JP2012166175A - 一酸化炭素酸化触媒 - Google Patents
一酸化炭素酸化触媒 Download PDFInfo
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- JP2012166175A JP2012166175A JP2011031307A JP2011031307A JP2012166175A JP 2012166175 A JP2012166175 A JP 2012166175A JP 2011031307 A JP2011031307 A JP 2011031307A JP 2011031307 A JP2011031307 A JP 2011031307A JP 2012166175 A JP2012166175 A JP 2012166175A
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 50
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000010949 copper Substances 0.000 claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 150000001879 copper Chemical class 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000010953 base metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 description 20
- 238000001816 cooling Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 229910052756 noble gas Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004885 tandem mass spectrometry Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- -1 xenon ions Chemical class 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002343 gold Chemical class 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
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
【解決手段】上記課題は、負電荷を帯びた銅クラスターを含む一酸化炭素酸化触媒により達成することができる。
【選択図】図2
Description
(1)負電荷を帯びた銅クラスターを含む一酸化炭素酸化触媒。
(2)前記銅クラスターが5又は9個の銅原子からなる、(1)に記載の一酸化炭素酸化触媒。
(3)前記銅クラスターが担体に担持されている、(1)又は(2)に記載の一酸化炭素酸化触媒。
(4)(1)〜(3)のいずれかに記載の一酸化炭素酸化触媒の存在下で一酸化炭素と酸素とを反応させることを含む、一酸化炭素の酸化方法。
(5)反応の温度が−200℃〜100℃である、(4)に記載の酸化方法。
本発明の一酸化炭素酸化触媒は負電荷を帯びた銅クラスターを含む。銅クラスターとは複数個の銅原子が結合した銅原子集団である。
本発明の一酸化炭素酸化触媒は液相中又は気相中で製造することができる。液相中においては一般的に知られている方法(例えば、Langmuir 2010, 26(6), 4473-4479など)を用いることができる。また、気相中においては、例えばイオンスパッタリング法、プラズマ放電法、レーザー蒸発法などを用いることができる。以下、本実施例で採用されているイオンスパッタリング法について図1を参照して説明する(特開2003−185632号公報も参照されたい)。
本発明は、上記の一酸化炭素酸化触媒の存在下で一酸化炭素と酸素とを反応させることを含む一酸化炭素の酸化方法を包含する。本発明の方法では高温条件だけでなく低温条件においても反応を進行させることができる。温度条件は特に限定されないが、例えば−200℃〜100℃、好ましくは−100℃〜85℃、より好ましくは−50℃〜70℃、更に好ましくは−25℃〜55℃、特に好ましくは0℃〜40℃である。反応の際に温度を上げる又は下げるためのエネルギーを低減する観点からは、室温で反応させることが最も好ましい。
銅クラスターの形成及び活性評価は、図1に示す銅クラスター衝突反応実験装置を使用したイオンスパッタリング法及びタンデム質量分析法により行った。装置は、イオン銃1(Rokion Ionenstrahl-Technologie社、CORDIS Ar25/35c)、イオンレンズ3、冷却室4、四重極質量分析器5(Extrel社、162-8)、反応室6、四重極質量分析器7(Extrel社、162-8)、及び二次電子増倍管8(Burle社、Channeltron 4139S)を組み合わせることにより製造することができる。
正電荷を帯びた銅クラスター上では、以下の式に示すように、酸素と一酸化炭素とが共吸着して反応が停止した。
生成したCun −は一酸化炭素の酸化触媒として更に機能する。
2 銅ターゲット
3 イオンレンズ
4 冷却室
5 四重極質量分析器
6 反応室
7 四重極質量分析器
8 二次電子増倍管
Claims (5)
- 負電荷を帯びた銅クラスターを含む一酸化炭素酸化触媒。
- 前記銅クラスターが5又は9個の銅原子からなる、請求項1に記載の一酸化炭素酸化触媒。
- 前記銅クラスターが担体に担持されている、請求項1又は2に記載の一酸化炭素酸化触媒。
- 請求項1〜3のいずれかに記載の一酸化炭素酸化触媒の存在下で一酸化炭素と酸素とを反応させることを含む、一酸化炭素の酸化方法。
- 反応の温度が−200℃〜100℃である、請求項4に記載の酸化方法。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015011560A1 (en) | 2013-07-25 | 2015-01-29 | Toyota Jidosha Kabushiki Kaisha | Nitric oxide reducing catalyst, method for reducing nitric oxide, method for producing nitrogen, method for treating nitric oxide and carbon monoxide |
Citations (7)
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JP2000173444A (ja) * | 1998-12-04 | 2000-06-23 | Agency Of Ind Science & Technol | 電界放出型冷陰極及びその製造方法 |
