WO2003099717A1 - Nanocornes de carbone haute densite et leur procede de production - Google Patents

Nanocornes de carbone haute densite et leur procede de production Download PDF

Info

Publication number
WO2003099717A1
WO2003099717A1 PCT/JP2003/001927 JP0301927W WO03099717A1 WO 2003099717 A1 WO2003099717 A1 WO 2003099717A1 JP 0301927 W JP0301927 W JP 0301927W WO 03099717 A1 WO03099717 A1 WO 03099717A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon nanohorn
density
aggregate
aggregates
nanohorn
Prior art date
Application number
PCT/JP2003/001927
Other languages
English (en)
Japanese (ja)
Inventor
Sumio Iijima
Masako Yudasaka
Katsuyuki Murata
Katsumi Kaneko
Elena Hristova
Original Assignee
Japan Science And Technology Agency
Nec Corporation
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 Japan Science And Technology Agency, Nec Corporation filed Critical Japan Science And Technology Agency
Priority to JP2004507381A priority Critical patent/JP3854294B2/ja
Publication of WO2003099717A1 publication Critical patent/WO2003099717A1/fr

Links

Classifications

    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • 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
    • C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls

Definitions

  • the invention of this application relates to a high-density carbon nanohorn and a method for producing the same. More specifically, the invention of this application relates to a high-density carbon nanohorn in which not only the carbon nanohorn aggregates are densified but also the adsorption characteristics are further improved, and a method for producing the same. Background art
  • the carbon nanohorn aggregate found by the inventors of the present application is a single-walled carbon nanotube having a shape in which one end of a single-walled carbon nanotube has a conical shape, and a carbon nanohorn is formed into a spherical shape having a diameter of about 80 to 10 O nm.
  • Dahlia-like carbon nanohorn agglomerates with their horn-shaped tips outside, and bud-like carbon nanohorn aggregates with smooth surfaces without horn-like protrusions Gathering is known.
  • the inventors of the present application have stated that these carbon nanohorn aggregates are lightweight and chemically stable because dalaite is a constituent unit, and have an adsorption function without any activation treatment.
  • It can be used as a new functional material such as a material (Japanese Patent Application No. 2000-35083), and by opening the wall and tip of the carbon nanohorn, it can be used not only on the surface of the carbon nanohorn but also inside it. It is possible to realize a new carbon nanohorn adsorbent with higher performance and higher functionality because it can adsorb the substance to be adsorbed and exhibits selective adsorption characteristics and a high-efficiency molecular sieving function. 2 0 0 2—2 0 7 7 3).
  • the adsorption capacity of the carbon nanohorn adsorbent is excellent as described above, it cannot be said that the carbon nanohorn adsorbent is sufficiently satisfactory, for example, in consideration of application to a hydrogen gas storage material, a methane gas storage material, or a fuel cell. Therefore, the invention of this application has been made in view of the circumstances described above, and solves the problems of the prior art. Not only is the carbon nanohorn aggregate increased in density, but the adsorption characteristics are further improved. It is an object of the present invention to provide a high-density carbon nanohorn and a method for manufacturing the same. Disclosure of the invention
  • the invention of this application provides a high-density single-bon nanohorn characterized by being a solid obtained by aggregating a plurality of carbon nanohorn aggregates at a high density.
  • the invention of the present application is directed to the high-density carbon characterized in that the carbon nanohorn aggregate is a Darier-like carbon nanohorn aggregate, a bud-like carbon nanohorn aggregate, or a mixture thereof.
  • the third is the high-density carbon nanohorn, which is characterized in that the carbon nanohorn aggregate has an opening in the wall of the carbon nanohorn tube.
  • the fourth is the bulk density of the carbon nanohorn aggregate, which is higher than the carbon nanohorn aggregate itself.
  • the high-density force-bonded carbon nanohorn is characterized by its increased specific surface area and pore volume.Fifth, it absorbs more gas per volume and weight than the carbon nanohorn aggregate itself.
  • a high-density carbon nanohorn is provided.
  • the invention of this application relates to a method for producing a high-density carbon nanohorn, comprising dispersing a plurality of carbon nanohorn aggregates in an organic solvent and evaporating the organic solvent.
  • a method for producing high-density carbon nanohorns which comprises dispersing a plurality of carbon nanohorn aggregates in an organic solvent and then irradiating ultrasonic waves, is eighth.
  • a method for producing high-density carbon nanohorns, which is characterized by pressurizing carbon nanohorns is to disperse a plurality of carbon nanohorn aggregates in an organic solvent.
