JPH10249208A - Binucleic iron complex catalyst - Google Patents
Binucleic iron complex catalystInfo
- Publication number
- JPH10249208A JPH10249208A JP9055233A JP5523397A JPH10249208A JP H10249208 A JPH10249208 A JP H10249208A JP 9055233 A JP9055233 A JP 9055233A JP 5523397 A JP5523397 A JP 5523397A JP H10249208 A JPH10249208 A JP H10249208A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- iron complex
- reduction
- oxygen
- oxygen reduction
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 150000004698 iron complex Chemical class 0.000 title claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000001301 oxygen Substances 0.000 claims abstract description 59
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims abstract description 5
- KSFOVUSSGSKXFI-GAQDCDSVSA-N CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O Chemical compound CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O KSFOVUSSGSKXFI-GAQDCDSVSA-N 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- HCIIFBHDBOCSAF-UHFFFAOYSA-N octaethylporphyrin Chemical compound N1C(C=C2C(=C(CC)C(C=C3C(=C(CC)C(=C4)N3)CC)=N2)CC)=C(CC)C(CC)=C1C=C1C(CC)=C(CC)C4=N1 HCIIFBHDBOCSAF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229950003776 protoporphyrin Drugs 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 52
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- -1 tetrabutylammonium tetrafluoroborate Chemical compound 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000036982 action potential Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この出願の発明は、鉄二核錯
体触媒に関するものである。さらに詳しくは、この出願
の発明は、水および有機溶媒中の溶存酸素の還元や、燃
料電池の酸素還元電極触媒、あるいは酸素酸化触媒等と
して有用な、新しい鉄二核錯体触媒に関するものであ
る。TECHNICAL FIELD The invention of this application relates to a dinuclear iron catalyst. More specifically, the invention of this application relates to a new iron dinuclear complex catalyst useful as a reduction of dissolved oxygen in water and an organic solvent, an oxygen reduction electrode catalyst of a fuel cell, an oxygen oxidation catalyst, and the like.
【０００２】[0002]
【従来の技術とその課題】従来より、酸素や電解還元に
ついては、１電子還元によるスーパーオキシドの生成
や、２電子還元による過酸化水素の生成が知られている
が、４電子還元による水の生成を可能とする方法やその
ための触媒に関してはあまり知られていない。４電子還
元では最も高い電位で酸素を還元することになるので、
この４電子還元を可能とする触媒が見出されるとする
と、この触媒は酸化力の強い酸化剤として利用されるこ
とにもなる。しかも４電子還元では水を生成するため、
そのための触媒は、クリーンなエネルギー変換系を提供
することができることになる。2. Description of the Related Art Conventionally, as for oxygen and electrolytic reduction, generation of superoxide by one-electron reduction and generation of hydrogen peroxide by two-electron reduction are known. Little is known about the methods that allow for the formation and the catalysts therefor. Since four-electron reduction reduces oxygen at the highest potential,
If a catalyst capable of performing this four-electron reduction is found, this catalyst will be used as an oxidizing agent having a strong oxidizing power. In addition, since water is generated by four-electron reduction,
A catalyst for that purpose can provide a clean energy conversion system.
【０００３】たとえばこれまでにも、平滑な白金電極
は、強酸性下で酸素４電子還元を可能とする酸素還元と
して燃料電池に使用されている。しかしながら、これま
での酸素４電子還元系では過電圧が大きいことから、こ
のエネルギーロスを解決することを必要となる。そこ
で、これまでにも、そのための手段として数多くの電子
移動速度増加剤、すなわち電極触媒系の提案がなされて
きている。まず、コバルトポルフィリン二核錯体による
解決方法が試みられている（たとえば、F.C. Ansonet,
al., J. Am. Chem. Soc.,１９８０，１０２，６０２
７）。だが、触媒の作動速度が遅く、酸素還元電流が低
いレベルに留まる結果となっている。しかも、錯体の合
成が極めて困難で収率も悪く、酸素と錯体の反応機構も
充分に解明されていない。[0003] For example, a smooth platinum electrode has been used in a fuel cell as an oxygen reduction which enables oxygen four-electron reduction under strong acidity. However, since the conventional oxygen four-electron reduction system has a large overvoltage, it is necessary to solve this energy loss. Therefore, a number of electron transfer speed increasing agents, that is, electrode catalyst systems have been proposed as means for that purpose. First, a solution using a cobalt porphyrin binuclear complex has been attempted (for example, FC Ansonet,
al., J. Am. Chem. Soc., 1980, 102, 602.
