JP3438041B2 - Catalyst solution for carbon nanotube synthesis - Google Patents
Catalyst solution for carbon nanotube synthesisInfo
- Publication number
- JP3438041B2 JP3438041B2 JP24510399A JP24510399A JP3438041B2 JP 3438041 B2 JP3438041 B2 JP 3438041B2 JP 24510399 A JP24510399 A JP 24510399A JP 24510399 A JP24510399 A JP 24510399A JP 3438041 B2 JP3438041 B2 JP 3438041B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- substrate
- carbon nanotubes
- particles
- base material
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 88
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 44
- 239000002041 carbon nanotube Substances 0.000 title claims description 29
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims description 29
- 230000015572 biosynthetic process Effects 0.000 title claims description 6
- 238000003786 synthesis reaction Methods 0.000 title claims description 6
- 239000000463 material Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 239000004530 micro-emulsion Substances 0.000 claims description 8
- 239000010419 fine particle Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000011882 ultra-fine particle Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 150000002736 metal compounds Chemical class 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000003093 cationic surfactant Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- UMGXUWVIJIQANV-UHFFFAOYSA-M didecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC UMGXUWVIJIQANV-UHFFFAOYSA-M 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 organic acid salts Chemical class 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000004075 acetic anhydrides Chemical class 0.000 description 1
- NEBFBVFMEJNMTO-UHFFFAOYSA-N acetylene;benzene Chemical compound C#C.C1=CC=CC=C1 NEBFBVFMEJNMTO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002238 carbon nanotube film Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、含炭素材料を熱分
解させてカーボンナノチューブを合成する際に用いられ
る触媒液、該触媒液を用いて形成された触媒基材及び該
触媒基材の存在下で含炭素材料を熱分解させるカーボン
ナノチューブの合成方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst solution used in thermally synthesizing a carbon-containing material to synthesize carbon nanotubes, a catalyst substrate formed using the catalyst solution, and the presence of the catalyst substrate. The present invention relates to a method for synthesizing carbon nanotubes in which a carbon-containing material is pyrolyzed below.
【０００２】[0002]
【従来の技術】カーボンナノチューブを合成するため
に、カーボンナノチューブ合成用触媒微粒子を表面に有
する基材の存在下で含炭素材料を熱分解し、その基材上
にカーボンナノチューブを成長させる方法〔化学蒸着法
（ＣＶＤ法）〕は知られている。この場合の基材の作製
方法としては、（ｉ）基材に微細な細孔を作り、そこに
触媒粒子を埋め込む方法及び（ii）金属板のエッチング
により微小な触媒粒子を基材上に形成する方法等が知ら
れている。このような触媒基材を用いるときには、その
基材上に垂直で密に詰まったカーボンナノチューブ膜が
得られるが、その基材の作製に大きな困難を要するとい
う問題がある。2. Description of the Related Art In order to synthesize carbon nanotubes, a method of thermally decomposing a carbon-containing material in the presence of a base material having catalyst fine particles for synthesizing carbon nanotubes on the surface and growing the carbon nanotubes on the base material [Chemical Vapor deposition method (CVD method)] is known. In this case, the base material can be prepared by (i) forming fine pores in the base material and burying catalyst particles therein, and (ii) forming fine catalyst particles on the base material by etching a metal plate. There are known methods for doing so. When such a catalyst substrate is used, a vertically densely packed carbon nanotube film can be obtained on the substrate, but there is a problem that preparation of the substrate requires great difficulty.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、含炭素材料
を熱分解させてカーボンナノチューブを合成する際に用
いられる触媒液、該触媒液を用いて形成された触媒基
材、該触媒液を用いる触媒基材の作製方法及び該触媒基
材を用いるカーボンナノチューブの合成方法を提供する
ことをその課題とする。DISCLOSURE OF THE INVENTION The present invention relates to a catalyst solution used when thermally decomposing a carbon-containing material to synthesize carbon nanotubes, a catalyst substrate formed by using the catalyst solution, and the catalyst solution. It is an object of the present invention to provide a method for producing a catalyst base material to be used and a method for synthesizing carbon nanotubes using the catalyst base material.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、溶媒中にカーボンナ
ノチューブ合成用触媒超微粒子を分散させたマイクロエ
マルジョンからなり、該触媒微粒子の平均粒径が１〜２
０ｎｍであり、該触媒微粒子の液中濃度が０．１〜１０
重量％であることを特徴とするカーボンナノチューブ合
成用触媒液が提供される。また、本発明によれば、前記
触媒液から形成された触媒超微粒子を表面に有すること
を特徴とするカーボンナノチューブ合成用触媒基材が提
供される。さらに、本発明によれば、前記触媒液を用い
て基材上に触媒超微粒子を付着させることを特徴とする
触媒基材の作製方法が提供される。さらにまた、本発明
によれば、前記触媒基材の存在下で含炭素材料を熱分解
させて該基材上にカーボンナノチューブを生成させるこ
とを特徴とするカーボンナノチューブの合成方法が提供
される。The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, Ri microemulsion Tona obtained by dispersing carbon nanotube catalyst for synthesizing ultrafine particles in a solvent, the average particle size of the catalyst particles is 1 to 2
0 nm, and the concentration of the catalyst fine particles in the liquid is 0.1 to 10
Carbon nanotube synthesis catalyst solution is provided you wherein the percentages by weight. Further, according to the present invention, there is provided a catalyst base material for synthesizing carbon nanotubes, which has catalyst ultrafine particles formed from the catalyst liquid on the surface. Further, according to the present invention, there is provided a method for producing a catalyst base material, which comprises depositing ultrafine catalyst particles on a base material using the catalyst liquid. Furthermore, according to the present invention, there is provided a method for synthesizing carbon nanotubes, which comprises thermally decomposing a carbon-containing material in the presence of the catalyst substrate to generate carbon nanotubes on the substrate.
