increase the flow rate and perform a large amount of processing.
- Automatic separation using a chromatographic apparatus is also possible. Even when columns connected in series are used, it is possible to automate the entire separation process by arranging appropriate valves before and after the column.
- separation can be achieved by increasing the adsorption force by changing the concentration of the dispersant in the solution used for separation.
- a dispersant such as a surfactant can be used.
- ultraviolet-visible-near-infrared absorption spectrum measurement is used.
- the absorption wavelength band (M 11 , S 11 , S 22 , S 33 ) varies depending on the average diameter of the CNT to be measured. It shifts to the short wavelength side as the average diameter becomes thin, and shifts to the long wavelength side as the average diameter becomes thick.
- metal-type and semiconductor-type CNTs can be detected for each chirality, but only information derived from some existing CNTs can be obtained.
- metal-type CNT cannot be measured, but semiconductor-type CNT can be distinguished and detected for each chirality.
- the result of measurement using HiPco-CNT before separation as a sample is (FIG. 4B).
- the vertical axis represents the excitation wavelength
- the horizontal axis represents the fluorescence wavelength
- the fluorescence intensity is represented by a contour map showing the color intensity. Fluorescence derived from a single chiral semiconductor type CNT appears as a spot. The corresponding chirality is shown beside the spot.
- Example 1 By adding a large excess of CNT sample to the column, single chiral semiconductor CNTs were separated and recovered.
- CNI Hipco-CNT
- SDS aqueous solution
- the dispersion obtained by sonication was subjected to ultracentrifugation (197,000 ⁇ g, 15 minutes), and then 80% of the supernatant was recovered. This solution was used as a CNT dispersion.
- Gel beads (Sephaacryl S-300, GE Healthcare) were used as a column carrier. Gel beads were packed in a plastic column having a length of 7.5 cm and an inner diameter of 1.5 cm so as to have a height of about 2 mm, passed through deionized water, and then equilibrated with a 2% SDS aqueous solution. Thereto, 5 ml of CNT dispersion was added.
- a peak of M 11 is observed around. These absorption peaks have different peak wavelengths depending on their diameters, and shift to the long wavelength side if the CNT has a large diameter and to the short wavelength side if the CNT has a small diameter.
- the synthesized CNT is a mixture of CNTs of various types and diameters, and the light absorption spectrum is observed as a superposition of the peaks of these mixtures.
- 2A shows a number of peaks in the CNT (Pristine) before the separation, but the adsorbed and eluted column (Col1) is in the S 11 , S 22 , and S 33 regions. One peak was observed in each, suggesting that single-chirality semiconductor CNTs were separated.
- the vertical axis represents the excitation wavelength
- the horizontal axis represents the fluorescence wavelength
- the fluorescence intensity is represented by a contour map showing the color intensity. Fluorescence derived from a single semiconductor CNT appears as a spot. A number of spots were observed in the sample before separation (FIG. 4A), but the spectrum of the sample after separation was found to be only a single spot of (6,5) CNT.
- Example 2 In the same experiment as in Example 1, by connecting a plurality of columns in series, CNTs with different chiralities were adsorbed to different columns at once, and then the CNTs adsorbed on the columns were recovered after dividing into each column. By doing so, CNTs having different chiralities were separated at once.
- Preparation and separation of column As shown in FIG. 1, six columns were connected in series. Separation is possible using either Sephacryl S-200 or Sephacryl S-300, but Sephacryl S-300 having good (6,5) CNT purity was used for the first and second columns. The first column was packed with Sephacryl S-300 having a height of 2 mm and the second column having a height of about 3.5 mm. The third to sixth columns were packed with Sephacryl S-200 so that the height was about 6 mm. Prior to separation, the column was sequentially equilibrated with deionized water, 2% aqueous SDS.
- the separation was performed at a low concentration of the dispersant. Specifically, the passed CNT dispersion was precipitated by ultracentrifugation (197,000 ⁇ g, 3 hours), concentrated, diluted to a final concentration of 1.5% SDS, and diluted to 5 ml. And used as a sample for separation. Separation was performed in the same procedure as the second separation except that 1.5% SDS aqueous solution was used as the column equilibration and unadsorbed CNT eluent, and the obtained column adsorption fractions were designated as Col13 to Col18. The CNT solution that was not adsorbed on the column in the third separation was again applied to the column and separated using 1.5% SDS, and the obtained fractions were designated as Col19 to Col24.
- the final concentration is 1% SDS.