  • a method for producing high-density carbon nanohorns, which comprises evaporating the medium and pressurizing the precipitated carbon nanohorn aggregates is described in the tenth aspect. Provided is a method for producing a high-density carbon nanohorn.
  • the invention of this application is directed to the method of the invention described above, wherein, firstly, the carbon nanohorn aggregates are chemically modified in advance to increase the affinity between the carbon nanohorn aggregates.
  • FIG. 1 is a diagram illustrating the results obtained by examining the nitrogen gas adsorption characteristics of the high-density carbon nanohorns (A) and (B) of the invention of the present application and the Darrier-type SWNH aggregate (C).
  • FIG. 2 is a diagram exemplifying the results of examining the methane gas adsorption characteristics of the high-density carbon nanohorn of the invention of the present application and Darrie-type SWNH aggregates.
  • FIG. 3 is a diagram illustrating a result of examining nitrogen gas adsorption characteristics of the OH-modified high-density carbon nanohorn of the invention of this application.
  • Figure 4 shows examples of (a) nitrogen adsorption isotherm at 77 K, (b) pore size distribution, and (c) FHH plot for as-grown SWNH, eth-SWNH and compressed SWNH.
  • FIG. 4 shows examples of (a) nitrogen adsorption isotherm at 77 K, (b) pore size distribution, and (c) FHH plot for as-grown SWNH, eth-SWNH and compressed SWNH.
  • FIG. 5 is a diagram exemplifying (a) a nitrogen adsorption isotherm at 77 K and (b) a pore size distribution for o ⁇ 3 ⁇ 1 ⁇ 11 compression 0 X —SWNH.
  • the high-density carbon nanohorn provided by the invention of this application is characterized in that the carbon nanohorn aggregate is a solid that is aggregated at high density.
  • the carbon nanohorn aggregate includes a Darya-like carbon nanohorn aggregate in which a plurality of carbon nanohorns are gathered with the angular tip outside, and a smooth surface without horn-like protrusions on the surface. And a mixture thereof and the like.
  • these carbon nanohorn aggregates may have openings formed in the tube wall of the carbon nanohorn.
  • “high density” means that the bulk density is 0.5 mg Zm 1 or more, and practically, it is in the range of about 0.5 to 2.5 mg / ml. This is, for example, 10 times or more higher than the bulk density of the as-produced dahlia-like carbon nanohorn aggregates being about 0.01 to 0.05 mgZml.
  • the high-density carbon nanohorn of the invention of this application has a higher bulk density than the ordinary carbon nanohorn aggregate itself.
  • the specific surface area and pore (micropore) capacity have also been increased.
  • specific examples for example, typical values of the specific surface area and pore volume per unit volume of the dahlia shaped Kabon'nanoho over down agglomerates as produced, respectively 3 0 8 m 2 // g, whereas a 0. LLML / g, dense carbon nanohorn of the invention of this application, respectively 3 5 0 ⁇ 6 0 0 m 2 Z g, increased to 0. 1 3 ⁇ 0. 40m l / g It will be realized as a result.
  • the invention of this application consisting of a Darya-like carbon nanohorn aggregate having pores For high-density carbon nanohorns, these values will be significantly increased to 100 to 1200 m2Zg and 0.4 to 0.7 ml / g, respectively.
  • the high-density carbon nanohorn of the invention of this application also has a higher gas adsorption amount per volume and weight than the carbon nanohorn aggregate itself in terms of adsorption characteristics.
  • the methane gas adsorption amount per weight (per volume) of the as-produced dahlia-like carbon nanohorn aggregates is 15 to 2 at 303 K and 3.5 MPa. 0 mg / g (approximately 10 mg / ml), whereas the high-density carbon nanohorn of the invention of the present application adsorbed methane gas at 35 to 40 mg / g (about 25 mg / m1). ), which is about twice as high. It has been confirmed that the adsorption characteristics of this high-density carbon nanohorn are improved for most gases other than hydrogen and helium in addition to the methane gas exemplified here.
  • the high-density carbon nanohorn of the invention of this application as described above can be manufactured by, for example, the following method for manufacturing a high-density carbon nanohorn provided by the invention of this application. That is, the method for producing the high-density carbon nanohorn of the present invention is as follows.
  • the carbon nanohorn aggregates as a starting material include Bon nanohorn agglomerates, bud-like carbon nanohorn agglomerates, those having openings in them, and mixtures thereof can be used.
  • a carbon nanohorn aggregate having an opening in the carbon nanohorn tube wall In order to increase the specific surface area, the pore volume, the adsorption capacity, and the like, it is preferable to use a carbon nanohorn aggregate having an opening in the carbon nanohorn tube wall.
  • the carbon nanohorn aggregate as a starting material is dispersed in an organic solvent.
  • the organic solvent is not limited to the organic solvent, and various solvents can be used as long as the carbon nanohorn aggregate can be dispersed.