【０００５】[0005]
【発明の実施の形態】本発明の触媒液は、含炭素材料を
熱分解してカーボンナノチューブを合成する際の触媒と
なる触媒超微粒子を溶媒中に分散させたマイクロエマル
ジョンからなる。この触媒液において、その触媒として
は、通常、遷移金属が用いられる。この触媒金属として
は、特にＶからVIII族の金属、例えば、ニッケル、コバ
ルト、モリブデン、Ｆｅ、Ｃｕ、Ｖ、Ｐｄ等が挙げられ
る。本発明で用いる触媒は、金属であることができる
他、金属の化合物、例えば金属ホウ化物、金属酸化物等
であることができ、カーボンナノチューブの合成に触媒
作用を有するものであればどのようなものでもよい。そ
の触媒は溶媒中に超微粒子状で分散し、その平均粒径
は、通常、１〜２０ｎｍ程度である。その触媒超微粒子
の液中濃度は０．１〜１０重量％、好ましくは１〜５重
量％である。その溶媒としては、水及び各種の有機溶媒
が用いられる。有機溶媒には、アルコール、ケトン、エ
ステル、炭化水素等が包含される。その具体例として
は、例えば、メタノール、プロピルアルコール、アミル
アルコール、ヘキサノール、シクロヘキサノール、ヘプ
タノール、オクチルアルコール、シクロヘキサン、メチ
ルエチルケトン、ジエチルケトン、シクロヘプタン、ｎ
−ヘキサン、ｎ−ヘプタン、イソオクタン、ｎ−デカ
ン、ベンゼン、トルエン、キシレン等が挙げられる。本
発明では、その沸点が５０〜２００℃の範囲にある有機
溶媒の使用が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The catalyst solution of the present invention comprises a microemulsion in which ultrafine catalyst particles, which serve as a catalyst for synthesizing carbon nanotubes by thermally decomposing a carbon-containing material, are dispersed in a solvent. In this catalyst liquid, a transition metal is usually used as the catalyst. Examples of the catalyst metal include metals of Group V to VIII, such as nickel, cobalt, molybdenum, Fe, Cu, V, and Pd. The catalyst used in the present invention can be a metal as well as a metal compound, such as a metal boride, a metal oxide, etc., as long as it has a catalytic action in the synthesis of carbon nanotubes. It may be one. The catalyst is dispersed in a solvent in the form of ultrafine particles, and the average particle size thereof is usually about 1 to 20 nm. The concentration of the catalyst ultrafine particles in the liquid is 0.1 to 10% by weight, preferably 1 to 5% by weight. Water and various organic solvents are used as the solvent. Organic solvents include alcohols, ketones, esters, hydrocarbons and the like. Specific examples thereof include, for example, methanol, propyl alcohol, amyl alcohol, hexanol, cyclohexanol, heptanol, octyl alcohol, cyclohexane, methyl ethyl ketone, diethyl ketone, cycloheptane, n.
-Hexane, n-heptane, isooctane, n-decane, benzene, toluene, xylene and the like. In the present invention, it is preferable to use an organic solvent having a boiling point in the range of 50 to 200 ° C.