- the sample was diluted to 5 ml and used as a sample for separation. Separation was performed in the same procedure as the second separation except that a 0.5% SDS aqueous solution was used as an eluent for column equilibration and unadsorbed CNT, and the column adsorption fractions obtained were Col25 to Col30.
- the CNT solution that was not adsorbed on the column in the fifth separation was again applied to the column for separation, and the obtained fractions were designated as Col31 to Col36.
- FIG. 2A shows the results of pre-separation (Pristine), post-separation metal-type CNT (Metal), and fractions Col1 to Col7 bound to the column
- FIG. 2B shows the results extracted from Col8 to Col31.
- Different peak shapes are recognized in each fraction, and it can be seen that the structure separation of the semiconductor CNT occurs.
- FIG. 2C shows the result of measuring the Raman spectrum of the separated sample. From the results of Raman measurement, a tendency for CNTs having a small diameter to bind to the column quickly was confirmed, which was consistent with the result obtained from the light absorption spectrum.
- FIG. 3 is a photograph of the solution of each separated fraction.
- the metal type is brown, and the semiconductor type fraction has a vivid color change from purple to green.
- FIG. 4B shows excerpts of the results of fractions eluted from each column (Col1 to Col31).
- Example 3 The same experiment as in Example 2 was performed using different types of CNTs (CoMoCAT-CNT, Southwest Nano Technologies, diameter 0.8 ⁇ 0.1 nm). As the column, 6 pieces of Sephacryl S-300 packed were connected and used, and 10 ml of CNT dispersion was added. Separation using a 2% SDS aqueous solution as a developing solvent was repeated two cycles, and a CNT solution that did not bind to any column was recovered as metal-type CNT (Metal). Since this CNT has a small diameter and strong adsorption to the gel, almost all semiconductor CNTs were adsorbed with the 2% SDS solution. Therefore, the third adsorption experiment with the SDS concentration lowered was not performed.
- CNTs CoMoCAT-CNT, Southwest Nano Technologies, diameter 0.8 ⁇ 0.1 nm.
- CoMoCAT-CNT is a sample that originally contained a lot of (6,5) CNT (FIG. 6A, unseparated sample).
- the ratio of (6,5) CNT in the Col1 fraction after separation reached a peak intensity of about 85%, and CNTs with higher unity were obtained than when HiPco-CNT was used as a sample. .
- the color of the solution was gold for metallic CNT, Col 1 for thistle, and Steel blue for Col 6 (FIG. 7).
- CNT Since CNT has a structure in which graphene is rolled into a cylindrical shape, it has an electronic structure similar to that of graphene. Similar to graphene, in CNT, there are ⁇ electrons that do not participate in bonding in addition to electrons involved in bonding, and the properties of the ⁇ electrons determine the properties of CNT. ⁇ electrons have their electron orbits perpendicular to the hexagonal lattice, but in CNT, the graphene sheet is rounded and has a curvature, so the ⁇ orbit inside CNT has a large overlap with the adjacent ⁇ electron orbit. Thus, the overlap of the ⁇ electron orbit outside the CNT becomes smaller.
- the ⁇ electrons project out of the CNT by shifting the center of gravity of the orbit in an attempt to avoid the overlap of the orbits.
- CNTs having a larger bond curvature of sp 2 bonds (deviation from the original plane of the sp 2 hybrid orbital) (that is, CNTs having a smaller local curvature radius) have a greater outward protrusion of ⁇ -electron activation. Since the interaction between the ⁇ -electron and the Sephacryl molecule increases as the CNT having a larger ⁇ -electron orbit on the outer side of the CNT, the bond between the CNT and the gel becomes stronger. As a result, as shown in FIG. It is considered that the structural separation of the CNTs was realized in the order of the radius.