  • the type of the organic solvent is not particularly limited. Examples thereof include hydrocarbons such as benzene, toluene, and xylene, alcohols such as ethanol, methanol, ethylene glycol, and glycerin, ethers such as dimethyl ether, and esters.
  • Various organic solvents such as derivatives thereof can be used. For the sake of simplicity, it is preferable to use a volatile organic solvent having a high vapor pressure even at normal temperature and a low boiling point at normal pressure.
  • desired solvents such as ethyl ether, ethanol, ethyl acetate, benzene and hexane are used.
  • Use of an organic solvent having volatility near the temperature of the production atmosphere is exemplified as a simple method.
  • the organic solvent can be selected in consideration of this point. Specifically, for example, when ethanol is used as the organic solvent, the specific surface area and the pore (micropore) volume of the obtained high-density carbon nanohorn are 509 m 2 Z, respectively. g, 0.20 m 1 / g, but when glycerin is used, it is exemplified that it becomes 385 m 2 Zg, 0.16 ml / g.
  • the amount of the organic solvent in which the carbon nanohorn aggregates are dispersed there is no particular limitation on the amount of the organic solvent in which the carbon nanohorn aggregates are dispersed, and the amount may be such that the carbon nanohorn aggregates can be dispersed in the organic solvent without being aggregated. Wear. However, if the amount of the organic solvent with respect to the carbon nanohorn aggregates is too large, the efficiency of the next evaporation will decrease, so the standard is, for example, 100 mg of carbon nanohorn aggregates. Thus, an example in which the organic solvent is set to 10 m 1 or more, for example, about several 10 m 1 is shown. In dispersing the carbon nanohorn aggregate, operations such as stirring can be performed as necessary.
  • the carbon nanohorn aggregates may be dispersed in an organic solvent and then irradiated with ultrasonic waves.
  • This ultrasonic irradiation can disperse the carbon nanohorn aggregates in the organic solvent and have the effect of bringing the arrangement (the degree of clogging) closer to the closest packing.
  • the carbon nanohorn aggregates dispersed in the organic solvent gradually begin to precipitate by evaporating the organic solvent. It is preferable that the organic solvent be evaporated slowly and completely. For example, when ethanol is used as the organic solvent, a preferable example is that the organic solvent is naturally evaporated to dryness at room temperature. Of course, depending on the type of the solvent, for the sake of simplicity, the evaporation of the organic solvent can be performed, for example, by heat treatment, vacuum treatment, or a combination thereof. During this precipitation, the carbon nanohorn aggregates naturally form a close-packed structure, A high-density carbon nanohorn according to the present invention, in which the bon nanohorn aggregates approach each other in an efficient arrangement, will be obtained.
  • the carbon nanohorn aggregates are pressed to mechanically bring the carbon nanohorn aggregates closer together to obtain the high-density carbon nanohorn of the invention of the present application.
  • the method of pressurization in this case is not particularly limited, but the pressure applied to the carbon nanohorn aggregate is 5 MPa or more, more preferably about 10 to 50 MPa, more specifically about 5 OMPa.
  • the strength of the obtained high-density force-bonded nanohorn can be made to a certain degree.
  • a high-density carbon nanohorn can be obtained as a solid, but it becomes brittle.
  • the carbon nanohorn aggregate without pores is used as a starting material, the high density in the invention of this application can be easily achieved.
  • the carbon nanohorn aggregates can be formed into a desired shape under pressure.
  • the high-density carbon nanohorn obtained by the second method does not have a close-packed structure, it has a slightly sparser structure than that obtained by the first method, The connections themselves are considered to be the same.
  • TEM transmission electron microscopy
  • the second method is performed following the first method, and the carbon nanohorn aggregates are arranged closer to each other after being arranged efficiently.
  • a high-density carbon nanohorn with a higher bulk density is obtained.
  • the arrangement of the individual carbon nanohorn aggregates changes depending on the organic solvent, the presence or absence of pressurization, and the type or condition.
  • the structure of the pores will also change. So, for example, this When the high-density force nanohorn of the invention of the application is used as an adsorbent, its adsorbing ability can be adjusted, and an adsorbent having a desired pore structure can be easily realized. become.
  • the carbon nanohorn aggregates as the starting material are chemically modified in advance to increase the affinity of the carbon nanohorn aggregates.
  • a good orientation of the carbon nanohorn aggregate in the high-density carbon nanohorn can be obtained.
  • the carbon nanohorn aggregates can be brought closer to each other, and a high-density carbon nanohorn having a higher bulk density can be obtained.