【０００６】本発明の触媒液の調製方法としては、触媒
超微粒子を溶媒中に均一に分散し得る方法であればよ
く、任意の方法を用いることができる。その好ましい調
製方法においては、先ず、有機溶媒に界面活性剤を加え
て溶解させる。次に、この界面活性剤を含む有機溶媒に
対して、その有機溶媒に可溶性の触媒金属化合物を添加
し、溶解させる。次いで、この有機溶媒中の触媒金属化
合物を還元し、超微粒子状の不溶性触媒金属を生成させ
ることにより、触媒金属超微粒子を含むマイクロエマル
ジョンが得られる。前記界面活性剤としては、イオン性
界面活性剤、好ましくはカチオン性界面活性剤やアニオ
ン界面活性剤が用いられる。この場合、カチオン性界面
活性剤としては、炭素数８〜２２、好ましくは１２〜２
０の長鎖アルキル基やアルケニル基を有する第４級アン
モニウム塩を用いることができる。カチオン性界面活性
剤の具体例としては、ジデシルジメチルアンモニウムブ
ロマイド、ジデシルジメチルアンモニウムクロライド、
ジドデシルジメチルアンモニウムブロマイド（又はクロ
ライド）、セチルトリメチルアンモニウムブロマイド
（又はクロライド）、ドデシルトリメチルアンモニウム
ブロマイド（又はクロライド）等を挙げることができ
る。アニオン性界面活性剤の具体例としては、ジオクチ
ルスルホサッシネートナトリウム塩等が挙げられる。界
面活性剤の使用割合は、溶液中、１〜２０重量％、好ま
しくは７〜１５重量％である。前記可溶性触媒金属化合
物としては、触媒金属のハロゲン化物（塩化物、臭化物
等）、有機酸塩（酢酸塩等）、有機錯塩（アセチルアセ
テート塩等）、硝酸塩等が挙げられる。The method for preparing the catalyst solution of the present invention may be any method as long as it can uniformly disperse the catalyst ultrafine particles in the solvent, and any method can be used. In the preferable preparation method, first, a surfactant is added to an organic solvent and dissolved. Next, a catalyst metal compound soluble in the organic solvent is added to and dissolved in the organic solvent containing the surfactant. Then, the catalyst metal compound in the organic solvent is reduced to produce insoluble catalyst metal in the form of ultrafine particles, whereby a microemulsion containing the ultrafine particles of the catalyst metal is obtained. As the surfactant, an ionic surfactant, preferably a cationic surfactant or an anionic surfactant is used. In this case, the cationic surfactant has 8 to 22 carbon atoms, preferably 12 to 2 carbon atoms.
A quaternary ammonium salt having 0 long-chain alkyl group or alkenyl group can be used. Specific examples of the cationic surfactant include didecyldimethylammonium bromide, didecyldimethylammonium chloride,
Examples thereof include didodecyldimethylammonium bromide (or chloride), cetyltrimethylammonium bromide (or chloride), dodecyltrimethylammonium bromide (or chloride), and the like. Specific examples of the anionic surfactant include dioctylsulfosuccinate sodium salt and the like. The ratio of the surfactant used in the solution is 1 to 20% by weight, preferably 7 to 15% by weight. Examples of the soluble catalyst metal compound include halides (chlorides, bromides, etc.) of catalyst metals, organic acid salts (acetates, etc.), organic complex salts (acetyl acetate salts, etc.), nitrates, and the like.
【０００７】溶液中の触媒金属化合物の還元法として
は、水素ガスを用いる還元法の他、ヒドラジンや水素化
ホウ素ナトリウム等の化学的還元剤を用いる方法が挙げ
られるが、化学的還元剤の使用が好ましい。この化学的
還元剤を用いる還元方法は、常温において、理論量の１
モル倍以上、好ましくは２〜１０モル倍の化学的還元剤
を溶液に攪拌下で添加することによって実施される。こ
の場合、その化学的還元剤は、水溶液や有機溶媒溶液の
形態で添加することができる。Examples of the reduction method of the catalytic metal compound in the solution include a reduction method using hydrogen gas and a method using a chemical reducing agent such as hydrazine or sodium borohydride. Use of a chemical reducing agent Is preferred. The reduction method using this chemical reducing agent is a theoretical amount of 1 at room temperature.
It is carried out by adding a molar excess of a chemical reducing agent, preferably 2 to 10 molar times, to the solution under stirring. In this case, the chemical reducing agent can be added in the form of an aqueous solution or an organic solvent solution.
【０００８】前記のようにして得られる触媒超微粒子を
含むマイクロエマルジョンは、そのまま触媒液として使
用することができるが、このものはカーボンナノチュー
ブの合成及び微粒子膜の作製に好ましくない界面活性剤
を含むことから、その界面活性剤を除去して用いるのが
好ましい。マイクロエマルジョンからの界面活性剤の除
去は、そのマイクロエマルジョンを遠心処理して、触媒
相と溶媒相とに分離し、その溶媒相を除去した後、その
触媒相を溶媒中に再び分散させてマイクロエマルジョン
とする。このような操作を複数回、通常、２〜８回、好
ましくは３〜５回繰返すことにより、界面活性剤濃度が
１重量％以下、好ましくは０．１重量％以下の触媒液を
得る。その他の方法として、ウルトラフィルターを用い
た透析法により、超微粒子を抽出濃縮することも可能で
ある。The microemulsion containing the ultrafine catalyst particles obtained as described above can be used as it is as a catalyst solution, but it contains a surfactant which is not preferable for the synthesis of carbon nanotubes and the preparation of a fine particle film. Therefore, it is preferable to remove the surfactant before use. The removal of the surfactant from the microemulsion is performed by centrifuging the microemulsion to separate it into a catalyst phase and a solvent phase, removing the solvent phase, and then redispersing the catalyst phase in the solvent. Emulsion. By repeating such an operation a plurality of times, usually 2 to 8 times, preferably 3 to 5 times, a catalyst liquid having a surfactant concentration of 1% by weight or less, preferably 0.1% by weight or less is obtained. As another method, ultrafine particles can be extracted and concentrated by a dialysis method using an ultrafilter.
