JP2018202327A - 金属中心ポルフィリン−炭素の複合体 - Google Patents
金属中心ポルフィリン−炭素の複合体 Download PDFInfo
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- JP2018202327A JP2018202327A JP2017110962A JP2017110962A JP2018202327A JP 2018202327 A JP2018202327 A JP 2018202327A JP 2017110962 A JP2017110962 A JP 2017110962A JP 2017110962 A JP2017110962 A JP 2017110962A JP 2018202327 A JP2018202327 A JP 2018202327A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 84
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- 150000004032 porphyrins Chemical class 0.000 claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims description 48
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000446 fuel Substances 0.000 claims description 12
- 229910052783 alkali metal Chemical group 0.000 claims description 10
- 150000001340 alkali metals Chemical group 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
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- 238000004090 dissolution Methods 0.000 claims description 4
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- 229910052703 rhodium Inorganic materials 0.000 claims description 4
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- 229910006127 SO3X Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 43
- 230000003647 oxidation Effects 0.000 abstract description 26
- 230000000052 comparative effect Effects 0.000 description 32
- 238000011156 evaluation Methods 0.000 description 26
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- 239000002904 solvent Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 7
- 239000008103 glucose Substances 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UJKPHYRXOLRVJJ-MLSVHJFASA-N CC(O)C1=C(C)/C2=C/C3=N/C(=C\C4=C(CCC(O)=O)C(C)=C(N4)/C=C4\N=C(\C=C\1/N\2)C(C)=C4C(C)O)/C(CCC(O)=O)=C3C Chemical compound CC(O)C1=C(C)/C2=C/C3=N/C(=C\C4=C(CCC(O)=O)C(C)=C(N4)/C=C4\N=C(\C=C\1/N\2)C(C)=C4C(C)O)/C(CCC(O)=O)=C3C UJKPHYRXOLRVJJ-MLSVHJFASA-N 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ALVPFGSHPUPROW-UHFFFAOYSA-N di-n-propyl disulfide Natural products CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229960003569 hematoporphyrin Drugs 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
Description
実施例の金属中心ポルフィリンを担持する多孔質炭素は、非特許文献1記載の方法によって合成した。なお、実施例1と実施例3では、水熱処理温度を130℃、焼成温度を900℃とした。実施例2と実施例4では、水熱処理温度を180℃、焼成温度を900℃とした。なお、本発明の複合体の特徴は、金属中心ポルフィリンを担持する多孔質炭素にある。このため、本発明の複合体を構成している多孔質炭素自体を、実施例1から実施例4で表記している。比較例についても同様で、多孔質炭素自体を比較例1から比較例4で表記している。
実施例と比較例で得られた多孔質炭素に金属中心ポルフィリンを担持して複合体を得た。用いた金属中心ポルフィリンの化学構造を下記に示す。
水0.25mL、エタノール0.25mL、およびナフィオン(Aldrich社、5%(w/w))5μLからなる混合液中に複合体5mgを加え、超音波分散機により、実施例または比較例の多孔質炭素を備える複合体を5分間分散させた。得られた複合体分散液から2μL分取し、ガラス状炭素電極上に滴下し、乾燥させて修飾電極を得た。
表3の条件下、掃引速度10mV/Sで、リニアスウィープボルタンメトリー測定により、修飾電極の酸素還元性能、CO酸化性能、またはグルコース酸化性能を評価した。なお、酸素還元性能は酸素雰囲気下で、CO酸化性能はCO雰囲気下でそれぞれ評価した。