7). However, the operation speed of the catalyst is slow, and the oxygen reduction current remains at a low level. Moreover, the synthesis of the complex is extremely difficult and the yield is poor, and the reaction mechanism between oxygen and the complex has not been sufficiently elucidated.
【０００４】また、酸素の４電子還元触媒として、一つ
のコバルトポルフィリン錯体に複数の電子供与錯体（た
とえばルテニウムアンミン錯体）を連結した多核錯体系
が報告されている（たとえば、F.C. Anson et, al., J.
Am. Chem. Soc.,１９９１，１１３，９５６４）。だ
が、観測された還元作動電位は期待されたほど高いもの
ではなく、しかも、錯体が分解したり、あるいは電極表
面から溶液中に溶け出す場合があり、とても実用に耐え
得ないのが実情である。As a four-electron reduction catalyst for oxygen, a polynuclear complex system in which a plurality of electron-donating complexes (for example, ruthenium ammine complexes) are linked to one cobalt porphyrin complex has been reported (for example, FC Anson et. Al. , J.
Am. Chem. Soc., 1991, 113, 9564). However, the observed reduction action potential is not as high as expected, and the complex may decompose or dissolve out of the electrode surface into the solution, making it extremely unpractical. .
【０００５】そこでこの出願の発明は、以上のとおりの
従来の技術的限界を越えて、酸素還元電位が高く、触媒
活性が高いと共にその安定性にも優れ、その調製も容易
な、酸素４電子還元を可能とする、鉄二核錯体触媒を提
供することを目的としている。Therefore, the invention of this application exceeds the conventional technical limits as described above, and has a high oxygen reduction potential, high catalytic activity, excellent stability, and easy preparation. An object of the present invention is to provide a dinuclear iron catalyst capable of reduction.
【０００６】[0006]
【課題を解決するための手段】この出願の発明は、上記
の課題を解決するものとして、０〜２Ｖまでの酸化還元
電位を有する酸素還元用の３価の二核鉄錯体触媒を提供
する。そして、この発明は、上記の態様として、二核の
鉄錯体は、二つの鉄原子がオキソ配位子によって架橋さ
れたものである酸素還元用鉄錯体触媒をはじめ、二核の
鉄錯体からなり、酸性条件下に使用される酸素還元用鉄
錯体触媒や、鉄錯体は、単核鉄錯体が強塩基との反応に
より形成される二核錯体である酸素還元用鉄錯体触媒、
配位子が、テトラフェニルポルフィリン、オクタエチル
ポルフィリン、プロトポルフィリンIXのような大環状配
位子である酸素還元用鉄錯体触媒等も提供する。DISCLOSURE OF THE INVENTION The present invention provides a trivalent dinuclear iron complex catalyst for oxygen reduction having an oxidation-reduction potential of 0 to 2 V as an object of the present invention. In the present invention, as the above embodiment, the binuclear iron complex includes a binuclear iron complex, including an oxygen reduction iron complex catalyst in which two iron atoms are cross-linked by an oxo ligand. An iron complex catalyst for oxygen reduction used under acidic conditions, and an iron complex is an iron complex catalyst for oxygen reduction, which is a binuclear complex formed by the reaction of a mononuclear iron complex with a strong base.
