JP2008055418A - 制御された金属クラスターサイズを有する支持された触媒 - Google Patents
制御された金属クラスターサイズを有する支持された触媒 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 118
- 239000002184 metal Substances 0.000 title claims abstract description 117
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000000412 dendrimer Substances 0.000 claims abstract description 72
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002114 nanocomposite Substances 0.000 claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000009826 distribution Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000010948 rhodium Substances 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 229910052703 rhodium Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
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- 238000010586 diagram Methods 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
【解決手段】a)溶液中でデンドリマーポリマーと金属塩とを混合して、金属イオン錯体を形成し、b)還元環境に該金属イオン錯体を曝して、デンドリマー金属ナノ複合物を形成し、c)触媒支持材の上に、該デンドリマー金属ナノ複合物を堆積し、d)該デンドリマー金属ナノ複合物から溶媒を除去して、金属クラスターを形成すし、e)該デンドリマーポリマーを除去して、触媒を生成するステップを含む。触媒金属が2〜150原子のサイズを有するクラスター中で生成される。クラスターは隣接した金属クラスター間で2〜100ナノメートルの間隔を有してもよい。触媒を含む金属クラスターが、該クラスターの70%が該平均直径の0.6nm以内であり、そして該粒子の99%が該平均直径の1.5nm以内にあるサイズ分布を有する。
【選択図】図6
Description
G4OHデンドリマーに対して所望のモル比の金属を得るために、適当な量のH2PtCl66H2Oの2.5x10−2M水溶液を、窒素気流下で、G4OHデンドリマーの0.17M水溶液に加えた。混合物を窒素気流下で3日間攪拌して、溶液中でデンドリマーの官能基とPtカチオンとの錯体を形成させた。取り込まれるPtカチオンの還元をさらに促進するために、デンドリマーPt錯体をその後に新たに調製したNaBH4溶液(BH4 −:金属カチオンのモル比=8:1)と混合した。このステップに続き、標準の湿式含浸によって、あらかじめ焼成(大気中500℃で一晩)したγ−Al2O3の上にPt−デンドリマー金属ナノ複合物を堆積させた。溶媒を攪拌によって蒸発させ、周囲条件でスラリーを生じさせた。
このアプローチをRh−デンドリマーナノ複合物の合成に広げた。3日の金属デンドリマー錯体形成の代わりに、Rh試料はわずか1日しかデンドリマー内への取り込みに要しなかった。同様に、ロジウムデンドリマー金属ナノ複合物を商用ZrO2支持体(非焼成)上に堆積した。この研究で使用される両者の支持された金属触媒の公称金属ローディングは、1重量%であった。
Pdデンドリマーナノ複合体も合成し、そして該方法は、Rhデンドリマー金属ナノ複合体の調製方法と同じである。パラジウム前駆体K2PdCl4の錯体形成は、わずか1日しかデンドリマー内への取り込みに要しなかった。溶液中NaBH4での還元後、残余Pdデンドリマーナノ複合体を焼成した酸化アルミニウム上に堆積させた。
例2に記載したように調製したRh−ZrOaの触媒のサンプルを、プロピレンヒドロホルミル化反応の図2を参照して、上記に記載したように従来技術の触媒と比較した。反応を図7中に要約し、反応中に生成した種々の生成物を示す。使用したサンプルは、従来の初期湿潤含浸で製造した1重量%Rh/ZrO2およびG4−PAMAMデンドリマーで製造した1重量% Rh20G4OH/ZKX (20原子Rhクラスター)であった。使用された反応条件は、100psigおよび温度180℃〜250℃の固定床触媒反応器であった。100sccm ( SV=24,000hr−1)の流速下で200mgの触媒を反応で使用した。反応混合物は、5% CO、20% H2、20% C3H6と調整用Heであった。反応器中のCOの濃度を例のパラメーターのように変化させた。2つの異なるサンプルでの反応の結果を図8に示す。図に示すように、2つのサンプルで反応生成物の選択性は異なり、2つのサンプルで異なる反応メカニズムを示す。テストされた状態では、デンドリマー誘導触媒は、所望の酸素化された生成物の生成で、従来触媒の9%の選択性に比較して、改善された14%の選択性を示した。
