JP2002263496A - Catalyst composition, manufacturing method thereof and method of manufacturing carbon nanofiber - Google Patents
Catalyst composition, manufacturing method thereof and method of manufacturing carbon nanofiberInfo
- Publication number
- JP2002263496A JP2002263496A JP2001069808A JP2001069808A JP2002263496A JP 2002263496 A JP2002263496 A JP 2002263496A JP 2001069808 A JP2001069808 A JP 2001069808A JP 2001069808 A JP2001069808 A JP 2001069808A JP 2002263496 A JP2002263496 A JP 2002263496A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- catalyst
- metal particles
- catalyst composition
- catalyst metal
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 69
- 239000002923 metal particle Substances 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 238000010891 electric arc Methods 0.000 claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 9
- 238000004220 aggregation Methods 0.000 claims description 7
- 230000002776 aggregation Effects 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 11
- 230000008016 vaporization Effects 0.000 abstract 2
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 238000009834 vaporization Methods 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- -1 carbon nanofibers Chemical compound 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、カーボンナノファ
イバー等のナノ構造炭素の製造に用いられる触媒組成物
とその製造方法とに関するものである。また、本発明
は、前記カーボンナノファイバーの製造方法にも関する
ものである。[0001] The present invention relates to a catalyst composition used for producing nanostructured carbon such as carbon nanofibers, and a method for producing the same. The present invention also relates to a method for producing the carbon nanofiber.
【０００２】[0002]
【従来の技術】近年、Ｃ６０フラーレン、カーボンナノ
チューブ、グラファイトナノファイバー等のナノメート
ルオーダーの大きさを有するナノ構造炭素が注目されて
いる。前記ナノ構造炭素は、その特殊な構造のために、
特殊な機能的性質、構造的性質を備えている。例えば、
数ナノメートルの微細な大きさを備えるグラファイトナ
ノファイバーは、水素吸蔵、電池電極、キャパシタ等に
応用する用途がある。2. Description of the Related Art In recent years, attention has been paid to nanostructured carbon having a size on the order of nanometers, such as C60 fullerene, carbon nanotube, and graphite nanofiber. The nanostructured carbon, due to its special structure,
Has special functional and structural properties. For example,
Graphite nanofibers having a fine size of several nanometers have applications to hydrogen storage, battery electrodes, capacitors and the like.
【０００３】前記ナノ構造炭素の製造方法として、例え
ば、特開平１１−２５６４３０号記載の技術が知られて
いる。前記公報記載の技術は、炭素、黒鉛、無機酸化物
からなる支持体粒子上に多価遷移金属触媒の粒子を担持
させ、水素と炭化水素との混合ガスをチューブに流通す
ると共に、該チューブに該触媒を導入するものである。
ここで、前記公報には、前記遷移金属触媒の粒子を前記
支持体粒子上に担持させる際に、３．５〜７０μｍ、好
ましくは６〜３０μｍの間隔で離散させることが、前記
ナノ構造炭素を製造するために重要であるとされてい
る。As a method for producing the nanostructured carbon, for example, a technique described in Japanese Patent Application Laid-Open No. H11-256430 is known. The technology described in the above-mentioned publication discloses a method in which particles of a polyvalent transition metal catalyst are supported on support particles made of carbon, graphite, and an inorganic oxide, and a mixed gas of hydrogen and a hydrocarbon flows through the tube, The catalyst is introduced.
Here, the publication discloses that when the particles of the transition metal catalyst are supported on the support particles, the particles are dispersed at intervals of 3.5 to 70 μm, preferably 6 to 30 μm. It is considered important for manufacturing.
【０００４】ところが、前記支持体粒子として黒鉛等の
炭素系材料を用いると、前記遷移金属触媒の粒子が凝集
してしまう傾向があり、前記のような離散した状態を作
ることが難しいとの問題がある。そこで、従来、前記支
持体として、比表面積を増加させるために多孔質とした
アルミナ基板を用い、該アルミナ基板上に前記遷移金属
触媒の粒子を離散した状態で配置し、該アルミナ基板上
に水素と炭化水素との混合ガスを流通させて、前記ナノ
構造炭素を製造させることが行われている。However, if a carbon-based material such as graphite is used as the support particles, the transition metal catalyst particles tend to agglomerate, making it difficult to form the discrete state as described above. There is. Therefore, conventionally, a porous alumina substrate was used as the support to increase the specific surface area, and the transition metal catalyst particles were arranged in a discrete state on the alumina substrate, and hydrogen was placed on the alumina substrate. The production of the nanostructured carbon is carried out by flowing a mixed gas of carbon and hydrocarbon.
