WO2011108530A1 - Particle coated with carbon nanotubes, and method for producing same - Google Patents

Particle coated with carbon nanotubes, and method for producing same Download PDF

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WO2011108530A1
WO2011108530A1 PCT/JP2011/054602 JP2011054602W WO2011108530A1 WO 2011108530 A1 WO2011108530 A1 WO 2011108530A1 JP 2011054602 W JP2011054602 W JP 2011054602W WO 2011108530 A1 WO2011108530 A1 WO 2011108530A1
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carbon nanotubes
coated
particles
swnt
silica gel
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PCT/JP2011/054602
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French (fr)
Japanese (ja)
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直敏 中島
剛彦 藤ヶ谷
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国立大学法人九州大学
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • C09C1/3054—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • C01B32/16—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data

Definitions

  • the present invention belongs to the field of nanotechnology, and particularly relates to a novel technique for coating carbon nanotubes.
  • CNT carbon nanotubes
  • Patent Document 1 there is a technique of coating CNTs on titanium oxide particles by chemical vapor deposition (see, for example, Patent Document 1). Also disclosed is a titania-supporting CNT composite material in which titania (titanium oxide) is supported on CNTs using a sol-gel method under acidic conditions (see, for example, Patent Document 2).
  • a method of introducing a substituent by acid treatment to CNT For example, a terminal carboxyl group introduced on CNT is reacted with a diamine organic compound to form a diamine monomolecular layer, and a diamine monomolecular layer is formed.
  • Techniques for reacting with carboxylated CNTs for example, see Patent Document 3
  • hydrophilic CNTs having a structure in which a substituted or unsubstituted amino group is bonded to a carbon atom of the CNTs are also disclosed (for example, see Patent Document 4). ).
  • An object of the present invention is to establish a novel CNT coating technology that retains the characteristics of CNTs by coating intact (untreated) CNTs, and based on the CNT coating technology, novel particles coated with CNTs. And providing a manufacturing method thereof.
  • the present inventors have found that intact CNTs can be coated by dispersing CNTs in a specific polar solvent and stirring them with specific modified particles, thereby deriving the present invention.
  • intact CNTs are dispersed in a nitrogen atom-containing polar solvent, and the particles whose surfaces are modified with polar functional groups or atomic groups are stirred in the dispersion.
  • a method for producing particles coated with CNTs is provided.
  • the particles coated with the CNTs of the present invention can retain the excellent properties of the CNTs without any loss, they have a wide range of uses such as chromatography stationary phases.
  • FIG. 1 shows a scanning electron micrograph of silica gel particles coated with CNTs according to the present invention using NMP as a solvent.
  • the experimental result using solvents other than NMP of the silica gel particle coated with CNT concerning the present invention is shown.
  • the experimental result regarding the silica gel particle coated by metal SWNT which concerns on this invention is shown.
  • the experimental result which used the silica gel particle coated with CNT concerning this invention for column chromatography is shown.
  • Experimental results of titanium oxide and zinc oxide coated with CNTs according to the present invention are shown.
  • the scanning photomicrograph of the silica gel particle from which the particle diameter coated with CNT concerning this invention differs is shown.
  • a scanning electron micrograph is shown when CNT coating is attempted on silica gel surface-modified with a functional group that is not a polar functional group.
  • 2 shows a scanning electron micrograph of silica gel particles coated with semiconductor CNTs according to the present invention.
  • the scanning electron microscope result of the carboxyl group modification silica gel particle coated with CNT concerning the present invention is shown.
  • It is a chromatogram which shows the interaction of various molecules and CNT by the chromatography using the silica gel particle coated with CNT concerning the present invention.
  • the absorption spectrum of the supernatant of a phthalocyanine solution to which silica gel coated with CNTs according to the present invention is added is shown.
  • the particles coated with carbon nanotubes of the present invention are obtained by dispersing carbon nanotubes in a nitrogen atom-containing polar solvent, and stirring the particles whose surfaces are modified with polar functional groups or atomic groups in the dispersion. Manufactured.
  • the obtained carbon nanotube coating particles can be confirmed by observation with SEM or the like or spectrum (ultraviolet-visible spectrophotometer (UV-vis-NIR) absorption spectrum, Raman spectrum) measurement or the like (see Examples described later).
  • the nitrogen atom-containing polar solvent used in the present invention is a solvent comprising a polar molecule represented by a chemical structural formula containing a nitrogen atom.
  • various solvents that can disperse CNTs are applicable.
  • NMP N-methylpyrrolidone
  • 1-methyl-2-pyrrolidone 1,3- Cyclic amide polar solvents such as dimethyl-2-imidazolidinone
  • chain amide polar solvents such as dimethylformamide (DMF) and dimethylacetamide (DMAc)
  • preferred examples include NMP, DMF, and DMAc, and particularly preferred examples are NMP and DMAc.
  • silica gel particles are preferred because a wide variety of types and particle sizes that are surface-modified with polar functional groups (atomic groups), which will be described later, are obtained, and control of CNT coating is easy.
  • particles whose surfaces are modified with polar functional groups or atomic groups are used.
  • the functional group or atomic group having these polarities is not particularly limited, and examples thereof include amino groups, carboxyl groups, mercapto groups, hydroxy groups, aldehyde groups, acetyl groups, carbonyl groups, imino groups, cyano groups, azo groups, Examples thereof include an adi group, a thiol group, an epoxy group, a sulfo group, a nitro group, a vinyl group, an allyl group, a phenyl group, a naphthyl group, and a benzyl group.
  • an amino group, a carboxyl group, and a hydroxy group are preferable, and an amino group is particularly preferable because of the polarity and ease of handling. Particles whose surface is modified with these functional groups or atomic groups are easily dispersed even with the above-mentioned nitrogen atom-containing polar solvent.
  • Particles whose surface is modified with polar functional groups or atomic groups as described above are particles whose surfaces are modified with these functional groups or atomic groups using a well-known coupling agent. . These may be prepared according to a known method at the time of use, but generally many types are commercially available, and those commercially available can be used as they are in the present invention.
  • coupling agents include silane coupling agents, cationic silanes, Si functional silyl isocyanates, titanate coupling agents, aluminum coupling agents, zirconium coupling agents, and the like. In general, many products produced with silane coupling agents are available.
  • CNT has single-walled carbon nanotubes (Single-Walled Carbon Nanotube (SWNT), multi-walled carbon nanotube (Multi-Walled) Carbon Nanotube (MWNT), and the present invention can be applied to any CNT.
  • SWNT Single-Walled Carbon Nanotube
  • MWNT multi-walled carbon nanotube
  • CNTs have armchair type, zigzag type, and chiral type depending on the geometrical characteristics of interatomic bonds. Accordingly, since the metal phase and the semiconductor phase are interchanged, there are CNTs exhibiting metallic properties (conductivity) and CNTs exhibiting semiconductor properties, but the present invention can be applied to any of these CNTs in the same manner. it can. Since these CNTs having various structures are commercially available, they can be used according to the purpose in the present invention.
  • the CNT is characterized by being intact (untreated) CNT.
  • “intact (untreated) carbon nanotubes (CNT)” is also referred to as pristine carbon nanotubes in the field, and is manufactured by a method such as a CVD method or an HPco method. It means a carbon nanotube as it is, which has not been subjected to any chemical modification or physical treatment, and which excludes impurities such as those attached to the catalytic metal by-produced during production and amorphous ones.
  • the CNTs are overlaid by chemical interaction between the CNTs, and the coating surface is uneven (high roughness)
  • the present invention since intact CNTs can be used, new particles having a uniform and smooth coating surface can be obtained.
  • the density of the CNT coating on the particles can be controlled by increasing or decreasing the amount of the particles or CNTs.
  • the CNT coated particles of the present invention when used for a stationary phase of chromatography, they can be used for controlling the number of theoretical plates of chromatography, and when used as an abrasive, as an abrasive. Smooth and rough ones can be made separately, and when used as a light collecting material, the amount of collected light received as the light collecting material can be varied.
  • the particles coated with the CNTs of the present invention produced as described above can be used, for example, in the development of a functional material from CNTs and various substances, for easy evaluation of the interaction between the CNTs and the substances. It can be used as a stationary phase (column) for lithography. Since such a chromatographic stationary phase is in an intact state of CNT, it can be used as a new material capable of accurately evaluating the affinity with CNT.
  • the particles coated with the CNTs of the present invention can be used as a light collecting material for collecting light. Since such a light collecting material is in an intact state of CNTs, the characteristics of CNTs that absorb light in all wavelength regions from the ultraviolet-visible region to the near-infrared region can be utilized to the maximum, and there is no conventional one. It becomes a new material capable of collecting a quantity of light.
  • the particles coated with CNTs according to the present invention can be used as a slurry for surface polishing. Since such a surface polishing slurry is in an intact state of CNT, the mechanical strength of CNT can be utilized to the maximum, and a high-speed and smooth polishing surface can be obtained due to its high mechanical polishing effect. It can be used as a new material. Thus, since the particles coated with the CNTs of the present invention are in an intact state, the CNTs are novel materials that exhibit characteristics derived from the various characteristics of the CNTs themselves.
  • a single-walled carbon nanotube (Single-Walled) manufactured by Unidym is used as an example of CNT.
  • Carbon Nanotube (SWNT) was used, but multi-walled carbon nanotube (Multi-Walled It will be apparent to those skilled in the art that the present invention can be similarly applied to Carbon Nanotube (MWNT).
  • FIG. 1 shows a scanning electron microscope result of silica gel particles coated with CNTs according to the present invention using NMP as a solvent.
  • SWNT solubilization solution (SWNT / NMP, 1 mg / mL) was prepared and further diluted 100-fold with NMP to prepare a 0.01 mg / mL SWNT / NMP solubilization solution (The Journal of Physical Chemistry, 110 (32), 15708 (2009).), 10, 20, 30, 40, 50, 60, 90 mL of NH 2 -silica gel was added in 3 mL portions. These solutions were stirred (1 hour, 300 r / min) and then centrifuged (1.5 hours, 4700 x g).
  • FIG. 1 shows the result of observing the state of adsorption with a scanning electron microscope (SEM) after filtering and collecting the precipitate. From this result, the uniformity of adsorption can be visually judged from the SEM image, and it is understood that the addition amount of NH 2 -silica gel and the adsorption amount of SWNT have a regular relationship.
