JP6305349B2 - メソ多孔性黒鉛粒子上に担持された、高度に焼結安定性の金属ナノ粒子およびその使用 - Google Patents
メソ多孔性黒鉛粒子上に担持された、高度に焼結安定性の金属ナノ粒子およびその使用 Download PDFInfo
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- JP6305349B2 JP6305349B2 JP2014556082A JP2014556082A JP6305349B2 JP 6305349 B2 JP6305349 B2 JP 6305349B2 JP 2014556082 A JP2014556082 A JP 2014556082A JP 2014556082 A JP2014556082 A JP 2014556082A JP 6305349 B2 JP6305349 B2 JP 6305349B2
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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Description
a)多孔性基本骨格体を有する粒子を、黒鉛化性/炭化性有機化合物で含浸する工程、
b)工程a)で得られた粒子を高温黒鉛化プロセスに供し、黒鉛骨格体を多孔性基本骨格体中に備えさせる工程、
c)こうして得られた黒鉛化された粒子を、基本骨格体を除去するプロセスに供し、メソ多孔性黒鉛骨格体を備えさせる工程、
d)工程c)で得られたメソ多孔性黒鉛粒子を、塩を含めて、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Al、Mo、Se、Sn、Pt、Ru、Pd、W、Ir、Os、Rh、Nb、Ta、Pb、Bi、Au、Ag、Sc、Yおよびこれらの混合物から選択された、有利に金属塩の溶液またはこれらの混合物の形の触媒活性金属で含浸する工程、
e)工程d)で得られたメソ多孔性黒鉛粒子を水素化プロセスに供し、触媒活性金属部位をメソ多孔性黒鉛粒子上および/またはメソ多孔性黒鉛粒子中に備えさせる工程、
f)工程e)で得られたメソ多孔性黒鉛粒子を、600〜1400℃、有利に600〜1000℃の高温範囲内で金属粒子およびメソ多孔性黒鉛粒子に対して不活性である雰囲気中でさらなる温度処理に供し、ミクロ構造を変性し、触媒活性金属部位を化学的性質および電気化学的性質の改善のためにメソ孔に閉じ込める工程
を含む。
− 温度は、600〜700℃まで安定し、および黒鉛ドメイン40%の温度は、800℃まで安定したままであること。
− BET表面積:1000m2/g超、有利に1200〜1500m2/g、
− 狭い細孔径分布2〜6nm、有利に中心にある狭い細孔径分布3〜4nm、
− Feの残り0.5質量%未満。
a.少なくとも1つの加水分解可能なケイ素化合物を少なくとも1つの細孔形成剤、例えば炭化水素ケイ素化合物の存在下に反応させ、SiO2前駆物質骨格体粒子を形成させ、こうして得られた粒子を乾燥させ、かつこの粒子をか焼し、多孔性シリカ粒子を得る工程、
b.工程a)で得られた多孔性シリカ粒子を黒鉛化触媒としての金属塩の溶液で処理し、および液状の黒鉛性および/または重合性の有機モノマーおよび開始剤を添加する工程、
c.工程b)で得られた粒子を高温処理の黒鉛化プロセスに供する工程、
d.こうして得られた黒鉛化された粒子を、SiO2を溶かすためのフッ化水素酸での当該粒子の処理によって、脱ケイ化プロセスに供し、任意にその後に、酸で処理し、黒鉛化触媒を除去する工程、
e.工程d)で得られた黒鉛中空粒子を、好ましくは、金属塩の溶液量が粒子の細孔内に完全に吸収される含浸工程を経て、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Al、Mo、Se、Sn、Pt、Ru、Pd、W、Ir、Os、Rh、Nb、Ta、Pb、Biから選択された、触媒活性金属の塩の溶液または様々な前駆物質の混合物、または二成分混合物および三成分混合物を含めて、これらの任意の組合せで処理し、含浸されたHGSを10〜60分間、殊に20〜40分間、例えば30分間、超音波処理に供し、HGSのメソ孔系によって金属活性相の分散度を改善し、その後に、溶剤は、100℃でアルゴン流の下で30〜90分間、殊に60〜90分間蒸発されうる工程、