WO2005095408A1 (ja) * | 2004-03-30 | 2005-10-13 | Nagoya Institute Of Technology | ケージ状配位子を有する多核金属錯体 |
JP2006202688A (ja) * | 2005-01-24 | 2006-08-03 | Asahi Kasei Corp | 金属錯体の燃料電池用電極触媒 |
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JP2009136807A (ja) * | 2007-12-07 | 2009-06-25 | Nagoya Institute Of Technology | 酸化触媒およびその利用 |
JP2010215603A (ja) * | 2009-02-23 | 2010-09-30 | Sumitomo Chemical Co Ltd | 環状化合物、その金属錯体及び変性金属錯体 |
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Patent Citations (7)
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JP2000173444A (ja) * | 1998-12-04 | 2000-06-23 | Agency Of Ind Science & Technol | 電界放出型冷陰極及びその製造方法 |
WO2005095408A1 (ja) * | 2004-03-30 | 2005-10-13 | Nagoya Institute Of Technology | ケージ状配位子を有する多核金属錯体 |
JP2006202688A (ja) * | 2005-01-24 | 2006-08-03 | Asahi Kasei Corp | 金属錯体の燃料電池用電極触媒 |
JP2009523066A (ja) * | 2006-01-10 | 2009-06-18 | キャボット コーポレイション | 合金触媒組成物ならびに同組成物の製造方法および使用方法 |
JP2007238601A (ja) * | 2006-02-08 | 2007-09-20 | Sumitomo Chemical Co Ltd | 多核金属錯体変性物及びその用途 |
JP2009136807A (ja) * | 2007-12-07 | 2009-06-25 | Nagoya Institute Of Technology | 酸化触媒およびその利用 |
JP2010215603A (ja) * | 2009-02-23 | 2010-09-30 | Sumitomo Chemical Co Ltd | 環状化合物、その金属錯体及び変性金属錯体 |
Non-Patent Citations (8)
Title |
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JPN6014011598; TANG, D. Y. et al: 'Theoretical Study on Mechanism of Cu2--Catalyzed CO Oxidation' Acta Chimica Sinica Vol.68, No.14, 2010, p.1379-1384 * |
JPN6014011601; HU, J.-P. et al: 'Reaction Mechanisms of CO Oxidation Catalyzed by Binary Copper Group Cluster Anions' Acta Physico-Chimica Sinica Vol.27, No.2, 20110105, p.329-336 * |
JPN6014011604; REVELES, J. U. et al: 'Reactivity Trends in the Oxidation of CO by Anionic Transition Metal Oxide Clusters' J. Phys. Chem. C Vol.114, No.12, 20091124, p.5438-5446 * |
JPN6014011605; MANZOLI, M. et al: 'CO oxidation over CuOx-CeO2-ZrO2 catalysts: Transient behaviour and role of copper clusters in conta' Applied Catalysis B: Environmental Vol.61, No.3-4, 20050623, p.192-205 * |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015011560A1 (en) | 2013-07-25 | 2015-01-29 | Toyota Jidosha Kabushiki Kaisha | Nitric oxide reducing catalyst, method for reducing nitric oxide, method for producing nitrogen, method for treating nitric oxide and carbon monoxide |
JP2015042401A (ja) * | 2013-07-25 | 2015-03-05 | トヨタ自動車株式会社 | 一酸化窒素還元触媒、一酸化窒素の還元方法、窒素の製造方法、排気ガス浄化触媒、及び排気ガスの浄化方法 |
US20160175773A1 (en) * | 2013-07-25 | 2016-06-23 | Toyota Jidosha Kabushiki Kaisha | Nitric oxide reducing catalyst, method for reducing nitric oxide, method for producing nitrogen, method for treating nitric oxide and carbon monoxide |
US9707514B2 (en) | 2013-07-25 | 2017-07-18 | Toyota Jidoahs Kabushiki Kaisha | Nitric oxide reducing catalyst, method for reducing nitric oxide, method for producing nitrogen, method for treating nitric oxide and carbon monoxide |
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