JP3616819B2 - Method for producing boron / carbon / nitrogen nanotubes - Google Patents
Method for producing boron / carbon / nitrogen nanotubes Download PDFInfo
- Publication number
- JP3616819B2 JP3616819B2 JP2002331409A JP2002331409A JP3616819B2 JP 3616819 B2 JP3616819 B2 JP 3616819B2 JP 2002331409 A JP2002331409 A JP 2002331409A JP 2002331409 A JP2002331409 A JP 2002331409A JP 3616819 B2 JP3616819 B2 JP 3616819B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- nitrogen
- nanotubes
- boron
- bcn
- 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
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
この出願の発明は、ホウ素・炭素・窒素ナノチューブの製造方法に関するものである。さらに詳しくは、この出願の発明は、実用に適用できる有用な特性と容易に変容しない安定した物性を有し、安価で大量に提供できるホウ素・炭素・窒素ナノチューブの製造方法に関するものである。
【０００２】
【従来の技術】
カーボンナノチューブの発見以来、窒化ホウ素ナノチューブ、炭化ホウ素ナノチューブ、ホウ素・炭素・窒素（ＢＣＮ）ナノチューブ等の多元素系のナノチューブの研究に多大な関心が寄せられるようになってきた。最近では、これらのナノチューブの中にモリブデン、鉄−ニッケル、銅などの金属を内含させてもいる。
【０００３】
以上の多元素系ナノチューブは、絶縁性、化学的安定性、耐酸化性、耐食性等に優れているため、ナノスケールの電子デバイスやナノ構造のセラミック材料として用いられることが期待されている。しかしながら、現状では、実用に適した安定した物質を安価に、大量に提供できる段階に至ってはいない。このため、実用に適用可能な有用な特性と安定した物性を有し、安価で大量に、ホウ素・炭素・窒素を構成元素とするナノチューブを提供する方法が望まれている（たとえば、特許文献１参照）。
【０００４】
【特許文献１】
特開平０７−１８７８８３号公報
【０００５】
【発明が解決しようとする課題】
この出願の発明は、上記のとおりの事情に鑑みてなされたものであり、実用に適用でき
る有用な特性と容易に変容しない安定した物性を有し、安価で大量に提供できるホウ素・炭素・窒素ナノチューブの製造方法を提供することを解決すべき課題としている。
【０００６】
【課題を解決するための手段】
この出願の発明は、上記の課題を解決するものとして、構成元素がホウ素、炭素及び窒素であるナノチューブであり、ナノチューブの長さ方向に構成元素比率が異なっているホウ素・炭素・窒素ナノチューブの製造方法であって、鉄のナノ粒子を保持したアルミナを触媒とし、（ＣＨ 3 ） 2 ＮＨ・ＢＨ 3 を窒素気流中で横型調整炉を用いて１０００℃〜１２００℃の温度域に加熱し、熱分解反応させることを特徴とするホウ素・炭素・窒素ナノチューブの製造方法を提供する。
【０００７】
【発明の実施の形態】
この出願の発明のホウ素・炭素・窒素（ＢＣＮ）ナノチューブは、以下の二つの方法で製造する。
［１］硝酸第二鉄の水溶液に窒素ガスを吹き込み、流動しているカーボンブラックの中に導入し、１３００℃〜１５００℃の温度域で一酸化炭素を発生させる。次いで、窒素及び一酸化炭素を含む気体を垂直式誘導炉に導入し、先駆物質であるＢ4Ｎ3Ｏ2Ｈを１６００℃〜１８００℃の温度域で分解させて気体状の酸化ホウ素を生成させる。上記温度域は、最適反応温度の常識的な変動幅であり、すなわち、１４００℃±１００℃であり、１７００℃±１００℃である。そして、引き続き、窒素及び一酸化炭素の雰囲気中において硝酸第二鉄を触媒として還元させることにより、長さ方向に構成元素比率が異なる若しくは中心から半径方向に構成元素比率の異なる層が積層したホウ素・炭素・窒素（ＢＣＮ）ナノチューブが得られる。さらに鉄が充填された上記のホウ素・炭素・窒素（ＢＣＮ）ナノチューブが得られる。
［２］先駆物質（ＣＨ3）2ＮＨ・ＢＨ3に、鉄のナノ粒子を保持したアルミナを触媒として作用させ、窒素ガス雰囲気下で横型調整炉中において１０００℃〜１２００℃の温度域に加熱し、熱分解反応させることにより長さ方向に構成元素比率が異なるホウ素・炭素・窒素（ＢＣＮ）ナノチューブが得られる。上記温度域も最適反応温度の常識的な変動幅であり、すなわち、１１００℃±１００℃である。
【０００８】