f.工程e)で得られた、金属塩で負荷された粒子を、有利に200〜500℃の高められた温度で10時間までの時間に亘って、水素での水素化プロセスに供し、金属または合金の前駆物質の完全な還元を達成する工程、
g.得られた粒子を、600〜1400℃の温度範囲内で処理し、ミクロ構造を変性し、HGSの細孔系内でのナノ粒子の閉じ込めを、化学的性質および電気化学的性質の改善のために、促進させる工程
を含む方法によって得ることができる。
a.多孔性黒鉛粒子を、好ましくは、単数または複数の金属塩の溶液量が粒子の細孔内に完全に吸収される含浸工程を経て、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Al、Mo、Se、Sn、Pt、Ru、Pd、W、Ir、Os、Rh、Nb、Ta、Pb、Bi、Au、Ag、Sc、Yおよびこれらの混合物から選択された、少なくとも1つの触媒活性金属の塩の溶液で処理し、および任意にメソ孔系内の金属前駆物質を超音波処理によって分散させ、および最終的に、得られた粒子を不活性雰囲気下で乾燥させる工程、
b.工程a)で得られた、金属塩で負荷された粒子を、200〜500℃の高められた温度で10時間までの時間に亘って水素化プロセス、有利に水素での気相水素化に供して、任意の塩残留物、例えばハロゲン化水素化物を除去し、および金属で負荷された粒子を乾燥させる工程、および
c.得られた粒子を600〜1400℃、有利に1000℃までの温度範囲内で処理/熱処理し、前記粒子のミクロ構造を変性し、担体のメソ孔系内の粒子の閉じ込めを促進させ、こうして熱的および電気化学的に安定した粒子を得る工程
を含む、多孔性黒鉛体上に担持された、高度に焼結安定性の金属ナノ粒子を製造する方法も提供する。
図1は、エキソテンプレートとしてのSiO2@m−SiO2を用いる、DVBのナノキャスト処理およびFe(NO3)3×9H2Oでの触媒黒鉛化を経てのHGS合成を示す。この方法は、窒素でドープされた中空炭素球(NHCS)を製造するために、任意の他のポリマー前駆物質、例えばアクリロニトリルに適用されうる。さらに、この方法は、様々な炭素球を製造するために、黒鉛化なしに適用されてもよい。
A)SiO2@m−SiO2シリカテンプレートのTEM顕微鏡写真、
B)HGSレプリカのTEM顕微鏡写真、
C)中空黒鉛球(HGS)のHR−SEM顕微鏡写真、
D)HGSの黒鉛シェルのHR−TEM、
E)Pt@HGSシェルの代表的範囲のHR−TEM、
F)850℃での熱処理後のPt@HGSの横断切断面のDF−STEM。
A)850℃での熱処理後のPt@HGS、
B)850℃での熱処理後のPtNi@HGS、
C)850℃での熱処理後のPt@NHCS、
D)850℃での熱処理後のPt@mGC。
本発明は、次の実施例によってさらに説明される。実施例において、次の方法が適用された。
高解像度透過型電子顕微鏡(HR−TEM)画像は、冷電界エミッタ(CFE)を装備しかつ200kVの最大加速電圧で操作されるHF−2000顕微鏡で得られた。典型的には、試料を銅グリッドによって支持されたLaceyカーボンフィルム上に置いた。固体の試料が予めの溶解なしにLaceyカーボンフィルム上に沈殿された。
測定法は、K.J.J.Mayrhofer,D.Strmcnik,B.B.Blizanac,V.Stamenkovic,M.Arenz,N.M.Markovic,Measurement of oxygen reduction activities via the fotating disc electrode method:From Pt model surfaces to carbon−suppoted high surface area catalysts,Electrochimica Acta,53(2008)3181−3188中に記載された基本的なガイドラインに従う。
中実のコアメソ多孔性シリカテンプレートの合成を、G.Buchel et al.,Adv.Mater.1998,10,1036−1038による記載と同様の手段に合わせて実施する。