  • adsorbents for gas storage require high specific surface area and well-developed micropores, as well as high bulk density. Therefore, it can be said that the high-density nanohorn of the invention of this application is extremely useful as an adsorbent for gas storage.
  • the pellets were slowly evaporated, and then pressurized at 50 kgf / cm 2 to obtain pelleted high-density carbon nanohorns.
  • the bulk density of this high-density carbon nanohorn was investigated and is shown in Table 1. This The bulk density of the high-density carbon nanohorn was 0.6 to 0.8 g / cm 3 , and it was confirmed that the bulk density was higher than that of the Darier-type carbon nanohorn aggregate used and general activated carbon.
  • a high-density carbon nanohorn (A) produced in Example 1 a high-density carbon nanohorn (B) produced by dispersing Darrie-type SWNH aggregates in ethanol and slowly evaporating the ethanol, and The Darrier-type carbon nanohorn aggregate (C) was examined for nitrogen gas adsorption characteristics. The results are shown in FIG. 1 and Table 2.
  • the high-density nanohorn (A) (B) It was confirmed that the adsorption characteristics were improved. In addition, it was confirmed that the adsorption characteristics of the high-density nanohorn (A), which was further pressurized, were significantly improved, compared to the high-density nanohorn (B), which was densified by ethanol evaporation. . The adsorption surface area and pore volume of (A) and (B) were also clearly increased compared to (C).
  • the Darrier-type carbon nanohorn aggregate was dispersed in ethanol, the ethanol was slowly evaporated, and then pressurized at 50 kgf Z cm 2 to obtain a pellet-like high-density carbon nanohorn.
  • the methane gas adsorption characteristics of the high-density carbon nanohorn and the Darrier-type carbon nanohorn aggregate were examined, and the results are shown in FIG. Table 3 shows the amount of methane gas adsorbed at 3.5 MPa.
  • the high-density nanohorn of the invention of this application is superior to the as-produced Darier-type carbon nanohorn aggregate.
  • the adsorption of methane gas on the high-density nanohorn was more than twice that of the as-produced dary-type carbon nanohorn aggregate.
  • the Darrier-type carbon nanohorn aggregate heat-treated at 420 ⁇ was mixed with an aqueous hydrogen peroxide solution, immersed for 24 hours, filtered, and the filtrate was dried at 6 ox :.
  • this Dary-type nano-bonnet aggregate is heat-treated at 900 in argon, and the force whose surface is modified with OH group One bon nanohorn aggregate was obtained.
  • the OH group-modified force one Bon'nanohon aggregate was dispersed in ethanol, after boiled create evaporated ethanol, by pressurizing at 50 kgf Z cm 2, to obtain a pelletized high density OH modified carbon nanohorn.
  • the bulk density of this high-density OH-modified carbon nanohorn was 0.6 to 0.8 gZ cm 3 .
  • the specific surface area, micropore volume, and nitrogen gas adsorption characteristics were examined. The results are shown in Table 4 and FIG. The results are also shown for the high-density OH-modified carbon nanohorn and OH-modified carbon nanohorn fabricated without pressurization.
  • This high-density OH-modified carbon nanohorn was confirmed to have improved dispersibility due to the addition of the OH group, and also increased both the amount of dissolved pores and the specific surface area.
  • FIG. 4 a shows nitrogen adsorption isotherms at 77 K for as-grown SWNH, eth-SWNH, and compressed SWNH. Prior to the adsorption test, each sample was preheated at 423 K for 2 hours in a vacuum of 10-4 Pa or less. In the markers in the figure, triangles indicate as-grown SWNH, diamonds indicate eth-S WNH, and circles indicate compressed SW N H, respectively.
  • the adsorption isotherm of as-grown SWNH was in the middle between Type I and IV.
  • the hysteresis-free behavior seen in this isotherm is related to the presence of wedge-shaped mesopores formed at the junction of two adjacent spherical SWNH aggregate particles.
  • the isotherm of the compressed SWNH has a narrow hysteresis loop of type HI according to the IUPAC classification, indicating that spherical SWNH aggregate particles of almost uniform size are aggregated or densely packed. In other words, it indicates that when the SWNH aggregate particles were dispersed in ethanol and dried, they rearranged due to the surface tension of ethanol and formed a close-packed structure with meso-sized particle gaps. And capillary condensation in this particle gap, This gives a hysteresis loop in the isotherm.
  • the isotherm of the compressed SW NH is compared with as-grown S WNH and eth-S WNH, it is PZP.
  • the Ds rating includes:
  • the FHH equation represented by The FHH plot is shown in Fig. 4c.
  • the linearity collapses in the region where the POZP is extremely low and deviates downward due to the filling of the micropores.
  • the FHH plot of the compressed SWNH is deviated downward even at relatively high pressure, and it is considered that the SWNH particles are well packed so as not to leave macropores (5 O nm or more).
  • Opening can be made in the closed nanohorn by heat treatment in oxygen.