ホウ素・炭素・窒素（ＢＣＮ）ナノチューブは、透過型電子顕微鏡を用いて観察することにより、内部に中空部分を有するナノチューブ構造であり、内部に鉄が充填されている部分が存在することが確認される。また、ナノチューブの中空部分はナノチューブの長さ方向に貫通していなく、仕切られた区画室が形成されていることが確認される。一本のナノチューブの中に長い区画室と短い区画室が存在する。電子エネルギー損失スペクトル分析の結果から、長い区画室の成分組成は窒化ホウ素（ＢＮ）が多く、短い区画室の成分組成は炭素（Ｃ）が多いことが確認される。一方、鉄が充填されているホウ素・炭素・窒素（ＢＣＮ）ナノチューブは、中心から半径方向に構成元素の比率が異なり、最外層は窒化ホウ素（ＢＮ）の含有量が多い層であり、内側の層は炭素（Ｃ）の含有量が多い層である。
【０００９】
（ＣＨ3）2ＮＨ・ＢＨ3を先駆物質に用いて合成したホウ素・炭素・窒素（ＢＣＮ）ナノチューブについて走査型電子顕微鏡で観察すると、ナノチューブが絡み合って屈曲し、コイル状となっていることが確認される。
【００１０】
いずれのホウ素・炭素・窒素（ＢＣＮ）ナノチューブも大量に製造され、しかも上記のとおり方法により製造されるため、安価となる。
【００１１】
【実施例】
（実施例１）
硝酸第二鉄の０．０５モル水溶液に窒素ガスを吹き込み、流動しているカーボンブラックの中に移送し、約１４００℃に加熱して一酸化炭素ガスを生成させた。その後、一酸化炭素ガス及び窒素ガスを垂直式誘導炉に導入し、Ｂ4Ｎ3Ｏ2Ｈを１７００℃で分解させて気体状の酸化ホウ素を発生させるとともに、一酸化炭素ガス及び窒素ガスにより還元してホウ素・炭素・窒素（ＢＣＮ）ナノチューブおよび鉄が充填されたホウ素・炭素・窒素（ＢＣＮ）ナノチューブを大量に得た。
【００１２】
図１＜ａ＞＜ｂ＞は、それぞれ、上記のホウ素・炭素・窒素（ＢＣＮ）ナノチューブを透過型電子顕微鏡で観察した顕微鏡像である。中空部分を有するナノチューブ構造であることが確認される。顕微鏡像で暗く写っている部分に鉄が充填されている。また、図１＜ｂ＞に示したように、ナノチューブの中空部分は、ナノチューブの長さ方向に貫通していなく、区画室で仕切られている。より詳しく観察すると、図２＜ａ＞＜ｂ＞に示したように、一本のナノチューブの中に長い区画室と短い区画室が存在していることが確認される。
【００１３】
それぞれの区画室について電子エネルギー損失スペクトルを測定したところ、長い区画室は窒化ホウ素（ＢＮ）の多い組成であり、短い区画室は炭素（Ｃ）の多い組成である。また、電子エネルギー損失スペクトルの測定結果から、鉄が充填されているホウ素・炭素・窒素（ＢＣＮ）ナノチューブは、中心から半径方向に構成元素の比率が異なり、最外層は窒化ホウ素（ＢＮ）の含有量が多く、内側の層は炭素（Ｃ）が多い。
【００１４】
（実施例２）
鉄のナノ粒子を保持したアルミナを触媒として、先駆物質である（ＣＨ3）2ＮＨ・ＢＨ3を窒素ガス気流中で横型調整炉を用いて１０５０℃に加熱し、熱分解反応を生起させ、ホウ素・炭素・窒素（ＢＣＮ）ナノチューブを得た。
【００１５】
図３＜ａ＞＜ｂ＞は、それぞれ、得られたホウ素・炭素・窒素（ＢＣＮ）ナノチューブを走査型電子顕微鏡を用いて観察した顕微鏡像である。ホウ素・炭素・窒素（ＢＣＮ）ナノチューブが絡み合って屈曲し、コイル状の形態になり、大量に得られている。
【００１６】
もちろんこの出願の発明は、以上の実施形態及び実施例により限定されるものではない。細部については様々な態様が可能である。
【００１７】
【発明の効果】
以上詳しく説明したとおり、この出願の発明によって、構成元素がホウ素、炭素、窒素であるナノチューブであり、ナノチューブの長さ方向に構成元素比率が異なる特殊な形態をした、実用に適用できる有用な特性と容易に変容しない安定した物性を有するナノチューブを、安価に大量に提供することができる。
【図面の簡単な説明】
【図１】＜ａ＞＜ｂ＞は、それぞれ、実施例１で得られたホウ素・炭素・窒素ナノチューブの透過型電子顕微鏡像である。
【図２】＜ａ＞＜ｂ＞は、それぞれ、実施例１で得られたホウ素・炭素・窒素ナノチューブの透過型電子顕微鏡像である。
【図３】＜ａ＞＜ｂ＞は、それぞれ、実施例２で得られたホウ素・炭素・窒素ナノチューブの走査型電子顕微鏡像である。[0001]
BACKGROUND OF THE INVENTION
The invention of this application relates to a method for producing boron / carbon / nitrogen nanotubes . More specifically, the invention of this application relates to a method for producing boron, carbon, and nitrogen nanotubes that have useful properties applicable to practical use and stable physical properties that do not easily change, and that can be provided in large quantities at low cost.
