JP5770166B2 - 調整可能な新種のガス貯蔵材料及びガス感知材料 - Google Patents
調整可能な新種のガス貯蔵材料及びガス感知材料 Download PDFInfo
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- JP5770166B2 JP5770166B2 JP2012510880A JP2012510880A JP5770166B2 JP 5770166 B2 JP5770166 B2 JP 5770166B2 JP 2012510880 A JP2012510880 A JP 2012510880A JP 2012510880 A JP2012510880 A JP 2012510880A JP 5770166 B2 JP5770166 B2 JP 5770166B2
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Description
特許文献2:特開第2003−225561号明細書
特許文献3:米国特許第6,280,697号明細書
特許文献4:米国特許出願公開第10/304,316号明細書
特許文献5:米国特許第5,973,444号明細書
非特許文献2:A. Chambers et al. J. Phys. Chem. B 102: 3378 (1998)
非特許文献3:Ong, et al. IEEE Sensors Journal, 2: 82 (2002)
非特許文献4:Journet et al Nature 388: 756 (1997)
非特許文献5:Harutyunyan et al, NanoLetters 2, 525 (2002)
非特許文献6:Carey and Sundberg "Advanced Organic Chemistry 3rd Ed." Vols.
A and B, Plenum Press, New York (1992)
非特許文献7:Cotton et al. "Advanced Inorganic Chemistry 6th Ed." Wiley,
New York (1999)
他の記載がない限り、明細書及び特許請求の範囲を含む本明細書中に使用する下記用語を下記のように定義する。明細書及び添付の特許請求の範囲中に用いられる、単数形「a」、「an」及び「the」は、文脈上明らかに違う場合を除き、複数への言及を含むことに留意しなければならない。標準的な化学用語の定義は、Carey and Sundberg (1992) "Advanced Organic Chemistry 3rd Ed." Vols. A and B, Plenum Press, New York, 及びCotton et al. (1999) "Advanced Inorganic Chemistry 6th Ed." Wiley, New Yorkをはじめとする参照文献にある。
本発明は、ガス貯蔵及びガス感知する組成物、方法及び製法を開示する。単層カーボンナノチューブ(SWNTs)又は複層カーボンナノチューブ、カーボンナノファイバー、膜等、さらに、Al、Ni、Ga、As及びそれらの合金などの金属ナノワイヤ及び薄膜などの一次元又は二次元材料を担体上に堆積させ、担体と吸着材料間のポテンシャル勾配の付与によって電子をドーピングする。印加ゲート電圧の変更及び担持材料の変更によって、特定のガスに最適となるように吸着材料の電子構造を調整できる。雰囲気温度及び雰囲気圧力でゲート電圧を変えることによってガス分子を放出できる。
本発明で用いる吸着材料は一次元又は二次元材料であってもよい。すなわち、吸着材料は、カーボンナノチューブ、活性炭、炭素粉末、非晶質又は不規則炭素、カーボンファイバー、カーボンナノファイバー、グラファイト及び薄膜であってもよい。さらに、Al、Ni、Ga、As及びそれらの合金などの金属ナノワイヤ及び薄膜を本発明の実施において使用できる。選択した吸着材料は市販源から購入又は公知の方法を用いて合成できる。具体的な吸着材料形成方法は本発明にとって重要ではなく、記載した方法は単なる例示であり、いかなる意味でも本発明を限定するものではない。
一次元又は二次元材料は、好適には担持材料上に載置してもよい。担体は、シリカ、アルミナ、MCM−41、MgO、ZrO2、アルミニウム安定化酸化マグネシウム、ゼオライト又は当該技術分野で公知の他の担体及びそれらの組み合わせであってもよい。例えば、Al2O3−SiO2ハイブリッド担体を使用してもよい。本発明の一つの特徴は、一次元又は二次元材料の合成を担持材料の存在下行ってもよいことである。担持材料を粉末化してもよく、粉末化によって小粒径及び大表面積がもたらされる。粉末化担持材料は、好適には粒径約0.01μm〜約100μm、より好適には粒径約0.1μm〜約10μm、さらに好適には粒径約0.5μm〜約5μm、最も好適には粒径約1μm〜約2μmである。粉末化担持材料は、好適には表面積約50〜約1000m2/g、より好適には表面積約200〜約800m2/gである。粉末化酸化物は、できたてを調製してもよく、又は市販されている。例えば、粒径1〜2μm及び表面積300〜500m2/gの適切なAl2O3粉末は、Alfa Aesar社(米国マサチューセッツ州)又はDegussa社(米国ニュージャージー州)から市販されている。粉末化酸化物と金属ナノ粒子を形成するために使用した金属の当初量との重量比を、所望の重量比にするように、粉末化酸化物を添加してもよい。典型的には、重量比は約10:1〜約15:1であってもよい。例えば、100mgの酢酸鉄を出発物質として用いる場合に、約320〜480mgの粉末化酸化物を溶液中に導入してもよい。金属ナノ粒子の粉末化酸化物に対する重量比は、例えば、1:1、2:3、1:4、3:4、1:5など、約1:1〜約1:10であってもよい。
