WO2011111791A1 - Procédé pour la production de nanotubes de carbone - Google Patents

Procédé pour la production de nanotubes de carbone Download PDF

Info

Publication number
WO2011111791A1
WO2011111791A1 PCT/JP2011/055689 JP2011055689W WO2011111791A1 WO 2011111791 A1 WO2011111791 A1 WO 2011111791A1 JP 2011055689 W JP2011055689 W JP 2011055689W WO 2011111791 A1 WO2011111791 A1 WO 2011111791A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon nanotubes
potential
carbon
working electrode
metal catalyst
Prior art date
Application number
PCT/JP2011/055689
Other languages
English (en)
Japanese (ja)
Inventor
敬 村越
保田　諭
シャウキィ アハマド
Original Assignee
国立大学法人北海道大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人北海道大学 filed Critical 国立大学法人北海道大学
Priority to JP2012504523A priority Critical patent/JPWO2011111791A1/ja
Publication of WO2011111791A1 publication Critical patent/WO2011111791A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials
    • 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
    • C01B32/166—Preparation in liquid phase
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals

Definitions

  • the present invention relates to a method for producing carbon nanotubes.
  • Multi-walled carbon nanotubes As a method for producing (multi-wall carbon nanotubes MWCNT), methanol (99.8% purity) in the catalyst (nickel acetate tetrahydrate: Ni (CH 3 COO) 2 ⁇ 4H 2 O) electrolytic plus A method is known in which a multi-walled carbon nanotube is deposited on a silicon substrate by immersing a silicon substrate and a graphite substrate in a liquid and applying a potential of 50 V for 3 hours (see, for example, Non-Patent Document 1).
  • the synthesis method is performed on a metal substrate on which a very large potential (50 V or more) is applied to the surface of the metal substrate, and on which a catalyst metal fine particle serving as a nucleus of tube generation is not supported.
  • a very large potential 50 V or more
  • a catalyst metal fine particle serving as a nucleus of tube generation is not supported.
  • nanotubes are generated in an environment of large thermal fluctuation.
  • the influence of the thermal fluctuation cannot be removed, and the structure-controlled tube cannot be synthesized.
  • carbon molecules that are the carbon source in the liquid are excessively thermally decomposed at the substrate-liquid interface and supplied to the catalyst, so that the resulting tube is also a multi-walled nanotube (MWNT), and various applications are expected.
  • MWNT multi-walled nanotube
  • SWNTs single-walled carbon nanotubes
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a structure-controlled carbon nanotube with low energy consumption.
  • the method for producing a carbon nanotube of the present invention is a state in which a working electrode having a metal catalyst attached is immersed in an electrolytic solution composed of an aqueous solution containing a substance containing carbon atoms and water.
  • a carbon nanotube can be produced by efficiently reacting a metal catalyst and a substance containing carbon atoms by applying a potential of only a few volts.
  • the metal catalyst is in a solid state, there is almost no influence of thermal fluctuations, and since rapid progress of the precipitation reaction can be suppressed, the structure-controlled carbon nanotube can be synthesized. Since no heat is generated at the interface between the electrode and the liquid, excessive pyrolysis of the substance containing carbon atoms does not occur, so that carbon nanotubes can be synthesized.
  • the carbon nanotube may be a single-walled carbon nanotube.
  • single-walled carbon nanotubes having properties different from those of multi-walled carbon nanotubes are produced.
  • Single-walled carbon nanotubes can exhibit semiconductor characteristics and metal characteristics by controlling chirality. Further, the band gap can be changed by controlling the diameter of the single-walled carbon nanotube.
  • the single-walled carbon nanotube by introducing defects or heterogeneous element substitution into the tube, the single-walled carbon nanotube functions as a catalytic active point, and higher oxygen reduction catalytic activity can be obtained. Therefore, application to electronic devices, optical devices, and catalyst materials is possible.