実施例1で得られたSiO2@m−SiO2材料1g(全細孔容積0.37cm3/g)を、Fe(NO3)3×9H2O 2M(0.8ml)のエタノール溶液で含浸し、かつ空気中で一晩中乾燥させた。その後に、DVB0.37mlとAIBN0.012gとの混合物を、Arの下で初期湿潤法によりSiO2@m−SiO2のメソ孔内に組み込む。生じる材料を75℃で24時間加熱し、ジビニルベンゼン(DVB)の重合をArの下で完結させる。メソ孔内への重合されたDVBの炭化/黒鉛化を、5℃/分の加熱速度で窒素流の下で1000℃で4時間、実施した。SiO2@m−SiO2シリカテンプレートを6時間水中の10%フッ化水素酸を用いることによって溶かした。HFの残りを除去した後、この材料を過剰の濃塩酸で処理し、Feを除去した。この材料を4回ミリポア(millipore)水で洗浄し、かつ1回エタノールで洗浄した。この洗浄プロセスをそのつど、遠心分離(14000rpm、5分間)および超音波による再分散(5分間)によって実施した。最後に、この材料を75℃で一晩中、乾燥させた。
Pt金属ナノ粒子(20質量%)を超音波による含浸およびさらに実施例2において得られたHGSの細孔構造におけるH2PtCl6×6H2Oのエタノール溶液の還元により合成した。特に、1.7cm3/gの全細孔容積を有するHGS100mgに対して、H2PtCl6×6H2O66mgをエタノール0.17mlに溶かす。生じる溶液をHGS担体上に含浸し、生じる含浸された固体をさらに30分間超音波処理する。その後に、エタノールをAr流の下で100℃で1時間ガラス管炉内で蒸発させる。その後に、還元工程を同じガラス管炉内でAr中のH230体積%の混合物を用いて実施する。次に、試料を2.5℃/分の速度で250℃へ加熱し、この温度で3時間維持する。還元が完結した後、H2流を止め、前記材料を850〜900℃の高温で5℃/分の速度でArの下で4〜10時間、熱処理する。
例えば、20質量%の最終的な全金属負荷量(様々なPt/Ni原子比)を達成するのに必要とされる、量の金属前駆物質を、Pt@HGS系について上記説明と同様に、HGSの細孔容積と等価の、正確な容量の水に溶かす。
実施例1で得られたSiO2@m−SiO2材料1g(全細孔容積0.37cm3/g)をアクリロニトリル0.37mlとAIBN3mgとの混合物で含浸する。この混合物を、Arの下で初期湿潤法によりSiO2@m−SiO2のメソ孔内に組み込む。生じる材料を鋼製オートクレーブに移し、かつ12時間50℃に加熱し、引き続きさらに60℃で8時間加熱する。その後に、ポリマー複合材を空気中で18時間200℃へ加熱する。メソ孔内でのポリアクリルニトリル(PAN)の炭化は、窒素流の下で4時間、850℃または1000℃への熱処理(5℃min-1の加熱速度)によって達成される。
Pt金属ナノ粒子(20質量%)を超音波による含浸およびさらに実施例5において得られたNHCSの細孔構造におけるH2PtCl6×6H2Oのエタノール溶液の還元により合成した。特に、1.3cm3/gの全細孔容積を有するNHCS100mgに対して、H2PtCl6×6H2O66mgをエタノール0.13mlに溶かす。生じる溶液をNHCS担体上に含浸し、生じる含浸された固体をさらに30分間超音波処理する。その後に、エタノールをAr流の下で100℃で1時間ガラス管炉内で蒸発させる。その後に、還元工程を同じガラス管炉内でAr中のH230体積%の混合物を用いて実施する。
m−SiO2シリカ球10gの典型的な合成は、以下のとおりである。アンモニア水32.9ml(28質量%)をエタノール500g(633ml)および脱イオン水120mlと混合した。約10分間の攪拌後、TEOS23.6ml(98%)とOTMS9.5mlとの混合物を添加し、この反応混合物を30分間攪拌し、かつさらに攪拌なしに5時間反応させた。生じるm−SiO2球を遠心分離によって前記溶液から分離し、75℃で一晩中、乾燥させ、さらに550℃で酸素雰囲気下でか焼し、最終的な均一な球状m−SiO2粒子を生じる。
実施例7で得られたm−SiO2材料1g(全細孔容積0.83cm3/g)を、Fe(NO3)3×9H2O 2M(1.6ml)のエタノール溶液で含浸し、かつ空気中で一晩中乾燥させた。その後に、DVB0.83mlとAIBN0.023gとの混合物を、Arの下で初期湿潤法によりm−SiO2のメソ孔内に組み込む。生じる材料を75℃で24時間加熱し、ジビニルベンゼン(DVB)の重合をArの下で完結させる。メソ孔内への重合されたDVBの炭化/黒鉛化を、5℃/分の加熱速度で窒素流の下で1000℃で4時間、実施した。
