JPS5840150A - Catalyst for reducing oxygen - Google Patents
Catalyst for reducing oxygenInfo
- Publication number
- JPS5840150A JPS5840150A JP56137249A JP13724981A JPS5840150A JP S5840150 A JPS5840150 A JP S5840150A JP 56137249 A JP56137249 A JP 56137249A JP 13724981 A JP13724981 A JP 13724981A JP S5840150 A JPS5840150 A JP S5840150A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- electrode
- taa
- activity
- metal complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000001301 oxygen Substances 0.000 title claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011572 manganese Chemical group 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000007772 electrode material Substances 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000007832 Na2SO4 Substances 0.000 abstract 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract 1
- 235000011152 sodium sulphate Nutrition 0.000 abstract 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 abstract 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 abstract 1
- 235000019801 trisodium phosphate Nutrition 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 18
- 239000000446 fuel Substances 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- SWGZHHCRMZDRSN-BTJKTKAUSA-N (Z)-but-2-enedioic acid 1-phenoxypropan-2-ylhydrazine Chemical compound OC(=O)\C=C/C(O)=O.NNC(C)COC1=CC=CC=C1 SWGZHHCRMZDRSN-BTJKTKAUSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- 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
- H01M4/9008—Organic or organo-metallic compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
不発、明は、有用な酸素還元触媒に関し、更に詳しくは
、カソード電極用酸素還元触媒に関し、その、目的とす
ると、ころは、白金以外の物質で、膳素の還元過電圧を
低くシ、かつ寿命の！い触媒を提供することにある。[Detailed Description of the Invention] The present invention relates to a useful oxygen reduction catalyst, and more particularly, to an oxygen reduction catalyst for cathode electrodes, the purpose of which is to reduce the amount of a nutrient using a substance other than platinum. Low overvoltage and long life! The goal is to provide a new catalyst.
従来、酸素還元触媒としては種々のものが公知である。Conventionally, various oxygen reduction catalysts are known.
これら酸素還元触媒の性能を評価する方法の一つとして
、カソード電極として用いる方法がある・これは、７ノ
ード極の燃料として、水素。One of the methods to evaluate the performance of these oxygen reduction catalysts is to use them as cathode electrodes.This method uses hydrogen as the fuel for the 7-node electrode.
メタン、メタノール、ギ醗、とドラジン等を用い。Using methane, methanol, vinegar, drazine, etc.
カソード極側に酸素、又は空気を用いて組み立てる燃料
電池等の電気化学的装置のカソード電極用としての評価
法であり、かつ燃料電池用カソード電極の実用評価と一
致している０ ′一方、白金は酸素還元触媒
としてよぐ知ら・れ、触媒性能の優れたものであるが、
コストと千′の資源的制約の問題があり、燃料電池を実
用化するときなどには問題点となっている。そのため、
白金に代わる酸素還元電位の低い高活性な触媒の開発が
望まれ、多くの物質が電極用触媒として評価されてきた
が、未だに高い特性を有する触媒は発見されていない。This is an evaluation method for cathode electrodes of electrochemical devices such as fuel cells assembled using oxygen or air on the cathode side, and is consistent with practical evaluation of cathode electrodes for fuel cells. is well known as an oxygen reduction catalyst and has excellent catalytic performance.
There are problems with cost and thousands of resource constraints, which are problems when putting fuel cells into practical use. Therefore,
It has been desired to develop a highly active catalyst with a low oxygen reduction potential to replace platinum, and many materials have been evaluated as electrode catalysts, but no catalyst with high properties has yet been discovered.
−
例えば、近年、エイチーアルド（Ｈ，Ａｌｔ）らによる
ジャーナλ・オプ・エレクトリアナリテイクΦケミスト
リー第３゛１巻１９頁（／９７／） ；エイチ・グンド
ナー（Ｈ，Ｂｉｎｄｎｓｒ ）らによるジャーナル・オ
プ・キャタリシス第コ１巻１頁（／９７３） ；西独特
公第２ｏｑｔＪｓｑ号； エフ・ベック（Ｆ’、 Ｂｅ
ａｋ ）らによるザイトシュリフト・ツユ・ナチュアホ
ルシュング第コｔａ巻１００９頁（／９７３）などに、
ポルフィリン、ブタロシアニン、テトラアザアヌレン等
の金属錯体が、拳素還元触媒として高い活性があること
が示されており、特に、これらの中でテトラアザアヌレ
ンの金属錯体（次の式（２）に示す構造を有し、Ｍ・−
ＴＡＡと略記する。Ｍ・は金属である。）は、活性が特
に優れていることが報告されているが、いずれも触媒寿
命が短いという欠点があった。- For example, in recent years, the journal λ op Electrical Analysis Φ Chemistry Vol. 3, p. 19 (/97/) by H. Alt et al.; Catalysis Vol. 1, page 1 (/973); West German Special Publication No. 2 oqtJsq; F', Be
ak) et al., vol. 1009 (/973), etc.