  • SEM scanning electron microscope
  • SWNT-coated silica gel was prepared in the same manner as described above using NH 2 -silica gel having particle diameters of 3.5 ⁇ m, 1 ⁇ m, 500 nm and 200 nm. That is, 3 mL of 0.01 mg / mL SWNT / NMP solution was added to 30 mg of NH 2 -silica gel with each particle size, and the resulting solution was stirred (1 hour, 300 rpm) and then centrifuged (1.5 hours, 4700 ⁇ g) Went. After removing the precipitate by filtration, SEM observation was performed. The result is shown in FIG.
  • SWNT solubilization solution NMP, 1 mg / mL
  • NMP 1 mg / mL
  • dilute it 100 times with NMP to prepare a 0.01 mg / mL SWNT / NMP solubilization solution.
  • These solutions were stirred (1 hour, 300 r / min) and then centrifuged (1.5 hours, 4700 ⁇ g).
  • FIG. 7 shows the results of observing the state of adsorption with a scanning electron microscope (SEM) (left: C8 silica gel, right: C16 silica gel). From this result, a non-uniform SWNT coating was confirmed, and it was shown that uniform coating is difficult when the surface functional group is a C8 or C16 group.
  • SWNT-coated silica gel using a solvent other than NMP was prepared. An experimental result is demonstrated based on FIG. FIG. 2 shows an experimental result using a solvent other than NMP of silica gel particles coated with CNTs according to the present invention.
  • a 0.01 mg / mL SWNT solubilized solution was prepared using two solvents, dimethylformamide (DMF) and dimethylacetamide (DMAc). 30 mg NH 2 -silica gel was added to 3 mL SWNT solubilization solution. The two solutions were stirred (1 hour, 300 r / min), and the ultraviolet-visible spectrophotometer (UV-vis-NIR) absorption spectrum of the supernatant after centrifugation (1.5 hours, 4700 ⁇ g) was measured. In addition, the Raman spectrum of the sample collected by filtration without centrifugation was measured and observed by SEM.
  • UV-vis-NIR ultraviolet-visible spectrophotometer
  • SWNTs were evenly dispersed in DMF and DMAc.
  • NH 2 -silica gel was added to these SWNT solubilized solutions, a change appeared in the absorption spectrum as shown in FIG. Further, as shown in FIG. 3C, a peak derived from SWNT was detected in the Raman spectrum of the sample collected by filtration.
  • SEM SEM
  • Silica gel coating was performed using metallic SWNT or semiconducting SWNT. 0.01 mg / mL m-SWNT / NMP or s-SWNT / NMP solubilized solution was prepared using metallic SWNT (m-SWNT) or semiconducting SWNT (s-SWNT). To 30 mL of this solution, 400 mg of NH 2 -silica gel was added and stirred (1 hour, 300 r / min). After this solution was filtered and dried, the Raman spectrum was measured and observed with SEM.
  • FIG. 3 shows the experimental results for silica gel particles coated with metallic SWNTs.
  • the m-SWNT / NMP solubilized solution showed a deep blue color, indicating that m-SWNT was uniformly dispersed in NMP.
  • a peak derived from m-SWNT was detected from m-SWNT-NH 2 -silica gel prepared using this solubilized solution.
  • SEM image of m-SWNT-NH 2 -silica gel it was observed that m-SWNT was adsorbed.
  • s-SWNT As for s-SWNT, it was understood that s-SWNT was uniformly dispersed in NMP because the s-SWNT / NMP solubilized solution showed brown. When NH 2 -silica gel was added to this solution, the color of the solution became lighter and a black precipitate was observed, indicating that s-SWNT was adsorbed on NH 2 -silica gel. When the SEM image obtained as a precipitate was observed, it was confirmed that s-SWNT was adsorbed as shown in FIG.
  • FIG. 4 shows the experimental results of subjecting silica gel particles coated with CNTs according to the present invention to column chromatography.
  • the SWNT-NH 2 -silica gel (346 mg) prepared above was added to a mixed solvent of NP slurry (2 mL) and chloroform (2 mL), and the mixture was put into a packer by ultrasonic irradiation. After the pressurized solvent (isopropanol-chloroform, 1: 1) was flowed and packed, the inside of the column was washed with a purge solvent (similar to the pressurized solvent). After washing sufficiently, the pressure was reduced and the column was removed.
  • a purge solvent similar to the pressurized solvent
  • SWNT-NH 2 - silica - column SWNT-NH 2 - column packed with silica gel
  • NH 2 - silica - column - comparing NH 2 column packed with silica gel
  • SWNT and NH 2 -silica gel are adsorbed by a strong interaction, and high performance liquid chromatography (High performance It was found to be used as a stationary phase for liquid chromatography (HPLC). Thereby, the interaction between CNT and molecules can be evaluated with high accuracy by a parameter called elution time in chromatography.
  • SWNT-coated titanium oxide In addition to the above-mentioned SWNT-coated silica gel, SWNT-coated titanium oxide was produced. An experimental result is demonstrated based on Fig.5 (a) and (b). 5 (a) and 5 (b) show the experimental results of titanium oxide coated with CNTs according to the present invention.
  • a 0.01 mg / mL SWNT-solubilized solution was prepared using dimethylformamide (DMF) as a solvent.
  • 30 mg NH 2 -titanium oxide was added to 3 mL SWNT solubilization solution.
  • the two solutions were stirred (1 hour, 300 r / min), and the ultraviolet-visible spectrophotometer (UV-vis-NIR) absorption spectrum of the supernatant after centrifugation (1.5 hours, 4700 ⁇ g) was measured.
  • UV-vis-NIR ultraviolet-visible spectrophotometer
  • Raman spectrum of the sample collected by filtration without centrifugation was measured and observed by SEM.
  • FIG. 5 (c) shows the experimental results of zinc oxide coated with CNTs according to the present invention.
  • a 0.01 mg / mL SWNT-solubilized solution was prepared using dimethylformamide (DMF) as a solvent.
  • 30 mg NH 2 -zinc oxide was added to 3 mL SWNT solubilization solution.
  • the two solutions were stirred (1 hour, 300 r / min), and the ultraviolet-visible spectrophotometer (UV-vis-NIR) absorption spectrum of the supernatant after centrifugation (1.5 hours, 4700 ⁇ g) was measured.
  • UV-vis-NIR ultraviolet-visible spectrophotometer
  • the Raman spectrum of the sample collected by filtration without centrifugation was measured.
  • FIG. 5C a peak derived from SWNT was detected in the Raman spectrum of the sample collected by filtration, and SWNT—NH 2 —zinc oxide was confirmed.
  • FIG. 9 shows a scanning electron microscope result of silica gel particles coated with SWNTs according to the present invention using NMP as a solvent.
  • FIG. 11 shows the experimental results regarding the adsorptivity evaluation of phthalocyanine and SWNT using SWNT—NH 2 -silica gel according to the present invention. Since phthalocyanine has a strong adsorptivity with SWNT, it is a molecule that is difficult to analyze without giving an elution in the adsorptive evaluation by the chromatography.
  • phthalocyanines 29H, 31H-phthalocyanine (PC-1), 2,3,9,10,16,17,23,24-Octakis (octyloxy) -29H, 31H-phthalocyanine (PC-2), 2, 11,20,29-Tetra-tert-butyl-2,3-naphthalocyanine (PC-3) and 2,9,16,23-Tetra-tert-butyl-29H, 31H-phthalocyanine (PC-4) Different types of molecules were used.

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Abstract

A novel carbon nanotube (CNT) coating technique is established that retains the characteristics of CNTs by coating with intact CNTs, and disclosed are a novel particle that is coated with CNTs on the basis of said CNT coating technique and a method for producing same. Intact carbon nanotubes are dispersed in a nitrogen-atom-containing polar solvent, and particles coated with carbon nanotubes are produced by means of agitating the particles, the surfaces of which are modified by a group of atoms or a functional group having polarity, within said dispersion.

Description

カーボンナノチューブでコーティングされた粒子およびその製造方法Particles coated with carbon nanotubes and method for producing the same
　本発明は、ナノテクノロジーの分野に属し、特に、カーボンナノチューブをコーティングする新規な技術に関する。 The present invention belongs to the field of nanotechnology, and particularly relates to a novel technique for coating carbon nanotubes.
　近年、カーボンナノチューブ（carbon nanotube；ＣＮＴ）が我が国で発見されてから、ＣＮＴが有する様々な特性について研究が盛んに行われている。ＣＮＴは、熱伝導性、電気伝導度、機械的強度等に関して優れた特性をもつ。この優れた特性に着目して、既存の粒子にＣＮＴをコーティングすることで、ＣＮＴの特性を活用した新規の機能性素材も研究されている。 In recent years, since the discovery of carbon nanotubes (CNTs) in Japan, various researches have been conducted on various properties of CNTs. CNT has excellent characteristics with respect to thermal conductivity, electrical conductivity, mechanical strength, and the like. Focusing on these excellent properties, new functional materials utilizing the properties of CNTs by coating CNTs on existing particles have been studied.
　従来のＣＮＴコーティングに関しては、化学蒸着処理により酸化チタン粒子にＣＮＴをコーティングする技術がある（例えば、特許文献１参照）。また、酸性条件下におけるゾルゲル法を用いてＣＮＴに対してチタニア（酸化チタン）を担持させたチタニア担持ＣＮＴ複合材料も開示されている（例えば、特許文献２参照）。 Regarding conventional CNT coating, there is a technique of coating CNTs on titanium oxide particles by chemical vapor deposition (see, for example, Patent Document 1). Also disclosed is a titania-supporting CNT composite material in which titania (titanium oxide) is supported on CNTs using a sol-gel method under acidic conditions (see, for example, Patent Document 2).
　また、ＣＮＴに酸処理して置換基を導入する方法もあり、例えば、ＣＮＴ上に導入された末端カルボキシル基をジアミン系有機化合物と反応させてジアミン単分子層を形成させ、ジアミン単分子層をカルボキシル化されたＣＮＴと反応させる技術（例えば、特許文献３参照）や、ＣＮＴの炭素原子に置換または無置換アミノ基が結合した構造の親水性ＣＮＴも開示されている（例えば、特許文献４参照）。 In addition, there is a method of introducing a substituent by acid treatment to CNT. For example, a terminal carboxyl group introduced on CNT is reacted with a diamine organic compound to form a diamine monomolecular layer, and a diamine monomolecular layer is formed. Techniques for reacting with carboxylated CNTs (for example, see Patent Document 3) and hydrophilic CNTs having a structure in which a substituted or unsubstituted amino group is bonded to a carbon atom of the CNTs are also disclosed (for example, see Patent Document 4). ).