上記で合成した担持材料は、選択ガスの貯蔵又は検知に使用できる。一つの特徴は、担体はガス分子が運動できる複数の貫通孔(図1)を備えることである。孔の形状は円形に限定されず、楕円形、多角形又はスリット状であってもよい。
金属塩溶液中に担持材料を含浸させて、触媒を調製した。典型的な手順では、Fe:Alのモル比1:2でFe(NO2)2を用いた。窒素雰囲気下、モル比1mM:20mMでFe(NO2)2を水に添加した。その後、亜硝酸アルミニウムを当該金属塩含有水溶液に添加した。当該反応混合物を、窒素雰囲気下、機械式撹拌機を用いて混合し、還流下90分間加熱した。溶媒を除去するため、混合物上にN2気流を流し続けながら、反応を約60℃に冷却した。黒色膜が反応フラスコの壁部上に形成した。黒色膜を集め、メノウ乳鉢で粉砕し、微細黒色粉末を得た。
カーボンナノチューブをHarutyunyan et al, NanoLetters 2, 525 (2002)に記載した実験装置を用いて合成した。バルク状SWNTsのCVD成長法合成は、例1で調製した触媒及び炭素源としてメタンを用いた(T=800℃、メタンガス流速:60sccm)。カーボンSWNTsを収率約40wt%(鉄/アルミナ触媒に対する炭素のwt%)で合成できた。作製したSWNTsの透過電子顕微鏡(TEM)像分析から、束状体が作製されたことが示された。λ=532nm及び785nmのレーザー励起光を用いて、上記方法で作製したカーボンSWNTsのラマンスペクトルが得られた。
Claims (21)
- ガス貯蔵装置であって、
ゲート上に堆積した担体であって、前記ゲートと電気的に接続する担体と、
前記担体上に堆積した炭素含有材料であって、前記担体が複数の貫通孔を持ち、前記担体をガスが通り抜ける運動ができるようになっており、前記担体が前記炭素含有材料と電気的に接続し、前記担体によって前記ゲートから分離される炭素含有材料と、
前記担体及び前記炭素含有材料と電気的に接続する前記ゲートを備える電源であって、前記ガス貯蔵装置の両端に印加する電圧を出力する電源と
を備え、
前記印加される電圧に応じて前記炭素含有材料がガスを吸着することを特徴とするガス貯蔵装置。 - 前記担体がSiO 2 を含むことを特徴とする請求項1に記載の装置。
- 前記担体がSi及びSiO 2 を含むことを特徴とする請求項1に記載の装置。
- 前記炭素含有材料を、カーボンナノチューブ及びナノワイヤからなる群から選択することを特徴とする請求項1に記載の装置。
- 前記炭素含有材料が、カーボンナノチューブであることを特徴とする請求項4に記載の装置。
- 前記カーボンナノチューブが、単層カーボンナノチューブ(SWNTs)であることを特徴とする請求項5に記載の装置。
- 前記炭素含有材料は、長さが2μmであることを特徴とする請求項1に記載の装置。
- 前記ガスが、水素、酸素、二酸化炭素、一酸化炭素、メタン、アンモニア又はNOであることを特徴とする請求項1に記載の装置。
- 前記ガスが、水素であることを特徴とする請求項8に記載の装置。
- 前記担体及び炭素含有材料間の前記電圧を低減することで前記ガスを放出することを特徴とする請求項1に記載の装置。
- 前記電圧を5%〜50%低減することで前記ガスを放出することを特徴とする請求項10に記載の装置。
- 前記電源が前記ガス貯蔵装置の両端に−50V〜+50Vの電圧を出力することを特徴とする請求項1に記載の装置。
- 前記電源が前記ガス貯蔵装置の両端に−20V〜+20Vの電圧を出力することを特徴とする請求項12に記載の装置。
- 前記電源が前記ガス貯蔵装置の両端に−15V〜+15Vの電圧を出力することを特徴とする請求項12に記載の装置。
- 前記電源が前記ガス貯蔵装置の両端に−10V〜+10Vの電圧を出力することを特徴とする請求項12に記載の装置。
- 前記SWNTsが半導電性であることを特徴とする請求項6に記載の装置。
- 前記ガスがNOであることを特徴とする請求項8に記載の装置。
- 前記炭素含有材料に金属がドープされていることを特徴とする請求項1に記載の装置。
- 前記金属がリチウム、ナトリウム又はカリウムであることを特徴とする請求項18に記載の装置。
- 前記担体が下部及び上部を備え、前記電源が負極及び正極を備え、前記電源の前記負極が前記ゲートを備え、前記電源の前記正極が前記担体の上部に接続することを特徴とする請求項1に記載の装置。
- 前記印加される電圧を変化させることによって前記炭素含有材料が吸着したガスを放出するようにさらに構成されていることを特徴とする請求項1に記載の装置。
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JP2012526720A (ja) | 2012-11-01 |
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US10071360B2 (en) | 2018-09-11 |
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