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Description
〈1〉 カラムに充填したゲルに対して過剰量のカーボンナノチューブ分散液を作用させて、ゲルに対して吸着力の強いカーボンナノチューブを該ゲルに吸着させ、前記ゲルに対して吸着力が弱く未吸着のカーボンナノチューブを含む溶液と、カーボンナノチューブを吸着したゲルを分離し、さらに前記分離後のゲルに溶出液を作用させることにより、ゲルに吸着したカーボンナノチューブを取り出すことを特徴とするカーボンナノチューブの分離回収方法。
〈2〉 カラムをn段直列して備え(n≧2、nは自然数)、第1段目のカラムに充填したゲルに対して過剰量のカーボンナノチューブ分散液を作用させて、第n段目のカラムのゲルにカーボンナノチューブが吸着するまで、第1段目のカラムにカーボンナノチューブ分散液を作用させることにより、n段の各カラムのゲルに吸着した1番目からn番目までの吸着力が強いカーボンナノチューブと、すべてのカラムのゲルに吸着しない吸着力の弱いカーボンナノチューブを含む溶液とを分離し、さらに各カラムに個別に溶出液を作用させることにより、各カラムのゲルに吸着したn種類の吸着力の異なるカーボンナノチューブを取り出すことを特徴とするカーボンナノチューブの分離回収方法。
〈3〉 前記、ゲルに対して過剰量のカーボンナノチューブ分散液とは、カラムに吸着することができるカーボンナノチューブの量を超える量のカーボンナノチューブを含む分散液であることを特徴とする〈1〉又は〈2〉に記載のカーボンナノチューブの分離回収方法。
〈4〉 分離後のゲルから吸着力の強い特定の構造を持つ半導体型のカーボンナノチューブを取り出すことを特徴とする〈1〉又は〈2〉に記載のカーボンナノチューブの分離回収方法。
〈5〉 分離後のゲルから特定の構造として特定の直径を持つ半導体型のカーボンナノチューブを取り出すことを特徴とする、〈4〉に記載のカーボンナノチューブの分離回収方法。
〈6〉 分離後のゲルから特定の構造として特定のカイラリティを持つ半導体型のカーボンナノチューブを取り出すことを特徴とする〈4〉に記載のカーボンナノチューブの分離回収方法。
〈7〉 分離後のゲルから特定の構造として特定の局所曲率半径を持つ半導体型のカーボンナノチューブを取り出すことを特徴とする〈4〉に記載のカーボンナノチューブの分離回収方法。
〈8〉 前記第n段目のカラムに充填したゲルに作用させるカーボンナノチューブ分散液の濃度を前記第n-1段目のカラムに充填したゲルに作用させるカーボンナノチューブ分散液の濃度より低くしたことを特徴とする〈2〉に記載のカーボンナノチューブの分離回収方法。
〈9〉 〈1〉又は〈2〉に記載のカラムに充填したゲルに対して過剰量のカーボンナノチューブ分散液を該ゲルに作用させて得られる、ゲルに対して吸着力の強いカーボンナノチューブ。
〈10〉 〈1〉又は〈2〉に記載のカーボンナノチューブの分離回収方法で得られるゲルに吸着しないカーボンナノチューブ。
合成されたCNTは通常、金属型CNTと半導体型CNTの両方を含む数十から数百本の束(バンドル)になっている。金属型CNTと半導体型CNTの分離、あるいはCNTの構造による分離に先立って、一本ずつに孤立した状態のCNTとして分散可溶化して、長時間安定に存在させておくことが肝要である。
[用いるゲルについて]
使用するゲルは、従来公知の糖質系のゲルである、デキストラン系ゲル(セファクリル:アリルデキストランとN,N’-メチレンビスアクリルアミドのホモポリマー、GEヘルスケア社)、アガロースゲル、デンプンゲルなどや、アクリルアミドゲルなどである。また、これらゲルの混合物、あるいは、これらゲルの構成成分や他の物質の混合物や化合物からなるゲルであってもよい。
カラムに大過剰のCNT試料を添加することにより、単一カイラリティの半導体型CNTを分離回収した。
[CNT分散液の調製]
100mgのHipco-CNT(CNI社、化学気相成長法で合成されたCNT、直径1.0±0.3nm)に、2%SDS水溶液(100ml)を加えた。その溶液をチップ型超音波破砕機(ソニファイアー、ブランソン社製、チップ先端径:0.5インチ)を用いて、冷水中で冷却しながら、出力20W/cm2で20時間超音波処理した。超音波処理よって得られた分散液を、超遠心分離(197,000×g、15分)にかけた後、上清を80%回収した。この溶液をCNT分散液とした。
[カラムの調製と分離]
ゲルビーズ(セファクリルS-300、GEヘルスケア社)をカラム担体に用いた。長さ7.5cm内径1.5cmのプラスチックカラムに高さが約2mmとなるようにゲルビーズを充填し、脱イオン水を通した後、2%SDS水溶液で平衡化した。そこへ、5mlのCNT分散液を添加した。その後、2%SDS水溶液を添加し、溶液が無色透明になるまでカラムを洗浄した。洗浄後のゲルは紫色を呈していた。ここへ、溶出液の0.05%DOC水溶液を添加することにより、カラムに吸着していたCNTを回収した。得られた水溶液の光吸収スペクトル(図2A、Col1)と蛍光スペクトル(図4B、Col1)を図1に示す。