  • heat treatment at 693 K holes are formed in almost all the tube walls of dahlia-shaped SWNH.
  • the oxidized SWNH aggregate was designated as oX-SWNH, and the oX-SWNH was dispersed in ethanol by ultrasonic treatment and compressed under the same conditions as ⁇ A>.
  • Nitrogen adsorption tests were performed on ox-SWNH and compressed oX-SWWH at 77 K, and the results are shown in Figure 5a. In the figure, diamonds indicate o X — SWN H, and circles indicate oX — S WWH.
  • the adsorption isotherm of the compressed o X — SWNH shows a greater increase in the amount of adsorption as seen between the as-grown SWN and the compressed SWNH in ⁇ A> above than the ox—SWNH without compression. Not observed. However, the hysteresis seen in the isotherm of the compressed 0X-SWNH is similar to that of the compressed SWNH in ⁇ A> above, indicating that the adsorbed molecules are blocked at the pore entrance. The difference between the isotherms of o X — S WNH and compression o X — S WWH was clearly observed at relatively high pressures.
  • SWNH samples oxidized at 693 K after compression showed the same nitrogen adsorption isotherm as compressed oX-SWNH. Therefore, when the compressed SWNH was subjected to oxygen treatment, there was no restriction on the permeation of oxygen into the SWNH, and it was confirmed that the compressed body was oxidized homogeneously.
  • the mesopore volume (Vme) of as-grown S WNH and eth-SWNH indicates that Vme greatly increases after ethanol treatment. confirmed.
  • the increased porosity of the mesopores is, as described above, a gap formed by the SWNH aggregates being in a close-packed state after the ethanol treatment.
  • the reason why Vme is larger in ox-SWNH than in as-grownS WNH is explained by the fact that mesopores of 2 nm or more were formed in the carbon nanohorn by oxidation treatment.
  • Vme is also reduced by compression for both eth-S WNH and oX_S WNH, but the application of such high pressure reduces the original gap of SWNH aggregate particles, When the corners protruding from are pushed into the bulk, they rearrange into a structure with a smooth surface, as shown by fractal analysis.
  • micropore volume of the compressed SWNH increases almost twice as large as as-grown SWN. This is thought to be due to the fact that the carbon nanohorns were partially opened by compression and the micropores increased.
  • Particle density S WNH aggregates obtained by helium method is to prove this hypothesis, the particle density of the compressed SWNH is than the density 1. 2 5 g cm 3 of as-grown S WNH Rukani It was large 1.69 g Z cm 3 . From this, it was confirmed that holes were formed in the defect site of the carbon nanohorn by mechanical compression. Also, the volume of the micropores were determined using Dubinin-Radushkevicli (DR) equation from put that C0 2 adsorption amount to 27 3 K.
  • DR Dubinin-Radushkevicli
  • the resulting narrow micropore volume was 0.10 cm 3 Zg, consistent with the micropore volume increase after compression. Furthermore, the pores formed after compression were shown to be mainly ultra-micro pores with a pore size of less than 0.7 nm. On the other hand, eth-S WNH also showed a slight increase in micropore volume. This is thought to be because ultrasonic irradiation during the ethanol treatment promoted the formation of holes in the carbon nanohorn and opened some of the defects.
  • o X The microvolume of SWNH remains almost unchanged after compression because almost all carbon nanohorns are open after oxidation. Therefore, nano gap between particles No increase in the new surface area and micropore volume due to the above. Note that such compression is not high enough to reduce the voids between SWNH aggregates to micropore size.
  • the bulk density and specific surface area of the Dahlia-like SWNH aggregate particles are significantly increased and the pore structure is changed by compressing subsequent to the pretreatment by ultrasonic treatment in ethanol. all right.
  • the bulk density and the specific surface area were further increased by providing openings in the Darrie-like SWNH aggregate.
  • the present invention provides a high-density carbon nanohorn in which not only the carbon nanohorn aggregates are densified but also the adsorption characteristics are further improved, and a method for producing the same.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne des nanocornes de carbone haute densité obtenues par dispersion d'agrégats de nanocornes dans un solvant organique, évaporation du solvant organique, et pression des agrégats de nanocornes de carbone résiduels de façon à unir ensemble les agrégats de nanocornes de carbone à haute densité. Ces nanocornes de carbone haute densité sont non seulement composées d'aggrégats de nanocornes de carbone hautement densifiés, mais possèdent également des caractéristiques d'adsorption renforcées.
PCT/JP2003/001927 2002-05-27 2003-02-21 Nanocornes de carbone haute densite et leur procede de production WO2003099717A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2004507381A JP3854294B2 (ja) 2002-05-27 2003-02-21 高密度カーボンナノホーンとその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-153101 2002-05-27
JP2002153101 2002-05-27