It has been shown that metal complexes such as porphyrins, butalocyanines, and tetraazaannulenes have high activity as hydrogen reduction catalysts. It has a structure, M・-
It is abbreviated as TAA. M. is metal. ) have been reported to have particularly excellent activity, but they all had the drawback of short catalyst life.
そこで、本発明者らは、新たにＭｓ −ＴＡＡの誘導体
についての探索を行ない、より寿命が長く、活性も高い
触媒の開発を進め、本発明に至った。Therefore, the present inventors conducted a new search for derivatives of Ms-TAA, proceeded with the development of a catalyst with a longer life and higher activity, and arrived at the present invention.
本発明で用いる金属錯体の分子構造を式（３）に示す。The molecular structure of the metal complex used in the present invention is shown in formula (3).
式（３）で示される化合物の一般名は、４． ／Ｊ−ジ
ピリジル−ｉ、ｒ−ジへイドロージベンゾ［ｂ＃ｉ ）
［／。The common name of the compound represented by formula (3) is 4. /J-dipyridyl-i,r-dihydrodibenzo [b#i)
[/.
ｑ、ｒ、ｕ］テトラアザシクロテトラデシンの金属錯体
であり、６位と１３位の２つのピリジル基が水素である
ものがテトラアザアヌレン（略してＴＡＡ ）であると
ころから、略してＭの−６，１３−ジピリジル−ＴＡＡ
と呼ばれる。本発明でも以下にこの略称を用いる。q, r, u] A metal complex of tetraazacyclotetradecine, in which the two pyridyl groups at positions 6 and 13 are hydrogen, is tetraazaannulene (abbreviated as TAA), so it is abbreviated as M. -6,13-dipyridyl-TAA
It is called. This abbreviation will be used hereinafter in the present invention as well.
中心金属は、コバルト、鉄、ニッケル、マンガンにおい
て高い活性と長い触媒寿命を示す。中でもコバルトが活
性寿命の双方において最も優れた特性を示した。The central metals exhibit high activity and long catalyst life in cobalt, iron, nickel, and manganese. Among them, cobalt showed the best properties in terms of both active life.
上記金属錯体の合成法は、シー・ライハルト（Ｃ，Ｒ＠
１ｃｈａｒｄｔ ）らにより、ザイトシュリフト・ナチ
ュアホルシュ（Ｚ、Ｎａｔｕｒｌｏｒｍｅｈ ＞、第Ｊ
Ｊｂ巻ＩＱ／コ頁（／９７１）に報告されている０
電極触媒として使用するときに用いる電解液は、削性で
は、例えば、硫酸、リン酸等、中性では、例えば、１％
８０４ 、１％Ｐ０４水溶液等、アルカリ性では例えば
、ＫＯＨ、ＮａＯＨ等、当分舒で広く使用されている電
解液が使用可能である。The synthesis method of the above metal complex is based on See Reichardt (C,R@
Seitschrift Naturhorsch (Z, Naturlormeh >, No. J
0 Reported in Volume Jb IQ/Page Co (/971) 0 The electrolytic solution used when used as an electrode catalyst has a machinability such as sulfuric acid or phosphoric acid, and a neutral one such as 1%
804, a 1% P04 aqueous solution, and alkaline electrolytes such as KOH and NaOH, which are widely used in modern society, can be used.
電極材料としては、カーボン、金属、酸化物等が使用で
きる。酸性電解液を用いる場合には、グラファイト粉末
、アセチレン・ブラック、活性炭、チタン、タンタル、
モリブデン、タングステン等が好ましく使用できる。ア
ルカリ性電解液を用いる場合には、グラファイト粉末、
アセチレン・ブラック、活性炭、ニッケル、鉄、コバル
）、ペロブスカイ）４１複含酸化物等が好ましく使用で
きる。Carbon, metal, oxide, etc. can be used as the electrode material. When using an acidic electrolyte, graphite powder, acetylene black, activated carbon, titanium, tantalum,
Molybdenum, tungsten, etc. can be preferably used. When using an alkaline electrolyte, graphite powder,
Acetylene black, activated carbon, nickel, iron, cobal), perovsky) 41 complex oxides, etc. can be preferably used.