【０００９】本発明による他の好ましい触媒液の調製方
法においては、水溶性の触媒金属化合物をあらかじめ水
溶液とし、この水溶液を界面活性剤の存在下で有機溶媒
中に超微粒子状で分散させ、得られたマイクロエマルジ
ョンを前記と同様にして後処理することにより実施され
る。水溶液中の触媒金属化合物の濃度は、０．０５モル
／リットル以下、好ましくは０．０２モル／リットル以
下であり、その下限値は特に制約されないが、通常、
０．０００１モル／リットル程度である。In another preferred method for preparing a catalyst liquid according to the present invention, a water-soluble catalytic metal compound is previously made into an aqueous solution, and this aqueous solution is dispersed in an organic solvent in the presence of a surfactant in the form of ultrafine particles to obtain a solution. It is carried out by post-treating the obtained microemulsion in the same manner as described above. The concentration of the catalytic metal compound in the aqueous solution is 0.05 mol / liter or less, preferably 0.02 mol / liter or less, and the lower limit thereof is not particularly limited, but is usually
It is about 0.0001 mol / liter.
【００１０】前記においては、液中に溶解する触媒金属
化合物を還元し、金属状態に還元する方法を示したが、
この還元法による金属への還元に代えて、金属水酸化物
や、金属酸化物、金属硫化物等の不溶性金属化合物の沈
殿を生成させる通常の沈殿法も採用することができる。In the above, the method of reducing the catalytic metal compound dissolved in the liquid to reduce it to the metallic state has been described.
Instead of the reduction to the metal by this reduction method, a usual precipitation method in which a precipitation of an insoluble metal compound such as a metal hydroxide or a metal oxide or a metal sulfide can be generated can also be adopted.
【００１１】本発明の触媒液を用いて触媒基材を作製す
るには、基材上に触媒液を塗布し、乾燥する。基材とし
ては、従来公知の各種のものを用いることができる。こ
の基材としては、シリコーンや、セラミックス、ステン
レス等の耐熱性の材料であればよく、特に制約されない
が、疎水性表面を有するものが好ましい。本発明では、
このような材料を少なくともその表面に有するものが用
いられる。その形状は、シート状、板体状、柱状、筒状
等であることができる。本発明では、平板状の大面積基
材を有利に用いることができる。この大面積基材は、平
面ディスプレイに用いられるフィールドエミッション用
電子源を作製する際の触媒基材として有利に用いられ
る。基材上に触媒液を塗布する方法としては、従来公知
の各種の方法を用いることができる。このような方法と
しては、ハケ塗り法、ロール塗布法、スプレー塗布法、
スピンコート法、表面改質した基材への含浸法等が包含
される。本発明では、スクリーン印刷等の印刷法や、微
小ノズルから液体を噴出させるインクジェット法等を好
ましく採用することができる。触媒液を基材上に塗布す
る場合、その触媒液は、基材に対して、その全面に均一
に塗布することができる他、線状、帯状、格子状、ドッ
ト状、その他の任意のパターン状に塗布することができ
る。触媒液の塗布された基材は、これを乾燥することに
より、表面に触媒超微粒子の付着した触媒基材を得るこ
とができる。基材上の触媒粒子は、カーボンナノチュー
ブの生成を促進させる状態であればよく、金属状態の
他、金属硫化物や金属ホウ化物、金属酸化物、金属水酸
化物等の状態であることができる。金属硫化物の場合に
は、その基材上の金属状態の超微粒子に対して、硫化水
素等の硫化剤を反応させることによって得ることができ
る。基材上の触媒超微粒子の付着量は、１００ｃｍ2当
り１０-10〜１０-1モルの割合である。To prepare a catalyst base material using the catalyst liquid of the present invention, the catalyst liquid is applied onto the base material and dried. As the base material, various conventionally known materials can be used. The base material is not particularly limited as long as it is a heat resistant material such as silicone, ceramics or stainless steel, but a base material having a hydrophobic surface is preferable. In the present invention,
A material having such a material at least on its surface is used. The shape can be a sheet shape, a plate shape, a column shape, a cylindrical shape, or the like. In the present invention, a flat large-area substrate can be advantageously used. This large-area substrate is advantageously used as a catalyst substrate when producing a field emission electron source used for a flat display. As a method of applying the catalyst liquid on the substrate, various conventionally known methods can be used. As such a method, a brush coating method, a roll coating method, a spray coating method,
The method includes a spin coating method, a method of impregnating a surface-modified base material, and the like. In the present invention, a printing method such as screen printing, an inkjet method of ejecting a liquid from a minute nozzle, or the like can be preferably adopted. When the catalyst liquid is applied on the base material, the catalyst liquid can be applied uniformly on the entire surface of the base material, and also linear, strip, grid, dot, or any other pattern. It can be applied in the form of. By drying the base material coated with the catalyst liquid, a catalyst base material having catalyst ultrafine particles attached to the surface thereof can be obtained. The catalyst particles on the base material may be in a state of promoting the production of carbon nanotubes, and may be in a state of metal sulfide, metal boride, metal oxide, metal hydroxide or the like in addition to a metal state. . In the case of a metal sulfide, it can be obtained by reacting the ultrafine particles in a metallic state on the base material with a sulfiding agent such as hydrogen sulfide. The amount of catalyst ultrafine particles deposited on the substrate is 10 -10 to 10 -1 mol per 100 cm 2 .