[光吸収スペクトル測定と蛍光スペクトル測定]
単一構造からなるCNTの光吸収スペクトルは、半導体型であれば、長波長側から、S11、S22、S33という吸収ピークが、金属型であれば、S22とS33の間のあたりに、M11というピークが観測される。これらの吸収ピークは直径によってピークの波長が異なり、直径の大きなCNTであれば長波長側、直径の小さなCNTであれば短波長側へとシフトする。合成されたCNTは、様々な種類・直径のCNTの混合物であり、光吸収スペクトルはこれら混合物のピークの重ねあわせとなって観測される。図2Aの光吸収スペクトル測定の結果を見ると、分離前のCNT(Pristine)ではいくつものピークが認められるが、カラムに吸着・溶出したもの(Col1)は、S11、S22、S33領域にそれぞれ1つずつのピークが認められ、単一カイラリティの半導体CNTが分離されたことが示唆された。
実施例1と同様の実験を、複数のカラムを直列に連結することにより、異なるカイラリティのCNTを別のカラムに一度に吸着させたのち、それぞれのカラムに分けてからカラムに吸着したCNTを回収することにより、カイラリティの異なるCNTを一度に分離回数した。
[カラムの調製と分離]
図1に示すように、6つのカラムを直列に連結した。セファクリルS-200、セファクリルS-300のどちらを用いても分離が可能であるが、(6,5)CNTの純度が良好なセファクリルS-300を1、2段目のカラムに用いた。1段目のカラムには高さ2mm、2段目には高さ3.5mm程度のセファクリルS-300を充填した。3~6段目のカラムには、セファクリルS-200を高さ6mm程度になるように充填し使用した。分離に先立って、カラムを脱イオン水、2%SDS水溶液で順に平衡化した。
[光吸収スペクトル測定とラマン測定]
分離した試料の光吸収スペクトルを図2A、Bに示す。図2Aには、分離前(Pristine)、分離後金属型CNT(Metal)、カラムに結合したフラクションCol1~Col7の結果を、図2Bには、Col8~Col31のうち抜粋した結果を示している。それぞれのフラクションで異なるピーク形状が認められ、半導体型CNTの構造分離が起きていることがわかる。S11またはS22に注目すると、フラクションが後になるほど、吸収ピークが長波長側へシフトしていく傾向が認められた。言い換えれば、直径の小さなCNTほど早くカラムに結合し、直径の大きなCNTほど後のカラムに結合する傾向があるということである。
[蛍光スペクトル測定]
上述のように、蛍光スペクトル測定により、単一構造の半導体型CNTを個別に検出することが可能であり、より詳細な情報を得ることができる。図4Bに、各カラムから溶出されたフラクション(Col1~Col31)の結果を抜粋して示す。Col1では(6,5)のCNTがほぼ単一にまで分離されており、同様にCol4に(7,5)、Col8に(7,6)、Col16に(8,6)、Col24に(10,2)、Col29に(11,3)といった様に特定のカイラリティのCNTが濃縮されていることが判明した。Col1フラクションにおける(6,5)CNTの割合は算出すると約80%のピーク強度に達していた。
実施例2と同様の実験を、異なる種類のCNT(CoMoCAT-CNT、サウスウェスト・ナノテクノロジーズ社、直径0.8±0.1nm)を用いて行った。カラムには、セファクリルS-300を充填したものを6個つなげて使用し、10mlのCNT分散液を添加した。2%SDS水溶液を展開溶媒に用いた分離を2サイクル繰り返し、いずれのカラムにも結合しなかったCNT溶液を、金属型CNT(Metal)として回収した。本CNTは直径が細くゲルへの吸着が強いため、2%SDS溶液でほぼすべての半導体CNTが吸着した。そのため、SDS濃度を下げての3回目の吸着実験は行わなかった。光吸収スペクトルの結果から、CoMoCAT-CNTを用いた時も、直径の小さなCNTが初めのカラムに吸着し、より太いCNTが遅れて吸着する傾向が認められた(図5)。蛍光スペクトル測定の結果を図6に示す。CoMoCAT-CNTは、元々(6,5)CNTを多く含む試料である(図6A、未分離試料)。分離後Col1フラクションの(6,5)CNTの割合はと約85%のピーク強度に達しており、HiPco-CNTを試料に用いた時よりも、単一性の高いCNTを得ることができた。溶液の色は、金属型CNTは金色、Col1はアザミ色、Col6はスチールブルーであった(図7)。
Claims (10)
- カラムに充填したゲルに対して過剰量のカーボンナノチューブ分散液を作用させて、ゲルに対して吸着力の強いカーボンナノチューブを該ゲルに吸着させ、前記ゲルに対して吸着力が弱く未吸着のカーボンナノチューブを含む溶液と、カーボンナノチューブを吸着したゲルを分離し、さらに前記分離後のゲルに溶出液を作用させることにより、ゲルに吸着したカーボンナノチューブを取り出すことを特徴とするカーボンナノチューブの分離回収方法。