触媒の電極への担持法としては、触媒を溶媒中に溶かし
たものに電極を浸す方法、蒸着による方法、スプレーに
よる吹きつけ法、刷毛による塗布法、電極材料粉末と触
媒を混合して電極をつくる方法等があるが、本発明の触
媒は、水溶性があるので、電解液に直接添加することに
よっても使用でき、電極の構造を簡素化できる。触媒の
電解液への溶解量は、／ ９／ｌから／４１までが好ま
しい。The catalyst can be supported on the electrode by dipping the electrode in a solution of the catalyst in a solvent, by vapor deposition, by spraying, by applying with a brush, and by mixing the electrode material powder and the catalyst. Although there are various methods for making the catalyst, since the catalyst of the present invention is water-soluble, it can also be used by directly adding it to an electrolytic solution, thereby simplifying the structure of the electrode. The amount of catalyst dissolved in the electrolyte is preferably from /9/l to /41/l.
電極材料粉末と触媒を混合して電極を作る方法の場合、
昔通電極材料粉末から電極を作る場合のように、バイン
ダーを使用することができ、混合粉末を加圧プレスする
ことにより、電極とすることができる。バインダーとし
ては、ぎリピニルアルコール、ポリ四フッ化エチレン、
〆リエチレン、ポリプロピレン、〆リスチレン等が使用
できる。In the case of the method of making electrodes by mixing electrode material powder and catalyst,
As in the case of making electrodes from powdered conductive electrode materials in the past, a binder can be used, and electrodes can be made by pressing the mixed powder under pressure. As a binder, polypinyl alcohol, polytetrafluoroethylene,
Polyethylene, polypropylene, restyrene, etc. can be used.
なお、このように、バインダーを用いて得られた電極は
、さらにアルゴン、又は窒素雰囲気中で熱処理すること
により、電極としての活性が向上する。Note that the electrode obtained using the binder in this manner is further heat-treated in an argon or nitrogen atmosphere to improve its activity as an electrode.
触媒の混合量は、電極材料粉末の６００１重量％から１
０重量−までが好重しい。少なすぎると触媒活性が十分
発揮されなく、又多すぎると電流が流れにくくなる。The amount of catalyst mixed is from 6001% by weight to 1% by weight of the electrode material powder.
Weight up to 0 weight is preferable. If it is too small, the catalyst activity will not be sufficiently exhibited, and if it is too large, it will be difficult for current to flow.
電極は、室温から１１０℃まで好ましく使用できるｄ〕
電極触媒としての活性の測定は、下記の２種類の方法で
行なった。The electrode can be preferably used from room temperature to 110° C. d] The activity as an electrode catalyst was measured by the following two methods.
測定法ｌ）水素−酸素燃料電池を構成し発生する電流−
電位をｍ走する。Measurement method l) Current generated by composing a hydrogen-oxygen fuel cell
Run the potential m.
カソード電極は、以下の方法で作製した。The cathode electrode was produced by the following method.
アセチレン・ブラック等の炭素粉末ｌｏｇと該触媒１Ｏ
１１９をバインダーであるポリ四フッ化エチレン水懸濁
液で攪拌し、これを電子集合体であるチタンメツシュに
吹きつける・さらにその上から多孔性ポリ四７ツ化エチ
レン展をのせ、３００９．−の圧力で加圧圧着を行なう
。これを３ｏｏ−ＩＩｏｏ″Ｃでアルゴン、又は窒素雰
囲気中で熱処理を行ない、これをカソード電極とした。Carbon powder log such as acetylene black and the catalyst 1O
119 is stirred with an aqueous suspension of polytetrafluoroethylene, which is a binder, and this is sprayed onto a titanium mesh, which is an electron assembly. Further, porous polytetrafluoroethylene is placed on top of the titanium mesh, and 3009. - Perform pressure bonding at a pressure of -. This was heat-treated at 3oo-IIoo''C in an argon or nitrogen atmosphere, and was used as a cathode electrode.
同様の作製方法で、触媒として白金黒を用いてアノード
電極を作った。An anode electrode was fabricated using a similar fabrication method using platinum black as a catalyst.
