JP2017222565A - 高品質なカーボン単層ナノチューブの合成 - Google Patents
高品質なカーボン単層ナノチューブの合成 Download PDFInfo
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- JP2017222565A JP2017222565A JP2017113758A JP2017113758A JP2017222565A JP 2017222565 A JP2017222565 A JP 2017222565A JP 2017113758 A JP2017113758 A JP 2017113758A JP 2017113758 A JP2017113758 A JP 2017113758A JP 2017222565 A JP2017222565 A JP 2017222565A
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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Abstract
【解決手段】担持された金属触媒と炭素前駆体ガスを提供する工程であって、第1の炭素前駆体ガス濃度で780torrの圧の炭素前駆体ガスが、担持された金属触媒と接触したときに、炭素前駆体ガスは、第1のカーボン単層ナノチューブ合成開始温度を有し、担持された金属触媒を、炭素前駆体ガスを有するガスと接触させる工程であって、第1のカーボン単層ナノチューブ合成開始温度より高い、第2のカーボン単層ナノチューブ合成開始温度以上で、かつ、炭素前駆体ガスの熱分解温度より低い温度で、担持された金属触媒を炭素前駆体ガスを有するガスと接触させ、そして、炭素前駆体ガスを有するガスの炭素前駆体ガス濃度は、第1の炭素前駆体ガス濃度より低い第2の炭素前駆体ガス濃度である、との2つの工程を有するカーボン単層ナノチューブを合成する方法。
【選択図】なし
Description
特に断らない限り、明細書および請求の範囲を含む本出願に使用した次の用語は、以下に示すように定義する。なお、明細書および添付した請求の範囲に使用したように、「a」、「an」および「the」がつく単数形は、明確に別の記載がない限り複数形の意味も含む。また、標準的な化学用語の定義は、非特許文献5および非特許文献6を含む参考書籍を参照されたい。
本発明は、炭素蒸着法を用いた高品質なカーボン単層ナノチューブ(SWNT)および構造体を合成する方法およびプロセスを開示する。SWNT合成には、粉末Al2O3に担持した触媒を使用する。前記触媒は、Feと、Mo、Niなどの少なくとも他の1つの金属を有することが好ましい。合成は濃度が減少した炭化水素前駆体ガスにおいて実行されることが好ましく、反応温度は、炭化水素前駆体ガスの熱分解温度より低く、SWNT合成の開始温度より約10℃から約50℃だけ高くなるように選択される。従って、本発明の方法は熱分解を最小化し、この結果、アモルファス炭素または非晶質炭素の生成、および多層カーボンの生成を最小化する。従って、高品質なSWNTが製造される。
触媒の組成は、当業者に知られた任意の触媒組成でよい。こうした触媒は、例えば、鉄、酸化鉄、モリブデン、またはコバルト、ニッケル、クロム、イットリウム、ハフニウム、またはマンガンなどのフェライトを含む、金属または合金であるのが好ましい。本発明の有用な触媒は、全体として5nmから約1μmの平均粒径を有することが好ましいが、しかし、個々の粒径は一般に約5nmから約1μmであってよい。
カーボンナノチューブは、炭素含有ガスなどの炭素前駆体を用いて合成することができる。一般に、800℃から1200℃までの温度で熱分解しない炭素含有ガスであれば、所定の流量に対してどのようなガスを用いてもよい。好ましい炭素含有ガスの例としては、一酸化炭素、メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、エチレン、アセチレン、およびプロピレンなどの飽和および不飽和の脂肪族炭化水素、アセトンおよびメタノールなどの酸化炭化水素、ベンゼン、トルエン、およびナフタレンなどの芳香族炭化水素、更にこれらの混合物、例えば、一酸化炭素とメタンの混合物などが含まれる。一般に、アセチレンを用いた場合は、多層カーボンナノチューブの生成が促進されるが、一方、単層カーボンナノチューブの生成にはCOおよびメタンが供給気体として好ましい。また、水素、ヘリウム、アルゴン、ネオン、クリプトン、キセノン、またはこれらの混合物などからなる希釈用ガスを、炭素含有ガスに随意混合してもよい。
本発明の方法およびプロセスは、高品質なSWNT合成方法を提供する。本発明のある態様では、粉末酸化物に担持した触媒を、 Harutyunyan et al., NanoLetters 2, 525 (2002) に記載した文献方法の反応温度で、炭素源と接触させることができる。あるいは、酸化物粉末に担持した触媒をエアロゾル化して、前記反応温度で反応室の中に導入できる。同時に、炭素前駆体ガスを反応室に導入する。反応室内のこれら反応原料の流れを制御して、反応室の壁面に付く炭素生成物の量を減少させることができる。こうして、製造したカーボンナノチューブを回収し、分離することができる。
アルミナエアロゲル担持バイメタルFe/Mo触媒(モル比Fe:Mo:Al2O3=1:0.2:10.16)を、ゾルゲル法を用いて調製し、続いて超臨界乾燥を行った。sec−ブトキシアルミニウム 5.28g(97%、Alfa Aesar)を加熱した200プルーフのエタノール 35mlに希釈し、続いて、4μg/mlの硝酸エタノール溶液 20mlを加えた。この混合物を2時間撹拌しながら80℃で加熱還流した。次に、硝酸鉄(III)水和物(99.999%、Alfa Aesar Puratronic)426.5mgおよび酸化モリブデン(VI)ビス(2,4−ペンタンジオネート)(99%、Alfa Aesar) 68.7mgの20mlエタノール溶液を加えた。反応混合物を1時間撹拌しながら80℃で加熱還流し、その後室温にまで冷却した。こうして室温に戻した溶液に、水酸化アルミニウム(微量金属グレード、Fisher)1mlおよび5mlエタノールで希釈した水1mlの溶液を、激しく撹拌しながら加えると、ゲル状になった。こうして得られたゲルを終夜放置し、翌日100気圧を超える圧力で、270℃にて超臨界乾燥処理した。得られたエアロゲル粉末を1時間500℃にて空気気流中で焼成し、更に1時間820℃にてアルゴン気流中で熱処理した。