【０００５】しかしながら、前記のようにアルミナ基板
上に前記遷移金属触媒を配置して前記ナノ構造炭素を製
造すると生成したナノ構造炭素にアルミナが不純物とし
て混入してしまい、該不純物を除去して高純度に精製す
るためにフッ酸等の強力な酸処理工程が必要になるとの
不都合がある。However, when the transition metal catalyst is disposed on the alumina substrate to produce the nanostructured carbon as described above, alumina is mixed with the generated nanostructured carbon as an impurity. There is an inconvenience that a strong acid treatment step such as hydrofluoric acid is required for purification to a purity.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、かかる不都
合を解消して、炭素系材料からなる支持体に対して触媒
粒子を離散した状態で配置することができる触媒組成物
及びその製造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention is directed to a catalyst composition and a method for producing the same, which are capable of solving the above disadvantages and disposing catalyst particles in a discrete state on a support made of a carbon-based material. The purpose is to provide.
【０００７】また、本発明は、高純度のカーボンナノフ
ァイバーを容易に得ることができるカーボンナノファイ
バーの製造方法を提供することを目的とする。Another object of the present invention is to provide a method for producing carbon nanofibers that can easily obtain high-purity carbon nanofibers.
【０００８】[0008]
【課題を解決するための手段】かかる目的を達成するた
めに、本発明の触媒組成物は、表面が炭素で被覆された
直径３〜２０ｎｍの触媒金属粒子と、該触媒金属粒子の
周囲に分散されて該触媒金属粒子の凝集を妨げるナノ構
造炭素とからなることを特徴とする。In order to achieve the above object, a catalyst composition of the present invention comprises catalyst metal particles having a surface coated with carbon and having a diameter of 3 to 20 nm, and dispersed around the catalyst metal particles. And nano-structured carbon that prevents aggregation of the catalytic metal particles.
【０００９】本発明の触媒組成物によれば、前記触媒金
属粒子の表面が炭素で被覆されており、しかも該触媒金
属粒子間に前記ナノ構造炭素が介在している。そこで、
本発明の触媒組成物を炭素基板上に配置したときに、前
記触媒金属粒子は前記ナノ構造炭素により凝集を妨げら
れ、離散した状態を維持することができる。According to the catalyst composition of the present invention, the surface of the catalyst metal particles is coated with carbon, and the nanostructured carbon is interposed between the catalyst metal particles. Therefore,
When the catalyst composition of the present invention is disposed on a carbon substrate, the catalytic metal particles are prevented from aggregating by the nanostructured carbon, and can maintain a discrete state.
【００１０】従って、本発明の触媒組成物によれば、炭
素基板を用いてナノ構造炭素を製造することができ、高
純度のナノ構造炭素を得ることができる。Therefore, according to the catalyst composition of the present invention, nanostructured carbon can be produced using a carbon substrate, and high-purity nanostructured carbon can be obtained.
【００１１】本発明の触媒組成物は、前記触媒金属粒子
として、例えば、Ｔｉ，Ｚｒ，Ｆｅ，Ｃｏ，Ｎｉ，Ｙか
らなる群から選択される少なくとも１種の金属粒子を用
いることができる。また、本発明の触媒組成物における
前記ナノ構造炭素としては、例えばカーボンナノファイ
バーを挙げることができる。In the catalyst composition of the present invention, for example, at least one kind of metal particles selected from the group consisting of Ti, Zr, Fe, Co, Ni, and Y can be used as the catalyst metal particles. In addition, examples of the nanostructured carbon in the catalyst composition of the present invention include carbon nanofibers.
【００１２】本発明の触媒組成物は、触媒金属と炭素材
料とを共に蒸発させた後、蒸発した触媒金属と炭素材料
との蒸気を急冷することにより、表面が炭素で被覆され
た直径３〜２０ｎｍの触媒金属粒子と、該触媒金属粒子
の周囲に分散されて該触媒金属粒子の凝集を妨げるナノ
構造炭素とからなる触媒組成物を生成させる製造方法に
より、有利に製造することができる。前記触媒金属と炭
素材料とを共に蒸発させる方法としては、例えば、前記
触媒金属の粉末と、前記炭素材料としての黒鉛粉末とを
混合してなる電極を用いてアーク放電を行う方法を用い
ることができる。The catalyst composition of the present invention is characterized in that the catalyst metal and the carbon material are co-evaporated, and then the vapor of the evaporated catalyst metal and the carbon material is rapidly cooled, so that the diameter of the carbon material is 3 to 3 mm. It can be advantageously produced by a production method for producing a catalyst composition comprising 20 nm of catalytic metal particles and nanostructured carbon dispersed around the catalytic metal particles and preventing aggregation of the catalytic metal particles. As a method of evaporating the catalyst metal and the carbon material together, for example, a method of performing an arc discharge using an electrode formed by mixing the catalyst metal powder and the graphite powder as the carbon material may be used. it can.
【００１３】また、本発明のカーボンナノファイバーの
製造方法は、表面が炭素で被覆された直径３〜２０ｎｍ
の触媒金属粒子と、該触媒金属粒子の周囲に分散されて
該触媒金属粒子の凝集を妨げるナノ構造炭素とからなる
触媒組成物を炭素基板上に配置する工程と、前記炭素基
板上に配置された前記触媒組成物を酸化雰囲気に曝露
し、前記触媒金属粒子の表面を被覆している炭素と、前
記ナノ構造炭素とを酸化して除去することにより該触媒
金属粒子を分散した状態で該炭素基板上に担持せしめる
工程と、前記触媒金属粒子を担持している炭素基板上
に、水素と炭化水素との混合ガスを流通することによ
り、カーボンナノファイバーを生成せしめる工程とを備
えることを特徴とする。The method for producing carbon nanofibers according to the present invention is characterized in that the surface is coated with carbon and has a diameter of 3 to 20 nm.
Disposing a catalyst composition comprising catalyst metal particles and a nanostructured carbon dispersed around the catalyst metal particles to prevent aggregation of the catalyst metal particles on a carbon substrate, and disposing the catalyst composition on the carbon substrate. The catalyst composition is exposed to an oxidizing atmosphere, and the carbon coating the surface of the catalyst metal particles and the nanostructured carbon are oxidized and removed to remove the carbon in a state where the catalyst metal particles are dispersed. A step of causing a mixed gas of hydrogen and hydrocarbon to flow on a carbon substrate supporting the catalytic metal particles, thereby forming carbon nanofibers. I do.
【００１４】本発明のカーボンナノファイバーの製造方
法によれば、前記本発明の触媒組成物を炭素基板上に配
置するので、触媒金属粒子が該炭素基板上で凝集するこ
とを防止して、離散した状態で配置することができる。
前記炭素基板上に配置された触媒組成物は、次いで、酸
化雰囲気に曝露されることにより、前記触媒金属粒子の
表面を被覆している炭素と、前記ナノ構造炭素とが酸化
されて除去される。この結果、前記触媒金属粒子を凝集
させることなく、前記のように離散した状態のままで、
前記炭素基板上に担持させることができる。According to the method for producing carbon nanofibers of the present invention, the catalyst composition of the present invention is disposed on a carbon substrate. It can be arranged in the state where it was done.
The catalyst composition disposed on the carbon substrate is then exposed to an oxidizing atmosphere, whereby the carbon coating the surface of the catalyst metal particles and the nanostructured carbon are oxidized and removed. . As a result, without aggregating the catalyst metal particles, in the discrete state as described above,
It can be carried on the carbon substrate.
【００１５】そこで、次に、前記触媒金属粒子を担持し
ている炭素基板上に、水素と炭化水素との混合ガスを流
通することにより、基板から炭素以外の物質が不純物と
して混入することを防止して、高純度のカーボンナノフ
ァイバーを生成させることができる。Then, by flowing a mixed gas of hydrogen and hydrocarbon over the carbon substrate carrying the catalyst metal particles, it is possible to prevent substances other than carbon from being mixed as impurities from the substrate. As a result, high-purity carbon nanofibers can be generated.
【００１６】[0016]
【発明の実施の形態】次に、添付の図面を参照しながら
本発明の実施の形態についてさらに詳しく説明する。図
１は本実施形態の触媒組成物の説明図であり、図２は本
実施形態の触媒組成物を製造するアーク放電装置のシス
テム構成図、図３は本実施形態のカーボンナノファイバ
ーの製造方法を示す工程図である。Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. FIG. 1 is an explanatory view of the catalyst composition of the present embodiment, FIG. 2 is a system configuration diagram of an arc discharge device for producing the catalyst composition of the present embodiment, and FIG. 3 is a method for producing carbon nanofibers of the present embodiment. FIG.
【００１７】本実施形態の触媒組成物は、図１示のよう
に、触媒金属粒子１と、その周囲に分散されたカーボン
ナノファイバー２とからなり、触媒金属粒子１の表面は
炭素被覆層３により被覆されている。As shown in FIG. 1, the catalyst composition of the present embodiment is composed of catalytic metal particles 1 and carbon nanofibers 2 dispersed around the catalytic metal particles 1. Coated with
【００１８】前記触媒金属粒子１は、Ｔｉ，Ｚｒ，Ｆ
ｅ，Ｃｏ，Ｎｉ，Ｙからなる群から選択される少なくと
も１種であり、本実施形態ではＴｉ，Ｎｉ，Ｙが１：
１：１の原子比率で混合されている。前記触媒金属粒子
１は、それぞれ実質的に純物質であればよく、不可避的
不純物を含んでいてもよい。The catalyst metal particles 1 are made of Ti, Zr, F
e, Co, Ni, and Y are at least one member selected from the group consisting of Ti, Ni, and Y in the present embodiment.
They are mixed at an atomic ratio of 1: 1. The catalyst metal particles 1 may be substantially pure substances, and may contain unavoidable impurities.
【００１９】また、触媒金属粒子１は、３〜２０ｎｍの
直径を備えている。触媒金属粒子１の直径が２０ｎｍを
超えると、このような触媒金属粒子１を用いてナノ構造
炭素を生成させることが難しくなる。また、触媒金属粒
子１の直径を３ｎｍ未満とするには、特殊な装置等を必
要とし、コスト増が避けられない。The catalytic metal particles 1 have a diameter of 3 to 20 nm. When the diameter of the catalyst metal particles 1 exceeds 20 nm, it becomes difficult to generate nanostructured carbon using such catalyst metal particles 1. Further, in order to reduce the diameter of the catalyst metal particles 1 to less than 3 nm, a special device or the like is required, and an increase in cost cannot be avoided.
【００２０】前記カーボンナノファイバー２は、例え
ば、直径０．７〜５ｎｍ、長さ１０〜１０００ｎｍの範
囲にあることにより、炭素層３で被覆された触媒金属粒
子１の凝集を好適に妨げることができる。When the carbon nanofibers 2 have a diameter of, for example, 0.7 to 5 nm and a length of 10 to 1000 nm, the aggregation of the catalytic metal particles 1 covered with the carbon layer 3 can be preferably prevented. it can.
【００２１】前記触媒組成物は、例えば、図２示のよう
な構成のアーク放電装置１１を用いて製造することがで
きる。アーク放電装置１１は、開閉自在のアーク放電チ
ャンバ１２内に固定された負極１３と、負極１３に対し
て進退自在に備えられた正極（消耗電極）１４とを備
え、負極１３と正極１４とは電源装置１５に接続されて
いる。また、アーク放電チャンバ１２は、開閉弁１６を
介して図示しない真空ポンプに接続されており、開閉弁
１７を介して図示しないヘリウムガス源に接続されてい
る。尚、このようなアーク放電装置１１としては、例え
ば、特開平１１−２６３６０９号公報記載の装置等を用
いることができる。The above-mentioned catalyst composition can be produced, for example, by using an arc discharge device 11 having a structure as shown in FIG. The arc discharge device 11 includes a negative electrode 13 fixed in an openable and closable arc discharge chamber 12 and a positive electrode (consumable electrode) 14 provided to be able to move forward and backward with respect to the negative electrode 13. It is connected to the power supply 15. The arc discharge chamber 12 is connected to a vacuum pump (not shown) via an on-off valve 16 and to a helium gas source (not shown) via an on-off valve 17. In addition, as such an arc discharge device 11, for example, the device described in JP-A-11-263609 can be used.
【００２２】前記負極１３、正極１４は軸方向に沿って
中空部を備える中実円筒形状の高純度黒鉛電極であり、
前記中空部には触媒金属粒子１と黒鉛粉末との混合物が
充填されている。本実施形態では、Ｎｉ：Ｙ：Ｔｉ：黒
鉛＝１：１：１：９７の原子比率で混合した混合物を前
記中空部に充填した負極１３、正極１４を用い、０．０
５５ＭＰａのヘリウム雰囲気下、１００Ａ、３０Ｖの電
流、電圧条件で、アーク放電を行う。The negative electrode 13 and the positive electrode 14 are solid cylindrical high-purity graphite electrodes having hollow portions along the axial direction.
The hollow portion is filled with a mixture of the catalyst metal particles 1 and graphite powder. In the present embodiment, a negative electrode 13 and a positive electrode 14 are used, in which a mixture obtained by mixing Ni: Y: Ti: graphite at an atomic ratio of 1: 1: 1: 97 into the hollow portion is used.
The arc discharge is performed under a helium atmosphere of 55 MPa, under a current and voltage condition of 100 A and 30 V.
【００２３】この結果、前記アーク放電により、負極１
３、正極１４から触媒金属粒子１と炭素材料としての黒
鉛とが蒸発し、それぞれの蒸気が生成する。このとき、
アーク放電チャンバ１２内は、前記アーク放電を行って
いる負極１３、正極１４の近傍は高温であるが、負極１
３、正極１４から離れた領域は遙かに低温になってい
る。そこで、触媒金属粒子１と黒鉛との蒸気は、負極１
３、正極１４から離れると、急冷され、図１示のような
触媒組成物が生成する。前記触媒組成物は、前記アーク
放電終了後、アーク放電チャンバ１２内から回収するこ
とができる。As a result, the arc discharge causes the negative electrode 1
3. The catalyst metal particles 1 and the graphite as a carbon material evaporate from the positive electrode 14 to generate respective vapors. At this time,
In the arc discharge chamber 12, the temperature near the negative electrode 13 and the positive electrode 14 performing the arc discharge is high.
3. The region far from the positive electrode 14 is at a much lower temperature. Therefore, the vapor of the catalyst metal particles 1 and graphite is applied to the anode 1
3. When it is separated from the positive electrode 14, it is quenched to produce a catalyst composition as shown in FIG. The catalyst composition can be recovered from the arc discharge chamber 12 after the completion of the arc discharge.
【００２４】次に、図１示の触媒組成物を用いてカーボ
ンナノファイバーを製造する方法について説明する。Next, a method for producing carbon nanofibers using the catalyst composition shown in FIG. 1 will be described.
【００２５】本実施形態では、まず、前記触媒組成物を
エタノール中に投入し、該エタノールに超音波を印加す
ることにより、前記触媒組成物を十分に分散、懸濁させ
て懸濁液を調製する。次に、図３（ａ）示のように前記
懸濁液を炭素基板２１上に塗布し、乾燥することにより
エタノールを除去して、炭素基板２１上に前記触媒組成
物を配置する。前記触媒組成物は、表面が炭素被覆層３
で被覆された触媒金属粒子１間にカーボンナノファイバ
ー２が介在しているので、炭素基板２１上で触媒金属粒
子１が凝集することがない。尚、図３（ａ）では、説明
のために、触媒金属粒子１，１の間にカーボンナノファ
イバー２が１本ずつ規則正しく介在されているように図
示しているが、実際には触媒金属粒子１とカーボンナノ
ファイバー２との位置関係は不規則になっているのは言
うまでもない。In the present embodiment, first, the catalyst composition is poured into ethanol, and ultrasonic waves are applied to the ethanol to sufficiently disperse and suspend the catalyst composition to prepare a suspension. I do. Next, as shown in FIG. 3A, the suspension is applied on a carbon substrate 21 and dried to remove ethanol, and the catalyst composition is disposed on the carbon substrate 21. The catalyst composition has a carbon coating layer 3 on the surface.
Since the carbon nanofibers 2 are interposed between the catalyst metal particles 1 coated with the carbon nanotubes, the catalyst metal particles 1 do not aggregate on the carbon substrate 21. In FIG. 3A, for the sake of explanation, the carbon nanofibers 2 are regularly arranged one by one between the catalytic metal particles 1 and 1; It goes without saying that the positional relationship between 1 and the carbon nanofibers 2 is irregular.
【００２６】次に、図３（ｂ）示のように、前記触媒組
成物が配置された炭素基板２１を石英管２２内に投入す
る。そして、石英管２２に１０％の酸素を含むアルゴン
ガスを、５５０℃、１００ｃｃｍの速度で流通する。Next, as shown in FIG. 3 (b), the carbon substrate 21 on which the catalyst composition is disposed is put into a quartz tube 22. Then, an argon gas containing 10% oxygen flows through the quartz tube 22 at 550 ° C. at a speed of 100 ccm.
【００２７】前記のようにすると石英管２２内が酸化雰
囲気となり、前記触媒組成物は該酸化雰囲気に曝露され
て、カーボンナノファイバー２と炭素被覆層３とが二酸
化炭素ガスに酸化されて除去される。この結果、図３
（ｃ）示のように、炭素基板２１上には露出された触媒
金属粒子１のみが残り、しかも触媒金属粒子１は間にカ
ーボンナノファイバー２が介在していた状態のまま、凝
集することなく炭素基板２１に担持されている。As described above, the inside of the quartz tube 22 becomes an oxidizing atmosphere, the catalyst composition is exposed to the oxidizing atmosphere, and the carbon nanofibers 2 and the carbon coating layer 3 are oxidized to carbon dioxide gas and removed. You. As a result, FIG.
As shown in (c), only the exposed catalytic metal particles 1 remain on the carbon substrate 21, and the catalytic metal particles 1 are not aggregated with the carbon nanofibers 2 interposed therebetween. It is carried on a carbon substrate 21.
【００２８】そこで、次に、石英管２２に水素：メタン
＝４：１の混合ガスを、６００℃、１００ｃｃｍの速度
で流通することにより、カーボンナノファイバーを生成
せしめる。前記カーボンナノファイバーは、前記のよう
に凝集せず、離散した状態の触媒金属粒子１の上に成長
するので、触媒金属粒子１の粒子サイズに従ったカーボ
ンナノファイバーが得られる。Then, a mixed gas of hydrogen: methane = 4: 1 is passed through the quartz tube 22 at 600 ° C. at a speed of 100 ccm to generate carbon nanofibers. Since the carbon nanofibers do not aggregate as described above and grow on the catalyst metal particles 1 in a discrete state, carbon nanofibers according to the particle size of the catalyst metal particles 1 are obtained.
【００２９】本実施形態の製造方法によれば、得られた
カーボンナノファイバーは、前記触媒金属粒子１以外の
不純物を含んでいないので、触媒金属粒子１を常法によ
り除去することにより、容易に高純度化することができ
る。According to the manufacturing method of the present embodiment, the obtained carbon nanofibers do not contain impurities other than the catalyst metal particles 1, so that the catalyst metal particles 1 are easily removed by removing the catalyst metal particles 1 by a conventional method. It can be highly purified.
【００３０】尚、本実施形態では、前記触媒組成物を生
成させるために、触媒金属粒子１と炭素材料との蒸発を
アーク放電により行っているが、レーザー、プラズマ等
を熱源として蒸発させるようにしてもよい。In the present embodiment, the catalyst metal particles 1 and the carbon material are evaporated by arc discharge in order to form the catalyst composition. However, the catalyst metal particles 1 and the carbon material are evaporated using a laser, plasma or the like as a heat source. You may.
【図１】本実施形態の触媒組成物の説明図。FIG. 1 is an explanatory diagram of a catalyst composition of the present embodiment.
【図２】本実施形態の触媒組成物を製造するアーク放電
装置のシステム構成図。FIG. 2 is a system configuration diagram of an arc discharge device for producing the catalyst composition of the present embodiment.
【図３】本実施形態のカーボンナノファイバーの製造方
法を示す工程図。FIG. 3 is a process chart showing a method for producing a carbon nanofiber of the present embodiment.