Pt金属ナノ粒子(20質量%)を超音波による含浸およびさらに実施例8において得られたmGSの細孔構造におけるH2PtCl6×6H2Oのエタノール溶液の還元により合成した。特に、2.3cm3/gの全細孔容積を有するmGS100mgに対して、H2PtCl6×6H2O66mgをエタノール0.23mlに溶かす。生じる溶液をmGS担体上に含浸し、生じる含浸された固体をさらに30分間超音波処理する。その後に、エタノールをAr流の下で100℃で1時間ガラス管炉内で蒸発させる。その後に、還元工程を同じガラス管炉内でAr中のH230体積%の混合物を用いて実施する。次に、試料を2.5℃/分の速度で250℃へ加熱し、この温度で3時間維持する。還元が完結した後、H2流を止め、前記材料を850〜900℃の高温で5℃/分の速度でArの下で4〜10時間、熱処理する。
前記担体のホスティング(hosting)特性を試験するために、本発明者らは、Ptナノ粒子の熱安定性を試験し、その際にインサイチュー(in−situ)でのXRDによって前記挙動を監視し、かつ初期材料および最終材料をHR−TEM、HR−SEMおよびDF−STEMによって分析した。
メソ多孔性中空炭素球上に担持された白金ナノ粒子のボルタモグラムを、標準の燃料電池触媒(3nm、Tanaka)のボルタモグラムと比較する。HGSをベースとする触媒は、3nmの標準触媒と同じ特性をもつ白金の特徴を示す。いわゆるHupd領域が0.05V〜0.35Vで開始し、その後に二重層電位が開始し、および0.7Vを上回る電位で、酸素種の吸着が開始する。
− 均一な粒径、
− 中心にある狭い細孔径分布2〜6nm、有利に中心にある狭い細孔径分布3〜4nm、ここで、細孔の少なくとも50%、有利に60%超は、2〜6nmの範囲内の細孔径を有し、
− 1000m2/g超および1.3cm3/g超の大きな比表面積およびメソ孔の容積、
− 2〜6nmおよび6〜20nm、有利に3〜4nmおよび8〜12nmの十分に展開された3D(3次元)の連続二頂多孔度、
− 炭素の化学的性質の簡単な制御によって特徴付けられている。
Claims (24)
- メソ多孔性黒鉛粒子上に担持された、高度に焼結安定性の金属ナノ粒子を製造する方法であって、この方法は、工程:
a.多孔性基本骨格体を有する粒子を、黒鉛化性有機化合物で含浸する工程、
b.工程a)で得られた粒子を高温黒鉛化プロセスに供し、黒鉛骨格体を多孔性基本骨格体中に備えさせる工程、
c.こうして得られた黒鉛化された粒子を、基本骨格体を除去するプロセスに供し、メソ多孔性黒鉛骨格体を備えさせる工程、
d.工程c)で得られたメソ多孔性黒鉛粒子を、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Al、Mo、Se、Sn、Pt、Ru、Pd、W、Ir、Os、Rh、Nb、Ta、Pb、Bi、Au、Ag、Sc、Yおよびこれらの塩および混合物を含めて、これらから選択された、少なくとも1つの触媒活性金属で含浸する工程、
e.工程d)において得られたメソ多孔性黒鉛粒子を水素化プロセスに供し、触媒活性金属部位をメソ多孔性黒鉛粒子上および/またはメソ多孔性黒鉛粒子中に備えさせる工程、および
f.工程e)において得られたメソ多孔性黒鉛粒子を、600℃〜1400℃の高温範囲内で高温処理に供する工程
を含む、前記方法。 - 工程e)において得られたメソ多孔性黒鉛粒子を、600℃〜1000℃の高温範囲内で、高温処理に供する工程を含む、請求項1記載の方法。
- 工程e)において得られたメソ多孔性黒鉛粒子を、不活性雰囲気中で、前記高温処理に供する工程を含む、請求項1または2記載の方法。
- 工程a)において使用される粒子は、コアおよび多孔性シェルを有する、請求項1から3までのいずれか1項記載の方法。
- 工程a)において使用される粒子は、中実のコアまたは多孔性コアを有する、請求項4記載の方法。
- 工程a)において使用される粒子のコアおよび/またはシェルは、多孔性無機酸化物材料を含む、請求項5記載の方法。
- 多孔性無機酸化物材料は、シリカおよび/または二酸化ジルコニウムを含む、請求項6記載の方法。
