JPH0372622B2 - - Google Patents
Info
- Publication number
- JPH0372622B2 JPH0372622B2 JP57102543A JP10254382A JPH0372622B2 JP H0372622 B2 JPH0372622 B2 JP H0372622B2 JP 57102543 A JP57102543 A JP 57102543A JP 10254382 A JP10254382 A JP 10254382A JP H0372622 B2 JPH0372622 B2 JP H0372622B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon atoms
- taa
- present
- tetraazaannulene
- alkyl group
- 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.)
- Expired - Lifetime
Links
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000004700 cobalt complex Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Description
本発明は、新規なテトラアザアヌレン・コバル
ト錯体（以下Co−TAAと略記する）に関するも
のである。
本発明の新規なCo−TAAは、酸素還元触媒と
して有用な物質である。従来、酸素還元触媒とし
ては、種々のものが公知であるが、中でも白金
は、酸素還元触媒として良く知られ、触媒性能の
優れたものであるが、コスト資源的制約の問題が
あり、例えば、燃料電池を実用化するときの問題
点とされている。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
の物質が触媒として評価されて来たが、未だに、
高い特性を有する触媒は発明されていない。
近年、エフ・ベツク（F.Beck）らによるザイ
トシユリフト・フユ・ナチユアホルシユング第
28a巻1009頁（1973）；西独特許公開第2046354号
などにつぎの式(2)で示される構造を有するCo−
TAAが酸素還元触媒として高い活性を示すと報
告されている。しかし、触媒寿命が短いという欠
点のほか活性の面でも満足のいくものではなかつ
た。
また、ワイ・ニシダ（Ｙ、Nishida）らによつ
てプリテン・オブ・ザ・ケミカル・ソサエテイ
ー・オブ・ジヤパン第50巻2485頁（1977）に式(3)
で示されるCo−TAAが報告されている。
このCo−TAAは、この文献内には酸素還元触
媒としての特性については、記載されておらず、
本発明者らが追試を行つたところ、寿命の面では
充分長いものであつたが、活性の面では、不充分
なものであつた。
そこで、本発明者らは、上記欠点の改善され
た、より優れた触媒の開発を進め、多くのCo−
TAA誘導体を合成することによつて、触媒寿命
が長く、かつ、触媒活性の向上を可能にした新規
なCo−TAAを見い出し本発明を完成した。
本発明の対象である新規なCo−TAAは、下記
一般式(1)で示されるものである。
R1は、炭素数が１〜８のアルキル基であり、
R2，R3は、水素、又は、炭素数が１〜８のアル
コキシ基で、少なくともその一方が炭素数１〜８
のアルコキシ基である。中心金属はコバルトであ
る。
この内、酸素還元触媒として優れた活性と寿命
を示すものとしては、R1が炭素数１〜８のアル
キル基であり、R2，R3が、炭素数１〜８のアル
コキシ基であるものである。この具体例として
は、
等である。
本発明のCo−TAAの合成法を下記の反応式で
示す。
本発明のCo−TAAの合成法を下記の反応式で
示す。
原料(a)2.5ミリモルを酢酸コバルト1.25ミリモ
ルと原料(b)2.5ミリモルをジメチルホルムアミド
10mlに溶触し、アルゴン気流下で５時間加熱還流
する。冷却後、過し、メタノールで洗浄し、乾
燥して、生成物(c)を得る。生成物の確認は、可視
スペクトル、質量分析、及び元素分析によつて行
つた。
本発明のCo−TAAの触媒活性の測定は、ポテ
ンシオスタツト計を用いたサイクリツク・ボルタ
モグラム法によつた。
以下、本発明のCo−TAAについての実施例を
示して詳細に説明する。
実施例１〜32を表１に示す。
The present invention relates to a novel tetraazaannulene cobalt complex (hereinafter abbreviated as Co-TAA). The novel Co-TAA of the present invention is a substance useful as an oxygen reduction catalyst. Conventionally, various oxygen reduction catalysts have been known. Among them, platinum is well known as an oxygen reduction catalyst and has excellent catalytic performance, but has the problem of cost and resource constraints, such as: This is considered to be a problem when putting fuel cells into practical use. Therefore, there is a desire to develop a highly active catalyst with a low oxygen reduction potential to replace platinum, and many materials have been evaluated as catalysts, but still...