Publications (1)

Publication Number Publication Date
WO2003099717A1 true WO2003099717A1 (fr) 2003-12-04

Family

ID=29561291

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/001927 WO2003099717A1 (fr) 2002-05-27 2003-02-21 Nanocornes de carbone haute densite et leur procede de production

Country Status (2)

Country Link
JP (1) JP3854294B2 (fr)
WO (1) WO2003099717A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007063058A (ja) * 2005-08-30 2007-03-15 Aisin Seiki Co Ltd 黒鉛粒子の表面改質方法
WO2007077823A1 (fr) * 2006-01-06 2007-07-12 Daikin Industries, Ltd. Materiau de stockage de fluor
JP2007326732A (ja) * 2006-06-07 2007-12-20 Sumitomo Metal Mining Co Ltd 炭素ナノ構造体及びその製造方法
JP2008173608A (ja) * 2007-01-22 2008-07-31 Mitsubishi Chemicals Corp 気相成長炭素繊維製造用触媒及び気相成長炭素繊維
WO2008102813A1 (fr) * 2007-02-20 2008-08-28 National Institute Of Advanced Industrial Science And Technology Matériau de type poutre comprenant un nanotube de carbone, et son procédé de fabrication
JP2011047081A (ja) * 2009-08-27 2011-03-10 Ube Industries Ltd 嵩密度の高い微細な炭素繊維およびその製造方法
JP2012030979A (ja) * 2010-07-28 2012-02-16 Nagoya Univ カーボンナノホーン集合体、およびその製造方法
WO2013058383A1 (fr) 2011-10-19 2013-04-25 株式会社環境・エネルギーナノ技術研究所 Matériau poreux comprenant des nanocornets de carbone et son utilisation
WO2013058382A1 (fr) 2011-10-19 2013-04-25 株式会社環境・エネルギーナノ技術研究所 Matériau dense comprenant des nanocornets de carbone et son utilisation
JP2013079153A (ja) * 2011-09-30 2013-05-02 Daikin Industries Ltd カーボンナノホーンの製造方法、フッ素化カーボンナノホーン、及び、その製造方法
EP3263210A1 (fr) 2014-06-30 2018-01-03 Shinshu University Procédé de perforation d'un nanomatériau de carbone et procédé de production d'un article moulé de filtre
US9968890B2 (en) 2014-08-11 2018-05-15 Shinshu University Method for producing filter molded article
US10464025B2 (en) 2014-12-04 2019-11-05 Shinshu University Method for producing molded filter body