これらの電極を用いて電解液を／Ｎ硫酸とし、カソード
に酸素を、アノードに水素を圧入して、電圧４ｊＯｍＶ
において発生する電流を測定した。Using these electrodes, the electrolyte is /N sulfuric acid, oxygen is injected into the cathode, hydrogen is injected into the anode, and the voltage is 4jOmV.
The current generated was measured.
−電位を測定する。-Measure the electrical potential.
測定法ハで用いた水素−酸素燃料電池を用し１て。Using the hydrogen-oxygen fuel cell used in measurement method c.
電解液にｚｏＯｗｉ／ノの割合で触媒を添加し、電圧ｔ
ｌＯｍＶにおいて発生する電流を測定した。A catalyst is added to the electrolyte at a ratio of zoOwi/no, and the voltage t is
The current generated at lOmV was measured.
以下に本発明の該触媒についての実施例をもって詳細に
説明するが、本発明の該触媒の利用については、実施例
に限定されるものではない。The catalyst of the present invention will be described in detail below with examples, but the use of the catalyst of the present invention is not limited to the examples.
実施例１
本発明の触媒を用いて測定法ｌ）によって活性を測定し
た。比較のためＣｏ−ＴＡＡについても同様の測定を行
なった。結果を下記表７に示す。活性値は、電位４ｊＯ
ｍＶにおける発生電流値（単位ｍＡ ）とし、その経時
変化を示す。Example 1 The activity of the catalyst of the present invention was measured by measurement method l). For comparison, similar measurements were performed on Co-TAA. The results are shown in Table 7 below. The activation value is the potential 4jO
The generated current value in mV (unit: mA) is shown, and its change over time is shown.
表 １
本発明の触媒は、Ｃｏ−ＴＡＡと比較して初期の発生電
流では同じであるが、Ｃｏ−ＴＡＡが７００時間後から
活性が低下し、１ＯＯＯ時間後にはほとんど活性がなく
なっているのに対し、本発明の触媒は、１ｏｏｏ時間後
にも高い活性を維持していた。Table 1 The catalyst of the present invention has the same initial current generation as Co-TAA, but the activity of Co-TAA decreases after 700 hours and has almost no activity after 100 hours. In contrast, the catalyst of the present invention maintained high activity even after 100 hours.
実施例コ
本発明の触媒を用いて、測定法２）によって活性を測定
した。Ｃｏ−ＴＡＡは、非水溶性であるため測定法２）
による活性の測定は出来ない。結果を表２に示す。活性
値は、電位４ｊＯｍＶにおける発生電流値（単位ｒａＡ
）とし、その経時変化を示す。Example Using the catalyst of the present invention, activity was measured by measurement method 2). Co-TAA is water-insoluble, so measurement method 2)
It is not possible to measure activity by The results are shown in Table 2. The activation value is the generated current value (unit: raA) at a potential of 4jOmV.
) and its change over time is shown.
表 ２
本発明の触媒は、１ＯＯＯ時間後でも発生する電流値に
著しい変化はなかった。Table 2 With the catalyst of the present invention, there was no significant change in the current value generated even after 100 hours.
実施例３ 下記の触媒を用いて測定法ｌ）により活性を測定した。Example 3 Activity was measured by measurement method 1) using the following catalyst.
（１） Ｆｅ −４，／ｊ−ジピリジルＴＡＡ（２）
Ｎｉ −６，／３−ジピリジルＴＡＡ（８） Ｍ
ｎ−４／ｊ−ジピリジルＴＡＡ比較のため、Ｆｅ −Ｔ
ＡＡ 、Ｎｉ −ＴＡＡ 、 Ｍｎ−ＴＡＡについても
同様の条件で測定した〇
上記（１）〜（８）の化合物は、中心金属が同一なＴＡ
Ａと比較して高い活性を示し、かつ寿命の面において優
れた結果を示した。(1) Fe-4,/j-dipyridyl TAA (2)
Ni-6,/3-dipyridyl TAA (8) M
For n-4/j-dipyridyl TAA comparison, Fe-T
AA, Ni-TAA, and Mn-TAA were also measured under the same conditions. The compounds (1) to (8) above were TA with the same central metal.
Compared to A, it showed higher activity and better results in terms of life.
同一配位子における中心金属の活性に対する傾向は、Ｃ
ｏ ＞ Ｍｎ ＞ Ｆｅ ＞ Ｎｌの順であった。The tendency for central metal activity in the same ligand is C
The order was o>Mn>Fe>Nl.