  • the absolute value of the potential applied when depositing the carbon nanotubes may be 2 V or less. In this case, energy consumption can be greatly reduced. In addition, since the absolute value of the potential is as low as 2 V or less, rapid progress of the precipitation reaction can be suppressed. Therefore, not single-walled carbon nanotubes but single-walled carbon nanotubes (single-walled carbon nanotubes: SWCNT) can be produced.
  • the potential refers to the potential of the working electrode with respect to the reference electrode (Ag / AgCl) when a voltage is applied between the counter electrode and the working electrode.
  • the potential may be greater than 0V and greater than or equal to 0.5V.
  • the absolute value varies depending on the type of the reference electrode or the working electrode, it is preferable to express the energy with the equilibrium state of the system.
  • the working electrode may be made of gold.
  • the atomic level unevenness on the gold surface is smaller than the atomic level unevenness on the oxide or semiconductor surface, so that it can be uniformly electrolytically deposited on the surface of the catalyst metal fine particles of uniform size, and the structure control
  • the produced carbon nanotube can be produced at a low potential.
  • the reference electrode and the counter electrode may be immersed in the electrolytic solution.
  • the potential can be precisely controlled.
  • the aqueous solution may be an acetic acid aqueous solution.
  • acetic acid itself is weakly ionized, a current can be passed at a low potential without adding an alkali metal salt or the like, for example.
  • the carbon nanotube manufacturing method further includes a step of depositing the metal catalyst on the working electrode by electrolytic deposition, and an absolute value of a potential applied when depositing the metal catalyst is 1.2 V or less.
  • the time for applying the potential when depositing the metal catalyst may be 10 ms (milliseconds) or less. In this case, a structure-controlled single-walled carbon nanotube can be produced.
  • the metal catalyst may be metal particles, and the mode value of the particle size of the metal particles may be 4 nm or less. In this case, a structure-controlled single-walled carbon nanotube can be produced.
  • the particle size of the metal particles is, for example, the width of the particles in the direction along the surface of the working electrode.
  • the metal catalyst may be made of Ni. In this case, single-walled carbon nanotubes can be produced.
  • the absolute value of the potential applied when depositing the carbon nanotubes may be 1 V or less. In this case, single-walled carbon nanotubes can be produced.
  • FIG. 1 is a diagram schematically showing an electrochemical system for producing carbon nanotubes.
  • An electrochemical system 10 shown in FIG. 1 is a three-electrode electrochemical system.
  • the electrochemical system 10 includes a container 12 in which an electrolytic solution 14 is accommodated.
  • the electrolytic solution 14 is made of, for example, an aqueous solution containing a substance containing carbon atoms and water.
  • a working electrode 16, a reference electrode 18, and a counter electrode 20 are immersed in the electrolytic solution 14.
  • the working electrode 16, the reference electrode 18 and the counter electrode 20 are connected to a potentiostat (or galvanostat) 22 via wiring.
  • a computer 24 is connected to the potentiostat 22 via wiring.
  • a tube 26 for introducing the gas 28 into the electrolytic solution 14 may be inserted into the electrolytic solution 14.
  • Examples of the substance containing a carbon atom include alcohol (R—OH), ether (R—O—R ′), ketone (R—C ⁇ O), aldehyde (R—CHO), and carboxylic acid (R—COOH). , Esters (R—COOR ′), carboxylates (R—COO ⁇ ⁇ M + ), organic compounds such as amides (R—CO ⁇ NH 2 ), carbon dioxide (CO 2 ), and the like.
  • Examples of the alcohol include methanol (CH 3 OH), ethanol (CH 3 CH 2 OH), isopropanol (IPA: CH 3 CH 3 (OH) CH 3 ), and the like.
  • ether examples include methyl ethyl ether (CH 3 —O—C 2 H 5 ), diethyl ether (C 2 H 5 —O—C 2 H 5 ), tetrahydrofuran (THF: C 4 H 8 O), and the like. It is done.