【００１２】本発明の触媒基材を用いてカーボンナノチ
ューブを製造するには、その触媒基材の存在下で含炭素
材料を気体状で熱分解させる。To produce carbon nanotubes using the catalyst substrate of the present invention, the carbon-containing material is thermally decomposed in a gaseous state in the presence of the catalyst substrate.
【００１３】本発明で用いる含炭素材料は特に制約され
ず、高温で炭素化されるものであればよい。このような
ものとしては、一酸化炭素の他、メタン、エタン、プロ
パン、ブタン等の飽和炭化水素；エチレン、プロピレ
ン、ブテン、イソブテン等の不飽和炭化水素；アセチレ
ン等のアセチレン系化合物；ベンゼン、トルエン、キシ
レン、ナフタレン等の芳香族炭化水素、これらの混合物
（例えば、ナフサや軽油等）等が包含される。本発明で
は、取扱いの容易さや、価格の点、炭素含有率等の点か
ら、有機炭素材料、特に、沸点が８０〜１４４℃の液状
芳香族炭化水素、例えば、ベンゼル、トルエン、キシレ
ン、それらの混合物の使用が好ましい。The carbon-containing material used in the present invention is not particularly limited as long as it can be carbonized at a high temperature. Examples thereof include carbon monoxide, saturated hydrocarbons such as methane, ethane, propane and butane; unsaturated hydrocarbons such as ethylene, propylene, butene and isobutene; acetylene compounds such as acetylene; benzene and toluene. , Aromatic hydrocarbons such as xylene and naphthalene, and mixtures thereof (for example, naphtha and light oil) and the like. In the present invention, organic carbon materials, in particular, liquid aromatic hydrocarbons having a boiling point of 80 to 144 ° C., for example, benzene, toluene, xylene, and those from the viewpoint of ease of handling, price, carbon content, etc. The use of mixtures is preferred.
【００１４】含炭素材料を熱分解させる方法としては、
従来公知の方法が用いられる。このような方法には、電
気炉等による通常の加熱方法、マイクロ波による加熱方
法、レーザ加熱方法等が包含される。通常の加熱方法の
場合、その加熱温度は、６００〜１０００℃、好ましく
は７００〜９００℃である。前記含炭素材料を熱分解す
る場合、その含炭素材料の気体中に水素ガスをキャリア
ーガスとして混入することができる。また、含炭素材料
には、硫化水素やメルカプタン等のイオウ化合物を適量
加えることができる。これにより、基材上に真っ直ぐな
カーボンナノチューブを得ることができる。As a method of thermally decomposing a carbon-containing material,
A conventionally known method is used. Such methods include a normal heating method using an electric furnace or the like, a microwave heating method, a laser heating method, and the like. In the case of a usual heating method, the heating temperature is 600 to 1000 ° C, preferably 700 to 900 ° C. When the carbon-containing material is pyrolyzed, hydrogen gas can be mixed as a carrier gas in the gas of the carbon-containing material. Further, an appropriate amount of sulfur compound such as hydrogen sulfide or mercaptan can be added to the carbon-containing material. This makes it possible to obtain straight carbon nanotubes on the substrate.
【００１５】[0015]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。EXAMPLES Next, the present invention will be described in more detail by way of examples.