- コアと多孔性シェルとは、異なる材料から構成されている、請求項5または6記載の方法。
- 黒鉛化性有機化合物は、重合可能な炭化水素モノマーまたはポリマー構造を形成させるための有機反応成分の混合物である、請求項1から8までのいずれか1項に記載の方法。
- 重合可能な炭化水素モノマーまたはポリマー構造を形成させるための有機反応成分の混合物は、ラジカル的に重合可能である、請求項9記載の方法。
- 工程c)において、黒鉛化された粒子を無機酸で処理する、請求項1から10までのいずれか1項に記載の方法。
- 工程d)において、メソ多孔性黒鉛粒子を、前記の少なくとも1つの触媒活性金属の塩の溶液を用いて、単数または複数の金属塩の溶液量が黒鉛粒子のメソ孔内に完全に吸収される含浸工程において含浸する、請求項1から11までのいずれか1項に記載の方法。
- 得られた含浸された黒鉛粒子を、メソ多孔性黒鉛粒子内の金属前駆物質溶液の分散度を向上させるための超音波処理によってさらに処理し、および最終的に不活性雰囲気下での得られた粒子の乾燥によって後処理する、請求項12記載の方法。
- 工程e)において、工程d)で得られたメソ多孔性黒鉛粒子を気相水素化プロセスに供する、請求項1から13までのいずれか1項に記載の方法。
- 請求項1記載の、メソ多孔性黒鉛粒子上に担持された、高度に焼結安定性の金属ナノ粒子を製造する方法であって、この方法は、工程:
a.少なくとも1つの加水分解可能なケイ素化合物を少なくとも1つの細孔形成剤の存在下に反応させ、SiO2前駆物質骨格体粒子を備えさせ、こうして得られた粒子を乾燥させ、かつこの粒子をか焼し、多孔性シリカ粒子を得る工程、
b.工程a)で得られた多孔性シリカ粒子を黒鉛化触媒としての金属塩の溶液で処理し、および液状の黒鉛化および重合可能な有機モノマーならびに開始剤を添加する工程、
c.工程b)で得られた粒子を高温処理の黒鉛化プロセスに供する工程、
d.こうして得られた黒鉛化された粒子を、SiO2を溶かすためのフッ化水素酸または水酸化ナトリウム溶液での当該粒子の処理によって、脱ケイ化プロセスに供し、任意にその後に、酸で処理し、黒鉛化触媒を除去する工程、
e.工程d)で得られた黒鉛中空粒子を、金属塩の溶液量が粒子の細孔内に完全に吸収される含浸工程を経て、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Al、Mo、Se、Sn、Pt、Ru、Pd、W、Ir、Os、Rh、Nb、Ta、Pb、Bi、Au、Ag、Sc、Yおよびこれらの混合物から選択された、少なくとも1つの触媒活性金属の塩の溶液で処理し、含浸された粒子をさらに超音波処理に供し、メソ孔系内の金属前駆物質の分散度を改善し、最終的に不活性の雰囲気下で乾燥させる工程、
f.工程e)で得られた、金属塩で負荷された粒子を、200〜500℃の高められた温度で10時間までの時間に亘って、水素での水素化プロセスに供し、任意の金属塩残留物を除去し、こうして得られた粒子を乾燥させる工程、および
g.得られた粒子を600℃〜1000℃の温度範囲内で、および不活性雰囲気内で処理する工程
を含む、前記方法。 - メソ多孔性黒鉛体上に担持された、高度に焼結安定性の金属ナノ粒子を製造する方法であって、工程
a.多孔性黒鉛粒子を、単数または複数の金属塩の溶液量が粒子の細孔内に完全に吸収される含浸工程を経て、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Al、Mo、Se、Sn、Pt、Ru、Pd、W、Ir、Os、Rh、Nb、Ta、Pb、Bi、Au、Ag、Sc、Yおよびこれらの混合物から選択された、少なくとも1つの触媒活性金属の塩の溶液で処理し、任意にメソ孔系内の金属前駆物質を超音波処理によってさらに分散させ、および最終的に、得られた粒子を不活性雰囲気下で乾燥させる工程、
b.工程a)で得られた、金属塩で負荷された粒子を、200〜500℃の高められた温度で10時間までの時間に亘って、水素での気相水素化プロセスに供し、任意の金属塩残留物を除去し、および金属で負荷された粒子を乾燥させる工程、および
c.得られた粒子を600〜1400℃の温度範囲内で熱処理し、前記粒子のミクロ構造を変性し、担体のメソ孔系内の粒子の閉じ込めを促進させ、こうして熱的および電気化学的に安定した粒子を得る工程