[0002]
[Prior art]
Since the discovery of carbon nanotubes, there has been a great deal of interest in research on multi-element nanotubes such as boron nitride nanotubes, boron carbide nanotubes, and boron / carbon / nitrogen (BCN) nanotubes. Recently, metals such as molybdenum, iron-nickel, and copper are included in these nanotubes.
[0003]
The multi-element nanotubes described above are excellent in insulation, chemical stability, oxidation resistance, corrosion resistance, and the like, and thus are expected to be used as nanoscale electronic devices and nanostructure ceramic materials. However, at present, the stage has not yet reached a stage where stable materials suitable for practical use can be provided in large quantities at low cost. For this reason, there is a demand for a method of providing nanotubes having useful characteristics applicable to practical use and stable physical properties, and having boron, carbon, and nitrogen as constituent elements in large quantities at low cost (for example, Patent Document 1). reference).
[0004]
[Patent Document 1]
Japanese Patent Laid-Open No. 07-187883
[Problems to be solved by the invention]
The invention of this application has been made in view of the circumstances as described above, and has boron, carbon, and nitrogen that have useful properties applicable to practical use and stable physical properties that do not easily change, and can be provided in large quantities at low cost. Providing a method for producing a nanotube is an issue to be solved.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the invention of this application is a nanotube in which constituent elements are boron, carbon, and nitrogen, and manufacture of boron / carbon / nitrogen nanotubes in which constituent element ratios are different in the length direction of the nanotube In this method, alumina containing iron nanoparticles is used as a catalyst, and (CH 3 ) 2 NH · BH 3 is heated to a temperature range of 1000 ° C. to 1200 ° C. using a horizontal adjustment furnace in a nitrogen stream. Provided is a method for producing boron, carbon, and nitrogen nanotubes, characterized by causing a decomposition reaction.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The boron-carbon-nitrogen (BCN) nanotube of the invention of this application is produced by the following two methods.
[1] Nitrogen gas is blown into an aqueous solution of ferric nitrate and introduced into flowing carbon black to generate carbon monoxide in a temperature range of 1300 ° C to 1500 ° C. Next, a gas containing nitrogen and carbon monoxide is introduced into a vertical induction furnace, and the precursor B 4 N 3 O 2 H is decomposed in a temperature range of 1600 ° C. to 1800 ° C. to generate gaseous boron oxide. Let The above temperature range is a common-sense fluctuation range of the optimum reaction temperature, that is, 1400 ° C. ± 100 ° C. and 1700 ° C. ± 100 ° C. Subsequently, boron in which layers of different constituent element ratios in the length direction or different constituent element ratios from the center in the radial direction are laminated by reducing ferric nitrate as a catalyst in an atmosphere of nitrogen and carbon monoxide. Carbon / nitrogen (BCN) nanotubes are obtained. Further, the boron-carbon-nitrogen (BCN) nanotubes filled with iron are obtained.
[2] Precursor (CH 3 ) 2 NH · BH 3 is allowed to act as a catalyst with alumina holding iron nanoparticles, and heated in a horizontal adjustment furnace to a temperature range of 1000 ° C. to 1200 ° C. in a nitrogen gas atmosphere. Then, boron / carbon / nitrogen (BCN) nanotubes having different constituent element ratios in the length direction can be obtained by thermal decomposition reaction. The above temperature range is also a common-sense fluctuation range of the optimum reaction temperature, that is, 1100 ° C. ± 100 ° C.