【００１６】実施例１
（１）触媒液の調製
トルエン９ｇ中にカチオン性界面活性剤であるジデシル
ジメチルアンモニウムブロマイド（ＤＤＡＢ）を１ｇ溶
かし１時間攪拌する。次に塩化コバルト六水和物１２ｍ
ｇを溶液中に導入し、さらに１時間攪拌する。この溶液
は透明な水色を示す。その後、１０Ｍの水素化ホウ素ナ
トリウム水溶液を１５μｌ滴下して塩化コバルトを還元
する。滴下後、溶液は黒く懸濁し銀白色の沈殿物を生じ
る。次に、この沈殿物を含む溶液を１２０００ｒｐｍで
１０分間遠心分離機にかけ、上澄みを除去した後、トル
エンを追加して再分散し、遠心処理する工程を４回繰り
返すことにより、余分な界面活性剤を除去し、コバルト
粒子を精製する。このようにして得られた触媒液におい
て、そのコバルト粒子の平均粒径は、約４ｎｍである。
また、その界面活性剤濃度は、実質上ゼロ％１ｗｔ％以
下）である。Example 1 (1) Preparation of catalyst liquid 1 g of didecyldimethylammonium bromide (DDAB) which is a cationic surfactant was dissolved in 9 g of toluene and stirred for 1 hour. Next, cobalt chloride hexahydrate 12m
g is introduced into the solution and stirred for a further 1 hour. This solution shows a clear light blue color. Thereafter, 15 μl of 10 M sodium borohydride aqueous solution is dropped to reduce cobalt chloride. After the dropping, the solution is suspended black and a silver-white precipitate is formed. Next, the solution containing this precipitate was centrifuged at 12000 rpm for 10 minutes, the supernatant was removed, and then toluene was added to redisperse the solution, and the centrifugal treatment was repeated 4 times to remove excess surfactant. Are removed and the cobalt particles are purified. In the catalyst solution thus obtained, the average particle size of the cobalt particles is about 4 nm.
Further, the surfactant concentration is substantially zero% 1 wt% or less).
【００１７】（２）触媒基材の作製
前記（１）で得た触媒液を、５ｍｍ四方のシリコン基材
上に滴下して、均一な触媒液膜を形成した後、これを室
温で乾燥してその基材面にコバルト粒子を付着させた。
これにより、表面にコバルト粒子が均一に付着した触媒
基材を得ることができた。次に、この触媒基材のコバル
ト粒子に対して、硫化水素/水素混合ガス（硫化水素濃
度：１０モル％）を４００℃で２時間流通接触させて、
硫化水素の還元とコバルト粒子の硫化を同時に行って、
硫化コバルト粒子が表面に付着した触媒基材を得た。(2) Preparation of Catalyst Base Material The catalyst solution obtained in (1) above was dropped onto a 5 mm square silicon base material to form a uniform catalyst liquid film, which was then dried at room temperature. Cobalt particles were attached to the surface of the substrate.
As a result, it was possible to obtain a catalyst substrate having cobalt particles uniformly attached to the surface. Next, a hydrogen sulfide / hydrogen mixed gas (hydrogen sulfide concentration: 10 mol%) was made to flow and contact with the cobalt particles of the catalyst base material at 400 ° C. for 2 hours,
Simultaneous reduction of hydrogen sulfide and sulfurization of cobalt particles,
A catalyst substrate having cobalt sulfide particles attached to its surface was obtained.
【００１８】（３）カーボンナノチューブの合成
前記（２）で得た触媒基材を反応管に入れ、窒素気流中
で９００℃まで昇温した後、アセチレン／Ｎ2混合ガス
（アセチレン濃度：１モル％）を９００℃で１時間流通
させて反応を行った。この場合、その全流通ガス量は、
１５０ｃｍ3である。この反応により、基材上にカーボ
ンナノチューブが生成した。このカーボンナノチューブ
は、走査型電子顕微鏡（ＳＥＭ）により、シリコン基材
上に垂直に配向した真っ直ぐなチューブであり、直径２
０〜５０ｎｍ、長さ０．５〜５μｍのチューブを主体と
するものであることが確認された。(3) Synthesis of carbon nanotubes The catalyst substrate obtained in (2) above was put into a reaction tube, heated to 900 ° C. in a nitrogen stream, and then mixed with acetylene / N 2 gas (acetylene concentration: 1 mol). %) At 900 ° C. for 1 hour to carry out the reaction. In this case, the total amount of flowing gas is
It is 150 cm 3 . By this reaction, carbon nanotubes were produced on the substrate. This carbon nanotube is a straight tube vertically oriented on a silicon substrate by a scanning electron microscope (SEM), and has a diameter of 2 mm.
It was confirmed to be mainly composed of a tube having a length of 0 to 50 nm and a length of 0.5 to 5 μm.
【００１９】実施例２
実施例１において、未硫化の触媒基材を用いた以外は同
様にして実験を行った。この場合にも、その基材上にカ
ーボンナノチューブが生成されることが確認された。Example 2 An experiment was conducted in the same manner as in Example 1 except that an unsulfurized catalyst base material was used. Also in this case, it was confirmed that carbon nanotubes were formed on the base material.
