JP2013514457A - アルカリ性媒体における電気化学酸素還元法 - Google Patents
アルカリ性媒体における電気化学酸素還元法 Download PDFInfo
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- JP2013514457A JP2013514457A JP2012543678A JP2012543678A JP2013514457A JP 2013514457 A JP2013514457 A JP 2013514457A JP 2012543678 A JP2012543678 A JP 2012543678A JP 2012543678 A JP2012543678 A JP 2012543678A JP 2013514457 A JP2013514457 A JP 2013514457A
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- nitrogen
- carbon nanotubes
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- catalyst
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Abstract
Description
a)少なくとも0.5重量%の窒素の割合を有する窒素ドープカーボンナノチューブの、第1溶媒中の懸濁液(A)としての供給、
b)第2溶媒中の金属ナノ粒子の懸濁液(B)の供給工程、
c)懸濁液(A)および(B)を混合して懸濁液(C)を与える工程、および
d)金属ナノ粒子が添加された窒素ドープカーボンナノチューブの、懸濁液(C)からの分離工程
を含むことを特徴とする方法により得られる。
窒素ドープカーボンナノチューブを、WO2009/080204の実施例5に記載の通り、これからの唯一の差異としてピリジンを出発物質として用いて製造し、反応を700℃の反応温度にて行い、該反応時間を30分に制限した。
窒素ドープカーボンナノチューブを、反応を60分間行ったことを唯一の差異として実施例1と同じ方法により製造した。
実施例1に記載の実験を、市販のカーボンナノチューブ(BayTubesからのBayTubes(登録商標))を、実施例1に用いた窒素ドープカーボンナノチューブの代わりに用いたことを唯一の差異として行った。
窒素ドープカーボンナノチューブは、実施例1と同様の方法により製造した。実施例1に対し、次いで銀ナノ粒子を添加した。こうして得られた触媒を実施例8へ通した。
窒素ドープカーボンナノチューブ中の窒素の質量による割合および窒素ドープカーボンナノチューブに見出される窒素の質量による割合における種々の窒素種のモル割合を、実施例1および実施例2の間に、X線光電子分光法分析(ESCA、機器:ThermoFisher、ESCALab 220iXL、方法:製造業者の説明書による)により得られた窒素ドープカーボンナノチューブについて決定した。決定した値を、表1に集約する。
次いで、実施例1〜3に記載の通り得られた触媒を、透過型電子顕微鏡(TEM、Philips TECNAI 20、200kV加速電圧による)下で銀を添加することについて光学的に試験した。
まず、実施例1または実施例2からの80mgの触媒を50mLのアセトンに分散し、20μLのこの分散体を、いずれの場合にも回転円環板電極(Jaissle Elektronik GmbHから)の研磨電極表面上へ滴下した。
実施例7における実験と同一の実験を、実施例3および4による触媒を用いることを唯一の差異として行った。また、本発明によらない方法の結果は、実施例7について上述した通り、図4における実施例3による触媒について示される。実施例4による触媒を用いる本発明によらない方法からの結果は、明確さのために、図4にもはや示されない。実施例7および8についての集約した実験データを、図5に示す。実施例7の議論において上に示した通り、本発明によらない方法は、結果として酸素の還元のためのより高いエネルギー消費を有することが見られる。
Claims (10)
- 10を越えるpHを有するアルカリ性媒体中での酸素の電気化学還元法であって、2〜60重量%の割合で表面に存在する1〜15nmの範囲の平均粒度を有する金属ナノ粒子を含む窒素ドープカーボンナノチューブ(NCNT)を含む触媒の存在下で行うことを特徴とする、方法。
- 窒素ドープカーボンナノチューブ(NCNT)は、少なくとも0.5重量%の窒素の割合を有することを特徴とする、請求項1に記載の方法。
- 窒素ドープカーボンナノチューブ(NCNT)中の窒素は、ピリジン窒素として少なくとも部分的に存在することを特徴とする、請求項1または2に記載の方法。
- 少なくとも40モル%の窒素は、ピリジン窒素であることを特徴とする、請求項3に記載の方法。
- 金属ナノ粒子は、Fe、Ni、Cu、W、V、Cr、Sn、Co、Mn、Mo、Mg、Al、Si、Zr、Ti、Ru、Pt、Ag、Au、Pd、Rh、Ir、Ta、Nb、ZnおよびCdからなる群から選択される金属から構成されることを特徴とする、請求項1〜4のいずれかに記載の方法。
- 金属ナノ粒子は、銀(Ag)から構成されることを特徴とする、請求項5に記載の方法。
- 請求項1〜6のいずれかに記載の方法における使用のための触媒の製造方法であって、少なくとも以下の工程:
a)少なくとも0.5重量%の窒素の割合を有する窒素ドープカーボンナノチューブ(NCNT)の、第1溶媒における懸濁液(A)としての供給工程、
b)第2溶媒における金属ナノ粒子の懸濁液(B)の供給工程、
c)懸濁液(A)および(B)を混合して懸濁液(C)を与える工程、および
d)金属ナノ粒子が添加された窒素ドープカーボンナノチューブ(NCNT)の、懸濁液(C)からの分離工程
を含むことを特徴とする、方法。 - 懸濁液(B)は、
b1)金属塩を含有する溶媒(A)を供給する工程、および
b2)次いで溶媒(A)中の金属塩を、金属ナノ粒子へ還元して懸濁液(B)を与える工程
により得られることを特徴とする、請求項7に記載の方法。 - 前記方法の工程a)およびb)による第1溶媒および第2溶媒は、水、アルコール、トルエン、シクロヘキサン、ペンタン、ヘキサン、ヘプタン、オクタン、ベンゼン、キシレンおよびこれらの混合物からなる群から独立して選択することを特徴とする、請求項7または8に記載の方法。
- 10を越えるpHを有するアルカリ性媒体における酸素の電気化学還元のための、表面に金属ナノ粒子が添加された窒素ドープカーボンナノチューブ(NCNT)の使用。
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