を含む、前記方法。 - 工程c)を600℃〜1000℃の高温範囲内で実施する、請求項16記載の方法。
- 連続多孔性構造において高度に焼結安定性の触媒活性金属ナノ粒子を有するメソ多孔性黒鉛体であって、前記触媒活性金属ナノ粒子が連続3D細孔構造内に閉じ込められており、この触媒活性金属は、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Al、Mo、Se、Sn、Pt、Ru、Pd、W、Ir、Os、Rh、Nb、Ta、Pb、Bi、Au、Ag、Sc、Yおよびこれらの混合物から選択されたものである、前記メソ多孔性黒鉛体。
- 触媒活性金属がPtとFe、Co、Ni、Cu、Ru、Pd、Au、Ag、Sn、Mo、Mn、Y、Scのいずれかとの二成分または三成分の組合せから選択されている、請求項18記載の、連続多孔性構造において高度に焼結安定性の金属ナノ粒子を有するメソ多孔性黒鉛体。
- 中空のコアおよびメソ多孔性シェルを有する、請求項18または19記載の、連続多孔性構造において高度に焼結安定性の金属ナノ粒子を有するメソ多孔性黒鉛体。
- 600℃〜700℃まで温度安定性であり、1000m2/gを上回るBET表面積および2〜6nmの狭い細孔径分布を有する、請求項18から20までのいずれか1項に記載の、連続多孔性構造において高度に焼結安定性の金属ナノ粒子を有するメソ多孔性黒鉛体。
- 1200〜1500m2/gのBET表面積を有する、請求項21に記載の、連続多孔性構造において高度に焼結安定性の金属ナノ粒子を有するメソ多孔性黒鉛体。
- 3〜4nmの狭い細孔径分布を有する、請求項21または22に記載の、連続多孔性構造において高度に焼結安定性の金属ナノ粒子を有するメソ多孔性黒鉛体。
- PEM燃料電池におけるカソード側での酸素還元反応(ORR)のための、触媒としての請求項18から23までのいずれか1項に記載の前記のメソ多孔性黒鉛体の使用。
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JP2015513449A (ja) | 2015-05-14 |
EP2812114C0 (de) | 2023-12-13 |
CA2861448A1 (en) | 2013-08-15 |
KR20140126330A (ko) | 2014-10-30 |
CN104093482A (zh) | 2014-10-08 |
US9755248B2 (en) | 2017-09-05 |
EP2812114B1 (de) | 2023-12-13 |
KR102117722B1 (ko) | 2020-06-01 |
DE102012102120A1 (de) | 2013-08-08 |
CN104093482B (zh) | 2017-04-26 |
WO2013117192A1 (de) | 2013-08-15 |
EP2812110C0 (en) | 2023-12-13 |
US20150017555A1 (en) | 2015-01-15 |
CA2861412A1 (en) | 2013-08-15 |
EP2812110A1 (en) | 2014-12-17 |
CN104159666A (zh) | 2014-11-19 |
US9755247B2 (en) | 2017-09-05 |
CN104159666B (zh) | 2017-02-22 |
CA2861412C (en) | 2021-02-09 |
EP2812114A1 (de) | 2014-12-17 |
CA2861448C (en) | 2021-02-16 |
WO2013117725A1 (en) | 2013-08-15 |
EP2812110B1 (en) | 2023-12-13 |
US20150050583A1 (en) | 2015-02-19 |
KR102144419B1 (ko) | 2020-08-13 |
EP2626131A1 (en) | 2013-08-14 |
JP6305348B2 (ja) | 2018-04-04 |
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