【００２０】[0020]
【発明の効果】本発明の触媒液を用いることにより、触
媒基材の製作は容易になり、かつその基材上に付着させ
る触媒超微粒子のパターンも任意の形状にすることがで
きる。さらに、大面積基材を得ることも容易である。本
発明の触媒基材の存在下で含炭素材料を熱分解させるこ
とにより、その基材上に、任意のパターン状にカーボン
ナノチューブを生成させることができる。By using the catalyst solution of the present invention, the production of the catalyst substrate can be facilitated, and the pattern of the ultrafine catalyst particles deposited on the substrate can be formed in any shape. Furthermore, it is easy to obtain a large area base material. By thermally decomposing the carbon-containing material in the presence of the catalyst base material of the present invention, carbon nanotubes can be produced in an arbitrary pattern on the base material.
───────────────────────────────────────────────────── フロントページの続き (73)特許権者 597045538 大嶋 哲 千葉県我孫子市並木５−２−17 (73)特許権者 597045550 栗木 安則 茨城県つくば市並木２−142−102 (74)上記４名の代理人 100074505 弁理士 池浦 敏明 (72)発明者 吾郷 浩樹 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 湯村 守雄 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 大嶋 哲 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 栗木 安則 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (56)参考文献 特開 平６−269684（ＪＰ，Ａ) 特開 平９−31757（ＪＰ，Ａ) 特開 平11−194134（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 C01B 31/00 - 31/36 ─────────────────────────────────────────────────── ─── Continuation of the front page (73) Patent holder 597045538 Satoshi Oshima 5-2-17 Namiki, Abiko-shi, Chiba (73) Patent holder 597045550 Yasunori Kuriki 2-142-102 Namiki, Tsukuba, Ibaraki (74) Above 4 Attorney 100074505 Patent Attorney Toshiaki Ikeura (72) Inventor Hiroki Ago 1-1 1-1 Higashi Tsukuba-shi, Ibaraki Industrial Technology Institute, Institute of Materials Engineering (72) Inventor Morio Yumura 1-1-1 Higashi, Tsukuba-shi, Ibaraki Institute of Industrial Science and Technology (72) Inventor Satoshi Oshima 1-1 1-1 Higashi, Tsukuba, Ibaraki Industrial Technology Institute of Industrial Science and Technology (72) Inventor Yasunori Kuriki 1-1-1 East, Tsukuba, Ibaraki Industrial Technology (56) Reference JP 6-269684 (JP, A) JP 9-31757 (JP, A) JP 1 1-194134 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 21/00-38/74 C01B 31/00-31/36
Claims (4)
媒超微粒子を分散させたマイクロエマルジョンからな
り、該触媒微粒子の平均粒径が１〜２０ｎｍであり、該
触媒微粒子の液中濃度が０．１〜１０重量％であること
を特徴とするカーボンナノチューブ合成用触媒液。1. A microemulsion in which ultrafine catalyst particles for synthesizing carbon nanotubes are dispersed in a solvent.
The average particle diameter of the catalyst fine particles is 1 to 20 nm,
The concentration of the catalyst fine particles in the liquid is 0.1 to 10% by weight.
Carbon nanotube synthesis catalyst solution characterized.
微粒子を表面に有することを特徴とするカーボンナノチ
ューブ合成用触媒基材。2. A catalyst substrate for synthesizing carbon nanotubes, which has on its surface ultrafine catalyst particles formed from the catalyst liquid according to claim 1.
超微粒子を付着させることを特徴とする触媒基材の作製
方法。3. A method for producing a catalyst substrate, which comprises depositing ultrafine catalyst particles on a substrate using the catalyst liquid according to claim 1.