　さらに、ＣＮＴは凝集性が高いことから、該凝集性を解決するためにＣＮＴを分散させる分散溶液も検討されており、例えば、ＣＮＴをアミド系極性有機溶媒およびポリビニルピロリドン（ＰＶＰ）に分散したＣＮＴ分散溶液を作成する技術（例えば、特許文献５参照）や、双極性非プロトン溶剤を少なくとも含んだ有機溶剤にＣＮＴからなる微粒子を分散する技術（例えば、特許文献６参照）がある。 Furthermore, since CNT has high cohesiveness, a dispersion solution in which CNT is dispersed has been studied in order to solve the cohesiveness. There is a technique for creating a dispersion solution (for example, see Patent Document 5) and a technique for dispersing fine particles made of CNTs in an organic solvent containing at least a dipolar aprotic solvent (for example, see Patent Document 6).
特開２００９－２４９２０６号公報JP 2009-249206 A 特開２００７－５４６９４号公報JP 2007-54694 A 特開２００４－１４２０９７号公報JP 2004-142097 A ＷＯ２００７／０９７４０６号公報WO2007 / 097406 特開２００５－１６２８７７号公報JP 2005-162877 A 特開２００２－２５５５２８号公報JP 2002-255528 A
　しかしながら、上記に示されるように、ＣＮＴコーティングに関して、化学蒸着処理およびゾルゲル法を用いる場合には、コーティング対象にＣＮＴが均一にコーティングされ難いという課題がある。また、酸処理して置換基を導入する場合には、ＣＮＴ表面は、欠陥部位を多く持つこととなり、本来のＣＮＴの特性が失われるという課題がある。 However, as shown above, when the chemical vapor deposition process and the sol-gel method are used for the CNT coating, there is a problem that it is difficult to uniformly coat the CNT on the coating target. Further, when a substituent is introduced by acid treatment, the CNT surface has many defect sites, and there is a problem that the original characteristics of CNT are lost.
　さらに、ＣＮＴを分散させた分散溶液を用いる場合には、ＣＮＴを均一に分散させるにとどまっており、均一に分散させたＣＮＴを各種粒子に均一にコーティングすることは未だ技術的に困難であるという課題がある。 Furthermore, when using a dispersion solution in which CNTs are dispersed, the CNTs are only uniformly dispersed, and it is still technically difficult to uniformly coat the uniformly dispersed CNTs on various particles. There are challenges.
　本発明の目的は、インタクト（未処理）なＣＮＴをコーティングすることで、ＣＮＴの特性を保持した新規のＣＮＴコーティング技術を確立し、該ＣＮＴコーティング技術に基づいて、ＣＮＴがコーティングされた新規の粒子およびその製造方法を提供することにある。 An object of the present invention is to establish a novel CNT coating technology that retains the characteristics of CNTs by coating intact (untreated) CNTs, and based on the CNT coating technology, novel particles coated with CNTs. And providing a manufacturing method thereof.
　本発明者らはＣＮＴを特定の極性溶媒に分散して、特定の修飾された粒子と攪拌することにより、インタクトなＣＮＴをコーティングできることを見出し、本発明を導き出した。
　かくして、本発明に従えば、インタクトなＣＮＴを窒素原子含有極性溶媒に分散し、当該分散液中に、極性を有する官能基または原子団で表面が修飾された粒子を攪拌することを特徴とするＣＮＴでコーティングされた粒子の製造方法が提供される。
　また、本発明に従えば、上記の方法によって製造され、インタクトなＣＮＴでコーティングされていることを特徴とする粒子も提供される。 The present inventors have found that intact CNTs can be coated by dispersing CNTs in a specific polar solvent and stirring them with specific modified particles, thereby deriving the present invention.
Thus, according to the present invention, intact CNTs are dispersed in a nitrogen atom-containing polar solvent, and the particles whose surfaces are modified with polar functional groups or atomic groups are stirred in the dispersion. A method for producing particles coated with CNTs is provided.
According to the present invention, there is also provided a particle produced by the above method and coated with intact CNT.
　本発明のＣＮＴでコーティングされた粒子は、ＣＮＴの優れた特性を何ら損なうことなく保持できることから、クロマトグラフィー用固定相等の広汎な用途を有する。 Since the particles coated with the CNTs of the present invention can retain the excellent properties of the CNTs without any loss, they have a wide range of uses such as chromatography stationary phases.
溶媒としてＮＭＰを用いた本発明に係るＣＮＴでコーティングされたシリカゲル粒子の走査型電子顕微鏡写真を示す。1 shows a scanning electron micrograph of silica gel particles coated with CNTs according to the present invention using NMP as a solvent. 本発明に係るＣＮＴでコーティングされたシリカゲル粒子のＮＭＰ以外の溶媒を用いた実験結果を示す。The experimental result using solvents other than NMP of the silica gel particle coated with CNT concerning the present invention is shown. 本発明に係る金属製ＳＷＮＴでコーティングされたシリカゲル粒子に関する実験結果を示す。The experimental result regarding the silica gel particle coated by metal SWNT which concerns on this invention is shown. 本発明に係るＣＮＴでコーティングされたシリカゲル粒子をカラムクロマトグラフィーに供した実験結果を示す。The experimental result which used the silica gel particle coated with CNT concerning this invention for column chromatography is shown. 本発明に係るＣＮＴでコーティングされた酸化チタンおよび酸化亜鉛の実験結果を示す。Experimental results of titanium oxide and zinc oxide coated with CNTs according to the present invention are shown. 本発明に係るＣＮＴでコーティングされた粒子径の異なるシリカゲル粒子の走査顕微鏡写真を示す。The scanning photomicrograph of the silica gel particle from which the particle diameter coated with CNT concerning this invention differs is shown. 比較のための例として、極性官能基ではない官能基で表面修飾されたシリカゲルにＣＮＴコーティングを試みた場合の走査型電子顕微鏡写真を示す。As an example for comparison, a scanning electron micrograph is shown when CNT coating is attempted on silica gel surface-modified with a functional group that is not a polar functional group. 本発明に係る半導体ＣＮＴでコーティングされたシリカゲル粒子の走査型電子顕微鏡写真を示す。2 shows a scanning electron micrograph of silica gel particles coated with semiconductor CNTs according to the present invention. 本発明に係るＣＮＴでコーティングされたカルボキシル基修飾シリカゲル粒子の走査型電子顕微鏡結果を示す。The scanning electron microscope result of the carboxyl group modification silica gel particle coated with CNT concerning the present invention is shown. 本発明に係るＣＮＴでコーティングされたシリカゲル粒子を用いるクロマトグラフィによる各種の分子とＣＮＴとの相互作用を示すクロマトグラムである。It is a chromatogram which shows the interaction of various molecules and CNT by the chromatography using the silica gel particle coated with CNT concerning the present invention. 本発明に係るＣＮＴでコーティングされたシリカゲルが添加されたフタロシアニン溶液の上澄液の吸収スペクトルを示す。The absorption spectrum of the supernatant of a phthalocyanine solution to which silica gel coated with CNTs according to the present invention is added is shown.
　本発明のカーボンナノチューブでコーティングされた粒子は、カーボンナノチューブを窒素原子含有極性溶媒に分散し、当該分散液中に、極性を有する官能基または原子団で表面が修飾された粒子を攪拌することにより製造される。得られるカーボンナノチューブコーティング粒子は、ＳＥＭ等による観察やスペクトル（紫外可視分光光度計（UV-vis-NIR）吸収スペクトル、ラマンスペクトル）測定などにより確認することができる（後述の実施例参照）。 The particles coated with carbon nanotubes of the present invention are obtained by dispersing carbon nanotubes in a nitrogen atom-containing polar solvent, and stirring the particles whose surfaces are modified with polar functional groups or atomic groups in the dispersion. Manufactured. The obtained carbon nanotube coating particles can be confirmed by observation with SEM or the like or spectrum (ultraviolet-visible spectrophotometer (UV-vis-NIR) absorption spectrum, Raman spectrum) measurement or the like (see Examples described later).
　本発明で用いられる窒素原子含有極性溶媒とは、窒素原子を含む化学構造式で表される有極性の分子から成る溶媒である。この窒素原子含有極性溶媒としては、原理的には、ＣＮＴを分散させ得る各種の溶媒が適用可能であり、例えば、Ｎ－メチルピロリドン（ＮＭＰ）、１－メチル－２－ピロリドン、１，３－ジメチル－２－イミダゾリジノンなどの環状アミド系極性溶媒；ジメチルホルムアミド（ＤＭＦ）、ジメチルアセタミド（ＤＭＡｃ）などの鎖状アミド系極性溶媒を使用することができる。このうち好ましい例としては、ＮＭＰ、ＤＭＦ、およびＤＭＡｃを挙げることができ、特に好ましい例は、ＮＭＰおよびＤＭＡｃである。 The nitrogen atom-containing polar solvent used in the present invention is a solvent comprising a polar molecule represented by a chemical structural formula containing a nitrogen atom. As the nitrogen atom-containing polar solvent, in principle, various solvents that can disperse CNTs are applicable. For example, N-methylpyrrolidone (NMP), 1-methyl-2-pyrrolidone, 1,3- Cyclic amide polar solvents such as dimethyl-2-imidazolidinone; chain amide polar solvents such as dimethylformamide (DMF) and dimethylacetamide (DMAc) can be used. Among these, preferred examples include NMP, DMF, and DMAc, and particularly preferred examples are NMP and DMAc.
　本発明は、既存の各種の粒子をＣＮＴコーティングすることに適用することができるが、入手容易性などの点から、好ましい例として、シリカゲル(silica gel)、酸化チタン、酸化亜鉛などの粒子を挙げることができ、特に、後述する極性官能基（原子団）で表面修飾された広範な種類と粒径のものが得られＣＮＴのコーティングの制御が容易であることから、シリカゲルの粒子が好ましい。 Although the present invention can be applied to CNT coating of various existing particles, preferred examples include silica gel (silica gel) particles, titanium oxide, zinc oxide particles, and the like. In particular, silica gel particles are preferred because a wide variety of types and particle sizes that are surface-modified with polar functional groups (atomic groups), which will be described later, are obtained, and control of CNT coating is easy.