[0008]
Boron / carbon / nitrogen (BCN) nanotubes are observed with a transmission electron microscope and have a nanotube structure with a hollow portion inside, and it is confirmed that there is a portion filled with iron inside. The Further, it is confirmed that the hollow portion of the nanotube does not penetrate in the length direction of the nanotube, and a partitioned compartment is formed. There are long and short compartments within a single nanotube. From the result of the electron energy loss spectrum analysis, it is confirmed that the component composition of the long compartment is rich in boron nitride (BN), and the component composition of the short compartment is rich in carbon (C). On the other hand, boron-carbon-nitrogen (BCN) nanotubes filled with iron have different constituent element ratios in the radial direction from the center, and the outermost layer is a layer containing a large amount of boron nitride (BN). The layer is a layer having a high carbon (C) content.
[0009]
Boron / carbon / nitrogen (BCN) nanotubes synthesized using (CH 3 ) 2 NH · BH 3 as a precursor are observed with a scanning electron microscope, and the nanotubes are intertwined and bent to form a coil. It is confirmed.
[0010]
Any boron / carbon / nitrogen (BCN) nanotubes are produced in large quantities and are produced by the method as described above, so that the cost is low.
[0011]
【Example】
(Example 1)
Nitrogen gas was blown into a 0.05 molar aqueous solution of ferric nitrate, transferred into flowing carbon black, and heated to about 1400 ° C. to generate carbon monoxide gas. After that, carbon monoxide gas and nitrogen gas are introduced into the vertical induction furnace, B 4 N 3 O 2 H is decomposed at 1700 ° C. to generate gaseous boron oxide, and carbon monoxide gas and nitrogen gas are used. Reduction was performed to obtain a large amount of boron / carbon / nitrogen (BCN) nanotubes and boron / carbon / nitrogen (BCN) nanotubes filled with iron.
[0012]
FIG. 1 <a> and <b> are microscopic images obtained by observing the boron, carbon, and nitrogen (BCN) nanotubes with a transmission electron microscope, respectively. It is confirmed that the nanotube structure has a hollow portion. The portion of the microscopic image that is dark is filled with iron. Further, as shown in FIG. 1 <b>, the hollow portion of the nanotube does not penetrate in the length direction of the nanotube, and is partitioned by the compartment. When observed in more detail, as shown in FIGS. 2 <a><b>, it is confirmed that a long compartment and a short compartment exist in one nanotube.
[0013]
When the electron energy loss spectrum was measured for each of the compartments, the long compartment has a high boron nitride (BN) composition, and the short compartment has a carbon (C) rich composition. In addition, from the measurement results of the electron energy loss spectrum, boron-carbon-nitrogen (BCN) nanotubes filled with iron have different constituent element ratios in the radial direction from the center, and the outermost layer contains boron nitride (BN). The amount is large and the inner layer is rich in carbon (C).
[0014]
(Example 2)
Using alumina holding iron nanoparticles as a catalyst, the precursor (CH 3 ) 2 NH · BH 3 is heated to 1050 ° C. in a nitrogen gas stream using a horizontal adjustment furnace to cause a thermal decomposition reaction, Boron / carbon / nitrogen (BCN) nanotubes were obtained.
[0015]
FIGS. 3 <a> and <b> are microscopic images obtained by observing the obtained boron / carbon / nitrogen (BCN) nanotubes using a scanning electron microscope. Boron / carbon / nitrogen (BCN) nanotubes are intertwined and bent to form a coiled shape and are obtained in large quantities.
[0016]
Of course, the invention of this application is not limited by the above embodiments and examples. Various details are possible for the details.
[0017]
【The invention's effect】
As described above in detail, according to the invention of this application, it is a nanotube whose constituent elements are boron, carbon, and nitrogen, and has a special form in which the constituent element ratio is different in the length direction of the nanotube. Nanotubes having stable physical properties that are not easily transformed can be provided in large quantities at a low cost.
[Brief description of the drawings]
1 is a transmission electron microscope image of boron, carbon, and nitrogen nanotubes obtained in Example 1, respectively.
<a><b> are transmission electron microscope images of boron, carbon, and nitrogen nanotubes obtained in Example 1, respectively.
3 is a scanning electron microscope image of boron, carbon, and nitrogen nanotubes obtained in Example 2, respectively.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002331409A JP3616819B2 (en) | 2002-11-14 | 2002-11-14 | Method for producing boron / carbon / nitrogen nanotubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002331409A JP3616819B2 (en) | 2002-11-14 | 2002-11-14 | Method for producing boron / carbon / nitrogen nanotubes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004161571A JP2004161571A (en) | 2004-06-10 |
| JP3616819B2 true JP3616819B2 (en) | 2005-02-02 |
Family
ID=32808773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002331409A Expired - Lifetime JP3616819B2 (en) | 2002-11-14 | 2002-11-14 | Method for producing boron / carbon / nitrogen nanotubes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3616819B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006103996A (en) * | 2004-10-01 | 2006-04-20 | National Institute For Materials Science | Nitrogen atom-containing carbon nanotube and method for manufacturing the same |
| CN100390046C (en) * | 2004-12-17 | 2008-05-28 | 清华大学 | Synthesis method of iron nanotube array |
| JP5448067B2 (en) * | 2009-12-09 | 2014-03-19 | 独立行政法人物質・材料研究機構 | Method for producing boron nitride nanotubes |
| CN114146719B (en) * | 2021-11-22 | 2023-10-24 | 武汉科技大学 | Carbon plate-non-split-phase boron carbon nitrogen in-plane heterostructure and preparation method thereof |
| CN113976163A (en) * | 2021-11-22 | 2022-01-28 | 武汉科技大学 | Non-heterogeneous boron-carbon-nitrogen photocatalytic material and preparation method thereof |
-
2002
- 2002-11-14 JP JP2002331409A patent/JP3616819B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004161571A (en) | 2004-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vakifahmetoglu et al. | Growth of one‐dimensional nanostructures in porous polymer‐derived ceramics by catalyst‐assisted pyrolysis. Part I: iron catalyst | |
| Deepak et al. | Boron nitride nanotubes and nanowires | |
| Bystrzejewski et al. | Continuous synthesis of carbon-encapsulated magnetic nanoparticles with a minimum production of amorphous carbon | |
| Wang et al. | Inorganic polymer-derived tubular SiC arrays from sacrificial alumina templates | |
| EP3708535A1 (en) | Method of manufacturing mos2 having 1t crystal structure | |
| JP3616819B2 (en) | Method for producing boron / carbon / nitrogen nanotubes | |
| Li et al. | Synthesis of boron nitride nanotubes, bamboos and nanowires | |
| Han | Anisotropic Hexagonal Boron Nitride Nanomaterials-Synthesis and Applications | |
| Jeong et al. | Preparation of conductive Si/C/N/Ni ceramic nanocomposites using phenyl-substituted polysilazane and nickelocene as precursors | |
| Zhong et al. | Novel coaxial SiC–SiO2–BN nanocable: large-scale synthesis, formation mechanism and photoluminescence property | |
| JP2004231455A (en) | Manufacturing method of boron nitride nanotube | |
| JP2002097004A (en) | Method for manufacturing boron nitride nanotube by using oxide catalyst | |
| JP2000281323A (en) | Production of carbon nanotube containing boron | |
| KR100593268B1 (en) | A manufacturing process of Fe nano powder with carbide coating by Chemical Vapor Condensation | |
| JP3496050B2 (en) | Method for producing hollow particles of fullerene-like boron nitride | |
| Bai et al. | Controlling the catalytic synthesis of SiC nanowires, carbon nanotubes, and graphene from a multilayer film precursor | |
| JP3616818B2 (en) | Method for producing ternary nanotube comprising boron-carbon-nitrogen atoms | |
| Guo et al. | Solvothermal synthesis of Si3N4 nanomaterials at a low temperature | |
| JP4000371B2 (en) | Silicon nitride (Si3N4) nanorods and manufacturing method thereof | |
| Chesnokov et al. | Effect of the carbon nanomaterials structure on silica carbothermal reduction | |
| JP3658622B2 (en) | Method for producing boron carbide nanowire | |
| JP2004182547A (en) | Galium oxide nanowire and its manufacturing method | |
| Wang et al. | Synthesis and carbothermal nitridation mechanism of ultra-long single crystal α-Si3N4 nanobelts | |
| JP3834661B2 (en) | Method for producing silicon carbide-silicon dioxide-carbon coaxial nanocable and nanochain in which silicon carbide nanorods and carbon nanotubes are alternately joined at the tips | |
| TWI290910B (en) | Method for producing alpha-Fe2O3 nanomaterials and the product made therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040713 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040907 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20041012 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 3616819 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| 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 |