の多孔質炭素を備える複合体を用いた電極のCO酸化電流値は、比較例1の多孔質炭素を備える複合体を用いた電極のCO酸化電流値を上回った。実施例2の多孔質炭素を備える複合体を用いた電極のCO酸化電流値は、比較例1、比較例3、および比較例4(金属中心ポルフィリン担持時にエタノール溶媒を使用)の多孔質炭素を備える複合体を用いた電極のCO酸化電流値を上回った。
Claims (8)
- 大半が直径10〜100nmの細孔を有する担持部を備え、メソ−マクロ孔容量が0.1〜5mL/gである多孔質炭素と、
少なくとも前記多孔質炭素の前記担持部に担持された金属中心ポルフィリンと、
を有する複合体。 - 請求項1において、
前記多孔質炭素のメソ−マクロ孔容量が0.4〜0.8mL/gである複合体。 - 請求項1または2において、
前記多孔質炭素が、外径50nm〜10μmの樹枝状の炭素がつながった構造である複合体。 - 請求項1から3のいずれかにおいて、
前記金属中心ポルフィリンが下記の化学式(I)で表わされる複合体。
R1、R3、R4、R6、R7、R9、R10、およびR12は、独立して、水素原子、メチル基、エチル基、SO3X、QC(=O)OQ’、QC(=O)Q’、またはQOZである(Xは水素原子またはアルカリ金属である。Qは単結合、水素原子、炭素数1〜5のアルキル基、またはアルカリ金属である。Q’は水素原子、炭素数1〜5のアルキル基、またはアルカリ金属である。Zは水素原子またはアルカリ金属である)。
R2、R5、R8、およびR11は、独立して、水素原子または下記の化学式(II)で表わされる物質である(R1’、R2’、およびR3’は、独立して、水素原子、−COOT、−OCH2T、−OT(Tは水素原子、炭素数1〜5のアルキル基、またはアルカリ金属である))。)
- 請求項1から4のいずれかに記載された複合体の製造方法であって、
前記金属中心ポルフィリンを有機溶媒に溶解させて溶液を得る溶解工程と、
前記溶液に前記多孔質炭素を分散させて、前記金属中心ポルフィリンを前記多孔質炭素に浸漬させる浸漬工程と、
前記浸漬工程を経た前記溶液を、ろ過または溶媒蒸発乾固して複合体を得る複合化工程と、
を有する複合体の製造方法。 - 請求項1から4のいずれかに記載された複合体を有し、酸素還元能、ならびにCO、糖、およびアルコール酸化能を有する電極。
- 請求項6に記載の電極を有する固体高分子型燃料電池。
- 請求項6に記載の電極を有するCOセンサー、糖センサー、またはアルコールセンサー。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005507958A (ja) * | 2001-07-26 | 2005-03-24 | ユニベルシテ・ド・リエージュ | 多孔質炭素材料 |
JP2007099612A (ja) * | 2005-09-06 | 2007-04-19 | National Institute Of Advanced Industrial & Technology | 均一な粒子径を有するメソ多孔性炭素ビーズ、その製造方法および製造装置、ならびに該メソ多孔性炭素ビーズを担体とする水処理用触媒、該触媒の性能評価装置と、該触媒を用いた実廃水処理装置 |
JP2010284614A (ja) * | 2009-06-15 | 2010-12-24 | National Institute Of Advanced Industrial Science & Technology | 一酸化炭素の電気化学的酸化用触媒 |
JP2014506529A (ja) * | 2011-01-25 | 2014-03-17 | キャボット ノリット ネーデルラント ベスローテン フェンノートシャップ | 触媒活性のある活性炭の製造 |
JP2014154225A (ja) * | 2013-02-05 | 2014-08-25 | Sony Corp | 電極材料、電極及び電池 |
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2017
- 2017-06-05 JP JP2017110962A patent/JP6923189B2/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005507958A (ja) * | 2001-07-26 | 2005-03-24 | ユニベルシテ・ド・リエージュ | 多孔質炭素材料 |
JP2007099612A (ja) * | 2005-09-06 | 2007-04-19 | National Institute Of Advanced Industrial & Technology | 均一な粒子径を有するメソ多孔性炭素ビーズ、その製造方法および製造装置、ならびに該メソ多孔性炭素ビーズを担体とする水処理用触媒、該触媒の性能評価装置と、該触媒を用いた実廃水処理装置 |
JP2010284614A (ja) * | 2009-06-15 | 2010-12-24 | National Institute Of Advanced Industrial Science & Technology | 一酸化炭素の電気化学的酸化用触媒 |
JP2014506529A (ja) * | 2011-01-25 | 2014-03-17 | キャボット ノリット ネーデルラント ベスローテン フェンノートシャップ | 触媒活性のある活性炭の製造 |
JP2014154225A (ja) * | 2013-02-05 | 2014-08-25 | Sony Corp | 電極材料、電極及び電池 |
Non-Patent Citations (2)
Title |
---|
A. VINU ET AL., J. PHYS. CHEM. B, vol. 107, JPN6021005003, 2003, pages 8297 - 8299, ISSN: 0004446060 * |
S. KUBO ET AL., CHEMISTRY OF MATERIALS, vol. 25, JPN6021005006, 2013, pages 4781 - 4790, ISSN: 0004446061 * |
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