Catalysts with high properties have not been invented. In recent years, F. Beck et al.
Volume 28a, page 1009 (1973); West German Patent Publication No. 2046354, etc., describes Co-
It has been reported that TAA exhibits high activity as an oxygen reduction catalyst. However, it was not satisfactory in terms of activity as well as short catalyst life. In addition, Y. Nishida et al. published formula (3) in Preteen of the Chemical Society of Japan, Vol. 50, p. 2485 (1977).
Co-TAA shown by has been reported. This document does not describe the properties of Co-TAA as an oxygen reduction catalyst.
When the present inventors conducted a follow-up test, the product was found to have a sufficiently long life span, but was insufficient in terms of activity. Therefore, the present inventors have proceeded with the development of better catalysts that have improved the above-mentioned drawbacks, and have
By synthesizing TAA derivatives, we discovered a new Co-TAA that has a long catalytic life and improved catalytic activity, and completed the present invention. The novel Co-TAA that is the object of the present invention is represented by the following general formula (1). R 1 is an alkyl group having 1 to 8 carbon atoms,
R 2 and R 3 are hydrogen or an alkoxy group having 1 to 8 carbon atoms, and at least one of them is hydrogen or an alkoxy group having 1 to 8 carbon atoms;
is an alkoxy group. The central metal is cobalt. Among these, those showing excellent activity and life as oxygen reduction catalysts include those in which R 1 is an alkyl group having 1 to 8 carbon atoms, and R 2 and R 3 are alkoxy groups having 1 to 8 carbon atoms. It is. A specific example of this is: etc. The method for synthesizing Co-TAA of the present invention is shown by the following reaction formula. The method for synthesizing Co-TAA of the present invention is shown by the following reaction formula. 2.5 mmol of raw material (a), 1.25 mmol of cobalt acetate, and 2.5 mmol of raw material (b), dimethylformamide.
The mixture was dissolved in 10 ml and heated under reflux for 5 hours under an argon atmosphere. After cooling, filter, wash with methanol and dry to obtain product (c). Confirmation of the product was performed by visible spectrum, mass spectrometry, and elemental analysis. The catalytic activity of Co-TAA of the present invention was measured by a cyclic voltammogram method using a potentiostat. Hereinafter, examples of Co-TAA of the present invention will be shown and explained in detail. Examples 1 to 32 are shown in Table 1.
【表】【table】
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【表】
表１の質量分析の１）は、理論値、２）は、実
測値を示す。元素分析の１）は、理論値、２）
は、実測値を示す。可視スペクトルの(a)はシヨル
ダーを示す。
実施例 33
実施例１，５，16，22で示したCo−TAAにつ
いて、酸素還元触媒としての活性測定を行つた。
測定法は、ポテンシオスタツト計を用いたサイク
リツク・ボルタモグラム法によつた。
本発明のCo−TAA800mgを１のジメチルホ
ルムアミドに溶解したものの中に、表面を鏡面仕
上げしたグラツシー・カーボンを30分間浸し、取
り出した後、真空乾燥したものを、カソード電極
とした。対極のアノードは白金コイル、参照極は
カロメル電極、電解液は、1N硫酸、測定温度は
25℃とした。測定は、まず高純度酸素ガスを電解
液に吹きこみ、電位を＋800mVから−600mVま
で走査速度25mV／ｓでスキヤニングを行い発生
する電流を記録する。触媒活性は、＋375mVにお
ける発生電流値により評価した。触媒寿命は、こ
の測定を10回繰り返して評価した。
測定結果を表２に示す。[Table] In Table 1, mass spectrometry 1) shows the theoretical value, and 2) shows the measured value. Elemental analysis 1) is the theoretical value, 2)
indicates actual measured values. (a) in the visible spectrum indicates a shoulder. Example 33 The activity of Co-TAA shown in Examples 1, 5, 16, and 22 as an oxygen reduction catalyst was measured.