料を熱分解させて該基材上にカーボンナノチューブを生
成させることを特徴とするカーボンナノチューブの合成
方法。4. A method for synthesizing carbon nanotubes, which comprises thermally decomposing a carbon-containing material in the presence of the catalyst substrate according to claim 2 to produce carbon nanotubes on the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24510399A JP3438041B2 (en) | 1999-08-31 | 1999-08-31 | Catalyst solution for carbon nanotube synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24510399A JP3438041B2 (en) | 1999-08-31 | 1999-08-31 | Catalyst solution for carbon nanotube synthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001062299A JP2001062299A (en) | 2001-03-13 |
| JP3438041B2 true JP3438041B2 (en) | 2003-08-18 |
Family
ID=17128667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24510399A Expired - Lifetime JP3438041B2 (en) | 1999-08-31 | 1999-08-31 | Catalyst solution for carbon nanotube synthesis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3438041B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006030642A1 (en) | 2004-09-17 | 2006-03-23 | National Institute Of Advanced Industrial Science And Technology | Nanocapsule-type structure |
| JP2007268319A (en) * | 2006-03-08 | 2007-10-18 | Toyota Central Res & Dev Lab Inc | Catalyst for synthesizing carbon nano-tube and its manufacturing method, catalyst dispersion and manufacturing method for carbon nanotube |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4593816B2 (en) * | 2001-03-27 | 2010-12-08 | キヤノン株式会社 | Electron emitting device, image forming apparatus, and method of manufacturing electron emitting device |
| ES2238582T5 (en) | 2001-07-03 | 2010-05-26 | Facultes Universitaires Notre-Dame De La Paix | CATALYZER SUPPORTS AND CARBON NANOTUBES PRODUCED ON SUCH SUPPORTS. |
| KR100432056B1 (en) * | 2001-07-20 | 2004-05-17 | (주)케이에이치 케미컬 | Continuous preparation of carbon nanotubes |
| JP3710436B2 (en) | 2001-09-10 | 2005-10-26 | キヤノン株式会社 | Electron emitting device, electron source, and manufacturing method of image display device |
| US7378075B2 (en) | 2002-03-25 | 2008-05-27 | Mitsubishi Gas Chemical Company, Inc. | Aligned carbon nanotube films and a process for producing them |
| JP4656891B2 (en) * | 2003-08-28 | 2011-03-23 | キヤノン株式会社 | Carbon fiber assembly and method for producing the same |
| JP2005239504A (en) * | 2004-02-27 | 2005-09-08 | National Institute For Materials Science | Method of manufacturing fibrous carbon by heat transfer from heater and its manufacturing apparatus |
| JP4977351B2 (en) * | 2005-09-29 | 2012-07-18 | 新潟県 | Method for producing carbon nanotube |
| EP2543756A4 (en) | 2010-03-02 | 2013-12-18 | Showa Denko Kk | Process for production of carbon fibers |
-
1999
- 1999-08-31 JP JP24510399A patent/JP3438041B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006030642A1 (en) | 2004-09-17 | 2006-03-23 | National Institute Of Advanced Industrial Science And Technology | Nanocapsule-type structure |
| US7897536B2 (en) | 2004-09-17 | 2011-03-01 | National Institute Of Advanced Industrial Science And Technology | Nanocapsule-type structure |
| JP2007268319A (en) * | 2006-03-08 | 2007-10-18 | Toyota Central Res & Dev Lab Inc | Catalyst for synthesizing carbon nano-tube and its manufacturing method, catalyst dispersion and manufacturing method for carbon nanotube |
| JP4730707B2 (en) * | 2006-03-08 | 2011-07-20 | 株式会社豊田中央研究所 | Catalyst for carbon nanotube synthesis and method for producing the same, catalyst dispersion, and method for producing carbon nanotube |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001062299A (en) | 2001-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5156383B2 (en) | Catalyst for the synthesis of single-walled carbon nanotubes | |
| US10384943B2 (en) | Synthesis of small and narrow diameter distributed carbon single walled nanotubes | |
| CA2454009C (en) | Preparation of carbon nanotubes | |
| US7923615B2 (en) | Catalyst system for a multi-walled carbon nanotube production process | |
| US7871591B2 (en) | Methods for growing long carbon single-walled nanotubes | |
| JP3438041B2 (en) | Catalyst solution for carbon nanotube synthesis | |
| AU2001294278A1 (en) | Preparation of carbon nanotubes | |
| US20030042147A1 (en) | Method of forming a nano-supported catalyst on a substrate for nanotube growth | |
| JP4730707B2 (en) | Catalyst for carbon nanotube synthesis and method for producing the same, catalyst dispersion, and method for producing carbon nanotube | |
| US20090134363A1 (en) | Method for synthesis of carbon nanotubes | |
| JP2001080912A (en) | Production of carbon nanotube | |
| CN110494390A (en) | Use the preparation method of the multi-walled carbon nanotube of continous way process | |
| US9834444B2 (en) | Method for forming aluminum oxide/carbon nanotubes by ultrasonic atomization and chemical vapor deposition | |
| JP3463092B2 (en) | Catalyst pattern for carbon nanotube production | |
| JP6403144B2 (en) | Process for producing vapor-deposited fine carbon fiber | |
| JP2004261630A (en) | Catalyst for manufacturing carbon nanocoil, its manufacturing method, and method for manufacturing carbon nanocoil | |
| CN111943722A (en) | Controllable method for synthesizing carbon nano tube on surface of foamed ceramic and application thereof | |
| JP4674355B2 (en) | Raw material spray type high efficiency carbon nanostructure manufacturing method and apparatus | |
| JPH0751568A (en) | Carbon black composite and manufacture thereof | |
| JP2003137519A (en) | Catalyst dispersion for production of carbon nanotube and its production method | |
| Govindaraj et al. | Novel vapor phase reactions for the synthesis and modification of carbon nanotubes and inorganic nanowires | |
| CN117561119A (en) | Catalyst for producing carbon nanotubes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| R150 | Certificate of patent or registration of utility model |
Ref document number: 3438041 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |