JP2004189547A - Boron nitride (bn) nanotube as material for hydrogen storage, and production method thereof - Google Patents
Boron nitride (bn) nanotube as material for hydrogen storage, and production method thereof Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
この出願の発明は水素吸蔵用窒化ホウ素ナノチューブとその製造方法に関するものである。さらに詳細には、この出願の発明は、燃焼後の最終生成物が水だけであり、環境に対してクリーンで、人類にも全く悪い影響を及ぼさないエネルギー源である水素を効率よく吸着し、軽量で、しかも物質自体にも毒性の認められない、新しい窒化ホウ素ナノチューブとその製造方法に関するものである。
【０００２】
【従来の技術】
従来より、軽量で、有効な水素貯蔵用材料として、カーボンナノチューブが知られている。特に１層の壁で構成されている、つまり単層の、電気的に半導体の性質を有するカーボンナノチューブが有効であると言われている（文献１〜４）。
【０００３】
しかしながら、カーボンナノチューブは、その直径の大きさ、または捩れの存在の仕方で、金属的な性質を有したり、半導体的な性質を有したりすることがわかっている。また、カーボンナノチューブの製造には、触媒として種々の金属が使用される。このようなカーボンナノチューブの形状の違いとこれによる性質の相違により、また製造時の触媒金属の混入等により、水素貯蔵量が影響を受けることになる。だが、それにもかかわらず、現状ではその形状等を制御することは困難である。
【０００４】
さらにまた、現状では、水素吸蔵に有効な、壁が１層のみからなるカーボンナノチューブを他の生成物から分離することは困難である。このため、カーボンナノチューブの水素貯蔵性能については報告や研究発表によるばらつきが大きいのが現状である。
【０００５】
【文献】
１：Nature 1997, 386, 377
２：J.Phys.Chem., B 1998, 102, 4253
３：Science 1999, 286, 1127
４：Carbon 2001, 39, 1447
【０００６】
【発明が解決しようとする課題】
そこで、この出願の発明は上記の課題を解決するものとして、直径の大きさや捩れ等の存在によって、電気的な性質等が影響を受けず、触媒金属の残存による影響もなく、安定に水素を吸蔵することができ、しかもその製造が容易であって、軽量で、環境または人体への影響が殆ど無い、新しいナノチューブ構造体を提供することを課題としている。
【０００７】
【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、第１には、水素吸蔵量が、１０ＭＰａ、室温で、１．５重量％以上であり、直径が５〜５０ｎｍ、長さが１〜２０μｍの多層壁窒化ホウ素ナノチューブを提供する。
【０００８】
また、この出願の発明は、第２には、化学組成がＢ4Ｎ3Ｏ2Ｈである前駆体をＮ2とＮＨ3の混合ガス気流中で、１６００℃以上の温度で熱分解させることによる、水素吸蔵用材料としての多層壁窒化ホウ素ナノチューブの製造方法を提供する。
【０００９】
第３には、化学組成がＣ3Ｎ6Ｈ6であるメラミンと、化学組成がＨ3ＢＯ3であるホウ酸を１：２もしくはその近傍のモル比に混合し、空気中で４００℃〜５５０℃で加熱処理した後、得られた粉末を窒素中、７５０℃〜８５０℃で加熱処理することを特徴とする、多層壁窒化ホウ素ナノチューブを製造するための前駆体であるＢ4Ｎ3Ｏ2Ｈを得る方法を提供する。
【００１０】
またこの出願の発明は、第４には、室温での水素吸蔵量が、２ＭＰａで、０．７重量％、また１０ＭＰａで２．５重量％以上であり、直径が１０〜１００ｎｍ、長さが５０〜３００ｎｍのナノベル型の形態を有する窒化ホウ素ナノチューブが、５〜２０μｍの長さに繋がった竹の子状窒化ホウ素ナノチューブを提供する。
【００１１】
第５には、この出願の発明は、酸素含有量が１０〜２０％の窒化ホウ素粉末を、Ｎ2とＮＨ3の混合ガス気流中で、１６００℃以上の温度で熱分解させることを特徴とする水素吸蔵用材料としての竹の子状窒化ホウ素ナノチューブの製造方法を提供する。
【００１２】
【発明の実施の形態】
この出願の発明は、上記のとおりの特徴を有するものであるが、多層型または竹の子型の窒化ホウ素ナノチューブで、これらに有効な水素吸蔵効果のあることは、この出願の発明によってはじめて確認されたことである。同じように水素吸蔵効果が期待されているカーボンナノチューブに比較し、窒化ホウ素ナノチューブは形態から受ける影響が少ないことも確認されている。
【００１３】
この出願の発明では、カーボンナノチューブに比べて、形態の制御が容易な水素吸蔵材料としての、窒化ホウ素ナノチューブを２種類の形態のものとして提供する。一つは、たとえば図１に示すことのできる、直線状の形態で、多層壁構成からなるものであり、他は、たとえば図２に示すことのできる、ナノベルと呼ばれる特異な形状のものが繋がって、全体としては長い竹の子状になった水素吸蔵用窒化ホウ素ナノチューブである。
【００１４】
直線状の形態で、多層型の構成の窒化ホウ素ナノチューブについては、水素吸蔵量が１０ＭＰａ、室温で、１．５重量％以上であるという特性として規定することができるが、さらには、２ＭＰａ、室温で０．５重量％以上であることが好適である。そして、このものは、直径が５〜５０ｎｍ、長さ１〜２０μｍの範囲のものである。
【００１５】
このような直線状で多層壁構成の窒化ホウ素ナノチューブは、好適には、たとえば次のようなこの出願の発明の方法によって製造することができる。すなわち、まず、化学組成がＣ3Ｎ6Ｈ6であるメラミンと、化学組成がＨ3ＢＯ4であるホウ酸を１：２もしくはその近傍（±１０％の許容範囲）のモル比に混合し、空気中で４００℃から５５０℃で好適には３〜４時間加熱処理して、２ホウ酸メラミン（Ｃ3Ｎ6Ｈ6・２Ｈ3ＢＯ4）を得た後、この粉末を窒素中、７５０℃から８５０℃で好適には１〜２時間、加熱処理することで、非晶質の前駆体であるＢ4Ｎ3Ｏ2Ｈを製造する。
【００１６】
この前駆体である非晶質のＢ4Ｎ3Ｏ2Ｈには、ＢＮ結合がフレームとして存在し、酸素が２０〜３０重量％の割合で存在している。
【００１７】
次いで、この前駆体を１６００℃以上で、Ｎ2とＮＨ3の混合ガス気流中で熱分解する。この熱分解によって、Ｂ−Ｎ−Ｏからなる液状の非晶質体を介して、直線状の多層壁窒化ホウ素ナノチューブが生成する。この場合のナノチューブはチューブの両端にキャップを被っている。
【００１８】
またこの出願の発明は、前記のとおりの竹の子状窒化ホウ素ナノチューブも提供するものであるが、このものは、好適にはたとえば、酸素を１０〜２０％含有した窒化ホウ素粒子を、Ｎ2とＮＨ3の混合ガス気流中、１６００℃以上の温度で熱分解することによって製造することができる。ナノベル型のチューブが生成し、それらがベルの軸方向に繋がって、数ミクロンの長さになった竹の子状窒化ホウ素ナノチューブとなる。
【００１９】
水素吸蔵用カーボンナノチューブで報告されている結果との比較から、この竹の子状窒化ホウ素ナノチューブにおいても、単層の壁からなり、両端にキャップの無いナノチューブが、水素吸蔵にはより有効であると類推できる。
【００２０】
そこで以下に実施例を示し、さらに詳しく説明する。
【００２１】
もちろん以下の例により発明が限定されることはない。
【００２２】
【実施例】
次に実施例により、さらに詳しくこの発明について説明する。
＜実施例１＞
化学組成がＣ3Ｎ6Ｈ6であるメラミンと、化学組成がＨ3ＢＯ4であるホウ酸を１：２のモル比に混合し、空気中、５００℃で３時間加熱処理して２ホウ酸メラミン（Ｃ3Ｎ6Ｈ6・２Ｈ3ＢＯ4）を得た後、この粉末に対し窒素中、８００℃で１時間の加熱処理を行った。この加熱処理により非晶質のＢ4Ｎ3Ｏ2Ｈを得た。
【００２３】
次に、得られたＢ4Ｎ3Ｏ2Ｈ粉末を前駆体として、カーボン坩堝に入れ、それを筒状のカーボン発熱体中に設置し、１ｌ／ｍｉｎの窒素気流中で、縦型誘導加熱装置を用いて、１７００℃、２時間加熱処理を行った。
【００２４】
得られた試料を透過電子顕微鏡で観察した。図１は、多層壁窒化ホウ素ナノチューブ(multi-wall tube)で、直径が１０〜３０ｎｍ、長さは数μｍ、長さ方向の両端にキャップを被っている。
＜実施例２＞
また酸素を１０〜２０％含有した窒化ホウ素粒子に対し、Ｎ2とＮＨ3の混合ガス気流中、１６００℃以上の温度で２時間加熱処理を行った。
【００２５】
得られた試料を透過電子顕微鏡で観察した。図２は、直径が１０〜８０ｎｍのナノベル型の窒化ホウ素が軸方向に１０μｍ以上の長さに繋がった、竹の子状窒化ホウ素ナノチューブ(bamboo tube)を示している。
＜水素吸蔵特性＞
これら実施例１および実施例２の試料の水素吸蔵量をＣａｈｎ Ｄ１１０型の熱天秤を用いて、室温、水素気流中で測定した結果を図３に示した。比較のために、株式会社電化製の粒径が１０〜２０μｍの窒化ホウ素微粒子(bulk powder)の水素吸蔵測定結果も同じ図の中に示した。図３は横軸に水素を吸蔵させたときの水素の圧力、縦軸に試料の重量の増加分を示している。この図３からわかるように、窒化ホウ素ナノチューブの水素吸蔵量は、窒化ホウ素微粒子の水素吸蔵量に比べて、はるかに大きい。また図３でmodel tubeとして示した多層壁ナノチューブに比べ、図３でbamboo tubeとして示した、ナノベルを単位とした、竹の子型のナノチューブの方が、約１．５倍程度、多くの水素を吸蔵した結果が得られた。
【００２６】
【発明の効果】
以上詳しく説明したとおり、この出願の発明では、クリーンで、何処にでも存在するエネルギー源であり、その利用後の排出物としては水だけであることから、その実用化が非常に期待されている水素の吸蔵用材料として窒化ホウ素ナノチューブとその製造方法が提供される。
【００２７】
窒化ホウ素ナノチューブは軽量で、環境や人体に対する影響も殆ど無く、カーボンナノチューブに比べ、熱に強く、化学的にも安定な材料として期待される。
このため、安定で超寿命の水素吸蔵材料として利用でき、クリーン自動車の燃料母材等として、その経済的効果が大きい。
【図面の簡単な説明】
【図１】多層壁窒化ホウ素ナノチューブの透過型電子顕微鏡像の図面に代わる写真である。
【図２】ナノベル型のナノチューブを単位として、それらが軸方向に繋がった竹の子型の窒化ホウ素ナノチューブの透過型電子顕微鏡像の図面に代わる写真である。
【図３】多層壁窒化ホウ素ナノチューブと、竹の子状窒化ホウ素ナノチューブ及び比較としての窒化ホウ素微粒子の水素吸蔵量の測定結果を示した図である。横軸が水素の圧力、縦軸が試料の重量の増加分を示している。[0001]
TECHNICAL FIELD OF THE INVENTION
The invention of this application relates to a boron nitride nanotube for storing hydrogen and a method for producing the same. More specifically, the invention of this application is that the final product after combustion is only water, and it efficiently adsorbs hydrogen, which is an energy source that is clean to the environment and has no adverse effect on human beings, The present invention relates to a novel boron nitride nanotube which is lightweight and has no toxicity in the substance itself, and a method for producing the same.
[0002]
[Prior art]
Conventionally, carbon nanotubes have been known as a lightweight and effective material for hydrogen storage. In particular, it is said that a carbon nanotube having a single-layer wall, that is, a single-layer, electrically having semiconductor properties is effective (References 1 to 4).
[0003]
However, it has been found that carbon nanotubes have metallic properties or semiconducting properties depending on the size of the diameter or the manner of twist. Various metals are used as catalysts in the production of carbon nanotubes. The difference in the shape of the carbon nanotube and the difference in the properties due to the difference, and the mixing of the catalyst metal at the time of the production affect the hydrogen storage amount. Nevertheless, it is difficult at present to control its shape and the like.
[0004]
Furthermore, at present, it is difficult to separate a carbon nanotube having only one wall, which is effective for hydrogen storage, from other products. For this reason, at present, the hydrogen storage performance of carbon nanotubes varies greatly between reports and research presentations.
[0005]
[Literature]
1: Nature 1997, 386, 377
2: J. Phys. Chem., B 1998, 102, 4253
3: Science 1999, 286, 1127
4: Carbon 2001, 39, 1447
[0006]
[Problems to be solved by the invention]
Therefore, the invention of this application is intended to solve the above-mentioned problems. As a result, the electrical properties and the like are not affected by the presence of the size of the diameter or the torsion, and the hydrogen is stably produced without being affected by the remaining catalyst metal. It is an object of the present invention to provide a new nanotube structure which can be occluded, is easily manufactured, is lightweight, and has almost no effect on the environment or the human body.
[0007]
[Means for Solving the Problems]
The invention of this application solves the above-mentioned problems. First, the hydrogen storage amount is 10 MPa, at room temperature, 1.5% by weight or more, the diameter is 5 to 50 nm, and the length is 1 to 1. A 20 μm multi-wall boron nitride nanotube is provided.
[0008]
Secondly, the invention of this application is to thermally decompose a precursor having a chemical composition of B 4 N 3 O 2 H in a mixed gas stream of N 2 and NH 3 at a temperature of 1600 ° C. or more. To provide a method for producing a multi-walled boron nitride nanotube as a hydrogen storage material.
[0009]
Third, melamine having a chemical composition of C 3 N 6 H 6 and boric acid having a chemical composition of H 3 BO 3 are mixed at a molar ratio of 1: 2 or near the same, and the mixture is heated at 400 ° C. in air. after heat treatment at 550 ° C., in a nitrogen resulting powder, characterized in that heat treatment at 750 ℃ ~850 ℃, B 4 N 3 O is a precursor for the production of multi-walled boron nitride nanotube A method for obtaining 2 H is provided.
[0010]
Fourthly, the invention of the present application has a hydrogen storage amount at room temperature of 0.7% by weight at 2 MPa, 2.5% by weight or more at 10 MPa, a diameter of 10 to 100 nm, and a length of 10 to 100 nm. Boron nitride nanotubes having a nanobell morphology of 50-300 nm provide bamboo shoot-like boron nitride nanotubes connected to a length of 5-20 μm.
[0011]
Fifth, the invention of this application is characterized in that a boron nitride powder having an oxygen content of 10 to 20% is thermally decomposed at a temperature of 1600 ° C. or more in a mixed gas stream of N 2 and NH 3. The present invention provides a method for producing a bamboo shoot-like boron nitride nanotube as a hydrogen storage material.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
Although the invention of this application has the characteristics as described above, it was confirmed for the first time by the invention of this application that the multilayer or bamboo shoot-type boron nitride nanotubes have an effective hydrogen storage effect. That is. Similarly, it has been confirmed that boron nitride nanotubes are less affected by morphology than carbon nanotubes that are expected to have a hydrogen storage effect.
[0013]
In the invention of this application, there are provided two types of boron nitride nanotubes as a hydrogen storage material whose form is easier to control than carbon nanotubes. One is, for example, a linear form as shown in FIG. 1 and has a multi-layer wall configuration, and the other is connected to a unique shape called a nanobell, for example as shown in FIG. Thus, it is a long bamboo shoot-shaped boron nitride nanotube for hydrogen storage as a whole.
[0014]
In the case of boron nitride nanotubes having a linear configuration and a multi-layer structure, the hydrogen storage capacity can be defined as a characteristic of 10 MPa and 1.5 wt% or more at room temperature. Is preferably 0.5% by weight or more. This has a diameter of 5 to 50 nm and a length of 1 to 20 μm.
[0015]
Such a linear, multi-walled boron nitride nanotube can be suitably produced, for example, by the following method of the present invention. That is, first, melamine having a chemical composition of C 3 N 6 H 6 and boric acid having a chemical composition of H 3 BO 4 are mixed at a molar ratio of 1: 2 or its vicinity (an allowable range of ± 10%). After heating in air at 400 ° C. to 550 ° C., preferably for 3 to 4 hours, to obtain melamine diborate (C 3 N 6 H 6 .2H 3 BO 4 ), preferably 1 to 2 hours at 850 ° C. from 750 ° C., by heat treatment, to produce the B 4 N 3 O 2 H amorphous precursor.
[0016]
Amorphous B 4 N 3 O 2 H, which is the precursor, has a BN bond as a frame and oxygen at a ratio of 20 to 30% by weight.
[0017]
Next, the precursor is thermally decomposed at 1600 ° C. or higher in a mixed gas stream of N 2 and NH 3 . By this thermal decomposition, linear multi-walled boron nitride nanotubes are generated via a liquid amorphous body composed of B-N-O. The nanotube in this case has caps on both ends of the tube.
[0018]
The invention of this application also provides a bamboo shoot-like boron nitride nanotube as described above, which is preferably made, for example, by mixing boron nitride particles containing 10 to 20% of oxygen with N 2 and NH 2. It can be manufactured by thermal decomposition at a temperature of 1600 ° C. or more in a mixed gas stream of ( 3 ). Nanobell-shaped tubes are formed, which are connected in the axial direction of the bell to form bamboo shoot-like boron nitride nanotubes several microns in length.
[0019]
From comparison with the results reported for hydrogen storage carbon nanotubes, it is assumed that, even in this bamboo shoot-like boron nitride nanotube, a nanotube having a single-layer wall and having no cap at both ends is more effective for hydrogen storage. it can.
[0020]
Therefore, an embodiment will be shown below and will be described in more detail.
[0021]
Of course, the invention is not limited by the following examples.
[0022]
【Example】
Next, the present invention will be described in more detail with reference to examples.
<Example 1>
Melamine having a chemical composition of C 3 N 6 H 6 and boric acid having a chemical composition of H 3 BO 4 were mixed at a molar ratio of 1: 2, and heated in air at 500 ° C. for 3 hours to obtain 2 borane. after obtaining the melamine (C 3 N 6 H 6 · 2H 3 BO 4), under nitrogen to this powder was subjected to heat treatment for 1 hour at 800 ° C.. By this heat treatment, amorphous B 4 N 3 O 2 H was obtained.
[0023]
Next, the obtained B 4 N 3 O 2 H powder was used as a precursor, placed in a carbon crucible, placed in a tubular carbon heating element, and heated under a nitrogen flow of 1 l / min by vertical induction heating. Heat treatment was performed at 1700 ° C. for 2 hours using an apparatus.
[0024]
The obtained sample was observed with a transmission electron microscope. FIG. 1 shows a multi-walled boron nitride nanotube having a diameter of 10 to 30 nm, a length of several μm, and caps at both ends in the length direction.
<Example 2>
The boron nitride particles containing 10 to 20% of oxygen were subjected to a heat treatment at a temperature of 1600 ° C. or more for 2 hours in a mixed gas stream of N 2 and NH 3 .
[0025]
The obtained sample was observed with a transmission electron microscope. FIG. 2 shows a bamboo tube-shaped boron nitride nanotube in which nanobell-shaped boron nitride having a diameter of 10 to 80 nm is connected to a length of 10 μm or more in the axial direction.
<Hydrogen storage characteristics>
FIG. 3 shows the results of measuring the hydrogen storage amounts of the samples of Examples 1 and 2 using a Cahn D110-type thermobalance in a hydrogen stream at room temperature. For comparison, the hydrogen absorption measurement results of boron nitride fine particles (bulk powder) having a particle size of 10 to 20 μm manufactured by Denka Co., Ltd. are also shown in the same figure. FIG. 3 shows the hydrogen pressure when hydrogen is absorbed on the horizontal axis and the increase in the weight of the sample on the vertical axis. As can be seen from FIG. 3, the hydrogen storage capacity of the boron nitride nanotube is much larger than the hydrogen storage capacity of the boron nitride fine particles. In addition, the bamboo shoot-shaped nanotubes in nanobell units shown as bamboo tubes in FIG. 3 absorb about 1.5 times more hydrogen than the multi-wall nanotubes shown as model tubes in FIG. Results were obtained.
[0026]
【The invention's effect】
As described in detail above, in the invention of this application, since it is a clean and ubiquitous energy source and only water is used as a waste after its use, its practical application is highly expected. A boron nitride nanotube and a method for producing the same are provided as a material for storing hydrogen.
[0027]
Boron nitride nanotubes are lightweight, have little effect on the environment and the human body, are more resistant to heat than carbon nanotubes, and are expected to be chemically stable materials.
For this reason, it can be used as a stable and long-lasting hydrogen storage material, and has a great economic effect as a fuel base material for clean automobiles.
[Brief description of the drawings]
FIG. 1 is a photograph replacing a drawing of a transmission electron microscope image of a multi-walled boron nitride nanotube.
FIG. 2 is a photograph replacing a drawing of a transmission electron microscope image of a bamboo shoot-shaped boron nitride nanotube in which nanobell-shaped nanotubes are connected in a unit of an axial direction.
FIG. 3 is a view showing the results of measuring the hydrogen storage amounts of multi-walled boron nitride nanotubes, bamboo shoot-like boron nitride nanotubes, and boron nitride fine particles as a comparison. The horizontal axis indicates the hydrogen pressure, and the vertical axis indicates the increase in the weight of the sample.
Claims (5)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007099588A (en) * | 2005-10-07 | 2007-04-19 | National Institute For Materials Science | Boron nitride nanotube introduced with fluorine atom and manufacturing method |
| CN110104611A (en) * | 2019-05-15 | 2019-08-09 | 西安电子科技大学 | A kind of nanocomposite hydrogen storage material and preparation method thereof |
| CN114471654A (en) * | 2022-01-05 | 2022-05-13 | 兰州理工大学 | Preparation of boron nitride material anchoring cobalt ferrite composite catalyst and application of catalyst in catalytic degradation of oxytetracycline |
-
2002
- 2002-12-11 JP JP2002359911A patent/JP3997299B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007099588A (en) * | 2005-10-07 | 2007-04-19 | National Institute For Materials Science | Boron nitride nanotube introduced with fluorine atom and manufacturing method |
| JP4674353B2 (en) * | 2005-10-07 | 2011-04-20 | 独立行政法人物質・材料研究機構 | Boron nitride nanotubes introduced with fluorine atoms and method for producing the same |
| CN110104611A (en) * | 2019-05-15 | 2019-08-09 | 西安电子科技大学 | A kind of nanocomposite hydrogen storage material and preparation method thereof |
| CN114471654A (en) * | 2022-01-05 | 2022-05-13 | 兰州理工大学 | Preparation of boron nitride material anchoring cobalt ferrite composite catalyst and application of catalyst in catalytic degradation of oxytetracycline |
| CN114471654B (en) * | 2022-01-05 | 2024-03-29 | 兰州理工大学 | Preparation of boron nitride material anchored cobalt ferrite composite catalyst and application thereof in catalytic degradation of terramycin |
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