Also provided is an iron complex catalyst for oxygen reduction, wherein the ligand is a macrocyclic ligand such as tetraphenylporphyrin, octaethylporphyrin, and protoporphyrin IX.
【０００７】また、この出願の発明は、上記のいずれか
の酸素還元用触媒からなる有機物の酸素酸化触媒をも提
供する。たとえば、酸化電位０〜１．５Ｖの、芳香族化
合物の酸素酸化触媒等を提供する。The invention of this application also provides an organic oxygen oxidation catalyst comprising any of the above-described oxygen reduction catalysts. For example, an aromatic compound oxygen oxidation catalyst having an oxidation potential of 0 to 1.5 V is provided.
【０００８】[0008]
【発明の実施の形態】この出願の発明は、上記のとおり
の鉄錯体を触媒とすることにより酸素還元を可能とする
ものであるが、以下にさらに詳細に説明する。まず、こ
の発明の酸素還元触媒に用いる鉄錯体としては、たとえ
ば配位子がテトラフェニルポルフィリン、オクタエチル
ポルフィリン、プロトポルフィリンIXのような大環状配
位子で構成される二核錯体である。ここでは、二つの鉄
はオキソ配位子によって架橋されているものが特徴の一
つとして示される。たとえば、特に、テトラフェニルポ
ルフィリンが例示される。BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application enables oxygen reduction by using the above-mentioned iron complex as a catalyst, which will be described in more detail below. First, the iron complex used in the oxygen reduction catalyst of the present invention is, for example, a binuclear complex whose ligand is composed of a macrocyclic ligand such as tetraphenylporphyrin, octaethylporphyrin, and protoporphyrin IX. Here, one of the features is that the two irons are bridged by an oxo ligand. For example, particularly, tetraphenylporphyrin is exemplified.
【０００９】そしてこの発明の鉄系酸素還元触媒では、
活性状態での鉄の数が重要である。たとえば、この発明
により提供されるμ−オキソ型の二核錯体は単核の鉄錯
体よりも高い４電子還元反応選択性を持っていること
で、触媒活性が発現する。この発明に使用することので
きる鉄錯体を例示すれば、μ−オキソビス（テトラフェ
ニルポルフィリナート鉄（III)）錯体、μ−オキソビス
（オクタエチルポルフィリナート鉄（III)）錯体、μ−
オキソビス（プロトポルフィリナート−IX鉄（III)）錯
体等が挙げられる。In the iron-based oxygen reduction catalyst of the present invention,
The number of iron in the active state is important. For example, the μ-oxo-type binuclear complex provided by the present invention has higher four-electron reduction reaction selectivity than a mononuclear iron complex, and thus exhibits catalytic activity. Examples of iron complexes that can be used in the present invention include a μ-oxobis (tetraphenylporphyrinatoiron (III)) complex, a μ-oxobis (octaethylporphyrinatoiron (III)) complex, and a μ-oxobis (octaethylporphyrinatoiron (III)) complex.
Oxobis (protoporphyrinato-IX iron (III)) complex and the like.
【００１０】いずれのものにおいても、この発明では中
心金属の鉄の２価〜４価の原子価変換が触媒活性の役割
を担い、配位子は主に酸化還元電位の調節に寄与される
ものと考えている。このため、前記に例示の配位子以外
であっても、溶液中で安定に鉄二核錯体を形成するもの
は、この触媒に含まれるものである。この発明の酸素還
元触媒は、構造が明確であるうえ、これを溶存させると
酸性下で０Ｖ以上の高い電位で酸素の２電子、または４
電子での電解還元を選択度高く可能とする。そして、４
電子還元の選択性が高いため、均一系で、有機化合物の
酸素酸化反応を促進させる触媒としても働く。また、触
媒を電極表面に固定して、不均一系電極触媒とすること
もでき、燃料電池の酸素還元電極、酸素検出用センサー
などに利用することができる。[0010] In any of the present invention, divalent to tetravalent valence conversion of iron as the central metal plays a role of catalytic activity in the present invention, and the ligand mainly contributes to the regulation of redox potential. I believe. For this reason, even if it is other than the ligands exemplified above, those which stably form a binuclear iron complex in a solution are included in this catalyst. The oxygen reduction catalyst of the present invention has a well-defined structure and, when dissolved, has two electrons or four oxygen atoms at a high potential of 0 V or more under acidic conditions.