　本発明では、上記のような各種粒子のうち、極性を有する官能基または原子団で表面を修飾された粒子を使用する。
　これらの極性を有する官能基または原子団としては、特に限定されないが、例えば、アミノ基、カルボキシル基、メルカプト基、ヒドロキシ基、アルデヒド基、アセチル基、カルボニル基、イミノ基、シアノ基、アゾ基、アジ基、チオール基、エポキシ基、スルホ基、ニトロ基、ビニル基、アリル基、フェニル基、ナフチル基、ベンジル基などが挙げられる。このうち、極性の強さおよび取扱いの容易さから、アミノ基、カルボキシル基、ヒドロキシ基が好ましく、特にアミノ基が好ましい。これらの官能基または原子団で表面を修飾された粒子は、上述の窒素原子含有極性溶媒でも容易に分散される。 In the present invention, among the various particles as described above, particles whose surfaces are modified with polar functional groups or atomic groups are used.
The functional group or atomic group having these polarities is not particularly limited, and examples thereof include amino groups, carboxyl groups, mercapto groups, hydroxy groups, aldehyde groups, acetyl groups, carbonyl groups, imino groups, cyano groups, azo groups, Examples thereof include an adi group, a thiol group, an epoxy group, a sulfo group, a nitro group, a vinyl group, an allyl group, a phenyl group, a naphthyl group, and a benzyl group. Of these, an amino group, a carboxyl group, and a hydroxy group are preferable, and an amino group is particularly preferable because of the polarity and ease of handling. Particles whose surface is modified with these functional groups or atomic groups are easily dispersed even with the above-mentioned nitrogen atom-containing polar solvent.
　このように、極性の強い官能基を使用することで、ＣＮＴとπ電子間相互の電子間引力による親和性が得られることとなり、ＣＮＴをより強固に粒子にコーティングすることができるものと推察される。 In this way, by using a functional group having a strong polarity, it is assumed that the affinity between the CNT and the π-electron due to the mutual electron attractive force can be obtained, and that the CNT can be coated more firmly on the particles. The
　上記のように極性を有する官能基または原子団で表面が修飾された粒子は、一般によく知られたカップリング剤を用いて、それらの官能基または原子団で粒子の表面を修飾したものである。これらは、使用に際して既知の方法に従い調製してもよいが、一般に多くの種類のものが市販されており、本発明では、それらの市販されたものをそのまま用いることができる。 Particles whose surface is modified with polar functional groups or atomic groups as described above are particles whose surfaces are modified with these functional groups or atomic groups using a well-known coupling agent. . These may be prepared according to a known method at the time of use, but generally many types are commercially available, and those commercially available can be used as they are in the present invention.
　なお、カップリング剤としては、よく知られているように、シランカップリング剤、カチオニックシラン、Ｓｉ官能形シリルイソシアネート、チタネート系カップリング剤、アルミニウム系カップリング剤、ジルコニウム系カップリング剤などが挙げられるが、一般的には、シランカップリング剤で生成されたものが多く入手できる。 As well known, coupling agents include silane coupling agents, cationic silanes, Si functional silyl isocyanates, titanate coupling agents, aluminum coupling agents, zirconium coupling agents, and the like. In general, many products produced with silane coupling agents are available.
　本発明は、従来から知られた各種タイプのＣＮＴに適用することができる。よく知られているように、ＣＮＴには、単層カーボンナノチューブ(Single-Walled
Carbon Nanotube；ＳＷＮＴ)、多層カーボンナノチューブ(Multi-Walled
Carbon Nanotube；ＭＷＮＴ)があり、本発明はいずれのＣＮＴにも適用することができる。 The present invention can be applied to various types of CNTs conventionally known. As is well known, CNT has single-walled carbon nanotubes (Single-Walled
Carbon Nanotube (SWNT), multi-walled carbon nanotube (Multi-Walled)
Carbon Nanotube (MWNT), and the present invention can be applied to any CNT.
　その他、ＣＮＴには、原子間結合の幾何学的特徴に応じて、アームチェアー（armchair）型、ジグザグ（zigzag）型、カイラル(chiral)型といった構造があり、さらに、ＣＮＴの直径とカイラル角に応じて、金属相と半導体相が入れ替わることから、金属性（導電性）を呈するＣＮＴや、半導体性を呈するＣＮＴがあるが、本発明は、それらのＣＮＴのいずれにも同様に適用することができる。これらのＣＮＴも、各種の構造のものが市販されているので、本発明では、目的に応じて、それらを使用することができる。 In addition, CNTs have armchair type, zigzag type, and chiral type depending on the geometrical characteristics of interatomic bonds. Accordingly, since the metal phase and the semiconductor phase are interchanged, there are CNTs exhibiting metallic properties (conductivity) and CNTs exhibiting semiconductor properties, but the present invention can be applied to any of these CNTs in the same manner. it can. Since these CNTs having various structures are commercially available, they can be used according to the purpose in the present invention.
　上記の方法から理解されるように、本発明により製造されるＣＮＴでコーティングされた粒子においては、ＣＮＴは、インタクトな状態（未処理な状態）のＣＮＴであることが特徴である。ここで、本発明に関連して、「インタクト（未処理）なカーボンナノチューブ（ＣＮＴ）」とは、当該分野ではpristineカーボンナノチューブとも称されており、ＣＶＤ法やＨＰｃｏ法などの方法で製造されたままのカーボンナノチューブであって、何らの化学修飾や物理的処理を受けていないカーボンナノチューブであり、製造に際して副生する触媒金属に付着したものやアモルファスなものなどの不純物を除くものを意味する。 As understood from the above method, in the CNT-coated particles produced according to the present invention, the CNT is characterized by being intact (untreated) CNT. Here, in relation to the present invention, “intact (untreated) carbon nanotubes (CNT)” is also referred to as pristine carbon nanotubes in the field, and is manufactured by a method such as a CVD method or an HPco method. It means a carbon nanotube as it is, which has not been subjected to any chemical modification or physical treatment, and which excludes impurities such as those attached to the catalytic metal by-produced during production and amorphous ones.
　さらに、従来のような酸処理されたＣＮＴでコーティングされた粒子の場合では、ＣＮＴ同士の化学的相互作用でＣＮＴが重畳的にコーティングされてしまい、コーティング表面が凸凹状(ラフネスが高い状態)となっていたが、本発明では、インタクトなＣＮＴを使用できることから、コーティング表面が均一かつ滑らかな新規の粒子が得られる。 Furthermore, in the case of particles coated with acid-treated CNTs as in the past, the CNTs are overlaid by chemical interaction between the CNTs, and the coating surface is uneven (high roughness) However, in the present invention, since intact CNTs can be used, new particles having a uniform and smooth coating surface can be obtained.
　このように、粒子をコーティングするＣＮＴが、粒子の表層面のみに存在することから、粒子またはＣＮＴ量を増減させることにより、粒子に対するＣＮＴコーティングの粗密を制御することができる。この制御により、本発明のＣＮＴコーティング粒子を、クロマトグラフィーの固定相に使用する場合には、クロマトグラフィーの理論段数の制御に使用することができ、研磨材に使用する場合には、研磨材として滑らかなものや荒いものを作り分けることができ、光捕集材料に使用する場合には、光捕集材料として受光した光の収集量に変化をつけることができる。 Thus, since the CNTs that coat the particles exist only on the surface of the particles, the density of the CNT coating on the particles can be controlled by increasing or decreasing the amount of the particles or CNTs. By this control, when the CNT coated particles of the present invention are used for a stationary phase of chromatography, they can be used for controlling the number of theoretical plates of chromatography, and when used as an abrasive, as an abrasive. Smooth and rough ones can be made separately, and when used as a light collecting material, the amount of collected light received as the light collecting material can be varied.
　以上のように製造された本発明のＣＮＴでコーティングされた粒子は、例えば、ＣＮＴと各種の物質とから機能性材料を開発するのに際して、ＣＮＴと当該物質との相互作用を簡便に評価するクロマトグラフィー用固定相（カラム）として使用することができる。このようなクロマトグラフィー固定相は、ＣＮＴがインタクトな状態であるので、ＣＮＴとの親和性を精度よく評価することができる新規材料としての使用が可能である。 The particles coated with the CNTs of the present invention produced as described above can be used, for example, in the development of a functional material from CNTs and various substances, for easy evaluation of the interaction between the CNTs and the substances. It can be used as a stationary phase (column) for lithography. Since such a chromatographic stationary phase is in an intact state of CNT, it can be used as a new material capable of accurately evaluating the affinity with CNT.
　また、本発明のＣＮＴでコーティングされた粒子は、光線を捕集する光捕集材料として使用することができる。このような光捕集材料は、ＣＮＴがインタクトな状態であるので、紫外-可視領域から近赤外領域までのすべての波長領域を光吸収するＣＮＴの特性を最大限活用できることとなり、従来に無い量の光線を捕集することができる新規材料となる。 Moreover, the particles coated with the CNTs of the present invention can be used as a light collecting material for collecting light. Since such a light collecting material is in an intact state of CNTs, the characteristics of CNTs that absorb light in all wavelength regions from the ultraviolet-visible region to the near-infrared region can be utilized to the maximum, and there is no conventional one. It becomes a new material capable of collecting a quantity of light.
　さらに、本発明によるＣＮＴでコーティングされた粒子は、表面研磨用スラリーとして使用することができる。このような表面研磨用スラリーは、ＣＮＴがインタクトな状態であるので、ＣＮＴのもつ機械的強度を最大限活用できることとなり、その高い機械的研磨効果により、高速かつ平滑な研磨面を得ることができる新規材料としての使用が可能である。このように、本発明のＣＮＴでコーティングされた粒子は、ＣＮＴがインタクトな状態であるので、ＣＮＴの各種特性そのものに由来する特性を発揮する新規材料となる。 Furthermore, the particles coated with CNTs according to the present invention can be used as a slurry for surface polishing. Since such a surface polishing slurry is in an intact state of CNT, the mechanical strength of CNT can be utilized to the maximum, and a high-speed and smooth polishing surface can be obtained due to its high mechanical polishing effect. It can be used as a new material. Thus, since the particles coated with the CNTs of the present invention are in an intact state, the CNTs are novel materials that exhibit characteristics derived from the various characteristics of the CNTs themselves.
　本発明の特徴を更に具体的に示すため以下に実施例を記すが、本発明はこれらの実施例によって制限されるものではない。実施例で用いた試薬および機器を、以下に記載する。
（試薬）
・ＳＷＮＴ（HiPco）（Unidym社製、CNI、Lot.ATP029）
・金属性ＳＷＮＴ（純度99%，粉末，NanoIntegris社製）
・半導体性ＳＷＮＴ（純度99%，粉末，NanoIntegris社製）
・ＮＨ２－シリカゲル（ケムコ社製、粒子径：5μm，3.5μm）
・ＮＨ２－シリカゲル（コアフロント社製、粒子径：1μm，500nm，200nm.水中分散体として入手したものをろ過して使用）
・ＣＯＯＨ－シリカゲル（コアフロント社製、粒子径：5.0μm）
・ＮＨ２－酸化チタン（Aldrich社製、粒子径：5μm）
・ＮＨ２－酸化亜鉛（Aldrich社製、粒子径：5μm）
・１－メチル－２－ピロリドン（ＮＭＰ）（Acros Organics社製、spectrophotometric grade 99.0%）
・ジメチルホルムアミド（ＤＭＦ）（キシダ化学社製、99.5%）
・ジメチルアセタミド（ＤＭＡｃ）（Wako社製, 98.0%）
・テトラヒドロフラン（ＴＨＦ）（Wako社製、99.5%）
・ＮＰスラリー（ケムコ社製）
・ＲＰスラリー（ケムコ社製）
・メタノール（キシダ化学社製、99.5%）
・トルエン（Wako社製、HPLC、99.8%）
・水
（機器）
・バス型超音波照射機（BRANSON社製、5510）
・Ultrasonic Disruptor社製 UD-200
・VortexShaker UR-36、TAITEC社製
・Vacumn（KNF社製、LABOPORT）
・遠心分離機（日立社製、himacCF15R）
・分光光度計（Jasco社製、V670S、ダブルビーム）
測定モード：Abs、レスポンス：Fast、データ取込間隔：1.0nm
可視・紫外部のバンド幅：2.0 nm、近赤外部のバンド幅：8.0nm
セル長：1mm
・ラマン分光光度計（RXN1マクロ測定システム）
　　　波長：785nm
・走査型電子顕微鏡（scanning electron microscope；SEM）（JEOL社製、JSM6701F） Examples of the present invention will be described in more detail below, but the present invention is not limited to these examples. The reagents and equipment used in the examples are described below.
(reagent)
・ SWNT (HiPco) (Unidym, CNI, Lot.ATP029)
・ Metallic SWNT (purity 99%, powder, manufactured by NanoIntegris)
・ Semiconductor SWNT (purity 99%, powder, manufactured by NanoIntegris)
NH 2 -silica gel (Chemco, particle size: 5 μm, 3.5 μm)
・ NH 2 -silica gel (manufactured by Corefront Corporation, particle diameter: 1 μm, 500 nm, 200 nm. Used as a dispersion in water)
・ COOH-silica gel (manufactured by Corefront Corporation, particle size: 5.0μm)
NH 2 -titanium oxide (Aldrich, particle size: 5 μm)
NH 2 -zinc oxide (Aldrich, particle size: 5 μm)
1-methyl-2-pyrrolidone (NMP) (Acros Organics, spectrophotometric grade 99.0%)
・ Dimethylformamide (DMF) (Kishida Chemical Co., 99.5%)
・ Dimethylacetamide (DMAc) (Wako, 98.0%)
Tetrahydrofuran (THF) (Wako, 99.5%)
・ NP slurry (Chemco)
・ RP slurry (Chemco)
・ Methanol (Kishida Chemical, 99.5%)
・ Toluene (Wako, HPLC, 99.8%)
・ Water (equipment)
・ Bus-type ultrasonic irradiator (BRANSON, 5510)
・ Ultrasonic Disruptor UD-200
・ VortexShaker UR-36, TAITEC ・ Vacumn (KNF, LABOPORT)
・ Centrifuge (Hitachi, himacCF15R)
・ Spectrophotometer (Jasco, V670S, double beam)
Measurement mode: Abs, Response: Fast, Data capture interval: 1.0nm
Visible and ultraviolet bandwidth: 2.0 nm, near infrared bandwidth: 8.0 nm
Cell length: 1mm
・ Raman spectrophotometer (RXN1 macro measurement system)
Wavelength: 785nm
・ Scanning electron microscope (SEM) (JEOL, JSM6701F)
　以下の実施例では、ＣＮＴの対象例として、Unidym社製の単層カーボンナノチューブ(Single-Walled
Carbon Nanotube；ＳＷＮＴ)を使用したが、多層カーボンナノチューブ(Multi-Walled
Carbon Nanotube；MWNT)に対しても同様に本発明を適用できることは、当業者にとって明らかなことである。 In the following examples, a single-walled carbon nanotube (Single-Walled) manufactured by Unidym is used as an example of CNT.
Carbon Nanotube (SWNT) was used, but multi-walled carbon nanotube (Multi-Walled
It will be apparent to those skilled in the art that the present invention can be similarly applied to Carbon Nanotube (MWNT).
（ＮＭＰ溶媒を用いたＳＷＮＴコーティングシリカゲルの作製）
　アミノ基で表面が修飾されたシリカゲル(ＮＨ２－シリカゲル，粒子径５μm)に対して、ＣＮＴのコーティングを行った。実験結果を図１に基づいて説明する。図１は、溶媒としてＮＭＰを用いた本発明に係るＣＮＴでコーティングされたシリカゲル粒子の走査型電子顕微鏡結果を示す。 (Preparation of SWNT-coated silica gel using NMP solvent)
Silica gel whose surface was modified with amino groups (NH 2 -silica gel, particle diameter 5 μm) was coated with CNTs. An experimental result is demonstrated based on FIG. FIG. 1 shows a scanning electron microscope result of silica gel particles coated with CNTs according to the present invention using NMP as a solvent.
　ＳＷＮＴ可溶化溶液（ＳＷＮＴ／ＮＭＰ、1mg/mL）を調製しＮＭＰでさらに１００倍に希釈することで0.01mg/mLのＳＷＮＴ/ＮＭＰ可溶化溶液を調整し（The
Journal of Physical Chemistry, 110 (32),15708 (2009).）、10、20、30、40、50、60、90mgのＮＨ２－シリカゲルに3mLずつ加えた。これらの溶液を攪拌（1時間、300r/分）した後、遠心分離（1.5時間、4700
x g）を行った。 A SWNT solubilization solution (SWNT / NMP, 1 mg / mL) was prepared and further diluted 100-fold with NMP to prepare a 0.01 mg / mL SWNT / NMP solubilization solution (The
Journal of Physical Chemistry, 110 (32), 15708 (2009).), 10, 20, 30, 40, 50, 60, 90 mL of NH 2 -silica gel was added in 3 mL portions. These solutions were stirred (1 hour, 300 r / min) and then centrifuged (1.5 hours, 4700
x g).
　沈殿を濾過し回収した後、走査型電子顕微鏡(scanning electron microscope；ＳＥＭ)で吸着の様子を観察した結果を図１に示す。この結果から、ＳＥＭ像から吸着の均一性を視覚的に判断することができ、ＮＨ２－シリカゲルの添加量とＳＷＮＴの吸着量は規則的な関係であることが理解される。 FIG. 1 shows the result of observing the state of adsorption with a scanning electron microscope (SEM) after filtering and collecting the precipitate. From this result, the uniformity of adsorption can be visually judged from the SEM image, and it is understood that the addition amount of NH 2 -silica gel and the adsorption amount of SWNT have a regular relationship.
　吸着の均一性から、0.01mg/mLのＳＷＮＴ/ＮＭＰ可溶化溶液3mLに対して、10mg～40mgのＮＨ２－シリカゲルを加えることが好ましく、特に40mgのＮＨ２－シリカゲルを加えることが好ましい。同図から、上記溶液3mLに対して、40mg以上のＮＨ２－シリカゲルを加えた場合には、均一性が失われることが理解される。 From uniformity of the suction for SWNT / NMP solubilization solution 3mL of 0.01 mg / mL, NH of 10 mg ~ 40 mg 2 - it is preferably added silica gel, in particular NH 2 of 40 mg - it is preferable to add silica gel. From the figure, it is understood that the uniformity is lost when 40 mg or more of NH 2 -silica gel is added to 3 mL of the above solution.
　さらに、粒子径が3.5μm、1μm、500nmおよび200nmのＮＨ２－シリカゲルを用いて、上記と同様にＳＷＮＴコーティングシリカゲルを作製した。すなわち、0.01mg/mLのＳＷＮＴ／ＮＭＰ溶液3mLを30mgの各粒子径のＮＨ２－シリカゲルに添加し、得られた溶液を攪拌（1時間、300rpm）した後、遠心分離（1.5時間、4700xg）を行った。沈殿を濾過除去した後、ＳＥＭ観察した。その結果を図６に示す。粒子径3.5μmのＮＨ２－シリカゲルの場合は、上記の5μmのＮＨ２－シリカゲルと同様に均一で高密度のＳＷＮＴの観察が認められ（図６（Ａ））、粒子径1μmのＮＨ２－シリカゲルでも、3.5μmの場合ほどではないが、均一で高密度のＳＷＮＴコーティングが認められた（図６（Ｂ））。しかし、粒子径500nm（図６（Ｃ））および粒子径200nm（図６（Ｄ））においては、ＳＷＮＴコーティングは薄くなっている。この条件下において、均一で高密度のＳＷＮＴコーティングを得るには、粒子径の大きい方が好ましいことが示された。 Further, SWNT-coated silica gel was prepared in the same manner as described above using NH 2 -silica gel having particle diameters of 3.5 μm, 1 μm, 500 nm and 200 nm. That is, 3 mL of 0.01 mg / mL SWNT / NMP solution was added to 30 mg of NH 2 -silica gel with each particle size, and the resulting solution was stirred (1 hour, 300 rpm) and then centrifuged (1.5 hours, 4700 × g) Went. After removing the precipitate by filtration, SEM observation was performed. The result is shown in FIG. For silica, the above 5μm NH 2 - - NH 2 having a particle diameter of 3.5μm silica gel as well as uniform and dense SWNT observation was observed (FIG. 6 (A)), NH particle size 1 [mu] m 2 - Even with silica gel, a uniform and high-density SWNT coating was observed, although not as much as in the case of 3.5 μm (FIG. 6B). However, the SWNT coating is thin at a particle size of 500 nm (FIG. 6C) and a particle size of 200 nm (FIG. 6D). Under these conditions, it was shown that a larger particle size is preferable to obtain a uniform and high-density SWNT coating.
〔比較例１〕
（表面官能基の異なるシリカゲルを用いたＳＷＮＴコーティングシリカゲルの作製）
　表面官能基として極性の官能基ではないオクチル基またはオクタデシル基で表面が修飾された直径5.0μｍのシリカゲル（Ｃ8シリカゲルまたはＣ16シリカゲル）に対して、ＳＷＮＴのコーティングを行った。実験結果を図７に基づいて説明する。図７は、溶媒としてＮＭＰを用いたＳＷＮＴでコーティングされたシリカゲル粒子の走査型電子顕微鏡結果を示す。
　ＳＷＮＴ可溶化溶液（ＮＭＰ、1mg/mL）を調製しＮＭＰでさらに100倍に希釈することで0.01mg/mLのＳＷＮＴ／ＮＭＰ可溶化溶液を調製しこの溶液2mLに20mgのＣ8シリカゲルまたはＣ16シリカゲルを加えた。これらの溶液を攪拌（１時間、300ｒ／分）した後、遠心分離（1.5時間、4700xg）を行った。 [Comparative Example 1]
(Production of SWNT-coated silica gel using silica gels with different surface functional groups)
SWNT coating was performed on silica gel having a diameter of 5.0 μm (C8 silica gel or C16 silica gel) whose surface was modified with an octyl group or octadecyl group which is not a polar functional group as a surface functional group. An experimental result is demonstrated based on FIG. FIG. 7 shows a scanning electron microscope result of silica gel particles coated with SWNTs using NMP as a solvent.
Prepare a SWNT solubilization solution (NMP, 1 mg / mL) and dilute it 100 times with NMP to prepare a 0.01 mg / mL SWNT / NMP solubilization solution. Add 2 mg of this solution to 20 mg of C8 silica gel or C16 silica gel. added. These solutions were stirred (1 hour, 300 r / min) and then centrifuged (1.5 hours, 4700 × g).
　沈殿を濾過し回収した後、走査型電子顕微鏡（scanning electron microscope；ＳＥＭ）で吸着の様子を観察した結果を図７（左：Ｃ8シリカゲル、右：Ｃ16シリカゲル）に示す。この結果から、不均一なＳＷＮＴのコーティングが確認され、表面官能基がＣ8またはＣ16基の場合においては均一なコーティングが困難であることが示された。 After filtering and collecting the precipitate, the results of observing the state of adsorption with a scanning electron microscope (SEM) are shown in FIG. 7 (left: C8 silica gel, right: C16 silica gel). From this result, a non-uniform SWNT coating was confirmed, and it was shown that uniform coating is difficult when the surface functional group is a C8 or C16 group.
（ＮＭＰ以外の溶媒を用いたＳＷＮＴコーティングシリカゲルの作製）
　上記のＮＭＰ溶媒以外の溶媒を用いたＳＷＮＴコーティングシリカゲルを作製した。実験結果を図２に基づいて説明する。図２は、本発明に係るＣＮＴでコーティングされたシリカゲル粒子のＮＭＰ以外の溶媒を用いた実験結果を示す。 (Preparation of SWNT-coated silica gel using a solvent other than NMP)
SWNT-coated silica gel using a solvent other than the above NMP solvent was prepared. An experimental result is demonstrated based on FIG. FIG. 2 shows an experimental result using a solvent other than NMP of silica gel particles coated with CNTs according to the present invention.
　ジメチルホルムアミド（ＤＭＦ）、ジメチルアセタミド（ＤＭＡｃ）の２つの溶媒を用いて0.01mg/mLのＳＷＮＴ可溶化溶液を調製した。30mgのＮＨ２－シリカゲルを3mLのＳＷＮＴ可溶化溶液に加えた。
　この２つの溶液を攪拌（1時間、300r/分）し、遠心分離（1.5時間、4700 x g）を行った上澄みの紫外可視分光光度計（UV-vis-NIR）吸収スペクトルを測定した。また、遠心分離を行わずに濾過して回収したサンプルのラマンスペクトルを測定し、ＳＥＭで観察した。 A 0.01 mg / mL SWNT solubilized solution was prepared using two solvents, dimethylformamide (DMF) and dimethylacetamide (DMAc). 30 mg NH 2 -silica gel was added to 3 mL SWNT solubilization solution.
The two solutions were stirred (1 hour, 300 r / min), and the ultraviolet-visible spectrophotometer (UV-vis-NIR) absorption spectrum of the supernatant after centrifugation (1.5 hours, 4700 × g) was measured. In addition, the Raman spectrum of the sample collected by filtration without centrifugation was measured and observed by SEM.
　図２(ａ)に示すように、ＤＭＦとＤＭＡｃにおいてもＳＷＮＴが均一に分散した。これらのＳＷＮＴ可溶化溶液にＮＨ２－シリカゲルを添加したところ、同図(ｂ)に示すように、吸収スペクトルに変化が現れた。
　また、同図(ｃ)に示すように、濾過して回収したサンプルのラマンスペクトルにおいてＳＷＮＴ由来のピークが検出された。ＳＥＭで観察した結果、同図(ｄ)に示すように、ＳＷＮＴが均一に吸着したＳＷＮＴ－ＮＨ２－シリカゲルが確認された。 As shown in FIG. 2 (a), SWNTs were evenly dispersed in DMF and DMAc. When NH 2 -silica gel was added to these SWNT solubilized solutions, a change appeared in the absorption spectrum as shown in FIG.
Further, as shown in FIG. 3C, a peak derived from SWNT was detected in the Raman spectrum of the sample collected by filtration. As a result of observation by SEM, SWNT-NH 2 -silica gel in which SWNTs were uniformly adsorbed was confirmed as shown in FIG.
（金属性ＳＷＮＴまたは半導体性ＳＷＮＴコーティングシリカゲルの作製）
　金属性ＳＷＮＴまたは半導体性ＳＷＮＴを用いてシリカゲルのコーティングを行った。
　金属性ＳＷＮＴ（ｍ－ＳＷＮＴ）または半導体性ＳＷＮＴ（ｓ－ＳＷＮＴ）を用いて0.01mg/mLのｍ－ＳＷＮＴ/ＮＭＰまたはｓ－ＳＷＮＴ／ＮＭＰ可溶化溶液を調製した。この溶液30mLにＮＨ２－シリカゲルを400mg加えて攪拌（1時間、300r/分）した。この溶液を濾過して乾燥させた後、ラマンスペクトルを測定し、ＳＥＭで観察した。 (Production of metallic SWNT or semiconducting SWNT coated silica gel)
Silica gel coating was performed using metallic SWNT or semiconducting SWNT.
0.01 mg / mL m-SWNT / NMP or s-SWNT / NMP solubilized solution was prepared using metallic SWNT (m-SWNT) or semiconducting SWNT (s-SWNT). To 30 mL of this solution, 400 mg of NH 2 -silica gel was added and stirred (1 hour, 300 r / min). After this solution was filtered and dried, the Raman spectrum was measured and observed with SEM.
　図３は、金属性ＳＷＮＴでコーティングされたシリカゲル粒子に関する実験結果を示す。図３（ａ）に示すように、ｍ－ＳＷＮＴ/ＮＭＰ可溶化溶液は濃青色を示したことから、ｍ－ＳＷＮＴがＮＭＰにおいて均一に分散したことがわかる。また、同図（ｂ）のラマンスペクトルに示すように、この可溶化溶液を用いて作製したｍ－ＳＷＮＴ－ＮＨ２－シリカゲルからｍ－ＳＷＮＴ由来のピークが検出された。ｍ－ＳＷＮＴ－ＮＨ２－シリカゲルのＳＥＭ像を観察した結果、ｍ－ＳＷＮＴが吸着した様子が観察された。 FIG. 3 shows the experimental results for silica gel particles coated with metallic SWNTs. As shown in FIG. 3A, the m-SWNT / NMP solubilized solution showed a deep blue color, indicating that m-SWNT was uniformly dispersed in NMP. Further, as shown in the Raman spectrum of FIG. 5B, a peak derived from m-SWNT was detected from m-SWNT-NH 2 -silica gel prepared using this solubilized solution. As a result of observing an SEM image of m-SWNT-NH 2 -silica gel, it was observed that m-SWNT was adsorbed.
　ｓ－ＳＷＮＴについても、ｓ－ＳＷＮＴ／ＮＭＰ可溶化溶液が茶褐色を示したことから、ｓ－ＳＷＮＴがＮＭＰに均一に分散したことが理解された。この溶液にＮＨ２－シリカゲルを添加したところ、溶液の色が薄くなり黒色の沈殿が見られたことからｓ－ＳＷＮＴはＮＨ２－シリカゲルに吸着されたことがわかった。沈殿物として得られたＳＥＭ像を観察したところ、図８に示すように、ｓ－ＳＷＮＴが吸着された様子が確認された。 As for s-SWNT, it was understood that s-SWNT was uniformly dispersed in NMP because the s-SWNT / NMP solubilized solution showed brown. When NH 2 -silica gel was added to this solution, the color of the solution became lighter and a black precipitate was observed, indicating that s-SWNT was adsorbed on NH 2 -silica gel. When the SEM image obtained as a precipitate was observed, it was confirmed that s-SWNT was adsorbed as shown in FIG.
（ＳＷＮＴコーティングシリカゲルを用いたカラムの作製）
　以下のように、ＳＷＮＴコーティングシリカゲルを用いたカラムを作製した。実験結果を図４に基づいて説明する。図４は、本発明に係るＣＮＴでコーティングされたシリカゲル粒子をカラムクロマトグラフィーに供した実験結果を示す。 (Production of column using SWNT coated silica gel)
A column using SWNT-coated silica gel was prepared as follows. An experimental result is demonstrated based on FIG. FIG. 4 shows the experimental results of subjecting silica gel particles coated with CNTs according to the present invention to column chromatography.
　上記で作製したＳＷＮＴ－ＮＨ２－シリカゲル（346mg）をＮＰスラリー（2mL）とクロロホルム（2mL）の混合溶媒に加え、超音波照射してパッカーに入れた。加圧溶媒（イソプロパノール-クロロホルム、1:1）を流して充填させた後、パージ溶媒（加圧溶媒と同様）でカラムの中を洗浄した。十分洗浄したら圧力を下げ、カラムを取り出した。 The SWNT-NH 2 -silica gel (346 mg) prepared above was added to a mixed solvent of NP slurry (2 mL) and chloroform (2 mL), and the mixture was put into a packer by ultrasonic irradiation. After the pressurized solvent (isopropanol-chloroform, 1: 1) was flowed and packed, the inside of the column was washed with a purge solvent (similar to the pressurized solvent). After washing sufficiently, the pressure was reduced and the column was removed.
　このようにして作製されたＳＷＮＴ－ＮＨ２－シリカ－カラム（ＳＷＮＴ－ＮＨ２－シリカゲルを充てんしたカラム）とＮＨ２－シリカ－カラム（ＮＨ２－シリカゲルを充てんしたカラム）を比較し、カラムの評価を行った。 Thus prepared were SWNT-NH 2 - silica - column (SWNT-NH 2 - column packed with silica gel) and NH 2 - silica - column - comparing (NH 2 column packed with silica gel) column Evaluation was performed.
　移動相：トルエン、化合物：ＴＨＦ、ＮＭＰ、ＤＭＡｃ、ＤＭＦ、流量：0.1mL/分、圧力：0.5MPaでカラムに流入した結果として、図４に示すクロマトグラムが得られた。
　この結果から、ＳＷＮＴ－ＮＨ２－シリカ－カラムを使った場合およびＮＨ２－シリカ-カラムを使った場合のいずれも、左側のピークはTHF由来であり、右のピークは残りの3つの溶媒由来のピークが重なったものであることがわかった。この２つのピークに対してより分かれたクロマトグラムが得られたのはＳＷＮＴ－ＮＨ２－シリカ－カラムであったことから、ＳＷＮＴ－ＮＨ２－シリカ-カラムのほうがより分解能が良いことが認められた。 As a result of flowing into the column with mobile phase: toluene, compound: THF, NMP, DMAc, DMF, flow rate: 0.1 mL / min, pressure: 0.5 MPa, the chromatogram shown in FIG. 4 was obtained.
From this result, the left peak is derived from THF and the right peak is derived from the remaining three solvents in both the case of using the SWNT-NH 2 -silica column and the case of using the NH 2 -silica column. It was found that the peaks of were overlapped. Since it was SWNT-NH 2 -silica-column that the chromatograms separated for these two peaks were obtained, it was confirmed that SWNT-NH 2 -silica-column had better resolution. It was.
　このように、ＳＷＮＴとＮＨ２－シリカゲルは強い相互作用で吸着しており、高速液体クロマトグラフィー（High performance
liquid chromatography；ＨＰＬＣ）の固定相として用いられることが認められた。これにより、ＣＮＴと分子との相互作用をクロマトグラフィーにおける溶出時間というパラメータで高精度に評価することができる。 Thus, SWNT and NH 2 -silica gel are adsorbed by a strong interaction, and high performance liquid chromatography (High performance
It was found to be used as a stationary phase for liquid chromatography (HPLC). Thereby, the interaction between CNT and molecules can be evaluated with high accuracy by a parameter called elution time in chromatography.
（ＳＷＮＴコーティングした酸化チタンの作製）
　上記のＳＷＮＴコーティングシリカゲルの他に、ＳＷＮＴコーティングした酸化チタンを作製した。実験結果を図５(ａ)および(ｂ)に基づいて説明する。図５(ａ)および(ｂ)は、本発明に係るＣＮＴでコーティングされた酸化チタンの実験結果を示す。 (Production of SWNT-coated titanium oxide)
In addition to the above-mentioned SWNT-coated silica gel, SWNT-coated titanium oxide was produced. An experimental result is demonstrated based on Fig.5 (a) and (b). 5 (a) and 5 (b) show the experimental results of titanium oxide coated with CNTs according to the present invention.
　ジメチルホルムアミド（ＤＭＦ）を溶媒として0.01mg/mLのＳＷＮＴ可溶化溶液を調製した。30mgのＮＨ２－酸化チタンを3mLのＳＷＮＴ可溶化溶液に加えた。
　この２つの溶液を攪拌（1時間、300r/分）し、遠心分離（1.5時間、4700 x g）を行った上澄みの紫外可視分光光度計（UV-vis-NIR）吸収スペクトルを測定した。また、遠心分離を行わずに濾過して回収したサンプルのラマンスペクトルを測定し、ＳＥＭで観察した。 A 0.01 mg / mL SWNT-solubilized solution was prepared using dimethylformamide (DMF) as a solvent. 30 mg NH 2 -titanium oxide was added to 3 mL SWNT solubilization solution.
The two solutions were stirred (1 hour, 300 r / min), and the ultraviolet-visible spectrophotometer (UV-vis-NIR) absorption spectrum of the supernatant after centrifugation (1.5 hours, 4700 × g) was measured. In addition, the Raman spectrum of the sample collected by filtration without centrifugation was measured and observed by SEM.
　図５(ａ)に示すように、濾過して回収したサンプルのラマンスペクトルにおいてＳＷＮＴ由来のピークが検出された。ＳＥＭで観察した結果、同図(ｂ)に示すように、ＳＷＮＴが均一に吸着したＳＷＮＴ－ＮＨ２－酸化チタンが確認された。 As shown in FIG. 5A, a peak derived from SWNT was detected in the Raman spectrum of the sample collected by filtration. As a result of observation by SEM, SWNT-NH 2 -titanium oxide in which SWNTs were uniformly adsorbed was confirmed as shown in FIG.
（ＳＷＮＴコーティングした酸化亜鉛の作製）
　上記のＳＷＮＴコーティングシリカゲルの他に、ＳＷＮＴコーティングした酸化亜鉛を作製した。実験結果を図５(ｃ)に基づいて説明する。図５(ｃ)は、本発明に係るＣＮＴでコーティングされた酸化亜鉛の実験結果を示す。 (Production of SWNT-coated zinc oxide)
In addition to the above SWNT-coated silica gel, SWNT-coated zinc oxide was prepared. An experimental result is demonstrated based on FIG.5 (c). FIG. 5 (c) shows the experimental results of zinc oxide coated with CNTs according to the present invention.
　ジメチルホルムアミド（ＤＭＦ）を溶媒として0.01mg/mLのＳＷＮＴ可溶化溶液を調製した。30mgのＮＨ２－酸化亜鉛を3mLのＳＷＮＴ可溶化溶液に加えた。
　この２つの溶液を攪拌（1時間、300r/分）し、遠心分離（1.5時間、4700 x g）を行った上澄みの紫外可視分光光度計（UV-vis-NIR）吸収スペクトルを測定した。また、遠心分離を行わずに濾過して回収したサンプルのラマンスペクトルを測定した。
　図５(ｃ)に示すように、濾過して回収したサンプルのラマンスペクトルにおいてＳＷＮＴ由来のピークが検出され、ＳＷＮＴ－ＮＨ２－酸化亜鉛が確認された。 A 0.01 mg / mL SWNT-solubilized solution was prepared using dimethylformamide (DMF) as a solvent. 30 mg NH 2 -zinc oxide was added to 3 mL SWNT solubilization solution.
The two solutions were stirred (1 hour, 300 r / min), and the ultraviolet-visible spectrophotometer (UV-vis-NIR) absorption spectrum of the supernatant after centrifugation (1.5 hours, 4700 × g) was measured. In addition, the Raman spectrum of the sample collected by filtration without centrifugation was measured.
As shown in FIG. 5C, a peak derived from SWNT was detected in the Raman spectrum of the sample collected by filtration, and SWNT—NH 2 —zinc oxide was confirmed.
（カルボキシル基修飾シリカゲルを用いたＳＷＮＴコーティングシリカゲルの作製）
　極性官能基としてカルボキシル基で表面が修飾された直径5.0μmのシリカゲル（ＣＯＯＨシリカゲル)に対して、ＳＷＮＴのコーティングを行った。実験結果を図９に基づいて説明する。図９は、溶媒としてＮＭＰを用いた本発明に係るＳＷＮＴでコーティングされたシリカゲル粒子の走査型電子顕微鏡結果を示す。
　ＳＷＮＴ可溶化溶液（ＳＷＮＴ／ＮＭＰ、1mg/mL）を調製しNMPでさらに100倍に希釈することで0.01mg/mLのSＷＮＴ／ＮＭＰ可溶化溶液を調整しこの溶液3mLに30mgのＣＯＯＨシリカゲルを加えた。これらの溶液を攪拌（1時間、300r/分）した後、遠心分離（1.5時間、4700xg）を行った。
　沈殿を濾過し回収した後、走査型電子顕微鏡（scanning electron
microscope；ＳＥＭ）で吸着の様子を観察した結果を図９に示す。この結果から、ＳＷＮＴのコーティングが確認され、表面官能基がＣＯＯＨ基の場合においてもコーティングが可能であることが示された。 (Production of SWNT-coated silica gel using carboxyl group-modified silica gel)
SWNT coating was performed on 5.0 μm diameter silica gel (COOH silica gel) whose surface was modified with a carboxyl group as a polar functional group. An experimental result is demonstrated based on FIG. FIG. 9 shows a scanning electron microscope result of silica gel particles coated with SWNTs according to the present invention using NMP as a solvent.
Prepare SWNT solubilization solution (SWNT / NMP, 1 mg / mL) and dilute it 100 times with NMP to prepare 0.01 mg / mL SWNT / NMP solubilization solution. Add 3 mg of this solution to 30 mg COOH silica gel. It was. These solutions were stirred (1 hour, 300 r / min) and then centrifuged (1.5 hours, 4700 × g).
After filtering and collecting the precipitate, a scanning electron microscope (scanning electron microscope)
The result of observing the state of adsorption with a microscope (SEM) is shown in FIG. From this result, the coating of SWNT was confirmed, and it was shown that the coating is possible even when the surface functional group is a COOH group.
（ＳＷＮＴコーティングシリカゲルを用いたクロマトグラフィーによる分子とＳＷＮＴとの相互作用評価）
　実施例４と同様にして作製したＳＷＮＴ－ＮＨ２－シリカゲルを充填したカラムを用いるクロマトグラフィーにより、各種の芳香族分子とＳＷＮＴとの相互作用を調べた。移動相としてＴＨＦを用い、流量は0.1mL／分または0.5mL／分として、254nmまたは340nmにおける吸光度を測定した。
　得られたクロマトグラムを図１０に示す。保持時間が長い程、ＣＮＴとの相互作用が強いことを示しており、その順位は、ベンゼン（benzene）＜ナフタレン（naphthalene）＜ビフェニル（biphenyl）＜フルオレン（fluorene）＜フェナンスレン（phenanthrene）＜アントラセン（anthracene）～ピレン（pyrene）＜トリフェニレン（triphenylene）＜ｐ－テルフェニル（p-terphenyl）＜テトラフェン（tetraphene）＜テトラセン（tetracene）である。このように、本発明に従うＣＮＴコーティングシリカゲルはＣＮＴとの相互作用を評価するのに有用であることが確認された。 (Evaluation of SWNT interaction with SWNT coated silica gel by chromatography)
The interaction between various aromatic molecules and SWNTs was examined by chromatography using a column packed with SWNT-NH 2 -silica gel prepared in the same manner as in Example 4. Absorbance at 254 nm or 340 nm was measured using THF as the mobile phase at a flow rate of 0.1 mL / min or 0.5 mL / min.
The obtained chromatogram is shown in FIG. The longer the retention time, the stronger the interaction with CNT, and the ranking is as follows: benzene <naphthalene <biphenyl <fluorene <phenanthrene <anthracene (phenanthrene) anthracene) -pyrene <triphenylene <p-terphenyl <tetraphene <tetracene. Thus, it was confirmed that the CNT-coated silica gel according to the present invention is useful for evaluating the interaction with CNT.
（ＣＮＴコーティングシリカゲルを用いたフタロシアニン吸着能の評価）
　ＳＷＮＴ－ＮＨ２－シリカゲルを用いてフタロシアニンとＳＷＮＴとの吸着性について実験を行った。実験結果を図１１に基づいて説明する。図１１は本発明にかかるＳＷＮＴ－ＮＨ２－シリカゲルを用いたフタロシアニンとＳＷＮＴとの吸着性評価に関する実験結果を示す。フタロシアニンはＳＷＮＴとの吸着性が強いため、上記クロマトグラフィーによる吸着性評価においては溶出を与えず解析が困難な分子である。フタロシアニンとしては29H,31H-phthalocyanine（以下PC-1）,2,3,9,10,16,17,23,24-Octakis(octyloxy)-29H,31H-phthalocyanine（以下PC-2）,2,11,20,29-Tetra-tert-butyl-2,3-naphthalocyanine（以下PC-3）and2,9,16,23-Tetra-tert-butyl-29H,31H-phthalocyanine（以下PC-4）の４種類の分子を用いた。 (Evaluation of phthalocyanine adsorption capacity using CNT-coated silica gel)
An experiment was conducted on the adsorption properties of phthalocyanine and SWNTs using SWNT-NH 2 -silica gel. An experimental result is demonstrated based on FIG. FIG. 11 shows the experimental results regarding the adsorptivity evaluation of phthalocyanine and SWNT using SWNT—NH 2 -silica gel according to the present invention. Since phthalocyanine has a strong adsorptivity with SWNT, it is a molecule that is difficult to analyze without giving an elution in the adsorptive evaluation by the chromatography. As phthalocyanines, 29H, 31H-phthalocyanine (PC-1), 2,3,9,10,16,17,23,24-Octakis (octyloxy) -29H, 31H-phthalocyanine (PC-2), 2, 11,20,29-Tetra-tert-butyl-2,3-naphthalocyanine (PC-3) and 2,9,16,23-Tetra-tert-butyl-29H, 31H-phthalocyanine (PC-4) Different types of molecules were used.
　ＰＣ－１，ＰＣ－２，ＰＣ－３，ＰＣ－４のそれぞれの５μＭテトラヒドロフラン（ＴＨＦ）溶液を5mL調製した。この溶液にＳＷＮＴ－ＮＨ２－シリカゲルを30，60，90，120mgと量を変えて加えて振とう（１時間、300ｒ／分）した。この溶液を１時間静置した後、上澄み溶液を吸収分光測定装置により可視領域の吸収を測定した。
　図１１に示すように、ＰＣ－１，ＰＣ－２，ＰＣ－３，ＰＣ－４すべての溶液においてＳＷＮＴ－ＮＨ２－シリカゲルの添加量が増えるに従い吸収ピークが減少したことがわかる。この減少量からフタロシアニン構造の違いによるＳＷＮＴへの吸着性の違いが理解できる。実施例９のクロマトグラフィー法では吸着性の違いが評価できないような大きな分子に対してもＣＮＴとの相互作用を評価することが可能であり、本発明に従うＣＮＴコーティングシリカゲルの有用性が示された。
  5 mL of a 5 μM tetrahydrofuran (THF) solution of each of PC-1, PC-2, PC-3, and PC-4 was prepared. To this solution, SWNT-NH 2 -silica gel was added in different amounts of 30, 60, 90, 120 mg and shaken (1 hour, 300 r / min). The solution was allowed to stand for 1 hour, and the supernatant solution was measured for absorption in the visible region using an absorption spectrometer.
As shown in FIG. 11, it can be seen that the absorption peak decreased as the amount of SWNT-NH 2 -silica gel added increased in all solutions of PC-1, PC-2, PC-3, and PC-4. From this decrease, the difference in adsorptivity to SWNTs due to the difference in phthalocyanine structure can be understood. It was possible to evaluate the interaction with CNT even for large molecules for which the difference in adsorptivity could not be evaluated by the chromatography method of Example 9, and the usefulness of the CNT-coated silica gel according to the present invention was shown. .

Claims (14)

  1. 　インタクトなカーボンナノチューブを窒素原子含有極性溶媒に分散し、当該分散液中に、極性を有する官能基または原子団で表面が修飾された粒子を攪拌することを特徴とするカーボンナノチューブでコーティングされた粒子の製造方法。 Particles coated with carbon nanotubes, characterized in that intact carbon nanotubes are dispersed in a polar solvent containing nitrogen atoms, and particles whose surfaces are modified with polar functional groups or atomic groups are stirred in the dispersion. Manufacturing method.
  2. 　前記官能基または原子団が、アミノ基であることを特徴とする請求項１のカーボンナノチューブでコーティングされた粒子の製造方法。 The method for producing particles coated with carbon nanotubes according to claim 1, wherein the functional group or atomic group is an amino group.
  3. 　前記窒素原子含有極性溶媒が、１－メチル－２－ピロリドン（ＮＭＰ）、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡｃ）のうちのいずれかであることを特徴とする請求項１または請求項２記載のカーボンナノチューブでコーティングされた粒子の製造方法。 2. The nitrogen atom-containing polar solvent is any one of 1-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), and dimethylacetamide (DMAc). A method for producing particles coated with carbon nanotubes according to claim 2.
  4. 　前記カーボンナノチューブが、単層カーボンナノチューブであることを特徴とする請求項１～請求項３のいずれかのカーボンナノチューブでコーティングされた粒子の製造方法。 The method for producing particles coated with carbon nanotubes according to any one of claims 1 to 3, wherein the carbon nanotubes are single-walled carbon nanotubes.
  5. 　前記カーボンナノチューブが、多層カーボンナノチューブであることを特徴とする請求項１～請求項３のいずれかのカーボンナノチューブでコーティングされた粒子の製造方法。 The method for producing particles coated with carbon nanotubes according to any one of claims 1 to 3, wherein the carbon nanotubes are multi-walled carbon nanotubes.
  6. 　前記カーボンナノチューブが、金属性カーボンナノチューブであることを特徴とする請求項１～請求項５のいずれかのカーボンナノチューブでコーティングされた粒子の製造方法。 The method for producing particles coated with carbon nanotubes according to any one of claims 1 to 5, wherein the carbon nanotubes are metallic carbon nanotubes.
  7. 　前記カーボンナノチューブが、半導体性カーボンナノチューブであることを特徴とする請求項１～請求項５のいずれかのカーボンナノチューブでコーティングされた粒子の製造方法。 The method for producing particles coated with carbon nanotubes according to any one of claims 1 to 5, wherein the carbon nanotubes are semiconducting carbon nanotubes.
  8. 　前記カーボンナノチューブによりコーティングされる粒子が、シリカゲル粒子であることを特徴とする請求項１～請求項７のいずれかのカーボンナノチューブでコーティングされた粒子の製造方法。 The method for producing particles coated with carbon nanotubes according to any one of claims 1 to 7, wherein the particles coated with the carbon nanotubes are silica gel particles.
  9. 　前記カーボンナノチューブによりコーティングされる粒子が、酸化チタン粒子であることを特徴とする請求項１～請求項７のいずれかのカーボンナノチューブでコーティングされた粒子の製造方法。 The method for producing particles coated with carbon nanotubes according to any one of claims 1 to 7, wherein the particles coated with the carbon nanotubes are titanium oxide particles.
  10. 　前記カーボンナノチューブによりコーティングされる粒子が、酸化亜鉛粒子であることを特徴とする請求項１～請求項７のいずれかのカーボンナノチューブでコーティングされた粒子の製造方法。 The method for producing particles coated with carbon nanotubes according to any one of claims 1 to 7, wherein the particles coated with the carbon nanotubes are zinc oxide particles.
  11. 　インタクトなカーボンナノチューブでコーティングされていることを特徴とする粒子。 Particles characterized by being coated with intact carbon nanotubes.
  12. 　粒子がシリカゲル粒子であることを特徴とする請求項１１のカーボンナノチューブコーティング粒子。 The carbon nanotube-coated particles according to claim 11, wherein the particles are silica gel particles.
  13. 　カーボンナノチューブが単層カーボンナノチューブであることを特徴とする請求項１１または１２のカーボンナノチューブ粒子。 The carbon nanotube particle according to claim 11 or 12, wherein the carbon nanotube is a single-walled carbon nanotube.
  14. 　請求項１１～請求項１３のいずれかのカーボンナノチューブコーティング粒子を含有することを特徴とするクロマトグラフィー用カラム。
          A chromatography column comprising the carbon nanotube-coated particles according to any one of claims 11 to 13.
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