カーボンナノチューブは、 Harutyunyan et al., NanoLetters 2, 525 (2002) に記載した実験装置を用いて合成した。上記で製造された触媒を用いたSWNTのCVD成長は、メタンを炭素源として使用した。従って、製造されたカーボン単層ナノチューブは、λ=532nmのレーザー励起を使用するカーボンSWNTのラマンスペクトルを使用して特徴付けられた。一般に、高濃度のメタンは、メタンの非常に著しい熱分解が起き、カーボンにより反応器壁が著しく汚染された。メタン濃度を減少させることにより、この汚染を減少させた。また、合成されたナノチューブ材料のラマンスペクトルのDバンドも、アモルファス炭素の部分の減少を示すメタン濃度の減少とともに減少した。
炭素源の濃度が不活性ガスの付加によって制御され反応が大気圧において実行されたことを除き、カーボンナノチューブは実施例2に記載されるように合成されて特徴付けられた。
Claims (16)
- カーボン単層ナノチューブ(SWNTs)を合成する方法であって、前記合成する方法は、
担持された金属触媒と炭素前駆体ガスを提供する工程であって、第1の炭素前駆体ガス濃度で780torrの圧の炭素前駆体ガスが、担持された金属触媒と接触したときに、前記炭素前駆体ガスは、第1のカーボン単層ナノチューブ(SWNT)合成開始温度を有し、
前記担持された金属触媒を、前記炭素前駆体ガスを有するガスと接触させる工程であって、前記第1のカーボン単層ナノチューブ(SWNT)合成開始温度より高い、第2のカーボン単層ナノチューブ(SWNT)合成開始温度以上で、かつ、炭素前駆体ガスの熱分解温度より低い温度で、前記担持された金属触媒を前記炭素前駆体ガスを有するガスと接触させ、そして、前記炭素前駆体ガスを有するガスの炭素前駆体ガス濃度は、前記第1の炭素前駆体ガス濃度より低い第2の炭素前駆体ガス濃度である、との2つの工程を有する。 - 前記担持された金属触媒を、600torr以下の圧で前記ガスに接触させる、請求項1記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記担持された金属触媒を、200torr以下の圧で前記ガスに接触させる、請求項2記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記担持された金属触媒を、180torr以下の圧で前記ガスに接触させる、請求項3記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記ガスが前記炭素前駆体ガスからなる、請求項2記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記1種またはそれ以上の炭素前駆体は、メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、エチレン、アセチレン、プロピレン、アセトン又はメタノールである、請求項5記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記第2のカーボン単層ナノチューブ(SWNT)の合成開始温度が、前記第1のカーボン単層ナノチューブ(SWNT)の合成開始温度より少なくとも15℃高い、請求項1記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記第2のカーボン単層ナノチューブ(SWNT)の合成開始温度が、前記第1のカーボン単層ナノチューブ(SWNT)の合成開始温度より少なくとも25℃高い、請求項7記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記第2のカーボン単層ナノチューブ(SWNT)の合成開始温度が、前記第1のカーボン単層ナノチューブ(SWNT)の合成開始温度より少なくとも30℃高い、請求項7記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記炭素前駆体ガスがメタンであり、前記第1のカーボン単層ナノチューブ(SWNT)の合成開始温度が760℃であり、前記第2のカーボン単層ナノチューブ(SWNT)の合成開始温度が800℃より高い、請求項7記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記ガスは、前記炭素前駆体ガスと1種またはそれ以上の不活性ガスからなっており、前記炭素前駆体ガスと前記不活性ガスの分圧比が1:500〜1:1である、請求項1記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記ガスの全圧は1.0atm〜1.05atmである、請求項11記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記ガスの前記全圧は1.025atmである、請求項12記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記炭素前駆体ガスの前記分圧は、200torrより低い、請求項12記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記炭素前駆体ガスの前記分圧は、180torrより低い、請求項14記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
- 前記不活性ガスは、ヘリウム、アルゴン、ネオン、クリプトン、ゼノン又はそれの混合物を含む、請求項11記載のカーボン単層ナノチューブ(SWNTs)を合成する方法。
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JP2011519808A (ja) | 2011-07-14 |
US20090274609A1 (en) | 2009-11-05 |
JP6158981B2 (ja) | 2017-07-05 |
US20160023906A1 (en) | 2016-01-28 |
WO2010036393A1 (en) | 2010-04-01 |
US10850984B2 (en) | 2020-12-01 |
JP2015057367A (ja) | 2015-03-26 |
JP2016164122A (ja) | 2016-09-08 |
US9174847B2 (en) | 2015-11-03 |
JP6538115B2 (ja) | 2019-07-03 |
US20180118573A1 (en) | 2018-05-03 |
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