Electrolytic reduction with electrons can be performed with high selectivity. And 4
Since it has high selectivity for electron reduction, it also works as a catalyst that promotes the oxygen oxidation reaction of organic compounds in a homogeneous system. Further, the catalyst can be fixed on the electrode surface to form a heterogeneous electrode catalyst, and can be used for an oxygen reduction electrode of a fuel cell, a sensor for detecting oxygen, and the like.
【００１１】この発明の酸素還元触媒は、系の酸素還元
等に応じて２電子過程、４電子過程の制御が可能のほ
か、たとえば活性酸素の溶存が好ましくないような酸素
酸化反応、高電位（酸素４電子還元熱力学電位）での酸
素還元等の利用目的に応じての使い分けが可能である。
以下、実施例を示し、さらに詳しく発明の実施の形態に
ついて説明する。The oxygen reduction catalyst of the present invention can control a two-electron process and a four-electron process in accordance with the oxygen reduction of the system and the like. It can be used properly according to the purpose of use such as oxygen reduction at oxygen four-electron reduction thermodynamic potential).
Hereinafter, examples will be shown and embodiments of the present invention will be described in more detail.
【００１２】[0012]
【実施例】実施例１ 蒸留精製ジクロロメタン２５ｍＬにμ−オキソビス（テ
トラフェニルポルフィリナート鉄（III)）錯体０．０１
７ｇとテトラブチルアンモニウムテトラフルオロホウ酸
塩０．８３ｇを加え、純粋アルゴン気流下、常温で攪拌
しながらトリフルオロ酢酸５滴を滴下した。これを常温
で１０分程度攪拌したあと、アルゴン気流下で３室式電
気化学測定セルに移動し、密閉の後、系を酸素ガスで置
換した。 EXAMPLE 1 0.01 μ-oxobis (tetraphenylporphyrinato iron (III)) complex was dissolved in 25 mL of dichloromethane purified by distillation.
7 g and tetrabutylammonium tetrafluoroborate (0.83 g) were added, and 5 drops of trifluoroacetic acid were added dropwise while stirring at room temperature under a pure argon stream. After stirring the mixture at room temperature for about 10 minutes, the mixture was moved to a three-chamber electrochemical measurement cell under an argon stream, and after sealing, the system was replaced with oxygen gas.
【００１３】次いで、上記セルを用いて電解を行った。
電解には、作用電極にグラッシーカーボンディスク電
極、白金リング電極、対極に白金ワイヤー電極、参照電
極に銀／塩化銀電極を用いた。ディスク電極電位を掃引
して酸素還元電位に設定し、同時に生成する過酸化水素
を独立に一定電位に設定したリング電極で酸化すること
により検出した。Next, electrolysis was performed using the above cell.
For electrolysis, a glassy carbon disk electrode, a platinum ring electrode, a platinum wire electrode as a counter electrode, and a silver / silver chloride electrode as a reference electrode were used as working electrodes. The potential of the disk electrode was swept to set the oxygen reduction potential, and simultaneously detected hydrogen peroxide was detected by independently oxidizing with a ring electrode set to a constant potential.