  • ketone examples include dimethyl ketone (acetone: (CH 3 ) C ⁇ O)) and methyl ethyl ketone (MEK: CH 3 ⁇ C 2 H 5 ⁇ C ⁇ O).
  • aldehyde examples include formaldehyde (H ⁇ CH ⁇ O), acetaldehyde (CH 3 ⁇ CH ⁇ O), propionaldehyde (CH 3 ⁇ CH 2 ⁇ CH ⁇ O), and benzaldehyde (C 6 H 5 ⁇ CH ⁇ O).
  • carboxylic acid examples include acetic acid (CH 3 ⁇ COOH), benzoic acid (C 6 H 5 ⁇ COOH), and the like.
  • ester examples include ethyl acetate (CH 3 ⁇ COOC 2 H 4 ), methyl salicylate (HO ⁇ C 6 H 5 ⁇ COOCH 3 ), methyl benzoate (C 6 H 5 ⁇ COOCH 3 ), and the like.
  • Examples of the carboxylate include sodium acetate (CH 3 ⁇ COO ⁇ Na + ), potassium acetate (CH 3 ⁇ COO ⁇ K + ) and the like.
  • Examples of the amide include acetamide (CH 3 —CO ⁇ NH 2 ) and benzamide (C 6 H 5 —CO ⁇ NH 2 ).
  • a gas such as carbon dioxide may be introduced into the electrolytic solution 14 as the gas 28.
  • the concentration of the substance containing carbon atoms is preferably greater than 0% by mass and 10% by mass or less based on the mass of the entire electrolyte solution 14.
  • the electrolytic solution 14 may further include an acidic solvent such as H 2 SO 4 or an alkali metal salt so as to increase the conductivity of the liquid, lower the electrical resistance, and sufficiently inject the energy by applying a potential to the electrode.
  • an acidic solvent such as H 2 SO 4 or an alkali metal salt
  • the alkali metal salt include sodium sulfate (Na 2 SO 4 ).
  • the pH of the solution is preferably between 0 and 14.
  • the metal electrode is attached to the working electrode 16.
  • the working electrode 16 is preferably made of gold (Au).
  • Ni, Pt, Co, Fe, Cu, Ag, Pb, and Pd may be used for the working electrode.
  • the working electrode 16 may be a substrate or a wire.
  • the metal catalyst for example, nanoparticles composed of Ni, Co, Fe, Au, Ag, Cu, Pt, Mn, Pd, Pb, Cd, In, and Zn can be used.
  • the reference electrode 18 is made of, for example, Ag / AgCl.
  • the counter electrode 20 is made of Pt, for example.
  • FIG. 2 is a flowchart showing each step of the carbon nanotube manufacturing method according to the present embodiment.
  • the carbon nanotube manufacturing method according to the present embodiment is performed as follows using, for example, the electrochemical system 10 described above.
  • a metal catalyst is deposited on the working electrode by electrolytic deposition in a state where the working electrode is immersed in the electrolytic solution (step S1).
  • the electrolytic solution containing a metal includes, for example, NiSO 4 .
  • Ni nanoparticles are deposited on the surface of the working electrode.
  • the absolute value of the potential applied when depositing the metal catalyst may be 0.5 to 2V.
  • the time for applying the potential may be 1 ⁇ s to 10 minutes.
  • the temperature at which the metal catalyst is deposited is preferably room temperature.
  • the absolute value of the potential applied when carbon nanotubes are deposited is greater than 0V, 0.5V or more, or 0.9V or more. Further, the energy applied when the carbon nanotubes are deposited may be 10 V or less, 5 V or less, 2 V or less, or 1.1 V or less.
  • the time for applying the potential may be 1 to 60 minutes.
  • the temperature of the electrolytic solution 14 is preferably 50 ° C. or less, more preferably 10 to 30 ° C., and particularly preferably room temperature.
  • the carbon nanotube can be manufactured through the above-described steps.
  • the working electrode 16 to which the metal catalyst is attached may be prepared by immersing the working electrode in a solution containing the metal catalyst and then drying it.
  • the absolute value of the potential applied when depositing the carbon nanotubes may be 2 V or less. In this case, energy consumption can be greatly reduced. Further, when the absolute value of the applied potential is as low as 2 V or less, rapid progress of the precipitation reaction can be suppressed. For this reason, not single-walled carbon nanotubes but single-walled carbon nanotubes can be produced.
  • Single-walled carbon nanotubes have different properties from multi-walled carbon nanotubes.