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997032571A1 (fr) * 1996-03-06 1997-09-12 Hyperion Catalysis International, Inc. Nanotubes fonctionnalises
JP2001064004A (ja) * 1998-07-25 2001-03-13 Japan Science & Technology Corp 単層カーボンナノホーン構造体とその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997032571A1 (fr) * 1996-03-06 1997-09-12 Hyperion Catalysis International, Inc. Nanotubes fonctionnalises
JP2001064004A (ja) * 1998-07-25 2001-03-13 Japan Science & Technology Corp 単層カーボンナノホーン構造体とその製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BO LI et al:, "Aqueous Coluble Single-Wall Carbon Nanotube", Chemistry Letters, 05 July, 2001 (05.07.01), pages 598 to 599 *
E. BEKYAROVA et al:, "Oxidation and Porosity Evaluation of Budlike Single-Wall Carbon Nanohorn Aggregates", LANGMUIR, 14 May, 2002 (14.05.02), Vol. 18, pages 4138 to 4141 *
E. BEKYAROVA et al:, "Porosity Development of Single-Wall Carbon Nanohorn ÐAssemblies by High Pressure Compression", Bulletin of American Physical Society, 18 March, 2002 (18.03.02), Vol. 47, No. 1, page 938 *
S. IIJIMA et al:, "Nano-aggregates of single-walled graphitic carbon nano-horns", Chemical Physics Letters, 13 August, 1999 (13.08.99), Vol. 303, pages 165 to 170 *

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007063058A (ja) * 2005-08-30 2007-03-15 Aisin Seiki Co Ltd 黒鉛粒子の表面改質方法
WO2007077823A1 (fr) * 2006-01-06 2007-07-12 Daikin Industries, Ltd. Materiau de stockage de fluor
US8119094B2 (en) 2006-01-06 2012-02-21 Daikin Industries, Ltd. Fluorine storage material
JP5299943B2 (ja) * 2006-01-06 2013-09-25 ダイキン工業株式会社 フッ素貯蔵材料
JP2007326732A (ja) * 2006-06-07 2007-12-20 Sumitomo Metal Mining Co Ltd 炭素ナノ構造体及びその製造方法
JP2008173608A (ja) * 2007-01-22 2008-07-31 Mitsubishi Chemicals Corp 気相成長炭素繊維製造用触媒及び気相成長炭素繊維
WO2008102813A1 (fr) * 2007-02-20 2008-08-28 National Institute Of Advanced Industrial Science And Technology Matériau de type poutre comprenant un nanotube de carbone, et son procédé de fabrication
JPWO2008102813A1 (ja) * 2007-02-20 2010-05-27 独立行政法人産業技術総合研究所 カーボンナノチューブからなる梁状体及びその製造方法
JP2011047081A (ja) * 2009-08-27 2011-03-10 Ube Industries Ltd 嵩密度の高い微細な炭素繊維およびその製造方法
JP2012030979A (ja) * 2010-07-28 2012-02-16 Nagoya Univ カーボンナノホーン集合体、およびその製造方法
JP2013079153A (ja) * 2011-09-30 2013-05-02 Daikin Industries Ltd カーボンナノホーンの製造方法、フッ素化カーボンナノホーン、及び、その製造方法
WO2013058382A1 (fr) 2011-10-19 2013-04-25 株式会社環境・エネルギーナノ技術研究所 Matériau dense comprenant des nanocornets de carbone et son utilisation
WO2013058383A1 (fr) 2011-10-19 2013-04-25 株式会社環境・エネルギーナノ技術研究所 Matériau poreux comprenant des nanocornets de carbone et son utilisation
EP2769967A1 (fr) * 2011-10-19 2014-08-27 Environment Energy Nano Technical Research Institute Matériau dense comprenant des nanocornets de carbone et son utilisation
JPWO2013058383A1 (ja) * 2011-10-19 2015-04-02 株式会社環境・エネルギーナノ技術研究所 カーボンナノホーンを含む多孔質材料及びその利用
EP3263210A1 (fr) 2014-06-30 2018-01-03 Shinshu University Procédé de perforation d'un nanomatériau de carbone et procédé de production d'un article moulé de filtre
US9968890B2 (en) 2014-08-11 2018-05-15 Shinshu University Method for producing filter molded article
CN111249921A (zh) * 2014-08-11 2020-06-09 国立大学法人信州大学 过滤器成形体的制造方法
CN111249921B (zh) * 2014-08-11 2022-01-18 国立大学法人信州大学 过滤器成形体的制造方法
US10464025B2 (en) 2014-12-04 2019-11-05 Shinshu University Method for producing molded filter body