【００１４】測定は静止系（サイクリックボルタンメト
リー）と対流系（回転リングディスクボルタンメトリ
ー）の両方で実施し、検出電流をＸ−Ｙレコーダーを用
いてグラフ用紙に記録した。検出測定の結果、０．２Ｖ
に酸素４電子還元に由来する還元電流がディスク上で検
出された。リング電極で検出された過酸化水素の電流値
にごくわずかであった。使用した回転リングディスク電
極の形状に由来する補足率Ｎは、フェロセン／フェロセ
ニウム対を用いて０．３９と決定された。アルゴン雰囲
気下では、上述の酸素還元由来の還元電流は当然観測さ
れず、溶存錯体由来の酸化還元波（０．０５Ｖ）のみと
なる。酸素雰囲気下での補足率の値より、４電子還元の
選択性は９０％以上と決定された。The measurement was carried out in both a stationary system (cyclic voltammetry) and a convection system (rotating ring disk voltammetry), and the detected current was recorded on graph paper using an XY recorder. 0.2V as a result of detection measurement
A reduction current derived from oxygen four-electron reduction was detected on the disk. The current value of hydrogen peroxide detected at the ring electrode was very small. The capture factor N, derived from the shape of the rotating ring disk electrode used, was determined to be 0.39 using a ferrocene / ferrocenium pair. Under an argon atmosphere, the above-mentioned reduction current derived from oxygen reduction is naturally not observed, but only a redox wave (0.05 V) derived from a dissolved complex. The selectivity of the four-electron reduction was determined to be 90% or more from the value of the capture ratio under an oxygen atmosphere.
【００１５】この触媒系を用いてアルゴン雰囲気下で過
酸化水素の電解還元を実施したが、接触還元波は見られ
なかった。以上の事実より、触媒を介した酸素の直接４
電子還元による水生成が確認された。実施例２ 超純水２５ｍＬにアンモニウムヘキサフルオロリン酸塩
０．４１ｇをいれ、純粋アルゴン気流下、常温で攪拌し
ながらテトラフルオロホウ酸を０．５Ｍになるまで滴下
した。これを常温で１０分程度攪拌したあと、アルゴン
気流下で３室式電気化学測定セルに移動し、密閉の後、
系を酸素ガスで置換した。０．５ｍＭトルエン溶液５μ
Ｌのμ−オキソビス（テトラフェニルポルフィリナート
鉄（III)）錯体をスピンコーティングにより電極に修飾
した。[0015] Electrolytic reduction of hydrogen peroxide was carried out in an argon atmosphere using this catalyst system, but no catalytic reduction wave was observed. Based on the above facts, the direct transfer of oxygen through the catalyst
Water generation by electron reduction was confirmed. Example 2 0.41 g of ammonium hexafluorophosphate was added to 25 mL of ultrapure water, and tetrafluoroboric acid was added dropwise to the mixture under a pure argon stream at room temperature while stirring at room temperature. This was stirred at room temperature for about 10 minutes, and then moved to a three-chamber electrochemical measurement cell under an argon stream, and after sealing,
The system was replaced with oxygen gas. 0.5mM toluene solution 5μ
The μ-oxobis (tetraphenylporphyrinatoiron (III)) complex of L was modified on the electrode by spin coating.
【００１６】電解には、作用電極にグラッシーカーボン
ディスク電極、白金リング電極、対極に白金ワイヤー電
極、参照電極に飽和カロメル電極を用い、ディスク電極
電位を掃引して酸素還元電位に設定、同時に生成する過
酸化水素を独立に一定電位に設定したリング電極で酸化
することにより検出した。測定は静止系（サイクリック
ボルタンメトリー）と対流系（回転リングディスクボル
タンメトリー）の両方で実施し、検出電流をＸ−Ｙレコ
ーダーを用いてグラフ用紙に記録した。In the electrolysis, a glassy carbon disk electrode and a platinum ring electrode are used as a working electrode, a platinum wire electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. Hydrogen peroxide was detected by independently oxidizing with a ring electrode set at a constant potential. The measurement was performed in both a stationary system (cyclic voltammetry) and a convection system (rotating ring disk voltammetry), and the detected current was recorded on graph paper using an XY recorder.