  • Single-walled carbon nanotubes can exhibit semiconductor characteristics and metal characteristics by controlling chirality. Further, the band gap can be changed by controlling the diameter of the single-walled carbon nanotube. Furthermore, in the single-walled carbon nanotube, high oxygen reduction catalytic activity can be obtained by introducing active sites. Therefore, application to electronic devices, optical devices, and catalyst materials is possible.
  • the diameter of the obtained carbon nanotube can be controlled by changing the time and potential of electrolytic deposition of the metal catalyst, for example.
  • the chirality, the introduction of the active site, and the length of the obtained carbon nanotube can be controlled, for example, by controlling the potential application time in units of ⁇ s.
  • the surface of the working electrode 16 is an Au (111) single crystal surface produced by using the Clavilier method, which is a metal single crystal production method.
  • This method is a method in which a gold wire is melted by a gas burner and microcrystals in the vicinity of the melted portion are coarsened to obtain large crystals.
  • crystal surfaces such as an Au (111) plane and an Au (100) plane can be produced.
  • a crystal surface having a plane orientation other than the (111) plane and the (100) plane can be produced. Since these crystal surfaces have only irregularities on the atomic level, carbon nanotubes can be electrolytically deposited uniformly on the surface of catalyst metal fine particles of uniform size, and structure-controlled carbon nanotubes are produced at a low potential. be able to.
  • the potential can be precisely controlled by using the working electrode 16, the reference electrode 18 and the counter electrode 20, the chirality of the obtained carbon nanotube, the introduction of the active site, the length, etc. can be controlled. It is.
  • the concentration of the acetic acid aqueous solution is preferably greater than 0% by mass and 10% by mass or less, and more preferably greater than 0% by mass and 5% by mass or less.
  • a two-electrode electrochemical system may be used as the electrochemical system 10.
  • an aqueous solution of sodium sulfate (0.1 M) containing no acetic acid as the electrolytic solution the electric potential was measured in the range of 0.5 to 2 V, and the current value was measured.
  • a sodium sulfate aqueous solution (0.1 M) to which a 1% by mass acetic acid aqueous solution was added as an electrolytic solution was used, and the current value was measured by changing the potential in the range of 0.5 to 2V. The results are shown in FIG.
  • the vertical axis of the graph in FIG. 3 represents the current value.
  • the horizontal axis of the graph in FIG. 3 represents the potential of the working electrode with respect to the reference electrode.
  • a solid line I 1 in FIG. 3 indicates a current value when an aqueous solution not containing acetic acid is used.
  • a solid line I 2 in FIG. 3 indicates a current value when a 1 mass% acetic acid aqueous solution is added.
  • Example 1 the metal catalyst was electrolytically deposited using a three-electrode electrochemical system as shown in FIG.
  • a gold wire was used as the working electrode, Ag / AgCl as the reference electrode, and Pt as the counter electrode.
  • As the electrolytic solution an aqueous solution composed of NiSO 4 (10 mM), H 3 BO 3 (10 mM), and H 2 SO 4 (0.1 mM) was used.
  • a potential of ⁇ 1.2 V (the potential of the working electrode with respect to the reference electrode) was applied for 0.1 second to deposit Ni nanoparticles on the gold wire at room temperature.
  • FIG. 4A shows an AFM photograph of the surface of the gold wire after electrolytic deposition of the metal catalyst.
  • FIG. 4B shows an AFM photograph of the surface of the gold wire after the electrolytic deposition of carbon.
  • Example 1 The peak around 240 cm ⁇ 1 is due to the tube structure (RBM: Radial breathing mode). The peak around 1300 cm ⁇ 1 is due to the defect structure (D-band). The peak around 1600 cm ⁇ 1 is attributed to a six-membered ring structure (G-band). Therefore, it was found that the precipitate obtained in Example 1 was a single-walled carbon nanotube. This single-walled carbon nanotube had the following characteristics.