Also Published As

Publication number Publication date
JP3854294B2 (ja) 2006-12-06
JPWO2003099717A1 (ja) 2005-09-22

Similar Documents

Publication Publication Date Title
JP3989256B2 (ja) カーボンナノホーン吸着材とその製造方法
Adeniran et al. Low temperature synthesized carbon nanotube superstructures with superior CO 2 and hydrogen storage capacity
EP1226294B1 (fr) Techniques d'oxydation de nanotubes de carbone a parois multiples
JP4819061B2 (ja) 多孔性繊維状ナノ炭素及びその製造方法
WO2003099717A1 (fr) Nanocornes de carbone haute densite et leur procede de production
Conte et al. Assessment of activated carbon fibers from commercial Kevlar® as nanostructured material for gas storage: Effect of activation procedure and adsorption of CO2 and CH4
Zhou et al. A 3D hierarchical hybrid nanostructure of carbon nanotubes and activated carbon for high-performance supercapacitors
Iqbal et al. In situ synthesis of carbon nanotube doped metal–organic frameworks for CO 2 capture
JP2015218085A (ja) 活性化グラフェンモノリスおよびその製造方法
TWM627054U (zh) 菸草製品之過濾器
Doğan et al. Storage of hydrogen in activated carbons and carbon nanotubes
JP6922893B2 (ja) 吸着材
US20070027029A1 (en) Catalyst support, gas storage body and method for producing these
Bai et al. The hydrogen storage capacity of metal-containing polyacrylonitrile-based electrospun carbon nanofibers
KR101780394B1 (ko) 에너지 저장 물질로 유용한 다공성 나노구조체 및 이의 제조 방법
Luxembourg et al. Hydrogen storage capacity at high pressure of raw and purified single wall carbon nanotubes produced with a solar reactor
Sun et al. Lignin-derived graphene-like carbon nanosheets as an efficient catalyst support for Fischer-Tropsch synthesis
KR20140045766A (ko) 구조체 내의 기공 또는 간극 표면에 탄소나노와이어를 고밀도로 합성하는 방법 및 이에 의하여 합성된 계층 구조체
Puthusseri et al. Gas adsorption capacity in an all carbon nanomaterial composed of carbon nanohorns and vertically aligned carbon nanotubes
Yang et al. Amorphous hollow carbon spheres synthesized using radio frequency plasma-enhanced chemical vapour deposition
Rajesh et al. Preparation of Pt-Ru bimetallic catalyst supported on carbon nanotubes
Faraji et al. Modifying the morphology and properties of aligned CNT foams through secondary CNT growth
Jagtoyen et al. Porosity of carbon nanotubes
Mohan et al. Ordered nanostructured carbons, NCCR-41 and CMK-3: Synthesis, characterization, and hydrogen sorption studies
Chang et al. A metal dusting process for preparing nano-sized carbon materials and the effects of acid post-treatment on their hydrogen storage performance

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP US

WWE Wipo information: entry into national phase

Ref document number: 2004507381

Country of ref document: JP