Claims (27)
- 以下のステップ:
a)溶液中でデンドリマーポリマーと金属塩とを混合して、金属イオン錯体を形成すること;
b)還元環境に該金属イオン錯体を曝して、デンドリマー金属ナノ複合物を形成すること;
c)触媒支持材の上に、該デンドリマー金属ナノ複合物を堆積すること;
d)該デンドリマー金属ナノ複合物から溶媒を除去して、金属クラスターを形成すること;
e)該デンドリマーポリマーを除去して触媒を生成すること
を含む触媒の生成方法。 - 該触媒が、大きさで2〜150原子の金属クラスターを有する請求項1の方法。
- 該混合ステップa)が、該金属イオン錯体中で所望の金属のローディングが維持されるように、金属塩のデンドリマーポリマーに対するモル比を維持することを含む請求項1の方法。
- 該所望の金属ローディングが、デンドリマーポリマー構造当たり2〜150金属原子である請求項3の方法。
- 該触媒が、該触媒の全重量に基づき0.0l重量%〜50重量%の金属含有率を有する請求項1の方法。
- 該金属塩とデンドリマーポリマー溶液とを不活性雰囲気下で混合し、そして該金属イオン錯体を形成するために充分な時間攪拌する請求項1の方法。
- 該ステップb)が、水素またはナトリウムホウ化水素から選択された還元剤を加えることを含む請求項1の方法。
- 該還元剤のアニオンの、該金属イオン錯体中の該金属のカチオンに対する比が、8:1である請求項7の方法。
- 該ステップc)が湿式含浸を使用して行われる請求項1の方法。
- 該ステップc)が、追加のデンドリマーポリマーを、該デンドリマー金属ナノ複合物に加えることを含む請求項1の方法。
- 該ステップd)が、蒸発によって該溶媒を除去することを含む請求項1の方法。
- 該ステップe)が、該デンドリマー金属ナノ複合物を、高温下で酸化環境に曝すことに続き、高温下で還元環境に曝すことを含む請求項1の方法。
- 該酸化ステップが、該デンドリマー金属ナノ複合物を、酸素およびヘリウム環境に、300〜500℃の温度で、所望の時間曝すことを含む請求項12の方法。
- 該還元ステップが、該デンドリマー金属ナノ複合物を、水素雰囲気に、200〜400℃の温度で、所望の時間曝すことを含む請求項12の方法。
- 該金属塩が、プラチナ、ロジウムおよびパラジウムから選択される請求項1の方法。
- 該デンドリマーポリマーが、G3, G4、およびG5ポリアミドアミンポリマーから選択される請求項1の方法。
- 該触媒支持体が、酸化アルミニウム、酸化マグネシウム/酸化セリウム、酸化ジルコニウム、二酸化ケイ素、二酸化チタン、これらの酸化物から選択された2種または3種以上の酸化物および活性炭素の、混合物および/または固体溶液から選択される請求項1の方法。
- 基材上に堆積された触媒金属を含む触媒、該触媒金属は、隣接した金属クラスター間で2〜100ナノメートルの間隔を有するクラスター中に形成される。
- 該金属クラスターが、2〜150原子のサイズを有する請求項18の触媒。
- 該触媒金属が、プラチナ、ロジウムおよびパラジウムから選択される請求項18の触媒。
- 該基材が、酸化アルミニウム、酸化マグネシウム、酸化セリウム、酸化ジルコニウム、二酸化ケイ素、二酸化チタン、これらの酸化物から選択された2または3以上の酸化物および活性炭素の混合物および/または固体溶液から選択される請求項18の触媒。
- 基材上に堆積された触媒金属を含む触媒、該触媒金属クラスターは、該クラスターの70%が該平均直径の0.6nm以内にあり、そして該粒子の99%が該平均直径の1.5nm以内にあるサイズ分布を有する。
- 該触媒金属が、プラチナ、ロジウムおよびパラジウムから選択される請求項22の触媒。
- 該基材が、酸化アルミニウム、酸化マグネシウム、酸化セリウム、酸化ジルコニウム、二酸化ケイ素、二酸化チタン、これらの酸化物から選択された2種または3種以上の酸化物および活性炭素の混合物および/または固体溶液から選択される請求項22の触媒。
- 基材上に堆積された触媒金属を含む触媒、該触媒金属は、2〜150原子のサイズを有するクラスター中で生成される。
- 該触媒金属が、プラチナ、ロジウムおよびパラジウムから選択される請求項25の触媒。
- 該基材が、酸化アルミニウム、酸化マグネシウム、酸化セリウム、酸化ジルコニウム、二酸化ケイ素、二酸化チタン、これらの酸化物から選択された2種または3種以上の酸化物および活性炭素の混合物および/または固体溶液から選択される請求項25の触媒。
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DE102011017732A1 (de) | 2010-04-28 | 2012-01-19 | Hitachi-Ge Nuclear Energy,Ltd. | Wasserstoff- und Sauerstoff-Rekombinationskatalysator, Rekombinationsgerät und kerntechnische Anlage |
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