  • ⁇ RBM represents the Raman shift of RBM, (n, m) represents chirality, d represents the diameter, and ⁇ represents the chiral angle.
  • Example 2 An experiment was conducted in the same manner as in Example 1 except that, when the carbon was electrolytically deposited, a 1 mass% acetic acid aqueous solution added with a Ni catalyst was used as the electrolytic solution. As a result, carbon nanotubes were obtained.
  • Example 3 An experiment was conducted in the same manner as in Example 1 except that, when the carbon was electrolytically deposited, a 1% by mass acetic acid aqueous solution containing Ni catalyst and sodium sulfate (0.1 M) was used as the electrolytic solution. As a result, carbon nanotubes were obtained.
  • Example 4 An experiment was conducted in the same manner as in Example 1 except that, when the carbon was electrolytically deposited, a 1% by mass methanol aqueous solution to which Ni catalyst and sodium sulfate (0.1 M) were added was used as the electrolytic solution. As a result, carbon nanotubes were obtained.
  • Example 5 Experiments were conducted in the same manner as in Example 1 except that, when the carbon was electrolytically deposited, a 1% by mass aqueous methanol solution containing an Fe catalyst and sodium sulfate (0.1 M) was used as the electrolytic solution. As a result, carbon nanotubes were obtained.
  • Comparative Example 1 Except that the metal catalyst was not subjected to electrolytic deposition, in the same manner as in Example 1, the carbon was subjected to electrolytic deposition, and Raman spectrum measurement was performed in order to identify the obtained precipitate. The results are shown in FIG. The vertical axis shows the Raman intensity. The horizontal axis represents the Raman shift. As shown in FIG. 6, 1300 cm -1, peak near 1600 cm -1 was observed. Therefore, it was found that the precipitate obtained in Comparative Example 1 was not a carbon nanotube.
  • FIG. 7 shows an STM photograph of the surface of the gold wire after electrolytic deposition of Ni nanoparticles.
  • FIG. 7A is an STM photograph when a potential is applied for 5 ms.
  • FIG. 7B is an STM photograph when a potential is applied for 10 ms.
  • FIG. 7C is an STM photograph when a potential is applied for 100 ms.
  • FIG. 8A and 9A are histograms when a potential is applied for 5 ms.
  • FIG. 8 and FIG. 9B are histograms when a potential is applied for 10 ms.
  • FIG. 8C and FIG. 9C are histograms when a potential is applied for 100 ms.
  • the vertical axis represents the number of Ni nanoparticles.
  • the horizontal axis represents the particle size (nm) of the Ni nanoparticles.
  • FIGS. 9A to 9C the horizontal axis represents the height (nm) of the Ni nanoparticles.
  • the mode value of the particle diameter of Ni nanoparticles is 4 nm or less.
  • the mode of the height of Ni nanoparticles does not change so much as about 0.4 to 0.6 nm.
  • the time for electrolytic deposition of Ni nanoparticles is increased, the Ni nanoparticles grow in an island shape along the surface of the gold wire.
  • a potential was applied for 30 minutes to deposit carbon on the gold wire.
  • Raman spectrum measurement was performed with an excitation wavelength of 785 nm. The results are shown in FIG. The vertical axis shows the Raman intensity. The horizontal axis represents the Raman shift.
  • a Raman spectrum Ia is a Raman spectrum of highly oriented pyrolytic graphite for reference.
  • the Raman spectrum Ib is a Raman spectrum of a single-walled carbon nanotube for reference.
  • Raman spectra I c is the Raman spectrum of diamond-like carbon as a reference.
  • the Raman spectrum Id is a Raman spectrum when carbon is deposited on the gold wire without depositing Ni nanoparticles on the gold wire.
  • the Raman spectrum Ie is a Raman spectrum when carbon is deposited after the electrolytic deposition time of Ni nanoparticles is set to 5 ms.
  • the Raman spectrum If is a Raman spectrum when carbon is deposited after the electrolytic deposition time of Ni nanoparticles is 10 ms.
  • the Raman spectrum Ig is a Raman spectrum when carbon is deposited after the electrolytic deposition time of Ni nanoparticles is set to 100 ms.
  • the Raman spectrum Ie in FIG. 10 shows that single-walled carbon nanotubes having a single diameter were obtained.