【００１７】検出測定の結果、−０．２Ｖに酸素４電子
還元に由来する還元電流がディスク上で検出された。リ
ング電極で検出された過酸化水素の電流値にごくわずか
であった。使用した回転リングディスク電極の形状に由
来する補足率Ｎは、フェロシアン／フェリシアン対を用
いて０．３６と決定された。アルゴン雰囲気下では、上
述の酸素還元由来の還元電流は当然観測されず、溶存錯
体由来の酸化還元電位（−０．３５）のみとなる。酸素
雰囲気下での補足率の値より、４電子還元の選択性は８
８％以上と決定された。As a result of the detection measurement, a reduction current derived from oxygen four-electron reduction was detected on the disk at -0.2 V. The current value of hydrogen peroxide detected at the ring electrode was very small. The capture rate N, derived from the shape of the rotating ring disk electrode used, was determined to be 0.36 using a Ferrocyan / Felician pair. Under an argon atmosphere, the above-described reduction current derived from oxygen reduction is naturally not observed, but only the redox potential (−0.35) derived from the dissolved complex. From the value of the capture rate under an oxygen atmosphere, the selectivity of four-electron reduction is 8
It was determined to be 8% or more.
【００１８】この触媒系を用いてアルゴン雰囲気下で過
酸化水素の電解還元を実施したが、接触還元波は見られ
なかった。以上の事実より、触媒を介した酸素の直接４
電子還元による水生成が確認された。Electrolytic reduction of hydrogen peroxide was carried out in an argon atmosphere using this catalyst system, but no catalytic reduction wave was observed. Based on the above facts, the direct transfer of oxygen through the catalyst
Water generation by electron reduction was confirmed.
【００１９】[0019]
【発明の効果】この発明の酸素還元触媒は、酸素還元電
位が高く、触媒活性が高く、その安定性にも優れてい
る。そして、これを均一系触媒として使用することによ
り、有機化合物の酸素酸化を図ることができ、進んで選
択的な４電子酸化による水の生成を伴う高い酸化電位を
引き出すことができる。また、不均一系電極表面触媒と
して用いることにより、燃料電池の酸素還元電極、酸素
センサーとしての用途を提供するため、産業に資すると
ころが極めて大きい。The oxygen reduction catalyst of the present invention has a high oxygen reduction potential, high catalytic activity, and excellent stability. By using this as a homogeneous catalyst, oxygen oxidation of an organic compound can be achieved, and a high oxidation potential accompanying water generation by selective four-electron oxidation can be obtained. In addition, the use as a heterogeneous electrode surface catalyst provides applications as an oxygen reduction electrode and an oxygen sensor of a fuel cell, and thus greatly contributes to industry.
Claims (8)
元用の３価の二核鉄錯体触媒。1. A trivalent dinuclear iron complex catalyst having an oxidation potential of 0 to 2 V for oxygen reduction.
配位子によって架橋されたものである請求項１の酸素還
元用鉄錯体触媒。2. The iron complex catalyst for oxygen reduction according to claim 1, wherein the binuclear iron complex has two iron atoms cross-linked by an oxo ligand.
用される請求項１の酸素還元用鉄錯体触媒。3. The iron complex catalyst for oxygen reduction according to claim 1, which comprises a binuclear iron complex and is used under acidic conditions.
により形成される二核錯体である請求項１の酸素還元用
鉄錯体触媒。4. The iron complex catalyst for oxygen reduction according to claim 1, wherein the iron complex is a binuclear complex formed by reacting a mononuclear iron complex with a strong base.
ン、オクタエチルポルフィリン、プロトポルフィリンIX
のような大環状配位子である請求項１の酸素還元用鉄錯
体触媒。5. The ligand is tetraphenylporphyrin, octaethylporphyrin, protoporphyrin IX.
The iron complex catalyst for oxygen reduction according to claim 1, which is a macrocyclic ligand such as
項１ないし５のいずれかの酸素還元用鉄錯体触媒。6. The oxygen reduction iron complex catalyst according to claim 1, wherein the complex is a μ-oxo binuclear complex.