- カラムをn段直列して備え(n≧2、nは自然数)、第1段目のカラムに充填したゲルに対して過剰量のカーボンナノチューブ分散液を作用させて、第n段目のカラムのゲルにカーボンナノチューブが吸着するまで、第1段目のカラムにカーボンナノチューブ分散液を作用させることにより、n段の各カラムのゲルに吸着した1番目からn番目までの吸着力が強いカーボンナノチューブと、すべてのカラムのゲルに吸着しない吸着力の弱いカーボンナノチューブを含む溶液とを分離し、さらに各カラムに個別に溶出液を作用させることにより、各カラムのゲルに吸着したn種類の吸着力の異なるカーボンナノチューブを取り出すことを特徴とするカーボンナノチューブの分離回収方法。
- 前記、ゲルに対して過剰量のカーボンナノチューブ分散液とは、カラムに充填されたゲルが吸着することができるカーボンナノチューブの量を超える量のカーボンナノチューブを含む分散液であることを特徴とする請求項1又は2に記載のカーボンナノチューブの分離回収方法。
- 分離後のゲルから吸着力の強い特定の構造を持つ半導体型のカーボンナノチューブを取り出すことを特徴とする請求項1又は2に記載のカーボンナノチューブの分離回収方法。
- 分離後のゲルから特定の構造として特定の直径を持つ半導体型のカーボンナノチューブを取り出すことを特徴とする請求項4に記載のカーボンナノチューブの分離回収方法。
- 分離後のゲルから特定の構造として特定のカイラリティを持つ半導体型のカーボンナノチューブを取り出すことを特徴とする請求項4に記載のカーボンナノチューブの分離回収方法。
- 分離後のゲルから特定の構造として特定の局所曲率半径を持つ半導体型のカーボンナノチューブを取り出すことを特徴とする請求項4に記載のカーボンナノチューブの分離回収方法。
- 前記第n段目のカラムに充填したゲルに作用させるカーボンナノチューブ分散液の濃度を前記第n-1段目のカラムに充填したゲルに作用させるカーボンナノチューブ分散液の濃度より低くすることを特徴とする請求項2に記載のカーボンナノチューブの分離回収方法。
- 請求項1又は2に記載のカラムに充填したゲルに対して過剰量のカーボンナノチューブ分散液を作用させて得られる、ゲルに対して吸着力の強いカーボンナノチューブ。
- 請求項1又は2に記載のカーボンナノチューブの分離回収方法で得られるゲルに吸着しないカーボンナノチューブ。
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CN103318868A (zh) * | 2012-03-21 | 2013-09-25 | 清华大学 | 半导体性单壁碳纳米管的制备方法 |
WO2014157338A1 (ja) * | 2013-03-26 | 2014-10-02 | 独立行政法人産業技術総合研究所 | 光学活性をもつカーボンナノチューブの分離回収方法及び光学活性をもつカーボンナノチューブ |
JPWO2014157338A1 (ja) * | 2013-03-26 | 2017-02-16 | 国立研究開発法人産業技術総合研究所 | 光学活性をもつカーボンナノチューブの分離回収方法及び光学活性をもつカーボンナノチューブ |
JP2017048085A (ja) * | 2015-09-02 | 2017-03-09 | 株式会社Nextコロイド分散凝集技術研究所 | 半導体型カーボンナノチューブの収集方法 |
WO2017038829A1 (ja) * | 2015-09-02 | 2017-03-09 | 株式会社Nextコロイド分散凝集技術研究所 | 半導体型カーボンナノチューブの収集方法 |
US11440800B2 (en) | 2018-07-27 | 2022-09-13 | National Institute Of Advanced Industrial Science And Technology | Method for separating and recovering carbon nanotubes |
Also Published As
Publication number | Publication date |
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KR20130006607A (ko) | 2013-01-17 |
CN102781829B (zh) | 2015-04-01 |
JP2011184225A (ja) | 2011-09-22 |
JP5553282B2 (ja) | 2014-07-16 |
US8715607B2 (en) | 2014-05-06 |
CN102781829A (zh) | 2012-11-14 |
US20130052120A1 (en) | 2013-02-28 |
KR101818531B1 (ko) | 2018-01-15 |
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