以上の実施例で具体的に説明したように、本発明の触媒
は最も活性が優れていると報告されているＴＡＡ錯体と
同等の活性を持ち、水溶性にすることにより欠点とされ
ていた寿命を著しく改善したものであり、工業的価値は
極めて大きい。As specifically explained in the examples above, the catalyst of the present invention has an activity equivalent to that of the TAA complex, which is reported to have the best activity, and has a lifespan that was considered a drawback by making it water-soluble. This is a significant improvement over the conventional method, and its industrial value is extremely large.
特許出原人 旭化成工業株式会社Patent originator: Asahi Kasei Industries, Ltd.
Claims (1)
。）で表わされる金属錯体からなる酸素還元触媒。 （２）、中心金属Ｍｅがコバルトである特許請求の範囲
第１項記載の酸素還元触媒。[Claims] (S) An oxygen reduction catalyst consisting of a metal complex represented by the general formula (1) (M represents cobalt, iron, nickel or manganese). (2) The central metal Me is cobalt. An oxygen reduction catalyst according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56137249A JPS5840150A (en) | 1981-09-01 | 1981-09-01 | Catalyst for reducing oxygen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56137249A JPS5840150A (en) | 1981-09-01 | 1981-09-01 | Catalyst for reducing oxygen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5840150A true JPS5840150A (en) | 1983-03-09 |
Family
ID=15194247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56137249A Pending JPS5840150A (en) | 1981-09-01 | 1981-09-01 | Catalyst for reducing oxygen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5840150A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005104275A1 (en) * | 2004-04-22 | 2005-11-03 | Nippon Steel Corporation | Fuel cell and gas diffusion electrode for fuel cell |
| JP2005332807A (en) * | 2004-04-22 | 2005-12-02 | Nippon Steel Corp | Fuel cell |
| JP2006120335A (en) * | 2004-10-19 | 2006-05-11 | Nippon Steel Corp | Gas diffusion layer for fuel cell, gas diffusion electrode for the fuel cell and the fuel cell |
| JP2006156013A (en) * | 2004-11-26 | 2006-06-15 | Nippon Steel Corp | Catalyst for oxygen electrode in polymer electrolyte fuel cell |
| JP2006202686A (en) * | 2005-01-24 | 2006-08-03 | Asahi Kasei Corp | Electrode catalyst for fuel cell of metallic compound |
| CN100466345C (en) * | 2004-04-22 | 2009-03-04 | 新日本制铁株式会社 | Fuel cell and gas diffusion electrode for fuel cell |
| JP2017010853A (en) * | 2015-06-24 | 2017-01-12 | 国立研究開発法人産業技術総合研究所 | Electrochemical oxygen reduction catalyst |
-
1981
- 1981-09-01 JP JP56137249A patent/JPS5840150A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005104275A1 (en) * | 2004-04-22 | 2005-11-03 | Nippon Steel Corporation | Fuel cell and gas diffusion electrode for fuel cell |
| JP2005332807A (en) * | 2004-04-22 | 2005-12-02 | Nippon Steel Corp | Fuel cell |
| CN100466345C (en) * | 2004-04-22 | 2009-03-04 | 新日本制铁株式会社 | Fuel cell and gas diffusion electrode for fuel cell |
| US9786925B2 (en) | 2004-04-22 | 2017-10-10 | Nippon Steel & Sumitomo Metal Corporation | Fuel cell and fuel cell use gas diffusion electrode |
| JP2006120335A (en) * | 2004-10-19 | 2006-05-11 | Nippon Steel Corp | Gas diffusion layer for fuel cell, gas diffusion electrode for the fuel cell and the fuel cell |
| JP4520815B2 (en) * | 2004-10-19 | 2010-08-11 | 新日本製鐵株式会社 | Gas diffusion layer for fuel cell, gas diffusion electrode for fuel cell, and fuel cell |
| JP2006156013A (en) * | 2004-11-26 | 2006-06-15 | Nippon Steel Corp | Catalyst for oxygen electrode in polymer electrolyte fuel cell |
| JP2006202686A (en) * | 2005-01-24 | 2006-08-03 | Asahi Kasei Corp | Electrode catalyst for fuel cell of metallic compound |
| JP2017010853A (en) * | 2015-06-24 | 2017-01-12 | 国立研究開発法人産業技術総合研究所 | Electrochemical oxygen reduction catalyst |
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