１…触媒金属粒子、 ２…ナノ構造炭素、 ３…炭素被
覆層、 ２１…炭素基板。DESCRIPTION OF SYMBOLS 1 ... Catalyst metal particle, 2 ... Nano structure carbon, 3 ... Carbon coating layer, 21 ... Carbon substrate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤原 良也 埼玉県和光市中央１丁目４番１号 株式会 社本田技術研究所内 (72)発明者 徳根 敏生 埼玉県和光市中央１丁目４番１号 株式会 社本田技術研究所内 Ｆターム(参考） 4G069 AA02 AA08 BA08A BA08B BB02A BB02B BC40A BC40B BC50A BC50B BC51A BC66A BC67A BC68A BC68B CB81 DA05 EB19 EC28 EC30 FA01 FB31 FB37 FB58 4L037 AT01 CS03 FA20 PA02 PA11 UA20 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiya Fujiwara 1-4-1 Chuo, Wako-shi, Saitama Prefecture Inside Honda R & D Co., Ltd. (72) Inventor Toshio Tokune 1-4-4 Chuo, Wako-shi, Saitama No. 1 F-term in Honda R & D Co., Ltd. (Reference) 4G069 AA02 AA08 BA08A BA08B BB02A BB02B BC40A BC40B BC50A BC50B BC51A BC66A BC67A BC68A BC68B CB81 DA05 EB19 EC28 EC30 FA01 FB31 FB37 PA02 PA01 AT02
Claims (6)
の触媒金属粒子と、該触媒金属粒子の周囲に分散されて
該触媒金属粒子の凝集を妨げるナノ構造炭素とからなる
ことを特徴とする触媒組成物。1. The diameter is 3 to 20 nm, the surface of which is coated with carbon.
And a nanostructured carbon dispersed around the catalytic metal particles to prevent aggregation of the catalytic metal particles.
Ｃｏ，Ｎｉ，Ｙからなる群から選択される少なくとも１
種の金属粒子であることを特徴とする請求項１記載の触
媒組成物。2. The catalyst metal particles include Ti, Zr, Fe,
At least one selected from the group consisting of Co, Ni, Y
The catalyst composition according to claim 1, wherein the catalyst composition is a seed metal particle.
バーであることを特徴とする請求項１または請求項２記
載の触媒組成物。3. The catalyst composition according to claim 1, wherein the nanostructured carbon is a carbon nanofiber.
後、蒸発した触媒金属と炭素材料との蒸気を急冷するこ
とにより、表面が炭素で被覆された直径３〜２０ｎｍの
触媒金属粒子と、該触媒金属粒子の周囲に分散されて該
触媒金属粒子の凝集を妨げるナノ構造炭素とからなる触
媒組成物を生成させることを特徴とする触媒組成物の製
造方法。4. After evaporating the catalyst metal and the carbon material together, the vapor of the evaporated catalyst metal and the carbon material is quenched to form catalyst metal particles having a surface coated with carbon and having a diameter of 3 to 20 nm. Producing a catalyst composition comprising nanostructured carbon dispersed around the catalyst metal particles and preventing aggregation of the catalyst metal particles.
ての黒鉛粉末とを混合してなる電極を用いてアーク放電
を行うことにより、該触媒金属と該炭素材料とを共に蒸
発させることを特徴とする請求項４記載の触媒組成物の
製造方法。5. An arc discharge using an electrode obtained by mixing the catalyst metal powder and the graphite powder as a carbon material, thereby evaporating the catalyst metal and the carbon material together. A method for producing a catalyst composition according to claim 4, characterized in that:
の触媒金属粒子と、該触媒金属粒子の周囲に分散されて
該触媒金属粒子の凝集を妨げるナノ構造炭素とからなる
触媒組成物を炭素基板上に配置する工程と、 前記炭素基板上に配置された前記触媒組成物を酸化雰囲
気に曝露し、前記触媒金属粒子の表面を被覆している炭
素と、前記ナノ構造炭素とを酸化して除去することによ
り該触媒金属粒子を分散した状態で該炭素基板上に担持
せしめる工程と、 前記触媒金属粒子を担持している炭素基板上に、水素と
炭化水素との混合ガスを流通することにより、カーボン
ナノファイバーを生成せしめる工程とを備えることを特
徴とするカーボンナノファイバーの製造方法。6. A diameter of 3 to 20 nm, the surface of which is coated with carbon.
Disposing a catalyst composition comprising catalyst metal particles of the following structure and nanostructured carbon dispersed around the catalyst metal particles to prevent aggregation of the catalyst metal particles on a carbon substrate, and disposing the catalyst composition on the carbon substrate. The catalyst composition is exposed to an oxidizing atmosphere, and the carbon coating the surface of the catalyst metal particles and the nanostructured carbon are oxidized and removed to remove the carbon in a state where the catalyst metal particles are dispersed. A step of causing a carbon nanofiber to be generated by flowing a mixed gas of hydrogen and a hydrocarbon on a carbon substrate supporting the catalytic metal particles. Of producing carbon nanofibers.
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| JP2001069808A JP2002263496A (en) | 2001-03-13 | 2001-03-13 | Catalyst composition, manufacturing method thereof and method of manufacturing carbon nanofiber |
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