  • the Raman spectrum If indicates that a mixture of single-walled carbon nanotubes having different diameters was obtained.
  • the Raman spectrum Ig shows that diamond-like carbon was obtained.
  • FIG. 11 shows AFM photographs of the surface of the gold wire after carbon is deposited on the gold wire.
  • A) of FIG. 11 is an AFM photograph in the case where carbon is deposited on a gold wire without depositing Ni nanoparticles on the gold wire.
  • B) of FIG. 11 is an AFM photograph in the case where carbon is deposited after setting the time for electrolytic deposition of Ni nanoparticles to 5 ms.
  • C) of FIG. 11 is an AFM photograph in the case where carbon is deposited after setting the time of electrolytic deposition of Ni nanoparticles to 100 ms.
  • FIG. 11A it can be seen that the precipitate has an island-like amorphous structure.
  • FIG. 11C it can be seen that the precipitate has a diamond-like carbon-like structure.
  • a Raman spectrum I 532 is a Raman spectrum when the excitation wavelength is 532 nm.
  • the Raman spectrum I 633 is a Raman spectrum when the excitation wavelength is 633 nm.
  • the Raman spectrum I 785 is a Raman spectrum when the excitation wavelength is 785 nm. Only in the Raman spectrum I 785 , a peak due to the tube structure (RBM) was confirmed. This indicates that single-walled carbon nanotubes having a single chirality were obtained.
  • the absolute value of the potential for electrolytic deposition of Ni nanoparticles is 1.2 V or less, and the time for electrolytic deposition of Ni nanoparticles is 10 ms or less (or the mode of the particle diameter of Ni nanoparticles). It was found that a structure-controlled single-walled carbon nanotube can be obtained when the thickness is 4 nm or less.
  • the electric potential of electrolytic deposition of Ni nanoparticles was changed to -0.57 V, -0.64 V, -0.8 V, -1.0 V, -1.2 V, -1.4 V, and the electric power of Ni nanoparticles was changed.
  • the carbon deposition was performed by changing the analysis output time to 1 ms, 5 ms, 10 ms, 100 ms, 1 second, 10 seconds, 20 seconds, 1 minute, and 30 minutes. As a result, better results were obtained when the potential was ⁇ 1.2 V and the time was 5 ms or 10 ms than the other cases. Therefore, the time for electrolytic deposition of Ni nanoparticles is preferably 5 to 10 ms.
  • Carbon deposition was carried out by changing the potential applied when carbon was deposited to -0.4V, -1.0V, and -2.0V. As a result, it was confirmed that single-walled carbon nanotubes were formed when the potential was ⁇ 0.4 V or ⁇ 1.0 V. When the potential was ⁇ 2.0 V, no precipitate was confirmed. Therefore, it was found that single-walled carbon nanotubes can be produced when the absolute value of the electrolytic deposition potential of the carbon nanotubes is 1 V or less.
  • a Raman spectrum I ON BARE is a Raman spectrum when carbon is deposited on a gold wire without depositing a metal catalyst on the gold wire.
  • the Raman spectrum IFE is a Raman spectrum when carbon is deposited after Fe nanoparticles are deposited on a gold wire.
  • the Raman spectrum ICO is a Raman spectrum when carbon is deposited after depositing Co nanoparticles on a gold wire.
  • the Raman spectrum I NI is a Raman spectrum when carbon is deposited after Ni nanoparticles are deposited on a gold wire.
  • the time for electrolytic deposition of carbon was 30 minutes.
  • the excitation wavelength of the Raman spectrum was 785 nm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention porte sur un procédé pour la production de nanotubes de carbone, dans lequel des nanotubes de carbone sont déposés sur une électrode de travail par électrodéposition dans un état où l'électrode de travail, sur laquelle un catalyseur métallique est collé, est immergée dans un électrolyte formé à partir d'une solution aqueuse comprenant une substance contenant des atomes de carbone et de l'eau.
PCT/JP2011/055689 2010-03-11 2011-03-10 Procédé pour la production de nanotubes de carbone WO2011111791A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012504523A JPWO2011111791A1 (ja) 2010-03-11 2011-03-10 カーボンナノチューブの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-054888 2010-03-11
JP2010054888 2010-03-11

Publications (1)

Publication Number Publication Date
WO2011111791A1 true WO2011111791A1 (fr) 2011-09-15

Family

ID=44563589

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/055689 WO2011111791A1 (fr) 2010-03-11 2011-03-10 Procédé pour la production de nanotubes de carbone

Country Status (2)

Country Link
JP (1) JPWO2011111791A1 (fr)
WO (1) WO2011111791A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015137408A (ja) * 2014-01-23 2015-07-30 国立大学法人東北大学 炭素材料の製造方法
WO2016013245A1 (fr) * 2014-07-23 2016-01-28 日本ゼオン株式会社 Matériau de catalyseur et son procédé de production
US9506156B2 (en) 2012-03-09 2016-11-29 The University Of Manchester Production of graphene
US9656872B2 (en) 2011-03-10 2017-05-23 The University Of Manchester Production of graphene
US10415143B2 (en) 2013-08-06 2019-09-17 The University Of Manchester Production of graphene and graphane
US11643735B2 (en) * 2016-11-16 2023-05-09 C2Cnt Llc Methods and systems for production of elongated carbon nanofibers

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005023408A (ja) * 2003-07-02 2005-01-27 Japan Science & Technology Agency ナノカーボン材料の製造方法、及び配線構造の製造方法
JP2008505044A (ja) * 2004-03-26 2008-02-21 フォスター−ミラー，インコーポレーテッド 電解析出によって製造されたカーボンナノチューブに基づく電子デバイス及びその応用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005023408A (ja) * 2003-07-02 2005-01-27 Japan Science & Technology Agency ナノカーボン材料の製造方法、及び配線構造の製造方法
JP2008505044A (ja) * 2004-03-26 2008-02-21 フォスター−ミラー，インコーポレーテッド 電解析出によって製造されたカーボンナノチューブに基づく電子デバイス及びその応用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KIM SUNG-KYOUNG: "Characteristics of Electrodeposited Single-Walled Carbon Nanotube Films", JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, vol. 6, 2006, pages 3614 - 3618 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9656872B2 (en) 2011-03-10 2017-05-23 The University Of Manchester Production of graphene
US9506156B2 (en) 2012-03-09 2016-11-29 The University Of Manchester Production of graphene
US10415143B2 (en) 2013-08-06 2019-09-17 The University Of Manchester Production of graphene and graphane
JP2015137408A (ja) * 2014-01-23 2015-07-30 国立大学法人東北大学 炭素材料の製造方法
WO2016013245A1 (fr) * 2014-07-23 2016-01-28 日本ゼオン株式会社 Matériau de catalyseur et son procédé de production
JPWO2016013245A1 (ja) * 2014-07-23 2017-04-27 日本ゼオン株式会社 触媒材料およびその製造方法
US11643735B2 (en) * 2016-11-16 2023-05-09 C2Cnt Llc Methods and systems for production of elongated carbon nanofibers

Also Published As

Publication number Publication date
JPWO2011111791A1 (ja) 2013-06-27

Similar Documents

Publication Publication Date Title
Douglas et al. Toward small-diameter carbon nanotubes synthesized from captured carbon dioxide: critical role of catalyst coarsening
Szabó et al. Synthesis methods of carbon nanotubes and related materials
Gooding Nanostructuring electrodes with carbon nanotubes: A review on electrochemistry and applications for sensing
WO2011111791A1 (fr) Procédé pour la production de nanotubes de carbone
US6939525B2 (en) Method of forming composite arrays of single-wall carbon nanotubes and compositions thereof
Chu et al. Carbon nanotubes combined with inorganic nanomaterials: Preparations and applications
US7592050B2 (en) Method for forming carbon nanotube thin film
Wei et al. A new method to synthesize complicated multibranched carbon nanotubes with controlled architecture and composition
Liu et al. Preparation and characteristics of carbon nanotubes filled with cobalt
Zheng et al. One-step preparation of single-crystalline β-MnO2 nanotubes
Lee et al. Temperature-dependent growth of vertically aligned carbon nanotubes in the range 800− 1100° C
Ding et al. Graphitic encapsulation of catalyst particles in carbon nanotube production
Xiang et al. Diameter modulation of vertically aligned single-walled carbon nanotubes
Liu et al. Growth of carbon nanocoils from K and Ag cooperative bicatalyst assisted thermal decomposition of acetylene
JP5358045B2 (ja) カーボンナノチューブの製造方法
Haniyeh et al. Controlled growth of well-Aligned carbon nanotubes, electrochemical modification and electrodeposition of multiple shapes of gold nanostructures
Zhao et al. Atomic-scale evidence of catalyst evolution for the structure-controlled growth of single-walled carbon nanotubes
JP4730618B2 (ja) 微粒子の製造方法
Li et al. Self-catalytic synthesis, structures, and properties of high-quality tetrapod-shaped ZnO nanostructures
Shawky et al. Room-temperature synthesis of single-wall carbon nanotubes by an electrochemical process
JP2007290892A (ja) ＺｎＯ系ナノチューブの製造方法及びそれによって得られたＺｎＯ系ナノチューブ
JPWO2019124026A1 (ja) 繊維状炭素ナノ構造体、繊維状炭素ナノ構造体の評価方法および表面改質繊維状炭素ナノ構造体の製造方法
Merchan-Merchan et al. Flame synthesis of zinc oxide nanocrystals
JP2006292739A (ja) 磁気ナノワイヤを物体に付着させる方法およびシステムならびにそれらから形成される装置
Zhang et al. High-Quality Single-Walled Carbon Nanotubes Synthesized by Catalytic Decomposition of Xylene over Fe− Mo/MgO Catalyst and Their Field Emission Properties

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11753449

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012504523

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11753449

Country of ref document: EP

Kind code of ref document: A1