The measurement method was a cyclic voltammogram method using a potentiostat. Grassy carbon with a mirror-finished surface was immersed in a solution of 800 mg of Co-TAA of the present invention dissolved in 1 part of dimethylformamide for 30 minutes, taken out, and dried under vacuum to form a cathode electrode. The counter anode is a platinum coil, the reference electrode is a calomel electrode, the electrolyte is 1N sulfuric acid, and the measurement temperature is
The temperature was 25℃. For the measurement, first, high-purity oxygen gas is blown into the electrolytic solution, and the potential is scanned from +800 mV to -600 mV at a scanning speed of 25 mV/s, and the generated current is recorded. Catalytic activity was evaluated by the generated current value at +375 mV. The catalyst life was evaluated by repeating this measurement 10 times. The measurement results are shown in Table 2.
【表】
比較のため、式(2)で示されるCo−TAAについ
て同様の触媒活性の評価を行つた結果、１回目の
測定で発生する電流は、145μA／cm2であつたが、
10回目の測定では、30μA／cm2に低下した。
本発明の実施例１，５，16，22の化合物は、表
２に示す結果より、触媒寿命が十分長いことが推
定され、触媒活性の面でも、式(2)で示されるCo
−TAAと同程度であることが明らかになつた。[Table] For comparison, we conducted a similar catalytic activity evaluation for Co-TAA shown by formula (2), and found that the current generated in the first measurement was 145 μA/cm 2 .
In the 10th measurement, it decreased to 30 μA/cm 2 . From the results shown in Table 2, the compounds of Examples 1, 5, 16, and 22 of the present invention are estimated to have a sufficiently long catalyst life, and in terms of catalytic activity, the Co
- It was revealed that the effect was on the same level as TAA.
Claims (1)
アヌレンのコバルト錯体： R1は炭素数が１〜８のアルキル基であり、R2，
R3は水素又は炭素数が１〜８のアルコキシ基で、
かつ、少なくともその一方が炭素数１〜８のアル
コキシ基である。 ２ R1が、炭素数１〜８のアルキル基であり、
R2，R3が異なる炭素数１〜８のアルコキシ基で
ある特許請求の範囲第１項記載のテトラアザアヌ
レンのコバルト錯体。 ３ R1が、炭素数１〜８のアルキル基であり、
R2，R3が、同一で、かつ、炭素数が１〜８のア
ルコキシ基である特許請求の範囲第１項記載のテ
トラアザアヌレンのコバルト錯体。[Claims] 1. A novel cobalt complex of tetraazaannulene represented by the following general formula (1): R 1 is an alkyl group having 1 to 8 carbon atoms, R 2 ,
R 3 is hydrogen or an alkoxy group having 1 to 8 carbon atoms,
And at least one of them is an alkoxy group having 1 to 8 carbon atoms. 2 R 1 is an alkyl group having 1 to 8 carbon atoms,
The cobalt complex of tetraazaannulene according to claim 1, wherein R 2 and R 3 are different alkoxy groups having 1 to 8 carbon atoms. 3 R 1 is an alkyl group having 1 to 8 carbon atoms,
The cobalt complex of tetraazaannulene according to claim 1, wherein R 2 and R 3 are the same alkoxy group having 1 to 8 carbon atoms.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10254382A JPS58219168A (en) | 1982-06-15 | 1982-06-15 | Novel cobalt complex of tetraazaannulene |
| US06/409,919 US4465630A (en) | 1981-08-24 | 1982-08-20 | Tetraazaannulene cobalt complex compounds and method for preparation therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10254382A JPS58219168A (en) | 1982-06-15 | 1982-06-15 | Novel cobalt complex of tetraazaannulene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58219168A JPS58219168A (en) | 1983-12-20 |
| JPH0372622B2 true JPH0372622B2 (en) | 1991-11-19 |
Family
ID=14330161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10254382A Granted JPS58219168A (en) | 1981-08-24 | 1982-06-15 | Novel cobalt complex of tetraazaannulene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58219168A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5763137A (en) * | 1980-10-04 | 1982-04-16 | Asahi Chem Ind Co Ltd | Catalyst for oxygen reduction |
-
1982
- 1982-06-15 JP JP10254382A patent/JPS58219168A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5763137A (en) * | 1980-10-04 | 1982-04-16 | Asahi Chem Ind Co Ltd | Catalyst for oxygen reduction |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58219168A (en) | 1983-12-20 |
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