触媒からなる有機物の酸素酸化触媒。7. An organic oxygen oxidation catalyst comprising the oxygen reduction catalyst according to claim 1.
族化合物の酸素酸化触媒。8. The catalyst for oxidizing oxygen of an aromatic compound according to claim 9, which has an oxidation potential of 0 to 1.5 V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05523397A JP3432692B2 (en) | 1997-03-10 | 1997-03-10 | Binuclear iron complex catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05523397A JP3432692B2 (en) | 1997-03-10 | 1997-03-10 | Binuclear iron complex catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10249208A true JPH10249208A (en) | 1998-09-22 |
| JP3432692B2 JP3432692B2 (en) | 2003-08-04 |
Family
ID=12992895
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05523397A Expired - Fee Related JP3432692B2 (en) | 1997-03-10 | 1997-03-10 | Binuclear iron complex catalyst |
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| Country | Link |
|---|---|
| JP (1) | JP3432692B2 (en) |
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| JP2003053192A (en) * | 2001-08-13 | 2003-02-25 | Osaka Gas Co Ltd | Electrode material-complex composite, electrode, electrode for oxidation and method of synthesizing alkanol |
| JP2006059578A (en) * | 2004-08-18 | 2006-03-02 | National Institute Of Advanced Industrial & Technology | Cathode electrode catalyst for polymer electrolyte fuel cell and production method thereof |
| JP2006202688A (en) * | 2005-01-24 | 2006-08-03 | Asahi Kasei Corp | Metal complex fuel cell electrode catalyst |
| JP2006202686A (en) * | 2005-01-24 | 2006-08-03 | Asahi Kasei Corp | Metal compound fuel cell electrode catalyst |
| JP2008258150A (en) * | 2007-03-09 | 2008-10-23 | Sumitomo Chemical Co Ltd | Fuel cell electrode catalyst |
| US8114803B2 (en) | 2005-02-03 | 2012-02-14 | Toyota Jidosha Kabushiki Kaisha | Catalyst material and process for preparing the same |
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1997
- 1997-03-10 JP JP05523397A patent/JP3432692B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003053192A (en) * | 2001-08-13 | 2003-02-25 | Osaka Gas Co Ltd | Electrode material-complex composite, electrode, electrode for oxidation and method of synthesizing alkanol |
| JP4646463B2 (en) * | 2001-08-13 | 2011-03-09 | 大阪瓦斯株式会社 | Electrode material-complex complex, electrode, electrode for oxidation, and method for synthesizing alkanol |
| JP2006059578A (en) * | 2004-08-18 | 2006-03-02 | National Institute Of Advanced Industrial & Technology | Cathode electrode catalyst for polymer electrolyte fuel cell and production method thereof |
| JP2006202688A (en) * | 2005-01-24 | 2006-08-03 | Asahi Kasei Corp | Metal complex fuel cell electrode catalyst |
| JP2006202686A (en) * | 2005-01-24 | 2006-08-03 | Asahi Kasei Corp | Metal compound fuel cell electrode catalyst |
| US8114803B2 (en) | 2005-02-03 | 2012-02-14 | Toyota Jidosha Kabushiki Kaisha | Catalyst material and process for preparing the same |
| JP2008258150A (en) * | 2007-03-09 | 2008-10-23 | Sumitomo Chemical Co Ltd | Fuel cell electrode catalyst |
| WO2019203051A1 (en) * | 2018-04-18 | 2019-10-24 | 国立大学法人名古屋大学 | Method for decomposing persistent organic substance using super-powerful catalyst, and super-powerful catalyst |
| JPWO2019203051A1 (en) * | 2018-04-18 | 2021-05-13 | 国立大学法人東海国立大学機構 | Decomposition method of persistent organic matter using super strong catalyst and super strong catalyst |
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